CN1077140A

CN1077140A - Production of alkenyl alkanoate catalysts

Info

Publication number: CN1077140A
Application number: CN92103424.5A
Authority: CN
Inventors: W·J·巴特利
Original assignee: Union Carbide Chemicals and Plastics Technology LLC
Current assignee: Union Carbide Chemicals and Plastics Technology LLC
Priority date: 1991-11-18
Filing date: 1992-03-30
Publication date: 1993-10-13
Anticipated expiration: 2007-03-30
Also published as: CN1036377C

Abstract

The invention provides a kind of technology of making the catalyzer that has improved, described catalyzer can be used for preparing alkenyl alkanoate by the reaction between a kind of alkene, a kind of paraffinic acid and a kind of oxygen-containing gas.Catalyzer contains palladium, gold and a kind of potassium promoter, it is characterized in that sodium content is reduced, thereby has improved activity of such catalysts.Total invention is made up of three embodiment (being embodiment A, Embodiment B and Embodiment C).

Description

Production of alkenyl alkanoate catalysts

The present invention relates to a kind of production catalyzer technology of (claiming that from now on they are " alkenyl alkanoate catalysts "), with raw material production alkenyl alkanoates such as cause alkene, paraffinic acid and a kind of oxygen-containing gass.

Known at present the technology of some production alkenyl alkanoate catalysts.

For example, disclose a kind of catalyzer in the U.S. Pat 4048096 of Bissot, the specific activity of this catalyzer is measured under 150 ℃ and per hour is at least about every gram precious metal catalyst generation 83 gram vinylacetates.The vingl acetate catalyst of Bissot is made up of following material basically: (1) a kind of particle diameter from about 3 to about 7mm, porosity is from about support of the catalyst of 0.2 to 1.5ml/g, the pH value of this support of the catalyst 10% weight aqeous suspension is about 3.0 to about 9.0; (2) be dispersed in a kind of polarium in the upper layer of support of the catalyst, this upper layer is distributed in the following about 0.5mm of carrier surface, to about 5.0 grams, gold content is from every liter of extremely about 2.25 grams of about 0.5 gram of catalyzer from every liter of about 1.5 grams of catalyzer for palladium content in the alloy; (3) contain the alkali-metal acetate of 5 grams of having an appointment in every liter of catalyzer to 60 grams.It is active catalytic metals that Bissot has also disclosed palladium, and gold is a kind of promotor.

Bissot also discloses a kind of technology of the Bissot of preparation catalyzer.With people's such as Kronig resemble process, the technology of Bissot also comprises metal salt precipitate on support of the catalyst.Bissot technology is made up of the following step: (1) is immersed support of the catalyst in the aqueous solution of the water miscible palladium and the compound of gold, (2) contact to form the mode of the water-fast palladium and the compound of gold with a kind of aqueous solution of the compound (preferably Starso) that can react by the support of the catalyst that makes dipping with the compound of water-soluble palladium and gold, water-fast palladium and the gold compound precipitation on support of the catalyst, (3) after a kind of reductive agent is handled, with above-mentioned water-fast palladium and the gold compound be transformed on the carrier palladium and the gold these two kinds of metals, (4) water cleaning catalyst, (5) make catalyzer drying (seeing the example 1 of Bissot), (6) with alkali-metal acetate promotor (as a kind of potassium promoter) impregnated catalyst, and (7) make the catalyzer drying.

The disclosed improvement of Bissot comprises that the palladium of alloy morphology and the golden upper layer that disperses to advance support of the catalyst, this upper layer is distributed in the following about 0.5mm of carrier surface.Impregnation steps is to be finished by the aqueous solution of a kind of palladium and gold compound; And the cumulative volume of solution is about 95 to 100% of a support of the catalyst adsorptive power.Settling step in the Bissot method is by finishing with the wet support of the catalyst of a kind of alkali-metal silicate solutions dipping, the definite of alkalimetal silicate amount should make when alkali metal silicate solutions contacts about 12 to 24 hours with support of the catalyst after, and the pH value of described solution is about 6.5 to about 9.5.

Bissot does not report the sodium content of catalyzer in the Bissot example.According to embodiment 1 report of Bissot, the catalyzer of this embodiment has the per hour activity of every liter of catalyst generation 560 gram vinylacetates.In the embodiment III below, discovery is respectively 0.32 and 0.38% weight with the sodium content of two kinds of catalyzer of the embodiment 1 disclosed method manufacturing of Bissot, and its activity reaches per hour every liter of catalyst generation 551 and 535 gram vinylacetates respectively.

Although the level of prior art technology is very high, people still wish further to improve the activity of alkenyl alkanoate catalysts.

On the whole, the invention provides a kind of technology, this technology is by the reaction between a kind of alkene, a kind of paraffinic acid and a kind of oxygen-containing gas, produce be used for improvement that alkenyl alkanoate produces catalyzer.These catalyzer contain palladium, gold and a kind of potassium promoter, and cause having the characteristics that improved catalytic activity owing to sodium content reduces.

In embodiments of the invention A, the reduction of sodium content is by using the starting material that is substantially free of sodium to realize in the technology of producing catalyzer.

In embodiments of the invention B, the reduction of sodium content is by the water cleaning catalyst, perhaps realizes with a kind of aqueous solution cleaning catalyst of potassium promoter after with a kind of potassium promoter impregnated catalyst.

In embodiments of the invention C, the reduction of sodium content is by realizing with the specific intermediate point cleaning catalyst of a kind of cationic exchange solution in the Catalyst Production process.

Embodiments of the invention A is based in part on following discovery: in the process of producing catalyzer, if employing is substantially free of the starting material of sodium and reduce its sodium content, then therefore the activity of alkenyl alkanoate catalysts will improve.

More particularly, embodiments of the invention A provides a kind of technology of producing catalyzer, this catalyzer can be used for the reaction of a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas and produces a kind of alkenyl alkanoate, and described catalyzer is made of carrier granule, and these carrier granules energy exchange cations and process dipping contain the acetate of palladium, gold and potassium.

Described technology comprises the steps:

(a) with the solution impregnating carrier particle of water-soluble palladium with the compound of gold;

(b) with a kind of precipitation agent from above-mentioned solution with water-fast palladium and the gold compound precipitation to carrier granule;

(c) with a kind of reductive agent with the compound of sedimentary water-fast palladium and gold change palladium and gold on the carrier granule into;

(d) water cleans carrier granule;

(e) make the carrier granule drying;

(f) use a kind of potassium promoter impregnated support particles again, and

(g) make impregnated particle drying to make catalyzer;

And what described technology adopted basically in step (b) with (c) is not contain the starting material of sodium so that reduce the amount of sodium in the catalyzer, and then strengthens activity of such catalysts.

Fig. 1 shows the anticipated impact of the vingl acetate catalyst performance that sodium produced foundation embodiment of the invention A.

When implementing embodiments of the invention A technology, in general can use the water-soluble palladium and/or the golden compound that contain sodium, just its consumption is generally not big to causing the degree that contains a large amount of sodium in the catalyzer.Sodium in the alkenyl alkanoate catalysts mainly comes the precipitation agent (for example Starso) of self-contained sodium and/or contains the promotor or the activator (as sodium acetate) of sodium.On lesser extent, some carriers and some reductive agents (as sodium borohydride) also can be introduced catalyzer with a large amount of sodium.Therefore, in this process of enforcement, the precipitation agent (as potassium hydroxide), promotor (as potassium acetate), reductive agent (as hydrazine) and the carrier thereof that are substantially free of sodium have correspondingly been adopted.When adopting potassium hydroxide as precipitation agent, can also in settling step, use a kind of suitable sylvite (as potassium acetate), replace the sodium that is strapped on the carrier to promote potassium.Preferably adopt the aqueous solution of potassium hydroxide and sylvite.The consumption of salt should be 1% to 10% in the total solution weight potassium content.Need during operation carefully with the unlikely height of potassium content in the catalyzer that guarantees to be generated to making catalyst activity be reduced to degree below the expected value.

Used carrier granule is a solid particulate materials in the embodiment of the invention A technology, these materials energy exchange cations (as under the condition that has SiOH or AlOH base), can contain palladium, gold and a kind of potassium promoter with dipping, and be inertia being used for producing under the condition of alkenyl alkanoate.For example, such carrier granule can be granular silica, alumina and silica-alumina.Silica is a carrier preferably.The surface-area of carrier is preferably 100 to 800 square metres of every grams.

The aqueous solution of the compound of used water-soluble palladium and gold comprises the aqueous solution of the compound of any suitable palladium or gold in the embodiment of the invention A technology, and these compounds can be Palladous chloride (II), the sour sodium (Na of tetrachloro palladium (II) ₂PdCl ₄), Palladous nitrate (II), palladous sulfate (II), gold trichloride (III) or tetrachloro gold (III) acid (HAuCl ₄).Liquor capacity is that carrier hole volumetrical 95 to 100% is relatively good, is 98 to 99% better.

Used precipitation agent comprises the silicate and the oxyhydroxide of lithium and potassium in the embodiment of the invention A technology.Precipitation agent preferably adopts the aqueous solution that contains excessive 1.6 to 1.8 moles precipitation agent.The volume of used solution preferably can just not have carrier granule.For avoiding the contingent degraded of carrier, the weight ratio of precipitation agent and carrier can not be too high.For instance, the weight ratio of potassium hydroxide and carrier is not cause carrier that significant degraded takes place at about 0.08: 1 o'clock.

The reductive agent that is adopted in the embodiment of the invention A technology comprises ethene, hydrazine, formaldehyde and hydrogen.Reductive agent preferably adopts and contains by 50: 1(or 10: 1 are better) the aqueous solution of the excessive reductive agent of mole number.If what adopt is hydrogen, need be heated to 100 to 300 ℃ to catalyzer to finish reduction process usually.

The potassium promoter that is adopted in the embodiment of the invention A technology comprises paraffinic acid potassium and any compound that can change a kind of potassium of paraffinic acid potassium in the reaction that generates alkenyl alkanoate into (described reaction is meant that promptly ethene, a kind of paraffinic acid and a kind of oxygen-containing gas under the effect at catalyzer generate a kind of reaction of alkenyl alkanoate).The potassium compound that is suitable for comprises Potassium ethanoate, saleratus, saltpetre, and can also be potassium hydroxide when using a kind of stable carrier.Preferably the form with the aqueous solution adds promotor.

Cleaning step in the embodiment of the invention A technology can intermittently carry out, and also can carry out continuously.Continuous wash efficient is higher, but is not the Catalyst Production that is suitable for extensive (for example plant size) most.In the continuous wash process, rinse water slowly and is continuously passed catalyzer in for some time (as 8 to 24 hours) lining.In interrupted cleaning process, mixture is stayed for some time (for example 0.5 to 2.0 hour), and then water and catalyst separating are opened.When interrupted the cleaning, usually need to carry out for several times (as 2 to 10 times, perhaps more preferably 4 to 6 times) such cleaning, so that impurity (as halogenide) content is reduced to below the aspiration level.No matter be interrupted the cleaning or continuous wash, its temperature range can be 20 ℃ to 80 ℃, and the volume ratio of rinse water and catalyzer all can be 2: 1 to 100: 1.By cleaning step, can from catalyzer, remove some impurity, particularly muriate.

The drying work to catalyzer corresponding to step (e) and step (g) in the embodiment of the invention A technology of producing alkenyl alkanoate catalyzer can any suitable mode be carried out.For instance, drying can carried out in a kind of forced ventilation baking oven 15 to 30 hours under 40 ℃ to 120 ℃ the temperature.

The example of embodiment A

In following example, used following abbreviation meaning is as follows:

The abbreviation meaning

Carrier I mean diameter is 5 to 6 millimeters, contain the silica beads of about 0.1 percent by weight sodium.The surface-area of these pearls is 150 to 200m ²/ g, pore space is 0.6-0.7ml/g.The carrier I contains the SiOH base of energy exchange cation.The carrier I is sold by Sud Chemie AG, and trade mark is " KA-160 ".

STY ^*Generating vinylacetate gram number with every liter of catalyst per hour is the space time yield (measuring of a kind of catalyst activity) of unit.

% selectivity optionally method of calculation is as follows: selectivity=100 * (vinylacetate mole number)/(vinylacetate mole number+1/2 * CO ₂Mole number).

AA analyzes atomic absorption spectrum

ICP inductively coupled plasma atomic emission assay method

The gram number of the g VA/l cat/hr vinylacetate that per hour every liter of catalyzer produced.

* all that reported in the example that occurs below are active all to be based on activity and the selectivity numerical value of being surveyed in 26 hours with following catalyst test method with selectivity numerical value after reaching sufficient oxygen supply.

The VA vinylacetate

The KOAc potassium acetate

E _CThe OAc ethyl acetate

The NaOAc sodium acetate

The % weight percent

The g gram

The ml milliliter

The mm millimeter

Hrs hour

Min minute

In following example, adopted following process:

Catalyst preparation process

Carrier I (15g) is added Na ₂PdCl ₄(35.86%Pd, 0.258g) and HAuCl ₄(48.95%Au 0.094g) is dissolved in the 9.0ml deionized water in the formed solution.Slowly stir the mixture that forms in this way and all be absorbed into carrier, make it at room temperature in an air-tight bottle, to leave standstill about 1 hour then, so that make palladium and golden salt on the carrier band up to all moisture.The potassium hydroxide solution (being dissolved with 0.371g in the 28ml water) that is used as a kind of precipitation agent floods wet catalyzer.In the settling step of a preferred embodiment of the invention, potassium acetate and potassium hydroxide are united use.After mixing several seconds, make mixture at room temperature keep being submerged and no longer be stirred and reach 23 hours, so that the compound of water-fast palladium and gold is deposited on the carrier.Then the hydrazine hydrate of 1.0g85% is added in the said mixture, palladium and gold just are reduced out.Stir the mixture several seconds, and make mixture at room temperature keep being covered and no longer be stirred to reach 23 hours again.Supernatant liquid is outwelled from catalyzer, and with water rinse several times catalyzer to remove the residual metal that exists on a small quantity.With the following thorough cleaning catalyst of post wash procedure to remove muriate and residual agent.Catalyzer place send on the stainless steel sift forced air draft oven 60 ℃ dry 20-24 hour down.With the potassium content in the AA analytical method analysis of catalyst.Then with the above-mentioned impregnation technology of palladium and golden salt that is used for the aqueous solution of catalyst soakage at the potassium acetate of institute's required amount.Made impregnated catalyzer dry 20-24 hour at 60 ℃ then.Measure the content of middle palladium, gold, sodium and the potassium make with the icp analysis method,, also determine the content of sodium and potassium with the AA analytical method simultaneously for for the purpose of accurate.Handle the catalyzer of making in this way with outer pickling process (promptly all basically palladiums and gold all are in the layer of 0.5mm under the carrier I bead surface).

The post wash procedure

Catalyzer is placed 1.24 inches high glass columns of 24 inches of a diameter, and (this chromatographic column is furnished with a Teflon ^TMStopcock) cleans in or clean again.Usually the 15g catalyzer is added in the post, and then inject water.Regulate hanging plug valve to such an extent that make the amount of effusive liquid from post be: at room temperature in about 24 hours time, have 1 liter of liquid to pass catalyzer approximately.During this period of time,, catalyzer is removed, and be dried by above-mentioned Preparation of Catalyst degree with excess liquid emptying from post.

The catalyst test method

Glass microballon dilute catalyst (2.5g 5 to 6mm catalyst spheres samples) with 10.5ml 0.5mm advances the mixture uniformly distributing in two arms of 316 stainless steel U type pipe reactors.3/8 inch of reactor external diameter, about 6 inches of total height.After the heatable catalyst and make system be in 115 pounds/square inch following time of pressure simultaneously, the ethene air-flow of 151ml/min begins to pass reactor when be controlled at 150 ℃ stove in temperature in.After keeping above-mentioned these conditions to reach 1.5 hours, acetic acid vapor is added in the ethene, make mixture pass catalyzer and reach 45 minutes.Air added in the unstripped gas with a speed that slowly increases in 45 fens clock times reach 105ml/min up to total flow rate.Before the beginning image data, catalyzer was stablized 2 hours.Final gaseous constituent is an ethene: acetate: oxygen: nitrogen=52.9: 10.7: 7.7: 28.7, and total gas phase hourly space velocity is about 3800hr ^-1, the hourly space velocity of acetic acid liquid is about 1hr ^-1With gas chromatographic analysis method assay products.The cyclic regeneration rate of used microreactor is about ± 10STY unit in these experiments.

Example 1

The carrier I just contains the sodium of 0.1% weight of having an appointment when manufactory buys.When adopting sodium hydroxide or Starso, also can introduce 0.4% to 0.8% sodium in addition as precipitation agent.As 3 parts of catalyzer of precipitation agent preparation, can reduce the sodium content in the final catalyzer with potassium hydroxide like this.The potassium acetate of different concns is added precipitant solution, the trim point of ion-exchange further is offset to potassium.Catalyzer is used with a collection of masterbatch and is prepared from, and the specified palladium loading level of this batch masterbatch is 0.58 weight %, and the Au/Pd ratio is 0.46.After having cleaned catalyzer with the hydrazine reduction and with the post wash procedure, sodium in the analysis of catalyst and potassium content.Need in addition then to add potassium acetate so that final potassium acetate content reaches about 5.3 weight %.Given result shows that the sodium content in the catalyzer has been lowered in the Table A.Along with the increase of potassium content in the precipitant solution, the sodium content in the catalyzer reduces without exception, and its catalytic activity also improves.

Table A

The preparation of low sodium catalyst

%KOA _c(a) %Na (b) STY % selectivity

0 0.186 576 93.4

2.5 0.121 603 93.2

5.0 0.091 597 93.4

(a) the Wt%(weight percent of potassium acetate in the adding precipitant solution).(b) the Wt% calculated value of sodium in the catalyzer of Sheng Chenging, they are analyzed based on the preceding AA of KOAc dipping, and have considered the amount of added KOAc.

Do with Starso that precipitation agent (replacement potassium hydroxide) is prepared to go out similar catalyzer, its STY is 544, and selectivity is 93.6, and sodium content is 0.44Wt%.In settling step, do not add any potassium acetate.

The example II

With studying sodium to the vingl acetate catalyst Effect on Performance by the experiment of statistical law design, and resulting model can be used for prediction with the performance of the made vingl acetate catalyst of the technology of any embodiment of the present invention (being embodiment A, B and C), and with above mentioned, and the performance of the vingl acetate catalyst of the technology manufacturing of two U.S. Patent applications submitting to simultaneously of the present patent application.The funtcional relationship of weight ratio, potassium content and the catalyst weight of measurable catalyst activity of these models and selectivity thereof and sodium content, palladium loading level, gold and palladium.Table B and C show these models respectively and reach data by it produced.

Because transformation efficiency is to influence the two principal element of catalyst production and selectivity, so can only carry out under constant conversion the significant comparison of catalyzer variable.Be the influence of prediction catalyst component under constant conversion, the oxygen transformation model among the rearrangement table B is to express catalyst weight and palladium content, gold/palladium ratio, the funtcional relationship between potassium content, sodium content and the transformation efficiency thereof.Replace catalyst weight item in STY and the selective model with this catalyst weight item then.Fig. 1 drawn sodium content increase to vingl acetate catalyst active with anticipated impact optionally.Used abbreviation meaning is as follows among table B and the C:

The Wt% of Pd palladium in catalyzer

The weight ratio of gold and palladium in the Au/Pd catalyzer

Cat, Wt are with the catalyst weight of gram expression

The Wt% of K potassium in catalyzer

The Wt% of Na sodium in catalyzer

The empty time yield that the gram numerical table of the vinylacetate that STY generates with every liter of catalyst per hour shows

R ²The correction coefficient of characterization data and model-fitting quality

The RSD relative standard deviation

EtOAc By-Product Rate is with the output of the ethyl acetate of the mole number expression of per hour every kg catalyst catalysis generation

%Heavies By-Product in VA uses the weight percent of the vinylacetate that is generated to represent heavy byproduct.Heavy byproduct is restricted to all products that elution goes out after acetate in the gas chromatographic analysis program.

Table D represents with the influence of the change of showing the sodium content that model prediction goes out among the B to catalyst activity.

(a) unless otherwise, palladium and gold content value are to record with the ICP method, and sodium and potassium value then are to record with atomic absorption analysis.

(b) catalyzer is to be prepared into by sodium acetate and potassium acetate being added in the catalyst II that cleans again by the described method of embodiment of the invention A.The composition of being reported is that basis is to the analysis of this catalyzer and calculating of added sodium acetate and potassium acetate.

Table D

Sodium is to the active anticipated impact of catalyzer *

The per-cent %** that %Na STY improves

0.1 665 0.0

0.2 649 2.5

0.3 633 5.1

0.4 618 7.6

0.5 603 10.3

0.6 581 14.5

0.7 574 15.9

0.8 560 18.8

0.9 546 21.8

^*Be set at 0.58%Pd at one, Au/Pd 0.45 and 2.2%k catalyzer are formed and are set at 35% oxygen conversion.

^*Sodium content is changed by the expection per-cent that the amount shown in first hurdle is reduced to 0.1% STY that causes.

The example III

United States Patent (USP) 4048096(Bissot) program of routine I is repeated below in: prepare two samples (control group 1 and 2), each all adopts 15g carrier I, 0.315g Na ₂PdCl ₄, 0.085g HAuCl ₄, 0.585g Na ₂SiO ₃9H ₂The hydrazine hydrate of O, 0.59g 85% and 0.823g potassium acetate.Owing to not disclose definite wash procedure in the example 1 of Bissot, so the catalyzer of control group 1 is an employing post wash procedure with every gram catalyzer 23ml H ₂The ratio of O is cleaned, the cleaning way of the catalyzer of control group 2 similarly, that just adopt is every gram catalyzer 31ml H ₂This ratio of O.With the palladium and the gold content of ICP method analysis of

control group

1 and 2 catalyzer, with AA method analysis potassium and sodium content wherein.The experimental error that sodium content is measured is estimated as pact ± 0.01 relative percentage.Catalyzer in the control group 1 is divided in duplicate to be analyzed.The results are shown in Table E.

Table E

%Pd %Au %K %Na STY selectivity

Control group 1 0.544 0.201 2.34 0.32 550 93.9

Control group 1 0.556 0.204 2.35 0.32

Control group 2 0.552 0.195 2.34 0.38 535 93.7

Bissot 0.578 ^*0.242 ^*2.08 ^*- 560 ^**93 ^**

* go out according to the Bissot data computation

Disclosed in the * Bissot example 1

The example IV

The measurement activity value of 3 kinds of commercial catalysts (catalyzer X, Y and Z) has been shown among the table F.In table F, the catalyzer (" model catalyst ") that has identical component among the activity of catalysis X agent and Y and any embodiment of the present invention is compared.The expection activity value is according to the model of table B and supposes that sodium content is 0.15% to determine.The expection activity value of model catalyst is relatively high.Because the composition of catalyzer Z is in beyond the table B model scope, so can not similarly compare it.

Catalyzer X is prepared from by this Preparation of Catalyst program.The difference of the preparation of the preparation of catalyzer X and catalyzer Y is in the preparation of catalyzer Y: (1) carries out drying treatment to catalyzer before precipitation, and (2) used precipitation agent is sodium hydroxide rather than Starso.The reduction of two kinds of catalyzer, cleaning, drying and potassium acetate impregnation steps are all identical.

As for catalyzer Y, nominally suffix A, the B of table among the F and C refer to the different sample (" criticize ") of catalyzer identical for catalyzer Y and Z,

suffix

1 and 2 fingers are to from the duplicate analytical results of doing of different samples with a collection of catalyzer.

Palladium content is higher among the catalyzer Z, and adopt a kind of cadmium promotor rather than with the gold.The toxicity of cadmium is much larger than gold.In addition, catalyzer Z is what to utilize with technology of the present invention prepared inequality basically, that is to say that catalyzer Z is by after drying is prepared into the acetate solution impregnated carrier of a kind of palladium, cadmium, potassium.The technology of preparation catalyzer Z need not precipitate, reduction or cleaning step.

Table F

%Pd %Au %Cd %K %Na STY

Catalyzer X ^*0.53 0.22 0 2.36 0.54 272

Model catalyst 0.53 0.22 0 2.36 0.15 589

Catalyzer YA-1 ^*0.49 0.19 0 2.29 0.60 360

Model catalyst 0.49 0.19 0 2.29 0.15 546

Catalyzer YA-2 ^*0.49 0.19 0 2.31 0.60 360

Model catalyst 0.49 0.19 0 2.31 0.15 545

Catalyzer YB ^*0.63 0.24 0 2.27 0.70 386

Model catalyst 0.63 0.24 0 2.27 0.15 669

Catalyzer YC-1 ^*0.61 0.24 0 2.24 0.69 395

Model catalyst 0.61 0.24 0 2.24 0.15 653

Catalyzer YC-2 ^*0.61 0.26 0 2.18 0.70 395

Model catalyst 0.61 0.26 0 2.18 0.15 658

Catalyzer Z-1 ^*2.16 0 1.88 1.89 0.08 685

Model catalyst is beyond model scope

Catalyzer Z-2 ^*2.16 0 1.89 1.92 0.09 685

Model catalyst is beyond model scope

^*Compare catalyzer

Embodiment of the invention B general introduction

Embodiments of the invention B part is based on following discovery: if reduced the sodium content in the catalyzer by water or with a kind of aqueous solution cleaning catalyst of potassium promoter afterwards in the step (7) of United States Patent (USP) 4048096 technologies, then the activity with the alkenyl alkanoate catalysts of this patent technology manufacturing is improved.

More particularly, embodiment of the invention B provides a kind of technology of producing a kind of catalyzer, this catalyzer can be used for the reaction of a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, this catalyzer is made of carrier granule, and these particles can also contain gold, palladium and a kind of potassium promoter through dipping by exchange cation.Described technology comprises the following steps:

(a) with the solution impregnating carrier particle of water miscible palladium and gold compound;

(b) be deposited on the carrier granule from above-mentioned solution with the compound of a kind of precipitation agent water-fast palladium and gold;

(c) with a kind of reductive agent with the compound of sedimentary water-fast palladium and gold change palladium and gold on the carrier granule into; And

(d) water cleans the carrier that is flooded;

(e) make the impregnated carrier drying of being cleaned;

(f) with the further impregnated support particles of a kind of potassium promoter;

(g) carrier drying that makes dipping like this is to generate the exsiccant catalyzer, and this catalyzer contains sodium owing to there being sodium to exist in one or more used in step (a) to (f) materials;

(h) water or with the aqueous solution cleaning-drying that contains a kind of potassium promoter catalyzer reducing the amount of the sodium in the catalyzer, and then improved activity of such catalysts, and

(i) make the catalyzer drying.

When the technology of embodiment embodiment of the invention B, be preferably in and use a kind of aqueous solution that contains potassium promoter in the step (h), be reduced to below the aspiration level with the concentration of avoiding potassium promoter (carrier floods with it exactly) in step (f).If make water after this manner in step (h), undesirable cocatalyst concentration will take place reduce phenomenon.But, if in step (h), used water and therefore caused cocatalyst concentration to reduce fallaciously, then also can follow a step (j) of flooding potassium promoter the second time after the step (i), and step of dry catalyst (k) for the third time then.In some cases, can use excessive potassium promoter in initial potassium promoter impregnation steps (step (f)), to guarantee both to have made water clean (step (h)), potassium promoter also can reach aspiration level in the product of step (i).The program in back also can avoid adopting step (j) and (k).

Owing to do not wish to be limited to any specific theory, it is believed that the potassium promoter that is adopted in the Preparation of Catalyst program of Bissot has been replaced at least partly to be bound by the sodium on the ion exchange site on the support of the catalyst.Sodium derives from Bissot(US4048096) the Preparation of Catalyst program in the starting material (especially precipitation agent) that adopted.Though replaced by potassium promoter, such sodium still suppresses in the catalyzer that active impurity is retained in the manufacturing of Bissot technology as a kind of.In technology of the present invention, only need water or a kind of aqueous solution cleaning catalyst (step (h)) that contains potassium promoter from catalyzer, to dispose those at an easy rate by metathetical sodium.By before the potassium promoter displacement,, can not from catalyzer, dispose sodium effectively in step (f) with simple water washing out method (promptly as step (d) as described in) because sodium very closely is combined on the carrier.But, step (d) can effectively be removed the impurity of nonbonding, particularly from step (a) to the muriate of (c) and excessive reagent.

Brief description to the Embodiment B synoptic diagram

Fig. 1 shows sodium to the anticipated impact according to the made vingl acetate catalyst performance of embodiment of the invention B.

The description of most preferred embodiment B

Used carrier granule is the solid granular material in the embodiment of the invention B technology, and these materials can exchange cation, can flood with palladium, gold and a kind of potassium promoter, and be inertia being used to make under the condition of alkenyl alkanoate.The example of these carrier granules can be particulate state silica, alumina and silica alumina.Silica is best carrier, the best 100-800m of the surface-area of carrier ²/ g.

The used water-soluble palladium and the aqueous solution of gold compound comprise any suitable palladium and the aqueous solution of gold compound in the embodiment of the invention B technology, and these compounds can be Palladous chloride (II), the sour sodium (Na of tetrachloro palladium (II) ₂PdCl ₄), Palladous nitrate (II), palladous sulfate (II), gold trichloride (III) or tetrachloro gold (III) acid (HAuCl ₄).The volume of solution is the 95-100% of suitable carrier porosity preferably, and certainly, 98-99% is better.

Used precipitation agent comprises the silicate and the oxyhydroxide of sodium, lithium, potassium in the Embodiment B of catalyst process of the present invention.Precipitation agent preferably adopts the aqueous solution form of the precipitation agent that contains excessive 1.6-1.8 mole.The amount of used above-mentioned solution preferably just enough there be not carrier granule.

Used reductive agent comprises hydrazine, ethene, formaldehyde, hydrogen and sodium borohydride in the embodiment of the invention B technology.Reductive agent preferably adopts and contains by 50: 1(10: 1 is better) the aqueous solution form of the excessive reductive agent of mole number.If usefulness is hydrogen, must be heated to 100 to 300 ℃ to catalyzer usually and just can finishes reduction process.

The used potassium promoter of Embodiment B technology that the present invention is used for making alkenyl alkanoate catalyzer comprises paraffinic acid potassium and can change a kind of compound of any potassium of paraffinic acid potassium in the reaction that forms alkenyl alkanoate (promptly existing ethene, a kind of paraffinic acid and a kind of oxygen-containing gas under the condition of catalyzer to generate a kind of reaction of alkenyl alkanoate) process.The potassium compound that is suitable for comprises potassium acetate, sodium bicarbonate, saltpetre, and can also be potassium hydroxide when using stable carrier.Preferably adopt the promotor of aqueous solution form.

Cleaning step (d) among the implementation of processes of the present invention example B and (h) can carry out intermittently or continuously.Continuous wash efficient is higher, but is not the Catalyst Production that is suitable for extensive (as plant size) most.In the continuous wash process, washing lotion slowly and is continuously passed catalyzer in for some time (as 8-24 hour) lining.In interrupted cleaning process, catalyzer is contacted with washing lotion, mixture is stayed for some time (as from 0.5-2.0 hour), again liquid and catalyst separating are opened.In interrupted cleaning process, often need carry out so several times cleaning (such as 2-10 time, 4-6 time better).Interrupted clean or the continuous wash process in all can to adopt temperature be that the volume ratio of 20-80 ℃ and scavenging solution and catalyzer is 2: 1-100: 1 such condition.

In the step (h) of implementation of processes of the present invention example B, water or with a kind of work of the aqueous solution flushing catalyzer that contains potassium promoter and to be used for making the potassium promoter impregnation steps of prior art technology of alkenyl alkanoate catalysts completely different.What the impregnation steps of above-mentioned prior art adopted is early stage wet processing or decant technology.In early days in the wet processing (seeing the example 5 in the English Patent 1215210 of National Distillers), catalyzer contacts with the minimum potassium promoter aqueous solution, these aqueous solution are only enough filled the hole of carrier and catalyzer are flooded, and make it to contain the potassium promoter of desired quantity.Then moisture evaporation is fallen.This technology can not be removed the sodium of a tiny bit from catalyzer.In decant technology, catalyzer (preferably exsiccant) is immersed in than in the bigger potassium promoter aqueous solution of amount used in the early stage wet processing.After hole is filled with solution, outwell excessive solution, again catalyzer is carried out drying treatment.Only carry out the operation of a submergence and decant, and duration of contact is shorter.Like this, can only from catalyzer, remove a spot of sodium with decant technology.Example 9 in people's such as sennewald the United States Patent (USP) 3743607 shows the decant technology that adopts a kind of moist catalysis.

The implementation of processes example B step (e), (g), (i) or the drying treatment to catalyzer (k) that are used for making alkenyl alkanoate catalysts according to the present invention can be carried out with any suitable mode.For instance, drying can carried out 15-30 hour in a forced ventilation baking oven under 40 ℃ to 120 ℃.

The example of Embodiment B is described

In the example of following explanation Embodiment B, used abbreviation and the above abbreviation same meaning that is used to illustrate the example defined of embodiment A.

At the following example that is used for illustrating Embodiment B, adopted follow procedure:

The Preparation of Catalyst program

A, carrier I (15g) is added Na ₂PdCl ₄(35.86%Pd, 0.258g) and HAucl ₄(48.95%Au 0.094g) is dissolved in the formed solution of 9.0ml deionized water.Slowly stir formed mixture, all absorb into carrier, mixture was stopped about 1 hour in the bottle of a sealing, so that make palladium and golden salt energy impregnated carrier up to all moisture.The sodium hydroxide (containing 0.236g in the 28ml water) or the Starso that are used as precipitation agent (contain Na in the 28ml water ₂SiO ₃0.837g) solution do not have wet catalyzer.After mixing several seconds, make mixture be submerged and not by the turbulent state under at room temperature kept 23 hours, do not amass to carrier with compound water-fast palladium and gold with.In said mixture, add the hydrazine hydrate of 1.0g 85% then to restore palladium and gold.Mixture is stirred several seconds, and then make it at room temperature to keep being covered and not by turbulent state 23 hours.From catalyzer, outwell supernatant liquid and water flushing catalyzer 4 times to remove remaining little metal.With post wash procedure or the following thorough cleaning catalyst of interrupted wash procedure.Catalyzer placed send into a forced ventilation baking oven on the stainless steel sift, 60 ℃ of oven dry 20-24 hour down.With the potassium content in the AA analytical method analysis of catalyst.Then with the above-mentioned impregnation technology that is used for palladium and golden salt, with the solution impregnating catalyst of a certain amount of potassium acetate.Then, impregnated catalyzer was descended dry 20-24 hour at 60 ℃.The technology of the prior art in the United States Patent (USP) 4048096 of Bissot (be above-mentioned step (e) to (g)) is so far.And the technology of embodiment of the invention B then also has other step (h) and (i), also (j) and (k) in steps if necessary, the narrations below these are visible.

B, measure the content of palladium, gold, sodium and potassium in the catalyzer make with the icp analysis method.In most of the cases, for the purpose of more accurate, also use the content of AA assay sodium and potassium.

C, except as otherwise noted, said procedure will be used for preparing the related all catalyzer of following example.When adopting the carrier I of different amounts, the amount of other used starting material is respective change also.

D, with a layer pickling process (promptly all basically palladiums and gold all concentrate in the layer within the following 0.5mm of carrier I bead surface) flood just like the such catalyzer of making described in following examples.Catalyzer wash procedure (identical) with the example of top explanation embodiment A.The catalyzer method of inspection (identical) with the example of top explanation embodiment A.

The example I

A, comparative example

An important step in the alkenyl alkanoate catalysts preparation process is exactly the muriate that discharges of the known removing of people and the water cleaning step of remaining starting material.In the laboratory, can place catalyzer one post to clean 20-24 hour easily with the ratio of the about 60-80ml water of every gram catalyzer.For reality and reason economically, the interrupted mode of cleaning in the time of a much shorter that extensive (as pilot plant) preparation is adopted, the used water yield of the catalyzer that unit volume is cleaned also significantly reduces.Have now found that the activity of such catalysts that the activity of such catalysts that large-scale equipment is produced is produced than laboratory scale is low.According to conjecture, its activity difference is because the cleaning efficiency in the large-scale equipment is lower.

The typical results of property of the catalyzer that the catalyzer that the table I has compared prepared in laboratory and the large-scale equipment of United States Patent (USP) 4048096 technologies of following Bissot are prepared.Say that exactly all catalyzer are all made as precipitation agent with Starso according to the Preparation of Catalyst program, difference is that the amount of starting material used in the mass preparation process increases in proportion, and the wash procedure of the two also has difference.Use to such an extent that be post wash procedure and mass preparation is used to such an extent that be interrupted wash procedure in the bench scale preparation.The prepared catalyzer of large-scale equipment comprises 80 liters of scale pilot plant samples and is entirely 260 liters of samples that equipment is produced commercially producing and design.The prepared catalyzer of large-scale equipment contains about palladium of 5 to 10Wt% than the catalyzer of prepared in laboratory usually, thereby large-scale equipment prepares the also correspondingly low approximately 5-10% of STY value of catalyzer.

B, embodiments of the invention B

Data in the table I show that the activity of such catalysts of large-scale equipment preparation is lower than the activity of such catalysts of bench scale preparation.For whether the reduction of the catalyst activity of determining extensive manufactured is because clean insufficient, adopt post wash procedure water to clean the catalyst sample (promptly showing sample I-7, I-9, I-12 and I-17 in the I) of (by the step (h) of technology of the present invention) 4 large-scale equipment preparations again, then it is carried out drying treatment (by the step (i) in the embodiment of the invention B technology).The 5th catalyst sample is to adopt Preparation of Catalyst program and interrupted wash procedure to be prepared from a laboratory scale, and a part of this sample adopts the post wash procedure to clean again by step (h) water in the technology of embodiment of the invention B, and then in addition dry by the step (i) of embodiment of the invention B technology.These five clean again and again each in the exsiccant catalyzer all flood again with 5% potassium acetate by the step (j) in the embodiment of the invention B technology so that replenish those supposition cleaning again and exsiccant process again (step in the embodiment of the invention technology (k), in the potassium acetate that has been removed.The results are shown in Table 2, these results show to clean again can both make the active 5-10% of raising

The table II

Again clean influence to catalyst activity

Whether number catalyzer cleans STY % change amount again

Extensive sample

1 ^*I-7 not 521-

2 I-7 are 557+7

3 ^*I-9 not 534 (2)-

4 I-9 are 566+6

5 ^*I-12 not 484-

6 I-12 are 537+11

7 ^*I-17 not 489 (2)-

8 I-17 are 524+5

The laboratory scale sample

9 ^*Not 508-

10 is 561+10

^*Comparative example

The example II

In the described experiment of routine I, suppose that cleaning (step of technology of the present invention (h)) has more also removed whole potassium acetates.So, in those experiments, having added potassium acetate (step of technology of the present invention (j)) again after cleaning again, the amount of adding equals the amount that adopts when catalyzer flooded first.8 hypothesis that the different catalyst sample of potassium loading level checks this and routine I to link with another series.The analytical results done of these 8 catalyzer (catalyst II-1 is to II-8) before the table III shows and to clean and afterwards.Analytical results shows, above the cleaning step again described in the routine I in fact do not dispose all potassium acetates.Result in the table III shows that the potassium of the 0.9Wt% that still has an appointment after cleaning again remains in the catalyzer.It is believed that potassium is attached on the carrier by ion-exchange mechanism.

The table III

Clean removing again with KOA

Wt%K

The difference of cleaning again that catalyzer is original

II-1 2.80 3.67 0.86

II-2 1.50 2.33 0.83

II-3 1.40 2.27 0.87

II-4 1.40 2.35 0.95

II-5 2.70 3.51 0.81

II-6 1.40 2.35 0.95

II-7 2.90 3.64 0.73

II-8 2.80 3.68 0.87

Mean value 0.86

%RSD(b) 8.30

A) use with raw catalyst in after the KOAc of existing identical Wt% floods again.

B) RSD is a relative standard deviation.

The example III

As seen, two shown in the his-and-hers watches II clean sample again and analyzed before replenishing potassium acetate in the data from the table III.Result (as follows) result general and in the table III conforms to.

The residual quantity of cleaning catalyst %K again

Ⅰ-12 0.88

Ⅰ-17 1.19

As a result, the potassium loading level of cleaning catalyst may be all than the high about 0.8-1.2% of desired value again for all that reported in the table II.Potassium content may cause catalyst activity to reduce than anticipation value height.The given enlightenment of these data is that with suitable (lower) final potassium loading level, catalyst activity may improve manyly than the 5-10% shown in the table II.When cleaning the added potassium amount in back more only for comparison test III-1 below realizing during to the initial filling aequum shown in the III-7, this point has obtained confirmation.

Comparison test III-1: measure a 2.5g and be used for the catalyzer that vinylacetate is produced, the given IV that the results are shown in Table.Some part this catalyzer are pressed III-2 is tested in interview and the described step of III-3 is cleaned again.

Test III-2: clean 3 parts from each part in the catalyzer of the 50g of test III-1 with the post wash procedure, analyze its potassium content again, recording the potassium content value is 0.92Wt%.The aqueous solution that is dissolved in the 9.0ml water with the 0.469g potassium acetate floods the such catalyst sample of 15g again, and is following dry 18 hours at 60 ℃ then.Analysis and test result that catalyzer is done see Table IV.

Test III-3: the program of test III-2 above adopting, different is only to have used 4 catalyst II samples, and every duplicate samples (200g) is cleaned 48 hours with 2 gallons waters with the post wash procedure.After will being cleaned material and combining, the potassium content of being measured is 0.86%.With the aqueous solution dipping 15g sample that contains 0.556g potassium acetate and 9.0ml water, then 60 ℃ of dryings 24 hours.Analysis and test result that catalyzer is done see Table IV.

Comparison test III-4: prepare this catalyst sample with the Preparation of Catalyst program, different is to regulate palladium and the concentration of golden salt in dipping solution and other starting material, makes loading level shown in the table IV.With catalyzer method of inspection evaluate catalysts, just catalyst levels only is 0.75g.Analysis and assay see Table IV.

Test III-5: adopt the post wash procedure, will clean 24 hours from the catalyzer of a 2.75g that tests III-4 with 500ml water.After the drying, the potassium acetate impregnated catalyst with capacity makes to contain potassium 3% in the catalyzer of making approximately.With catalyzer method of inspection evaluate catalysts, be that used catalyzer only is 0.75g.Analysis and assay see Table IV.

Comparison test III-6: use interview and test III-4 method and prepare this catalyst sample, different is to regulate palladium and the concentration of golden salt in dipping solution and other starting material, makes loading level shown in the table IV.With catalyzer method of inspection evaluate catalysts, be that used catalyzer only is 0.75g.Analysis and assay see Table IV.

Test III-7: adopt the post wash procedure, water cleans the catalyst sample from test III-6 again.With above-mentioned catalyzer method of inspection evaluate catalysts, be that used catalyzer only is 0.75g.Analysis and assay see Table IV.

The table IV

At constant potassium loading level (a)

Following effect of cleaning again

Test %Pd %Au %KOAc %Na cleans STY % variable quantity again

III-1 ^*0.55 0.22 5.8 0.45 No 565 -

III-2 0.55 0.22 5.3 0.14 Yes 615 +9

III-3 0.5 0.22 5.8 0.12 Yes 642 +14

III-4 ^*0.56 0.46 7.6 0.42 No 734(b) -

III-5 0.56 0.46 7.6 0.17 Yes 850(b) +15

III-6 ^*1.02 0.46 7.2 0.48 No 967(b) -

III-7 1.02 0.47 7.7 0.17 Yes 1141(b) +18

(a) the post wash procedure is used for initial preparation and cleaning process again.

(b) this catalyzer is tested under low-conversion, and this low-conversion is to cause the especially high reason of STY value measured under this metal filled level.

^*Comparative example

On the basis of The above results, study, also can cause above-mentioned effect to determine whether other impurity.To original catalyst and the icp analysis data of the distortion after cleaning again done comparison shows that the sodium content difference of the two is bigger, and the content of other impurity does not have marked difference.

The example IV

For of the influence of check sodium, a series of experiments (test) have been done to catalyst activity.In these trials, sodium content differs from one another, and potassium content remains unchanged.In the experiment of another series, the ratio of sodium and potassium changes, and alkali-metal total mole number remains unchanged.These two groups of experimental results see Table V, and these results confirm: sodium content improves determines to cause catalyst activity to reduce.

In the test 2 of table V, it is more high that the catalyzer of crossing with the sodium content solution impregnation suitable with initial not cleaning catalyst (showing the test 4 in the V) that cleaned again demonstrates activity.This provides an enlightenment, and another kind of detrimental impurity may also be eliminated in cleaning again.

The table V

Sodium is to the influence of catalyst performance

Test %

Number %K %Na STY selectivity

K content constant and Na contain and quantize to change (a)

1 2.24 0.117 642 93.1

2 2.22 0.457 609 93.5

3 2.18 0.912 540 94.1

4 2.31 0.453 563 93.4

Constant and the Na/k of basic metal mole number changes (b)

1 2.21 0.435 616 93.6

2 1.77 0.705 584 94.0

3 0.77 1.300 501 94.2

(a) carried out the catalyst II KOA that post cleans again _CAnd NaOA _CSolution floods again.

(b) in the sub-sample of catalyzer I masterbatch, suitably add KOA _CAnd NaOA _CAnd be prepared into.

Embodiment of the invention C general introduction

Embodiment of the invention C is partly based on following discovery: reduce its sodium content by the some specific intermediate point in Catalyst Production with a kind of cationic exchange solution cleaning catalyst, then therefore the activity of alkenyl alkanoate catalysts can increase.

More particularly, embodiments of the invention C provides a kind of technology of making a kind of catalyzer.This catalyzer can be used for the reaction of a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas and generates a kind of alkenyl alkanoate, and this catalyzer is made of carrier granule, and these carrier granule exchangeable cation also carried out dip treating with the acetate of palladium, gold and potassium to it.Described technology may further comprise the steps:

(a) the solution impregnating carrier particle of usefulness water-soluble palladium and gold compound;

(b) with a kind of precipitation agent from above-mentioned solution water-fast palladium and the gold compound precipitation on carrier granule;

(c) with a kind of reductive agent the water-fast palladium and the golden compound that are deposited on the carrier granule are converted into palladium and gold, so that prepare the impregnated carrier that contains sodium, containing sodium in the carrier is owing to there being sodium to exist in one or more used in step (a) to (c) materials;

(d) clean impregnated carrier granule with a kind of cationic exchange solution,, and improve activity of such catalysts so that reduce the amount of sodium in the catalyzer; And

(e) to carrying out drying treatment, to produce catalyzer through the carrier granule that cleans with dipping.

If think further to improve activity of such catalysts with the manufacturing of embodiment of the invention C technology, also can be succeeded by the following step after the above-mentioned steps:

(f) carrier granule of crossing with a kind of potassium promoter impregnation drying; And

(g) to carrying out drying treatment (test I-2A and Fig. 1 of face as follows) through the catalyzer that floods once more.

But, as above preferably by what realize below in conjunction with the described mode of most preferred embodiment of the present invention, this most preferred embodiment comprises that the specific ion exchanged soln (being potassium promoter solution) that uses specific concentrations and amount is to realize above-mentioned purpose (being also shown in following routine VII to XII and Fig. 3) in the further raising of catalyst activity.

Embodiments of the invention C also provides sodium content to reduce alkenyl alkanoate catalysts and with the technology of these Catalyst Production alkenyl alkanoates.

Owing to do not wish to be confined to any concrete theory, it is believed that the sodium impurity in the alkenyl alkanoate catalysts can reduce activity of such catalysts, and the positively charged ion in the used cationic exchange solution can be replaced sodium (perhaps can carry out other impurity of ion-exchange in addition) from carrier in the step (d) of embodiment of the invention C technology, and the result is (d) impurity on can the flush away carrier set by step.The result that sodium content reduces is that activity of such catalysts is improved.

The concise and to the point description of synoptic diagram to the explanation Embodiment C

Fig. 1 shows the anticipated impact of sodium to the vingl acetate catalyst performance made with the inventive method.

Fig. 2 shows the various interrupted cleaning experiment of being done according to embodiment of the invention C.

Fig. 3 shows the Preparation of Catalyst program in the most preferred embodiment of the preparation procedure of vingl acetate catalyst of United States Patent (USP) 4048096 and embodiment of the invention C.

Fig. 4 shows the influence of wash procedure to catalyst activity among the embodiment of the invention C.

Description to the most preferred embodiment of Embodiment C

The technology of preparation catalyzer

In the technology of the embodiment of the invention C that is used for making alkenyl alkanoate catalysts, used cationic exchange solution be those contain a kind of can with the solution of sodium exchange on the carrier, this positively charged ion can not weaken and preferably can improve activity of such catalysts.The cationic exchange solution that is suitable for includes, but is not limited to the solution of potassium promoter.Best cationic exchange solution contains the aqueous solution of a kind of compound (this compound contains a kind of suitable positively charged ion) of 0.01 to 20Wt% for those.These compounds include, but is not limited to potassium acetate, lithium acetate, saltpetre, salt of wormwood, volatile salt, ammonium acetate and magnesium acetate.It is the most desirable that preferable solution is that those contain 0.1-10Wt%(0.5-7Wt%) the solution that has a kind of suitable cationic compound.

For saving the consumption that in cationic exchange solution (these solution are used for making the technology of the embodiments of the invention C of alkenyl alkanoate catalysts), contains cationic compound, before with cationic exchange solution cleaning catalyst, elder generation's water cleans one or many, combines not tight impurity (as the sodium of muriate and nonbonding) with carrier to remove those.

The optimum concn that is used for producing the used ion exchanged soln of the embodiment of the invention C technology of alkenyl alkanoate catalysts depends on many factors, amount as the sodium content in the catalyzer, used cleaning solution, total scavenging period or the like is preferably determined by experiment.Contain a kind of suitable cationic compound concentrations and be about 10% or comparatively inadvisable when higher, because can waste these compounds like this and catalyst activity is reduced.

Be used for making used potassium promoter in the embodiment of the invention C technology step (d) of alkenyl alkanoate catalysts or the step (f) and comprise paraffinic acid potassium and any potassium compound that in the reaction that forms alkenyl alkanoate (promptly a kind of alkene, a kind of paraffinic acid and a kind of oxygen-containing gas generate a kind of reaction of alkenyl alkanoate under the condition that catalyzer exists) process, is converted into a kind of paraffinic acid potassium.The potassium compound that is suitable for comprises potassium acetate, saleratus, saltpetre, and can also be potassium hydroxide when a kind of stable carrier of employing.Preferably use the promotor of the aqueous solution.

When the positively charged ion in the used cationic exchange solution of the step (d) of the embodiment of the invention C technology that is used for producing alkenyl alkanoate catalysts was potassium ion, therefore potassium just be introduced in the catalyzer.In these cases, carry out dry to catalyzer and analyze wherein potassium content with determining step (f)) in add into how much potassium on earth.This program is necessary, and it can avoid the potassium content of the catalyzer produced excessive or not enough, and each in the both of these case can both make catalyst activity reduce.

The step (d) that is included in the most preferred embodiment that is used for making the embodiment of the invention C technology of alkenyl alkanoate catalysts adopts a kind of potassium promoter solution as cationic exchange solution and what adopt in this step is concentration and all enough potassium promoter solution of amount, so just no longer need to adopt potassium acetate impregnation steps (step (f)) and the second time drying step (step (g)).Fig. 3 shows present embodiment.

More particularly, the most preferred embodiment that is used to make the embodiment of the invention C technology of alkenyl alkanoate catalysts comprises the following steps:

(b) with a kind of precipitation agent from above-mentioned solution water-fast palladium and the gold compound precipitation to carrier granule;

(c) with a kind of reductive agent the compound of sedimentary water-fast palladium of institute and gold is converted into palladium and gold on the carrier granule, described impregnated carrier is owing to there being the sodium existence to contain sodium in one or more used in step (a) to (c) materials;

(d) clean carrier granule with a kind of potassium promoter solution, the concentration of described potassium promoter solution and amount all are enough to: (I) reduces the amount of sodium in the catalyzer to improve activity of such catalysts, and (II) further impregnated catalyst, to the potassium that wherein is injected to the necessary quantity of this activity of such catalysts of further raising;

(e) to carrying out drying treatment, to produce catalyzer through the carrier granule that cleans and further flood.

Suitable potassium promoter concentration will depend on many factors among the used cationic exchange solution in the cleaning step (d) of the most preferred embodiment of embodiment of the invention C, as the expection activity of ion-exchange performance and the pore space and the catalyzer of solid support material.For this reason, ideal concentration is preferably determined by normal experiment.Have now found that 5% potassium acetate solution can draw result preferably.

When the catalyst preparation process described in the United States Patent (USP) 4048496 that adopts Bissot, when cleaning, have some colloidal palladiums and be rinsed down from support of the catalyst with gold.Implementing another benefit of the present invention is, in the Preparation of catalysts process, metal can more effectively be utilized when adopting potassium acetate solution as cationic exchange solution.Beat all is that in implementing process of the present invention, when adopting potassium acetate solution as cationic exchange solution, the palladium of not discovery amount on detectability and gold are cleaned from support of the catalyst.Below routine I-1A and I-2A show, with Bissot technology from catalyzer flush away palladium and the gold of 1Wt%, do not measure these metals on detectability but found flush away with technology of the present invention.This advantage has not only improved the efficient of metal deposition, and has reduced the cost that reclaims precious metal from washing lotion.

Being used for making the carrier granule that the embodiment of the invention C technology of alkenyl alkanoate catalysts adopted is the solid granular material, these materials energy exchange cations, impregnated mistake contains palladium, gold and a kind of potassium promoter, and is inertia being used to make under the condition of alkenyl alkanoate.The example of above-mentioned carrier can be granular silica, alumina and silica alumina.Silica is best carrier.The surface-area of carrier is preferably 100-800m ²/ g.

Be used for making the used water-soluble palladium of the embodiment of the invention C technology of alkenyl alkanoate catalyzer and the aqueous solution of gold compound and comprise any suitable palladium or the aqueous solution of gold compound, these compounds such as Palladous chloride (II), the sour sodium (Na of tetrachloro palladium (II) ₂PdCl ₄), Palladous nitrate (II), palladous sulfate (II), gold trichloride (III) or tetrachloro gold (III) acid (HAuCl ₄).The 95-100%(98-99% that the amount of solution preferably is equivalent to the carrier pore space is better).

The used precipitation agent of embodiment of the invention C technology that is used for producing alkenyl alkanoate catalysts comprises the silicate and the oxyhydroxide of sodium, lithium and potassium.Precipitation agent preferably adopts the aqueous solution form of the precipitation agent that contains excessive 1.6-1.8 mole.The amount of used above-mentioned solution preferably just enough there be not carrier granule.

The used reductive agent of embodiment of the invention C technology that is used for making alkenyl alkanoate catalysts comprises hydrazine, ethene, formaldehyde, hydrogen and sodium borohydride.Reductive agent preferably adopts and contains by 50: 1(or 10: 1 are better) the aqueous solution form of the excessive reductive agent of mole number.If what adopt is hydrogen, need be heated to 100 ℃ to 300 ℃ to catalyzer to finish reduction process usually.

Being used for making the cleaning step (step (d)) that the embodiment of the invention C technology of alkenyl alkanoate catalysts adopted can intermittently also can carry out continuously.Continuous wash efficient is higher but be not the Catalyst Production that is suitable for extensive (as plant size) most.In the continuous wash process, cationic exchange solution slowly and continuously passes catalyzer in for some time (as 8-24 hour) lining.In interrupted cleaning process, catalyzer is contacted with cationic exchange solution, mixture is stayed for some time (as from 0.5-2.0 hour), again solution and catalyst separating are opened.In interrupted cleaning process, often need carry out so several times cleaning (such as 2-10 time, 4-6 time better), so that the sodium content in the catalyzer is reduced to aspiration level.Interrupted clean or the continuous wash process in all can to adopt temperature be 20-80 ℃ and cationic exchange solution and the ratio of catalyzer is 2: 1-100: 1 such condition.

Completely different with the potassium promoter impregnation steps of the prior art technology that is used for making alkenyl alkanoate catalysts according to the embodiment of the invention C technology step (d) that is used for making alkenyl alkanoate catalysts with a kind of step of cationic exchange solution cleaning catalyst.What the impregnation steps of above-mentioned prior art adopted is early stage wet processing or decant technology.In early days in the wet processing (seeing the example 5 in the English Patent 1215210 of National Distillers), catalyzer contacts with the minimum potassium promoter aqueous solution, these aqueous solution are only enough filled the hole of carrier and catalyzer are flooded, and make it to contain desired quantity potassium promoter.Then moisture evaporation is fallen, this technology can not be removed the sodium of a tiny bit from catalyzer.In decant technology, catalyzer (preferably doing) is immersed in than in the bigger potassium promoter aqueous solution of amount used in the early stage wet processing.After hole is filled with solution, outwell excessive solution, again catalyzer is carried out drying treatment.Only carried out the operation of a submergence and decant, and duration of contact is shorter.Like this, can only from catalyzer, remove a spot of sodium with decant technology.Example 9 in people's such as Sennewald the United States Patent (USP) 3743607 shows the decant technology that adopts a kind of moist catalysis.

Can carry out with any usual manner the drying treatment of catalyzer according to step (e) among the embodiment of the invention C that makes alkenyl alkanoate catalysts.For instance, drying can carried out 15-30 hour in a forced ventilation baking oven under 40 ℃ to 120 ℃.

The example of Embodiment C is described

In the example of following explanation Embodiment C, the abbreviation same meaning of those regulations that the example of used abbreviation and explanation embodiment A is used.

In following example, adopted follow procedure:

The Preparation of Catalyst program

A, carrier I (15g) is added Na ₂PdCl ₄(35.86%Pd, 0.258g) and HAuCl ₄(48.95%Au 0.094g) is dissolved in the formed solution of 9.0ml deionized water.Slowly stir formed mixture, all absorb into carrier, mixture is sealed in the bottle one stopped about 1 hour, so that impregnated carrier makes it contain the salt of palladium and gold up to all moisture.The sodium hydroxide (containing 0.236g in the 28ml water) or the Starso that are used as precipitation agent (contain Na in the 28ml water ₂SiO ₃0.837g) solution floods wet catalyzer.After mixing several seconds, make mixture be submerged and not by the turbulent state under at room temperature kept 23 hours, with water-fast palladium and the gold compound deposit on the carrier.In said mixture, add the hydrazine hydrate of 1.0g 85% then to restore palladium and gold.Mixture is stirred several seconds, and then make it at room temperature to keep being submerged and not by turbulent state 23 hours.From catalyzer, outwell supernatant liquid and water flushing catalyzer 4 times to remove remaining little metal.With post wash procedure or the following thorough cleaning catalyst of interrupted wash procedure.Catalyzer placed send into a forced ventilation baking oven on the stainless steel sift, 60 ℃ of oven dry 20-24 hour down.When implementing the most preferred embodiment of embodiment of the invention C, the Preparation of Catalyst program is so far.

B, at other embodiment that implements embodiment of the invention C and when implementing prior art program and following comparative example, the Preparation of Catalyst program also comprises following additional step: with the potassium content in the AA analytical method analysis of catalyst.Adopt the above-mentioned dipping technique that is used for palladium and golden salt then, impregnated catalyst makes it to contain the potassium acetate (being dissolved in the water) of desired quantity.Then the catalyzer that is flooded was descended dry 20-24 hour at 60 ℃.

C, measure palladium, gold, sodium and potassium content in the catalyzer generated with the ICP method.Under most of situations, for the purpose of accurately, also use AA assay sodium and potassium content.

D, except as otherwise noted, said procedure will be used for preparing all catalyzer of following example.When adopting the carrier of different amounts, the amount of other used starting material is respective change also.

E, flood catalyzer that all are made by the method described in the example that occurs below with outer pickling process (promptly all basically palladiums and gold all concentrate in the layer within the carrier I bead surface 0.5mm).

Method used in the example of catalyzer wash procedure and the catalyzer method of inspection and top explanation embodiment A is identical.

Example 1

Comparison test I-1A: as precipitation agent, flood 90g carrier I sample by method described in the Preparation of Catalyst journey with Starso.After reduction step, remove supernatant liquid, wet microballon is divided into three equal parts, represent with sample A, B, C.Keeping sample B and C are provided with the back and use.With sample A not drying directly send into washing unit, clean by post wash procedure water.Take from the palladium and the gold content of the black washings of the muddiness in the post with the analysis of ICP method.The result shows that every kind of metal in the catalyzer all has 1% to run off approximately in cleaning process.Catalyzer is sent into a forced ventilation baking oven, and drying is 4.5 hours under 60 ℃, analyzes potassium content (0.31Wt%) wherein then.According to the described program of Preparation of Catalyst program, be dissolved in formed solution impregnation catalyst (30.4g) in the 18.3ml water more than utilizing with the 1.62g potassium acetate.After under 60 ℃ dry 24 hours, the activity of detecting catalyst.The results are shown in Figure 1.

Test I-1B: adopt the post wash procedure, water is to being cleaned by the made a catalyzer of sample A described in above-mentioned test I-1B again, and carries out drying.And then add a certain amount of potassium acetate, to increase the content of potassium acetate, make it be returned to initial level.The results are shown in Figure 1.

Test I-2A: the still catalyst sample B of humidity for preparing among test I-1A above cleaning with above-mentioned post wash procedure, difference is to adopt is 1% potassium acetate solution (a kind of cationic exchange solution) rather than water.Washings is colourless, and can not detect palladium and gold with the ICP method.With aforesaid method the catalyzer that cleaned is carried out drying treatment, and analyze its potassium content (1.41%).With 0.608g potassium acetate formed solution impregnation catalyst in 17.8ml water, following dry 24 hours at 60 ℃ then.Test result is seen Fig. 1.

Test I-2B: adopt the post wash procedure, water cleans a catalyzer from top test I-2A again, carries out drying then.Add a certain amount of potassium acetate then to increase the content of potassium acetate, make it to be returned to its initial level.The results are shown in Figure 1.

Test I-3: by the sample C that tests I-1A above the method processing identical with testing I-2A sample B method above the processing, just the potassium hydroxide with 1% has substituted 1% potassium acetate solution in cleaning step.After static 12 hours, find that silica carrier is badly damaged, have to catalyzer is thrown away.This experiment shows under the condition that is adopted, and when the carrier that adopts the highly basic sensitivity, potassium hydroxide is unsuitable for being used as cationic exchange solution of the present invention.

Result among Fig. 1 shows, by adopting the potassium acetate washing lotion at the very start, or water cleans then water cleaning again after with the potassium acetate dipping during beginning, can improve activity of such catalysts equally.These results have confirmed a theory: when having detrimental impurity on catalyzer and the carrier, add potassium and help to remove this impurity.

The example II

It is believed that having the part muriate at least is to test the impurity of being removed described in the routine I above utilizing.But, the muriate analysis (see figure 4) that the catalyzer for preparing in the routine I is done shows that the chloride content before and after cleaning again only has faint difference subsequently.Other experiment that adds different quantities Repone K in catalyzer also shows only has atomic weak influence (seeing Table G) to activity of such catalysts.

Table G

Add muriatic influence

Muriate (ppm) STY % selectivity

0 605 93.7

50 601 93.7

100 598 93.5

Be used for the catalyzer of result shown in the acquisition table G with the Preparation of Catalyst program from the preparation of a collection of masterbatch, the specified palladium loading level of this batch masterbatch is 0.58%, the Au/Pd ratio is 0.5, KOAc loading level 5.3% estimates that initial chloride content is about 200ppm.Muriate adds the KOAc dipping solution with the form of KCl.

On the basis of The above results, study, to determine whether that other impurity can cause above-mentioned influence in addition.Will be to original catalyst and clean again after comparison shows that of carrying out of the icp analysis data done of modification; The sodium content difference of the two is bigger, and does not find that the content of other impurity has marked difference.

The example III

For of the influence of check sodium to catalyst activity, carried out a series of experiments (test), in these experiments, sodium content is different, and potassium content remains unchanged.In another group serial experiment (test), sodium is constant with the ratio variation and the maintenance basic metal total mole number of potassium.These two groups of serial experiments the results are shown in Table H.These results show that the increase of sodium content in fact makes catalyst activity reduce really.

In the test 2 of table H, a kind of impregnated contain with the cleaning again of the sodium of the primary quantity that cleaning catalyst (test 4 of following table H) is not close after catalyzer show quite high activity.This provides an enlightenment: may also have other detrimental impurity to be eliminated in the cleaning process again.

Table H

Sodium is to the influence of catalyst performance

Test number %K %Na STY % selectivity

K content constant and Na content change (a)

1 2.24 0.117 642 93.1

2 2.22 0.457 609 93.5

3 2.18 0.912 540 94.1

4 2.31 0.453 563 93.4

Na/K changes and basic metal mole number constant (b)

1 2.21 0.435 616 93.6

2 1.77 0.705 584 94.0

3 0.77 1.300 501 94.2

(a) with KOAc and NaOAc solution the catalyzer through post cleaning is once more flooded again.

(b) be prepared into by in the sub-sample of catalyzer I masterbatch, suitably adding KOAc and NaOAc.

The example IV

Do one group of experiment (following test IV-1 is to IV-4) with the influence shown in the routine I above further specifying.An other purpose of this group experiment is to think explanation: benefit of the present invention also can utilize interrupted wash procedure to obtain, and this program is more suitable in extensive Catalyst Production than the post wash procedure that has adopted in the top routine I.

Comparison test IV-1: adopt the Preparation of Catalyst program, prepare catalyzer with 80g carrier I.With sodium hydroxide as precipitation agent.After reduction step, liquid is discharged from the catalyzer microballon, get microballon express developed with the volume water roughly suitable then with catalyst volume.Catalyzer is divided into quarter, is designated as sample A, B, C and D.Sample B, C and D wait until in the later example and use.Adopt interrupted wash procedure to clean sample A, this program comprises with the 23ml deionized water there be not catalyzer, and makes it to stop 36 minutes.Outwell above-mentioned water and do not have catalyzer with the 23ml fresh water in addition.In this way, clean carrying out 5 times altogether in 3 hours altogether.After last the cleaning, water washes microballon once again, then 60 ℃ of down dry a whole nights.Potassium content in the analysis of catalyst (0.30%), the solution impregnation catalyst that in 11.7ml water, forms with the 0.955g potassium acetate then.After 60 ℃ of down dry a whole nights, catalyzer is made an appraisal, the results are shown in Table I.

Test IV-2: adopt with top test IV-1 in specified identical program, test the sample B in the IV-2 above cleaning with the potassium acetate solution of 23ml 5% is interrupted, in 3 hours, carry out 5 such cleanings altogether.After water has washed microballon, catalyzer 60 ℃ of down dry a whole nights, is analyzed its potassium content (1.42%) then.The solution impregnation catalyst that in 11.7ml water, forms with the 0.359g potassium acetate then.Make catalyzer after 60 ℃ of down dry a whole nights, evaluate catalysts, gained the results are shown in Table I.

Comparison test IV-3: by and the identical mode of top test IV-1, water cleans from the sample in the top test IV-1 C5 time, difference is each the cleaning lasting 96 minutes, scavenging period is altogether 8 hours.Analysis revealed, the potassium content after the cleaning are 0.33%.With 0.934g potassium acetate formed solution impregnation sample in 11.7ml water, then 60 ℃ of down dry a whole nights.Test result sees Table I.

Test IV-4: the program of test IV-3 above adopting, the potassium acetate solution with 5% cleans the sample D from top test IV-1, cleans altogether 5 times.Analysis revealed, the potassium content after the cleaning are 1.69%.With 0.216g potassium acetate formed solution impregnation sample in 11.7ml water, then 60 ℃ of down dry a whole nights.Test result sees Table I.

The table I

Intermittently clean with potassium acetate Effect on Performance

Test %K %Na STY

IV-1* 2.2 0.47 512

IV-2 2.4 0.22 531

IV-3* 2.1 0.47 535

IV-4 2.2 0.19 573

* comparative example

The example V

Carrying out one group further tests to determine to significantly improve the optimal cost benefit amount of active required potassium acetate.In these experiments, the catalyzer that portion is heavy dose of is at 6 equal portions shown in the preceding Fig. 2 of being divided into of cleaning step (being the step (d) of technology of the present invention).Adopt interrupted wash procedure, intermittently clean all catalyzer, clean altogether 5 times.The variation of the composition of cleaning solution as shown in Figure 2.Such as, can intermittently clean first part of catalyzer 5 times for water; Water cleans second part and cleans 2 times with 5% potassium acetate solution then for 3 times again, or the like.Make the catalyzer drying, use atomic absorption spectrometry potassium and sodium content then.Every part of catalyzer is subdivided into " A " and " B " two portions again.Handle each part with the potassium acetate of capacity then, make potassium content in the catalyzer of generation about 2.9%.Those catalyst members that are labeled as " B " have also absorbed the sodium acetate of capacity, make their final sodium contents be returned to the catalyzer that cleans through water in contained roughly the same level (level in the catalyzer that V-1 water cleans is tested in following interview).

So just obtained two groups of catalyzer: one group (" A " series) has shown that potassium acetate cleans the influence to catalyst performance; Second group (" B " series) has shown the contribution of suitable removing sodium to this influence.These results are summarized among the table J.

Comparison test V-1: adopt the Preparation of Catalyst program, prepare catalyzer with 100g carrier I and Starso.After the reduction step, outwell solution, water flushing catalyzer 4 times.Venting precipitation agent and reductant solution are divided into 6 equal portions with still moist catalyzer, are labeled as A, B, C, D, E and F respectively.Sample B to F waits until in the following example and uses.Intermittently cleaning sample A5 time with 20ml water in 8 hours altogether at every turn.After 60 ℃ of down dry a whole nights,, dry down at 60 ℃ then with the solution impregnation catalyst that the 1.098g potassium acetate forms in 9.6ml water.The catalyzer (its potassium, sodium content calculated value see Table J) that is generated is carried out the active evaluation of relevant vinylacetate.The results are shown in Table J.

Test V-2: by the interrupted sample B that cleans from top test V-1 of the mode identical with top test V-1, difference is that first three time water cleans, and back secondary cleans with 5% potassium acetate solution.After 60 ℃ of down dry a whole nights, catalyzer is halved.The solution impregnation first part that in 4.6ml water, forms with the 0.26g potassium acetate.After 60 ℃ of following dryings, catalyzer has the listed composition that calculates in the table J(test V-2A), and what provide the results are shown in the same table.Second the moiety sample of solution impregnation that in 4.6mL water, forms with 0.26g potassium acetate and 0.090g sodium acetate.Composition that calculates and test result see Table J(test V-2B).

Test V-3: by the interrupted sample C that cleans from top test V-1 of the mode identical with top test V-1, difference is preceding twice water for cleaning, the back potassium acetate solution that cleans with 5% for three times.After 60 ℃ of down dry a whole nights, catalyzer is halved.The solution impregnation first part that in 4.6ml water, forms with the 0.20g potassium acetate.After the drying, this catalyzer has the composition that calculates shown in the table J(test V-3A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.20g potassium acetate and 0.097g sodium acetate.Composition that calculates and test result see Table J(test V-3B).

Test V-4: by the interrupted sample D that cleans from top test V-1 of the mode identical with top test V-1, difference is water for cleaning for the first time, the back potassium acetate solution that cleans with 5% for four times.After 60 ℃ of down dry a whole nights, catalyzer is halved.The solution impregnation first part that in 4.6ml water, forms with the 0.155g potassium acetate.After the drying, this catalyzer has the listed composition that calculates in the table J(test V-4A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.155g potassium acetate and 0.094g sodium acetate.Dried composition that calculates and test result see Table J(test V-4B).

Test V-5: by the interrupted sample E that cleans from top test V-1 of the mode identical with top test V-1, difference is first three time water for cleaning, and twice cleaning in back is with 10% potassium acetate solution.After 60 ℃ of down dry a whole nights, catalyzer is halved.The solution impregnation first part that in 4.6ml water, forms with the 0.032g potassium acetate.After the drying, this catalyzer has the composition that calculates shown in the table J(test V-5A), and what provide the results are shown in the same table.Second moiety sample of formed solution impregnation in 4.6ml water with 0.032g potassium acetate and 0.098g sodium acetate.Dried composition that calculates and test result see Table J(test V-5B).

Test V-6: by the interrupted sample F of cleaning from top test V-1 of the mode identical with top test V-1, difference is preceding twice water for cleaning, then the potassium acetate solution that cleans with 10% for three times.After 60 ℃ of down dry a whole nights, catalyzer is halved.First part is no longer directly carried out drying and portioning with the further dipping of potassium acetate.The results are shown in the same table of catalyzer with composition that calculates listed in the table J(test V-6A).With 0.12g sodium acetate second moiety sample of formed solution impregnation in 4.6ml water.Dried composition that calculates and test result see Table J(test V-6B).

Table J

The interrupted cleaning studied

Test number %K (a) %Na (a) STY % selectivity washing lotion and order

Reduce sodium-" series A "

V-1* 2.83 0.518 527 93.7 5×H ₂O

V-2A 2.87 0.268 603 93.3 3 * H ₂O adds 2 * 5%KOAc

V-3A 2.88 0.249 615 93.2 2 * H ₂O adds 3 * 5%KOAc

V-4A 2.90 0.258 630 93.2 1 * H ₂O adds 4 * 5%KOAc

V-5A 2.94 0.247 604 93.3 3 * H ₂O adds 2 * 10%KOAc

V-6A 2.95 0.181 571 93.5 2 * H ₂O adds 3 * 10%KOAc

Reduce Na and then adding-" serial B "

V-1* 2.83 0.518 527 93.7 5×H ₂O

V-2B* 2.84 0.554 516 93.6 3 * H ₂O adds 2 * 5%KOAc

V-3B* 2.85 0.558 519 93.9 2 * H ₂O adds 3 * 5%KOAc

V-4B* 2.86 0.561 534 93.5 1 * H ₂O adds 4 * 5%KOAc

V-5B* 2.90 0.567 502 93.8 3 * H ₂O adds 2 * 10%KOAc

V-6B* 2.90 0.574 488 94.1 2 * H ₂O adds 3 * 10%KOAc

(a) estimated value.Amount according to AA analytical results before the KOAc/NaOAc dipping and the acetate that added is calculated.

* comparative example

As seen, take test V-1 to compare to V-6A with test V-2A from table J, " A series " activity of such catalysts significantly improves, and these raisings conform to the reduction of these catalyzer sodium contents substantially." B series " catalyst data shows, sodium added again the level (take test V-1 and test V-2B to V-6B relatively) that " A series " catalyzer can be reduced to catalyst activity the catalyzer initial, that water cleaned.These results have supported this viewpoint once more, i.e. the removal of sodium makes viewed active the raising.

The example VI

Come from the effluent of post wash procedure and interrupted wash procedure terminal several times in the catalyst preparation process with ion chromatography analysis.These tests comprise adopts water and potassium acetate solution as washing lotion simultaneously, and the purpose of these experiments is in order to detect any impurity that the icp analysis method may not measured.It seems that vitriol be major impurity, however according to estimates its content in original catalyst less than 100ppm.Detect the phosphoric acid salt and the muriate of lower aq simultaneously.For determining whether that vitriol can have disadvantageous effect to activity, the vitriolate of tartar of 500-1000ppm is added in two catalyst samples.As show shown in the K, it does not make significant difference to activity.

Table K

The influence of the vitriol that is added

Vitriol STY % selectivity

0 550 93.8

500 552 93.9

1000 577 93.8

(a) the ppm value of the vitriolate of tartar that adds with the potassium acetate promotor.

Following routine VII to XII shows most preferred embodiment of the present invention represented among Fig. 3.

The example VII

Adopt the Preparation of Catalyst program, with sodium hydroxide do precipitation agent Preparation of Catalyst on 50g carrier I.After the reduction step, liquid is discharged from catalyzer, clean microballon for 4 times to remove kish with moisture.Wet catalyzer is divided into three equal parts, is labeled as sample A, B and C.Sample B and C wait until in the following example and use.Interrupted wash procedure above adopting in the test IV-4, the potassium acetate solution with 23ml 5% cleans sample A5 time at every turn, and scavenging period is 8 hours altogether.The each cleaning continues 96 minutes.Water does not clean, and directly makes the catalyzer drying under 60 ℃, and estimates its vinylacetate activity under the condition that does not further add potassium acetate.Analysis and test result see Table L.

The example VIII

Clean sample B by the preparation of this example by mode described in the top routine VIII, difference is the preceding potassium acetate that cleans with 5% for 4 times, and each the cleaning continues 1 hour, the last cleaning lasting 4 hours.Non-flushing washing directly makes the catalyzer drying under 60 ℃.Analysis and test result see Table L.

The example IX

Clean sample C by the preparation of this example by mode described in the top routine VII, difference is that used is 7% potassium acetate solution.Non-flushing washing directly makes the catalyzer drying under 60 ℃.Analysis and test result see Table L.

The comparative example X

Adopting the Preparation of Catalyst program to prepare total amount in a pilot plant is 20 liters catalyzer, and cleans by interrupted wash procedure water.Analysis and test result see Table L.

The example XI

Go out 20 liters of catalyst samples with prepared described in the above-mentioned routine VII.Analysis and test result see Table L.

The example XII

In a commercialization manufacturer, prepare 520 liters of catalyst samples with technology described in the top routine VII.Analysis and test result see Table L.

Table L

Performance with the prepared catalyzer that goes out of five step preparation procedures

Test %Pd %Au %K %Na STY

IV-3* 0.54 0.19 2.2 0.47 535

VII -- 0.20 2.5 0.10 643

VIII 0.57 0.22 2.5 0.11 645

IX 0.56 0.22 2.9 0.10 592

X* 0.53 0.20 2.3 0.73 587

XI 0.56 0.26 2.9 0.12 695

XII 0.56 0.25 3.0 0.18 666

* comparative example (seven step preparation sample).

Data sheet is understood and to be utilized the obtained progress of the present invention among the table L.

Example X III

With the catalyst sample of potassium acetate solution dipping from top routine XII, strength of solution makes the potassium loading level improve about 0.8% probably.The catalyzer that is generated contains 0.56%Pd, 0.25%Au, 3.7%K and 0.17%Na, and its STY value is 550.

Following routine X IV to the purpose of XX IV is to show the use of various cationic exchange solution in embodiment of the invention C.

Comparative example X IV

According to the Preparation of Catalyst program, also prepare catalyzer as precipitation agent with sodium hydroxide with the 90g carrier.After reduction step, drain catalyzer, and water washes catalyzer 4 times altogether.Wet catalyzer is divided into 6 equal portions, is labeled as sample A, B, C, D, E and F respectively.Sample B to F waits until in the following Example and uses.Interrupted wash procedure described in the routine IV-3 above adopting is with the water cleaning sample A of 5 parts of 20ml.The evaluating catalyst that is generated be the results are shown in Table M.

Example X V

According to program described in the top routine X IV, clean from this routine sample B with the ammonium carbonate solution of every part of 20ml 2%.The evaluation result that the catalyzer of making is done sees Table M.

Example X VI

According to program described in the top routine X IV, clean from this routine sample C with the lithium acetate aqueous solution of every part of 20ml 2%.The evaluation result that catalyzer is done sees Table J.AA analyzes discovery, and the lithium content of the catalyzer of making is 0.18%.

Comparative example X VII

According to program described in the top routine X IV, clean from this routine sample D with the aqueous sodium acetate solution of every part of 20ml 2%.The evaluation result that catalyzer is done sees Table M.

Example X VIII

According to program described in the top routine X IV, clean from this routine sample E with the saltpetre aqueous solution of every part of 20ml 2%.The evaluation result that catalyzer is done sees Table M.

Example X IX

According to program described in the top routine X IV, clean from this routine sample F with the wet chemical of every part of 20ml 2%.The evaluation result that catalyzer is done sees Table M.

Table M

Various cationic exchange solution are to the influence of catalyst activity

Example salt %Pd %Au %K %Na STY

XV ^*None 0.58 0.22 2.23 0.37 474 ^**

XVI (NH ₄) ₂CO ₃0.58 0.22 2.20 0.13 527

XVII LiOAc 0.58 0.23 2.22 0.19 486

XVIII ^*NaOAc 0.57 0.22 2.26 0.79 447

XIX KNO ₃0.59 0.23 2.26 0.13 492

XX K ₂CO ₃0.59 0.23 3.06 0.14 523

* comparative example.

* STY is respectively the mean value of 453,498 and 470 three times tests.

The comparative example XX

Prepare catalyzer by top routine X V program.After reduction step, wet catalyzer is divided into 6 equal portions, be labeled as sample A, B, C, D, E and F respectively.Sample B to F waits until in the following example and uses.By the water cleaning sample A of mode described in the top routine X V with 5 parts of 20ml.To the N that the results are shown in Table that catalyzer judged.

Example XX I

According to mode described in the top routine X V, clean sample B from routine X XI with the ammonium acetate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyzer judged.

Example X XII

According to mode described in the top routine X V, clean sample C from routine X XI with the potassium acetate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyzer judged.

Example XX III

According to mode described in the top routine X V, clean sample D from routine X XI with the potassium sulfate solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyzer judged.Potassium sulfate solution is not very suitable cationic exchange solution, and is obviously quite slow because it is converted into effective form (potassium acetate).

Example XX IV

According to mode described in the top routine X V, clean sample F from routine X XI with the magnesium acetate aqueous solution of every part of 20ml 2%.To the N that the results are shown in Table that catalyzer judged.

Table N

Various cationic exchange solution are to the influence of catalyst activity.

Example salt %Pd %Au %K %Na STY

XXI ^*None 0.560 0.196 2.27 0.52 523

XXII NH ₄OAc 0.576 0.187 2.49 0.11 594

XXIII KOAc 0.613 0.209 2.13 0.13 561

XXIV K ₂SO ₄0.618 0.216 2.13 0.12 493 ^**

XXV Mg(OAc) 0.573 0.225 2.39 0.17 575

* comparative example.

* can't show the influence of this cationic exchange solution because the reaction times is not enough.

The composition of catalyzer of the present invention

All can be used for the reaction of a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate with the prepared catalyzer of the present invention of technology in any the foregoing description (being embodiment A, B or C), described catalyzer is made of carrier granule, these particles energy exchange cations, contain precipitation and the palladium, gold and a kind of potassium promoter that reduced through dipping, in the catalyzer existing any type of sodium preferably to be no more than the 0.3Wt%(total catalyst weight be 100Wt%).

Wish to be higher than the 0.25Wt% of total catalyst weight with the palladium content of the prepared catalyzer of the present invention of any the foregoing description technology, the 0.5Wt% that is higher than total catalyst weight is better, preferably can be higher than the 0.5-1.7Wt% of total catalyst weight.Better when the weight ratio of gold and palladium is 0.2-1.5 in the catalyzer, 0.4-1.2 is best.

The catalyzer that the catalyzer of being produced with any the foregoing description technology of the present invention preferably floods through layer, wherein the particle diameter of support of the catalyst is extremely about 7mm of about 3mm, porosity is 0.2-1.5ml/g.Palladium and gold preferably are distributed in the thick layer of catalyst carrier particle most external 1.0mm.Catalyzer preferably contains about potassium of 1.4 to about 3.8Wt%, and it is better to contain 2 to 3.6Wt% potassium, and these potassium come from potassium promoter.

The catalyzer of being produced with any the foregoing description technology of the present invention all makes sodium content reduce.Relatively good when the sodium content of catalyzer is no more than the 0.3Wt% of catalyst weight, it is better that the sodium content of catalyzer is no more than 0.2Wt%, and preferably the sodium content of catalyzer is no more than about the 0.1Wt% of catalyst weight.The amount of sodium will depend on many factors in the catalyzer of the present invention, as used starting material, wash number, total scavenging period, the amount of cleaning solution and the cation concn in the cationic exchange solution.

The catalyzer of being produced with any the foregoing description technology of the present invention can be made with above-mentioned technology of the present invention and with technology described in two U.S. Patent applications of submitting simultaneously with the application above-mentioned equally.

Be used to make the technology of the present invention of alkenyl alkanoate

The technology of the present invention that is used to make alkenyl alkanoate is included under the condition of the catalyzer of the present invention that has above-described catalytic amount a kind of alkene, a kind of paraffinic acid and a kind of oxygen-containing gas is reacted.This technology is being carried out better (be preferably under 140 ℃ to 200 ℃ and carry out) under 100 ℃ to 250 ℃ the temperature; Simultaneously, pressure is at 15psi(pound/square inch) to better between the 300psi, best between 90psi to 150psi.This technology is preferably in the gas phase carries out continuously.

The technology of the present invention that is used to make alkenyl alkanoate is characterised in that catalyzer has bigger activity.In general, these activity of such catalysts (alkenyl alkanoate that generates with unit time unit catalyst is a unit) than contained sodium from more than 0.3% to 1%(weight) and the identical activity of such catalysts of others is big by 5% to 25%.Though selectivity of catalyst (producing the trend of alkenyl alkanoate rather than carbonic acid gas and so on byproduct) can reduce slightly when sodium content reduced, this shortcoming is compensated by catalyst activity increases already, when particularly sodium content was in the content range (as sodium content up to about 1.0Wt%) of sodium in the commodity alkenyl alkanoate, situation was all the more so.

The best paraffinic acid starting material that technology of the present invention adopted that is used for making alkenyl alkanoate contains 2 to 4 carbon atoms (can be acetate, propionic acid and butyric acid such as these acid).Best alkene starting material contains 2 to 4 carbon atoms (can be ethene, propylene and n-butene such as these hydrocarbon).The best product of this technology is vinylacetate, vinyl propionic ester, vinyl butyrate and allyl acetic acid ester.

An aspect that is used to make the technology of the present invention of alkene alkanoates comprises and adopts the model shown in the previous table G to come pre-oxygen determination with respect to the transformation efficiency of vinylacetate, activity of such catalysts, the catalyzer output with respect to the output of the selectivity of vinylacetate, ethyl acetate byproduct and/or heavy byproduct.

The alkenyl alkanoate that technology of the present invention is produced be known compound with known application (such as, vinylacetate can be used for producing polyvinylacetate).

Claims

1, a kind of technology of making a kind of catalyzer, described catalyzer can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, described catalyzer is made of carrier granule, these particles energy exchange cations, through flooding the acetate that contains palladium, gold and potassium, described technology comprises that the sodium content by reducing catalyzer improves activity of such catalysts.

2, a kind of technology of making a kind of catalyzer, described catalyzer can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, described catalyzer is made of carrier granule, these particles energy exchange energy exchange cations, through flooding the acetate that contains palladium, gold and potassium, described technology comprises the following steps:

(b) with a kind of precipitation agent the compound of water-fast palladium and gold is deposited on the carrier granule from above-mentioned solution;

(c) with a kind of reductive agent the sedimentary water-fast palladium of institute and golden compound are converted into palladium and gold on the carrier granule;

(d) water cleans carrier granule;

(e) make the carrier granule drying;

(f) with the further impregnated support particles of a kind of potassium promoter; And

(g) make the particle drying that flooded preparing catalyzer, and

When implementing described technology, in step (b) with what adopt (c) in is the starting material that is substantially free of sodium, so that the content of sodium in the reduction catalyzer, and then the raising activity of such catalysts.

3, a kind of technology as claimed in claim 2, wherein potassium hydroxide as the precipitation agent in the step (b), and under the effect of potassium precipitation agent, increase the displacement of para-linkage sodium on carrier with sylvite.

4, a kind of technology of making a kind of catalyzer, described catalyzer can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, described catalyzer is made of carrier granule, these particles energy exchange cations, through flooding the acetate that contains palladium, gold and potassium, described technology comprises the following steps:

(a) aqueous solution with water miscible palladium and gold compound comes impregnated support particles;

(d) water cleans carrier granule;

(e) make the carrier granule drying;

(g) make as with the impregnated carrier drying of upper type preparing the exsiccant catalyzer, this catalyzer contains sodium owing to there being sodium to exist in one or more used in step (a) to (f) materials;

(h) water or with the aqueous solution cleaning-drying that contains a kind of potassium promoter catalyzer reducing the sodium content in the catalyzer, and then improve activity of such catalysts, and

(i) make the catalyzer drying.

5, a kind of technology of making a kind of catalyzer, described catalyzer can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, described catalyzer is made of carrier granule, these particles energy exchange cations, through flooding the acetate that contains palladium, gold and potassium, described technology comprises the following steps:

(c) with a kind of reductive agent the compound of sedimentary water-fast palladium of institute and gold is converted into palladium on the carrier granule and gold to prepare a kind of impregnated carrier, this impregnated carrier is owing to there being the sodium existence to contain sodium in one or more used in the step (a) to (c) materials;

(d) clean impregnated carrier granule with a kind of cationic exchange solution, reduced the amount of sodium in the catalyzer thus and improved activity of such catalysts; And

(e) make the impregnated carrier granule drying of being cleaned, to prepare catalyzer.

6, a kind of technology of making a kind of catalyzer, described catalyzer can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to generate a kind of alkenyl alkanoate, described catalyzer is made of carrier granule, these particles energy exchange cations, through flooding the acetate that contains palladium, gold and potassium, described technology comprises the following steps:

(d) clean carrier granule with a kind of potassium promoter solution, the concentration of described solution and amount should be enough to make its energy: (I) reduces the amount of sodium in the catalyzer to improve activity of such catalysts, and (II) flood this catalyzer, makes it contain the potassium of the necessary quantity of promising this activity of such catalysts of further raising; And

(e) make clean and the carrier granule drying of further flooding, to produce catalyzer.

7, catalyzer as claimed in claim 6, wherein potassium promoter solution is the aqueous solution of potassium acetate.

8, a kind of catalyzer, can be used for reaction between a kind of alkene of catalysis, a kind of paraffinic acid and a kind of oxygen-containing gas to produce a kind of alkenyl alkanoate, and constitute by carrier granule, these particles can also help shortization agent through flooding to have through precipitation and reductive palladium with gold and a kind of potassium by exchange cation, and the amount of all sodium that exist in the catalyzer is no more than the 0.3Wt% of catalyst weight.

9, a kind of catalyzer as claimed in claim 8 is characterized in that the amount of all sodium of existing in the catalyzer is no more than the 0.2Wt% of catalyst weight.

10, a kind of technology that is used to prepare a kind of alkenyl alkanoate comprises a kind of alkene, a kind of paraffinic acid and a kind of oxygen-containing gas are reacted under the condition of catalytic amount as defined in claim 8 or the claim 9 of catalyzer.