CN1102433C - Process for preparation of sulfur transfer catalyst - Google Patents
Process for preparation of sulfur transfer catalyst Download PDFInfo
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- CN1102433C CN1102433C CN99123823A CN99123823A CN1102433C CN 1102433 C CN1102433 C CN 1102433C CN 99123823 A CN99123823 A CN 99123823A CN 99123823 A CN99123823 A CN 99123823A CN 1102433 C CN1102433 C CN 1102433C
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Abstract
The present invention relates to a preparation method of a sulfur-transfer catalyst, which comprises the steps that a hydrated alumina microsphere prepared by a special method is soaked in a solution containing a cerium compound, dried and calcined. The sulfur-transfer catalyst prepared by the method has high wear-resistant performance.
Description
The invention relates to a kind of preparation method of sulfur transfer catalyst of salic and cerium, more specifically say so, be used for reducing catalytic cracking process regenerated flue gas SO about a kind of salic and cerium
XThe preparation method of the sulfur transfer catalyst of pollutant emission.
In fluid catalytic cracking (FCC) process,, make catalyst activity reduction because the reaction of hydrocarbon has caused the deposition of coke on catalyst.Simultaneously, a part of sulphur in the feedstock oil is deposited on the catalyst with coke.Subsequently, cracked product is by ejector, and after the catalyst that contains coke removes the hydrocarbon that is adsorbed on the catalyst through stripping section, is transported to regenerator.The catalyst that contains coke in regenerator at high temperature contacts with air, and the coke on the catalyst is burnt, thereby activity of such catalysts is recovered.Catalyst after the recovery activity is transported to reactor again, beginning reaction-regeneration cycle next time.
In regenerator, when making charcoal, catalyst generates CO, SO
X, CO
2Usually these gases all are discharged in the atmosphere CO in them, SO
XTo pollute atmosphere.
Reduce FCC regenerated flue gas SO
XThe method of discharging is a lot.For example, the method for catalytically cracked material hydrodesulfurization, the method for regenerated flue gas washing is bought the method for low-sulfur raw material and is selected SO for use
XThe technology of transfer agent.Wherein, the required expense of raw material hydrogenation and flue gas washing is the highest, and they not only will expend a large amount of device construction costs, and raw material sources also can be restricted.It should be noted that most in the several method and use SO
XTransfer techniques, it does not need catalytic cracking unit is transformed, and only need expend part catalyst cost.This process operation is convenient, need not change operating condition significantly, just can realize reducing SO on FCC apparatus
XThe purpose of discharging.
SO
XTransfer techniques is that sulfur transfer catalyst (abbreviation sulfur transfer additive) is added in the catalytic cracking unit, and with the Cracking catalyst physical mixed, sulfur transfer additive circulates between reactor and the regenerator with catalytic cracking catalyst.In regenerator, the SO in sulfur transfer additive and the flue gas
XReaction forms stable metal sulfate, on the surface attached to transfer agent, and is recycled in the reactor with the Cracking catalyst after regenerating, and in the reducing atmosphere of reactor, is reduced attached to the sulphur on the transfer agent with metallic salt form, directly with H
2The form of S discharges.This part H
2The H that S and cracking reaction generate
2S is transported to sulfur recovery facility together and reclaims.Obtain regeneration and in reactor, removed the transfer agent behind the sulphur, and be recycled to together in the regenerator, carry out SO next time in company with Cracking catalyst
XAdsorption reaction.The chemical reaction that transfer agent is taken place in regenerator and reactor can simply be described as: regenerator
Therefore, the effect of sulfur transfer additive is that it can remove SO from regenerator
3, this just requires sulfur transfer additive will promote SO effectively in regenerator
2Generate SO
3In order to realize this reaction, initial researcher thinks that best promoter is the Pt catalyst.Yet Pt costs an arm and a leg.Therefore, large quantities of research workers have developed the sulfur transfer additive cheap, that performance is suitable.
USP 5,021,228 disclose the method for removing gas sulphur component a kind of mist of the oxide from sulfur-bearing, this method is included under 800-1000 the condition, the mist of the oxide of described sulfur-bearing is contacted with a kind of composition (sulfur transfer additive), and described composition contains a kind of porous carrier and loads at least a actinide metals of the heavy % of 0.5-10 on this carrier and at least a alkali metal of the heavy % of 1-5.The preparation method of said composition comprises, with the solution impregnating carrier of the soluble compound of described metal,, pulverizes in 212-300 °F (100-140 ℃) dry 1-24 hour, and in 1300-1500 (704-816 ℃) roasting.In this patent embodiment preferred, used the sulfur transfer additive of thoriated, though the sulfur transfer additive of this thoriated has extraordinary sulphur transfer performance,, the Th that nature exists
232Be radioactive substance, this sulfur transfer additive needs before use through the many-side inspection, is lower than the level of requirement to guarantee radioactive dosage that operating personnel were absorbed, and therefore, this product is difficult to be used widely.
USP 4,992,161 disclose a kind of fluidized catalytic cracking method, this method is included in a kind of solid particle of circulation between the zone of cracking and the renewing zone, described solid particle contains three kinds of independently components, (1) a kind of graininess Cracking catalyst that contains zeolite under the situation that does not have hydrogen, (2) a kind of granular oxysulfide adsorbent, this adsorbent contains a kind of activated alumina that can adsorb sulfur trioxide, (3) a kind of graininess oxidizing sulfur dioxide promoter, this promoter containing loads on the chromium on the titanium dioxide carrier and the thing of combining closely of tin or chromium and tin compound.Described adsorbent is a kind of independently component, and described promoter is adopted methods such as dipping, ion-exchange or co-precipitation, the compound of chromium/tin is stated from the carrier and prepares.This system has good oxidation facilitation effect.Yet chromium is a kind of element of multivalence.Trivalent chromium toxicity is smaller relatively, and Cr VI has very big toxicity, is a kind of carcinogen.Comprise CrO, Cr in the used chromium oxide of this patent
2O
3And CrO
3Its chemical valence has divalence, trivalent and sexavalence.Therefore, although it has higher activity, yet its toxicity has limited it can not be widely used in industrial production.
USP 4,642,177 disclose a kind of catalyst cracking method, this method comprises a kind of graininess Cracking catalyst and a kind of sulfur absorbent is circulated between cracking reaction district and regenerative response district, in the cracking reaction district, described catalyst granules catalysis sulfur-bearing hydrocarbon raw material changes into the small-molecular weight product, in the renewing zone, under 1000-1250 temperature, the catalyst cracking particles that deposits coke is carried out roasting, described sulfur absorbent contains (1) a kind of rare earth component or mishmetal component and (2) a kind of cobalt component.Wherein, the rare earth component is that removing wherein, at least 50% fluorine prepares by the processing bastnasite.Though this sulfur transfer additive has higher sulphur transfer activity.Yet problem maximum in its preparation process is at first to remove the fluorine more than 50% in the bastnasite, and the appearance of toxic gas fluorine brings a lot of troubles for the industrial preparation of transfer agent, and the processing of fluorine has brought resistance for the industrial production of transfer agent.
USP 4,606,813 disclose a kind of fluidized catalytic cracking catalyst, this catalyst contains a kind of mixture, this mixture is made up of first component of catalytic activity and second component that can reduce sulfur oxide discharging in regenerator a kind of, this catalyst contains (1) but 10-70 weighs the particle of a kind of fluidisation of %, but the particle that is somebody's turn to do fluidisation contains the faujasite of at least 40 heavy %, (2) but the particle of second kind of fluidisation of the heavy % of 30-90, but the particle that is somebody's turn to do fluidisation contains at least 70 heavy %'s, and " balance " specific surface is a 40-100 rice
2The aluminium oxide of/gram.Described " balance " specific surface is a 40-100 rice
2The aluminium oxide of/gram can be under 750-1200 temperature, the aluminium oxide that obtained at least 1 hour by roasting α-gibbsite.Can also contain lanthanum, cerium, neodymium, praseodymium, samarium, dysprosium, platinum, ruthenium, rhodium, palladium, osmium, iridium or their components such as mixture in the catalyst.In order to increase the abrasion resistance of second component, one of its preparation method is included under 750-1200 the temperature, and the alumina component that is purchased is carried out roasting at least 1 hour under steam.Another kind of preparation method is that the alumina component that will be purchased is carried out rehydration, is about to itself and water making beating, is 9.3-9.5 at pH, and temperature is under 150 the condition heat treated 6-6.5 hour, filters, washing and drying.If contain aforesaid metal component, the introducing of metal component can be adopted infusion process.
USP4,589,978 disclose sulfur transfer additive of being made up of rare-earth oxide basically and preparation method thereof, this sulfur transfer additive contains the bond of cerium or cerium and lanthanum, rare earth metal can load on a kind of inert material, contains a kind of metal oxide under the preferable case, as aluminium oxide as SO
3Adsorbent.Described aluminium oxide can be gamma, eta and theta aluminium oxide.The carrier of described rare earth oxide and aluminium oxide is selected from silica, silica-alumina, zeolite, diatomite or aluminium oxide.Its preparation method comprises and perhaps, rare earth being mixed with aluminium oxide or its precursor with an amount of slaine impregnated carrier, mixture mixed with the gel of carrier, then spray-drying again.
As previously mentioned, in fluid catalytic cracking process,, want to make sulfur transfer additive to play a role better because sulfur transfer additive circulates between reactor and regenerator with catalytic cracking catalyst, sulfur transfer additive also must have higher abrasion resistance except that should having higher sulphur transfer activity.Have only the good sulfur transfer additive of abrasion resistance could reduce the loss of sulfur transfer additive in the course of reaction, reduce the amount of augmenting of transfer agent, save the cost of whole fluid catalytic cracking process.
Purpose of the present invention promptly provides a kind of preparation method of the new better sulfur transfer catalyst of anti-wear performance.
The preparation method of sulfur transfer additive provided by the invention comprises a kind of hydrated alumina microballoon of solution impregnation with cerium-containing compound, dry and roasting, and the preparation method of described hydrated alumina microballoon comprises the steps:
(1) part boehmite in the scheduled volume and deionized water are mixed, making solid content is the slurries of the heavy % of 5-30, add a kind of acid, the pH value of regulating slurries is 1.5-4.0, add the boehmite of surplus, be stirred to slurries and be equal colloid shape, wherein, in aluminium oxide, successively the weight ratio of the boehmite of Jia Ruing is 0.1-5;
(2) under agitation add aluminium colloidal sol, in aluminium oxide, the weight ratio of boehmite and aluminium colloidal sol is 1-50;
(5) 30-100 ℃ of aging slurries are more than 0.5 hour.
(6) spray drying forming is made the hydrated alumina microballoon.
Wherein, the used acid of adjusting pH value is selected from one or more in water-soluble inorganic acid and the organic acid.Acid commonly used is one or more in hydrochloric acid, nitric acid, the acetic acid.Wherein, more preferred hydrochloric acid or nitric acid.
Wherein, in aluminium oxide, the weight ratio of the boehmite that described priority adds is 0.1-5, more preferably 0.3-3.In aluminium oxide, the weight ratio of boehmite and aluminium colloidal sol is 1-50, more preferably 5-35.
Aging temperature behind the described adding aluminium colloidal sol is 30-100 ℃, and more preferably 40-80 ℃, ageing time is more than 0.5 hour, more preferably 0.5-4 hour.
The solid content of described slurries can be the heavy % of 5-30, is preferably the heavy % of 10-20.
The spray drying forming of described slurries adopts conventional method and condition, is 250 to 300 ℃ at the control exhaust temperature generally, and atomisation pressure is to carry out under 50-60 the atmospheric condition.
Describedly can adopt the method for existing impregnated alumina, just change aluminium oxide into hydrated alumina microballoon of the present invention and get final product with the solution impregnation hydrated alumina microballoon of cerium-containing compound.Drying behind the described dipping and roasting are carried out under the normal condition of this area.For example, dry temperature can be from room temperature to 300 ℃, and preferred 100-200 ℃, drying time is more than 0.5 hour, and preferred 1-10 hour, sintering temperature 400-700 ℃, preferred 450-650 ℃, roasting time was more than 0.5 hour, preferred 1-10 hour.
The consumption of the solution of described cerium-containing compound makes final sulfur transfer additive have conventional cerium content, generally speaking, and with CeO
2Meter, the described consumption that contains cerium solution make and contain the heavy % of cerium 5-30 in the final sulfur transfer additive, are preferably the heavy % of 10-25.Described cerium compound is selected from one or more in the solubility cerium compound, and under the preferable case, described cerium compound is selected from cerous chloride with or without the crystallization water, in the ammonium ceric nitrate one or more.
An outstanding advantage of method provided by the invention is, is greatly improved with the anti-wear performance of the sulfur transfer additive of this method preparation.When for example, adopting the abrasion index of the sulfur transfer additive of method provided by the invention preparation to have only 0.8-1.1%
-1And adopt the abrasion index of the sulfur transfer additive of art methods (comprising USP 4606,813 disclosed methods) preparation all to be higher than at 3% o'clock
-1
The outstanding advantage of another of method provided by the invention is that the sulfur transfer additive for preparing with this method has the active and release sulphur activity of higher suction sulphur.For example, under the oxidizing condition in being similar to catalytic cracking regenerator, be 73-76 mole % with the suction sulphur activity of the sulfur transfer additive of method provided by the invention preparation, and adopt the suction sulphur activity of the catalyst of prior art for preparing to have only 38-67 mole %.Under the reducing condition in being similar to catalyst cracker, be 19-24 mole % with the release sulphur activity of the sulfur transfer additive of method provided by the invention preparation, and adopt the release sulphur activity of the catalyst of prior art for preparing to have only 10-14 mole %.
In the preparation method of existing sulfur transfer additive, generally speaking, at first with the hydrated alumina moulding, dry and roasting forms alumina support afterwards, with the solution impregnation of alumina carrier that contains metal component, then, carry out dry and roasting (its preparation flow as shown in Figure 1) second time more again.Its reason is, adopt hydrated alumina easy aquation when using the solution impregnation that contains metal component of art methods preparation, on the one hand, hydrated alumina after the aquation splits away off from article shaped, on the other hand, the hydrated alumina after the aquation on the variable grain interosculates, and makes between the particle to be sticked together, this all makes the shape of carrier be seriously damaged, thereby influences its anti-wear performance.Therefore adopt art methods, must be through double roasting, complex steps, and expended the more energy.The present invention adopts a kind of special method, obtains a kind of hydrated alumina microballoon, floods this hydrated alumina microballoon with the metallic aqueous solution again, dry then and roasting (its preparation flow as shown in Figure 2).Adopt method provided by the invention, during the impregnating metal component, this hydrated alumina microballoon is aquation not, still keeps its original shape.Dipping cerium component and the sulfur transfer additive that obtains after roasting not only have anti-wear performance and the sulphur transfer activity higher than prior art, and have reduced by a calcination steps, have saved the energy.Therefore, the advantage that another of method provided by the invention gives prominence to is more simple, is more suitable for large-scale industrial production, and has saved the energy.
Fig. 1 is a prior art sulfur transfer additive preparation method schematic flow sheet;
Fig. 2 is a sulfur transfer additive preparation method schematic flow sheet provided by the invention;
The following examples will the present invention is described further.
Example 1
The preparation method of this example explanation hydrated alumina microballoon.
In 50 liters making beating jar, add under 18 kilograms of deionized waters, the stirring and add 13 kilograms of boehmite (Al
2O
3Content is 32.8 heavy %, and the Zhou village catalyst plant is produced), stir, being made into solid content is the slurries of 13.8 heavy %, adding concentration is the hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) of 21 heavy %, adjusts the pH=1.8 of slurries.Under agitation add 13 kilograms of above-mentioned boehmites, make slurries be uniform colloid shape.Under agitation add 5 kilograms of aluminium colloidal sol (Al
2O
3Content is 21.8 heavy %, and the Zhou village catalyst plant is produced) stir.In aluminium oxide, the weight ratio of the boehmite that front and back add is 1, and the weight ratio of the boehmite of adding and aluminium colloidal sol is 7.8.After 2 hours, is 260 ℃ at exhaust temperature at 60 ℃ of aging slurries, and atomisation pressure is under 50 atmospheric pressure, and spray drying forming obtains hydrated alumina microballoon X
1
Example 2
The preparation method of this example explanation hydrated alumina microballoon.
In 50 liters making beating jar, add 1.8 kilograms of deionized waters, add 3 kilograms of boehmite (Al under stirring
2O
3Content is 32.8 heavy %, and the Zhou village catalyst plant is produced), stir, add 0.4 kilogram of deionized water again, being made into solid content is the slurries of 18.9 heavy %, adding concentration is the hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) of 21 heavy %, adjusts the pH=3.5 of slurries.Under agitation, add 3 kilograms of boehmites, continue to stir, make slurries be uniform colloid shape, under agitation add 0.3 kilogram of aluminium colloidal sol (Al
2O
3Content is 21.8 heavy %, and the Zhou village catalyst plant is produced), stir.In aluminium oxide, the weight ratio of the boehmite that front and back add is 1, and the weight ratio of the boehmite of adding and aluminium colloidal sol is 30.After 0.5 hour, is 280 ℃ at exhaust temperature at 45 ℃ of aging slurries, and atomisation pressure is under 60 atmospheric conditions, and spray drying forming obtains hydrated alumina microballoon X
2
Example 3
The preparation method of this example explanation sulfur transfer additive.
With 23.84 gram CeCl
37H
2O is dissolved in 40 milliliters the deionized water, with the hydrated alumina microballoon X of solution impregnation 100 grams that obtain (solid content 65.74 heavy %) example 1 preparation
1Then, drying is 2 hours under 120 ℃ of temperature, and 600 ℃ of following roastings 3 hours, obtains adopting the sulfur transfer additive A of method preparation provided by the invention.CeO among the sulfur transfer additive A
2The specific surface of content, sulfur transfer additive A, abrasion index, average particulate diameter (abbreviation average grain diameter) and heap are than listing in the table 1.Wherein, specific surface adopts cryogenic nitrogen absorption BET method to measure.Abrasion index adopts the RIPP29-90 method to measure (referring to " petrochemical industry analytical method (RIPP test method) ", Science Press, 73-75,1990).Average grain diameter is measured with 3600E type laser particle analyzer (Britain Ma Erwen company product).
Example 4
The preparation method of this example explanation sulfur transfer additive.
(NH with 53.2 grams
4)
2Ce (NO
3)
6(chemical pure, Beijing Chemical Plant produce) is dissolved in 40 milliliters the deionized water, with the hydrated alumina microballoon X of solution impregnation 140 gram examples 1 preparation that obtains
1(solid content is 65.74 heavy %).Then, drying is 2 hours under 120 ℃ of temperature, and 600 ℃ of following roastings 3 hours, obtains adopting the sulfur transfer additive B of method preparation provided by the invention.CeO among the sulfur transfer additive B
2The specific surface of content, sulfur transfer additive B, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Example 5
The preparation method of this example explanation sulfur transfer additive.
Method by example 4 prepares sulfur transfer additive, different just (NH
4)
2Ce (NO
3)
6Consumption be 68.85 grams, obtain adopting the sulfur transfer additive C of method preparation provided by the invention.CeO among the sulfur transfer additive C
2The specific surface of content, sulfur transfer additive C, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Example 6
The preparation method of this example explanation sulfur transfer additive.
Method by example 3 prepares sulfur transfer additive, the different hydrated alumina microballoon X that just prepares with example 2
2(solid content also is 65.74 heavy %) replaces the hydrated alumina microballoon X of example 1 preparation
1, obtain the sulfur transfer additive D that adopts method provided by the invention to prepare.CeO among the sulfur transfer additive D
2Content, the specific surface of sulfur transfer additive D, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 1
The preparation of this Comparative Examples explanation reference sulfur transfer additive.
In 50 liters making beating jar, add 18 kilograms of deionized waters, add 13 kilograms of boehmite (Al under stirring
2O
3Content is 32.8 heavy %, and the Zhou village catalyst plant is produced), stir, being made into solid content is the slurries of 13.8 heavy %.Adding concentration is the hydrochloric acid (chemical pure, the Beijing Chemical Plant produces) of 21 heavy %, adjusts the pH=1.8 of slurries, continues to stir, and makes slurries be uniform colloid shape.After 1 hour, is 260 ℃ at exhaust temperature at 60 ℃ of aging slurries, and atomisation pressure is a spray drying forming under 50 atmospheric pressure, obtains reference hydrated alumina microballoon.With 23.84 gram CeCl
37H
2O is dissolved in 40 milliliters the distilled water, the reference hydrated alumina microballoon (solid content is 60 heavy %) that obtains with solution impregnation 109.6 grams that obtain.Then, drying is 2 hours under 120 ℃ temperature, and 600 ℃ of following roastings 3 hours, obtains reference sulfur transfer additive E.CeO among the reference sulfur transfer additive E
2Content, the specific surface of sulfur transfer additive E, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 2
The preparation of this Comparative Examples explanation reference sulfur transfer additive.
Method by Comparative Examples 1 prepares the reference sulfur transfer additive, and the different reference hydrated alumina microballoons that just obtained 600 ℃ of following roastings earlier before dipping 3 hours make it to change into aluminium oxide, and then dipping, obtain reference sulfur transfer additive F.CeO among the sulfur transfer additive F
2The specific surface of content, sulfur transfer additive F, heap ratio, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 3
The preparation method of this Comparative Examples explanation reference sulfur transfer additive.
The trade name that German Condea company is produced be the hydrated alumina microballoon of SB 600 ℃ of roastings 3 hours, obtain alumina support.With 23.84 gram CeCl
37H
2O is dissolved in 40 ml distilled waters, the alumina support that obtains with the solution impregnation that obtains 65.74 grams, and under 120 ℃ of temperature dry 2 hours, and, obtain reference sulfur transfer additive G 600 ℃ of roasting temperatures 3 hours.CeO among the sulfur transfer additive G
2The specific surface of content, sulfur transfer additive G, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 4
The preparation method of this Comparative Examples explanation reference sulfur transfer additive.
With 23.84 gram CeCl
37H
2O is dissolved in 40 ml distilled waters, with the 96 gram α-gibbsite microballoons (solid content is 68.48 heavy %) of the solution impregnation Shandong Aluminum Plant production that obtains.Under 120 ℃ of temperature dry 2 hours, and, obtain reference sulfur transfer additive H 600 ℃ of roasting temperatures 3 hours.CeO among the sulfur transfer additive H
2The specific surface of content, sulfur transfer additive H, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 5
The preparation method of this Comparative Examples explanation reference sulfur transfer additive.
Microballoon α-gibbsite that Shandong Aluminum Plant is produced obtains alumina support 600 ℃ of roastings 3 hours.With 23.84 gram CeCl
37H
2O is dissolved in 40 ml distilled waters, the alumina support that obtains with the solution impregnation that obtains 65.74 grams, and under 120 ℃ of temperature dry 2 hours, and, obtain reference sulfur transfer additive I 600 ℃ of roasting temperatures 3 hours.CeO among the sulfur transfer additive I
2The specific surface of content, sulfur transfer additive I, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Comparative Examples 6
The preparation method of this Comparative Examples explanation reference sulfur transfer additive.
Microballoon α-gibbsite that Shandong Aluminum Plant is produced was at 565 ℃, with 100% steam treatment 1 hour.With 23.84 gram CeCl
37H
2O is dissolved in 40 ml distilled waters, with the product after the solution impregnation that the obtains 96 gram steam treatment (solid content is 68.48 heavy %), and under 120 ℃ of temperature dry 2 hours, and, obtain reference sulfur transfer additive J 600 ℃ of roasting temperatures 3 hours.CeO among the sulfur transfer additive J
2The specific surface of content, sulfur transfer additive J, abrasion index, average grain diameter and heap ratio are listed in the table 1.
Table 1
| Example number | The transfer agent numbering | CeO 2Content, heavy % | Specific surface, rice 2/ gram | Abrasion index is during % -1 | The heap ratio | Average grain diameter, dust |
| 3 | A | 14.4 | 176 | 1.0 | 1.0 | 72.6 |
| 4 | B | 15.4 | 192 | 1.1 | 1.1 | 61.4 |
| 5 | C | 19.0 | 161 | 0.8 | 1.0 | 75.5 |
| 6 | D | 14.4 | 168 | 0.9 | 1.0 | 66.4 |
| Comparative Examples 1 | E | 14.4 | 142 | 5.4 | 0.6 | 65.4 |
| Comparative Examples 2 | F | 14.4 | 236 | 3.0 | 0.9 | 71.5 |
| Comparative Examples 3 | G | 14.4 | 220 | 6.1 | 0.6 | 57.0 |
| Comparative Examples 4 | H | 14.4 | 342 | 8.2 | 0.9 | 77.2 |
| Comparative Examples 5 | I | 14.4 | 333 | 7.5 | 0.9 | 78.3 |
| Comparative Examples 6 | J | 14.4 | 106 | 6.5 | 0.9 | 79.4 |
Example 7-10
Following example illustrates the sulphur transfer activity of the sulfur transfer additive of method preparation provided by the invention.
1. sulfur transfer additive is inhaled the mensuration of sulphur activity.
The part of sulfur transfer additive (fresh sulfur transfer additive) A-D that example 3-6 is prepared wore out 6 hours with 100% steam under 760 ℃ temperature respectively, the sulfur transfer additive A-D after obtaining wearing out.Respectively with fresh and aging after sulfur transfer additive A-D and the industrial trade mark be that the cracking poising agent of MZ-3 mixes, sulfur transfer additive accounts for 10 heavy % of mixture.The simulation regeneration fume from catalytic cracking is formed, and preparation contains SO
22000ppm, O2 5 body %, N
294.8 the mist of body %.The mixtures or 30 of 30 gram sulfur transfer additives and MZ-3 are restrained MZ-3 packs in the small fixed flowing bed reactor, flow velocity with 870 ml/min feeds reactor with above-mentioned mist, temperature of reactor is controlled at 600 ℃, and the gas that reaction generates feeds absorption liquid, and (absorption liquid is for containing H
2O
21.2 the H of heavy %
2O
2The aqueous solution) in, make SO
2Absorbed by this absorption liquid.Reaction continues 45 minutes.After finishing reaction, with the standard NaOH solution titration absorption liquid of 0.05N to solution changes color (indicator is methyl red and methine orchid compound indicator).Calculate the suction sulphur activity of sulfur transfer additive according to following formula.
SA
a%=(S
M-S
a)/S
MWherein, SA
aRepresent the suction sulphur activity of certain sulfur transfer additive a.S
aRepresent the equivalents of the NaOH that is consumed when 30 certain sulfur transfer additive a of gram and MZ-3 mixture of catalysts are housed in the reactor.S
MRepresent the equivalents of the NaOH that is consumed when 30 gram MZ-3 catalyst are housed in the reactor.
2. sulfur transfer additive discharges the mensuration of sulphur activity.
To suck reactor behind the sulphur in above-mentioned 1 at logical N
2Situation under lower the temperature, and temperature is controlled constant after 500 ℃, feed High Purity Hydrogen, exit gas is introduced in (this absorption liquid is that concentration is the zinc nitrate aqueous solution of 0.01N) in 150 milliliters of absorption liquids, reaction continues 3 hours.Filter absorption liquid, with the zinc ion in the 100 ml distilled water washing precipitations.Then, adding volume ratio with filtrate in the filtrate that obtains is that 1: 1 pH is 10 NH
3-NH
4Cl cushioning liquid adds the filtrate (indicator is an eriochrome black T) of cushioning liquid with the EDTA solution titration of 0.02N.Calculate the release sulphur activity of sulfur transfer additive by following formula.
SD
a%=(N
M-N
a)/N
MWherein, SD
aRepresent the sulphur of certain sulfur transfer additive a to discharge active.N
aRepresent the equivalents of the EDTA that is consumed when certain the sulfur transfer additive a that sucks behind the sulphur and MZ-3 mixture of catalysts are housed in the reactor.N
MRepresent the equivalents of the EDTA that is consumed when the MZ-3 catalyst that sucks behind the sulphur is housed in the reactor.
Table 2 listed sulfur transfer additive A-D suction sulphur active and discharge the sulphur activity.
Comparative Examples 7-12
The suction sulphur of following Comparative Examples explanation reference sulfur transfer additive is active and sulphur release is active.
Press the reference sulfur transfer additive E-J of the aging Comparative Examples 1-6 preparation of method of example 7-10, the method for press example 7-10 is measured the suction sulphur and the sulphur release activity of the reference sulfur transfer additive after fresh and aging, and the results are shown in Table 2.
Table 2
| Example number | The sulfur transfer additive numbering | Fresh dose | Aging agent | ||
| Inhale the active % of sulphur | Sulphur discharges active % | Inhale the active % of sulphur | Sulphur discharges active % | ||
| Example 7 | A | 73 | 20 | 43 | 20 |
| Example 8 | B | 76 | 19 | 46 | 25 |
| Example 9 | C | 70 | 24 | 44 | 25 |
| Example 10 | D | 75 | 20 | 52 | 24 |
| Comparative Examples 7 | E | 38 | 10 | 30 | 17 |
| Comparative Examples 8 | F | 60 | 10 | 43 | 17 |
| Comparative Examples 9 | G | 67 | 12 | 42 | 18 |
| Comparative Examples 10 | H | 59 | 14 | 47 | 14 |
| Comparative Examples 11 | I | 57 | 14 | 45 | 16 |
| Comparative Examples 12 | J | 51 | 11 | 44 | 15 |
Claims (8)
1. the preparation method of a sulfur transfer catalyst, it is characterized in that, this method comprises a kind of hydrated alumina microballoon of solution impregnation with cerium-containing compound, dry also roasting, wherein, the temperature of described drying is a room temperature to 300 ℃, sintering temperature 400-700 ℃, roasting time is 1-10 hour, and the preparation method of described aluminium hydroxide microballoon comprises the steps:
(1) part boehmite in the scheduled volume and deionized water are mixed, making solid content is the slurries of the heavy % of 5-30, add a kind of acid, the pH value of regulating slurries is 1.5-4.0, add the boehmite of surplus, be stirred to slurries and be equal colloid shape, wherein, in aluminium oxide, successively the weight ratio of the boehmite of Jia Ruing is 0.1-5;
(2) under agitation add aluminium colloidal sol, in aluminium oxide, the weight ratio of boehmite and aluminium colloidal sol is 1-50;
(3) 30-100 ℃ of aging slurries are more than 0.5 hour.
(4) spray drying forming is made the hydrated alumina microballoon.
2. method according to claim 1 is characterized in that, regulates the used acid of pH value and is selected from hydrochloric acid or nitric acid.
3. method according to claim 1 is characterized in that, in aluminium oxide, the weight ratio of the boehmite that described priority adds is 0.3-3, and the weight ratio of boehmite and aluminium colloidal sol is 5-35.
4. method according to claim 1 is characterized in that, the aging temperature behind the described adding aluminium colloidal sol is 40-80 ℃, and ageing time is 0.5-4 hour.
5. method according to claim 1 is characterized in that, the solid content of described slurries is the heavy % of 10-20.
6. method according to claim 1 is characterized in that, with CeO
2Meter, the consumption of described cerium-containing compound solution make and contain the heavy % of cerium 5-30 in the final sulfur transfer additive.
7. method according to claim 6 is characterized in that, with CeO
2Meter, the consumption of the solution of described cerium-containing compound make and contain the heavy % of cerium 10-25 in the final sulfur transfer additive.
8. according to claim 1,6 or 7 described methods, it is characterized in that described cerium compound is selected from cerous chloride with or without the crystallization water, in the ammonium ceric nitrate one or more.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123823A CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN99123823A CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
Publications (2)
| Publication Number | Publication Date |
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| CN1295877A CN1295877A (en) | 2001-05-23 |
| CN1102433C true CN1102433C (en) | 2003-03-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN99123823A Expired - Fee Related CN1102433C (en) | 1999-11-12 | 1999-11-12 | Process for preparation of sulfur transfer catalyst |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1333044C (en) | 2003-09-28 | 2007-08-22 | 中国石油化工股份有限公司 | Method for cracking hydrocarbon oil |
| US7347930B2 (en) | 2003-10-16 | 2008-03-25 | China Petroleum & Chemical Corporation | Process for cracking hydrocarbon oils |
| CN103920455B (en) * | 2013-01-14 | 2016-03-30 | 北京三聚环保新材料股份有限公司 | The preparation method of a kind of high activity and high-wearing feature microphere sulfur transfer agent |
| CN114345292B (en) * | 2022-01-14 | 2023-10-27 | 润和科华催化剂(上海)有限公司 | Sulfur transfer agent with strong base site and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423019A (en) * | 1979-04-11 | 1983-12-27 | Standard Oil Company (Indiana) | Process for removing sulfur oxides from a gas |
| US4497902A (en) * | 1979-04-11 | 1985-02-05 | Standard Oil Company (Indiana) | Composition for removing sulfur oxides from a gas |
| US4589978A (en) * | 1985-03-01 | 1986-05-20 | Mobil Oil Corporation | Catalyst for reduction of SOx emissions from FCC units |
-
1999
- 1999-11-12 CN CN99123823A patent/CN1102433C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4423019A (en) * | 1979-04-11 | 1983-12-27 | Standard Oil Company (Indiana) | Process for removing sulfur oxides from a gas |
| US4497902A (en) * | 1979-04-11 | 1985-02-05 | Standard Oil Company (Indiana) | Composition for removing sulfur oxides from a gas |
| US4589978A (en) * | 1985-03-01 | 1986-05-20 | Mobil Oil Corporation | Catalyst for reduction of SOx emissions from FCC units |
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| CN1295877A (en) | 2001-05-23 |
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