CN85106279A - Preparation of catalysts method and the purposes that will synthesize gas changing into methanol - Google Patents

Abstract

A kind of catalyst Precursors is used for after reduction activation synthetic gas changing into methanol, and this parent has following formula: Cu _aThA _bO _xWherein A is a basic metal, and a is from 0.1 to 4 value, and b is from 0 to 0.5, and x is the number that oxygen satisfies other element valence mumber requirement.Its preparation method comprises precipitation, recovery and three steps of thermolysis.In settling step, being lower than under 50 ℃ the temperature, be precipitation agent with the carbonate and/or the supercarbonate that contain basic metal and/or ammonium, metallic copper and the thorium form with insoluble heat decomposable compound is precipitated out; Recycling step obtains throw out; But heat-decomposing compound in the throw out that obtains is carried out thermolysis.Has formula Cu in addition _aTh O ₂Catalyst composition.

Description

Preparation of catalysts method and the purposes that will synthesize gas changing into methanol

The present invention relates to by employed catalyzer in the synthesis gas preparation methyl alcohol, prepare the method for this catalyzer and utilize the method for this Preparation of Catalyst methyl alcohol.

People recognize that already metal catalyst or metal oxide catalyst can be used for the process of the compound of production oxidation.And people think that always copper and thorium are this class activity of such catalysts components.For example referring to United States Patent (USP) 1,707,331; 2,061,470; 2,500,913; 1,741,307; 1,625,929 and 1,831,179.

United States Patent (USP) 1,625,929 have described the catalyst for methanol that contains three kinds of main components, promptly (1) one or more be difficult for the reductive metal oxide, as zinc, magnesium, cadmium, chromium, vanadium, tungsten, uranium, zirconium, titanium, aluminium, manganese, molybdenum, thorium, cerium etc.; (2) one or more easy reductive metal oxides are as copper, silver, iron, nickel, cobalt etc.; (3) fontanelle compound of metal.The improvement of these catalyzer is because the existence of fontanelle compound.

United States Patent (USP) 1,707,331 have introduced the catalyzer of producing methyl alcohol with hydrogen and carbon monoxide, and this catalyzer contains copper and rare earth metal fluorochemical.Suitable rare earth metal is designated as thorium, scandium, lanthanum, cerium, praseodymium, neodymium and samarium.This patent example 11 has been described by the heat deposition method and has been prepared the cupric fluoride/thorium catalyzer that is stated from the asbestos.

United States Patent (USP) 1,741,307 have described carbon monoxide and have contained CO (carbon monoxide converter) gas reductive method, this method comprises reacts above-mentioned gas in continuous stages with hydrogen-containing gas, generate formaldehyde and methyl alcohol, and need not to isolate the intermediate product of generation, and at least one section weak reducing catalyst of existence is together with oxide catalyst in the initial two-stage, and the latter is as the former carrier.Weak reducing catalyst comprises copper, manganese, cadmium, zinc, lead, tin, magnesium, silver, gold and platinum; Oxide catalyst comprises the compound of chromium, vanadium, manganese, titanium, molybdenum, tungsten, cerium, thorium, uranium and zirconium, and analogue.This is in the example 2 of part patent, the method of producing methyl alcohol with layered catalyst has been described, component (2) in the catalyzer is the Thorotrast with copper and spelter coating, is evaporated on the Thorotrast fragment and is obtained by the ammonium salt complex compound of cupric nitrate and zinc nitrate.

United States Patent (USP) 1,831,179 have described and have been similar to United States Patent (USP) 1,741, the segmentation method of introducing in 307.In the example 1 of this patent, in the fs of carbonic acid gas and hydrogen generation carbon monoxide and water, react employed catalyzer and constituted by 100 parts of pure copper carbonates that are stated from 1000 parts of Thorotrast fragments, copper carbonate is adhered with dextrin, and in hydrogen stream, reduce under 280 ℃ of temperature.

United States Patent (USP) 2,061,470 have described with catalyzer and have produced methyl alcohol by synthetic gas, and its catalyzer is made up of the reduzate of cupric oxide and manganese oxide or cupric oxide and zinc oxide molten mixture, wherein also contains one or more elements such as magnesium, aluminium, chromium, zirconium, vanadium, titanium, thorium, silicon and cerium.The catalyzer that this patent example 7 is described is made up of 78 parts of pure zirconia copper, 20 parts of pure Manganse Dioxide and two parts of pure zirconia thoriums.

United States Patent (USP) 2,500,913 have described the preparing gel oxo catalyst that contains silicon oxide and cobalt salt, thorium salt and mantoquita by dipping.

In above-mentioned catalyzer, only United States Patent (USP) 1,707, and the catalyzer of 331 narrations are to adopt the precipitation technology preparation, and relates to from hot solution and precipitate.

At last, United States Patent (USP) 4,298,354 have described the method for producing alcohol mixture, and this method comprises that the gas reactant that will contain carbon monoxide and hydrogen contacts with the oxide compound coordination catalyst of following formula:

Cua Th Mb Ac Ox

M is one or more Ca in the formula, Mo, Rh, Mn, Pt, Ce, Cr, Zn, Al, Ti, La, V, U, Ru, Re and Pd;

A is a basic metal;

A is 0.5 to 2.5;

B is 0.01 to 1.0;

C is 0.05 to 0.9;

X is that oxygen satisfies the number that the valence mumber of other element requires.

United States Patent (USP) 4,298,354 Preparation of catalysts programs relate to alkaline carbonate joined and contain decomposable thorium salt, in the aqueous solution of mantoquita and above-mentioned " M " element salt, preferably maintaining under the high temperature (as 80 to 95 ℃) pH value that keeps until system is raised to and is at least 7.5, be preferably at least 8, preferably be about 9.3 to 10, aging this throw out when keeping this temperature, acidifying PH to 6.8 is to 7, separate again, washing and dry sediment, but be enough to expel wherein remaining moisture content and decomposing the roasting temperature throw out of remaining decomposable ions then.In example 1 and subsequent instance, settling step carries out under 90 to 95 ℃ of temperature.

The invention provides the method for producing catalyst Precursors, be used for synthetic gas is converted into methyl alcohol after this parent reduction activation, the formula of parent is as follows:

Cua Th Ab Ox （Ⅰ）

A is a basic metal in the formula;

A is 0.1 to 4;

B is 0 to 0.5;

X is that oxygen satisfies the number that the valence mumber of other element requires.

This method comprises the steps:

(I) is precipitation agent with the carbonate and/or the supercarbonate that contain basic metal and/or ammonium, is being lower than under 50 ℃ the temperature, and metallic copper and the thorium form with its insoluble heat decomposable compound is precipitated out, and pH value is adjusted to 5.0 to 7.0 scope at last,

The throw out that obtains in (II) recycling step (I),

(III) carries out thermolysis to heat decomposable compound in the throw out that reclaims in the step (II), and the pyrolysated maximum temperature range is 300 to 600 ℃.

The preferable range of a value is 0.5 to 3 in the formula I, is more preferably 0.7 to 2.The b value better is less than 0.15 in the formula I, preferably 0.

Other metal M also can be incorporated in the catalyst Precursors of formula I, and the some of them effect is fine.Suitable metal M comprises Mo, Rh, and Mn, Pt, Ce, Cr, Zn, Al, Ti, La, V, U, Ru, Re, Pd, Ag, Au and alkaline-earth metal are as Ca.The amount of incorporating into of metal M can reach 20%(W/W).

After the reduction activation, the product of the inventive method then is the catalyzer of good production methyl alcohol.Can obtain very high methyl alcohol space-time yield and up to 99% methyl alcohol selectivity.And this catalyzer is also anti-to decompose regeneration easily.Relatively, other condition is all identical, but precipitates the catalyzer that legal system is equipped with down in higher temperature (as 90 ℃), and is much smaller for the activity of producing methyl alcohol.

Step in the aforesaid method (I) can be undertaken by variety of way, and with regard to final activity of such catalysts, it is better that some method then seems.Therefore, embodiment (A) is to be lower than under 50 ℃ the temperature, and with soluble metal mantoquita and thorium salt with contain the carbonate of basic metal and/or ammonium and/or the precipitation agent of supercarbonate adds in the solution together, pH value is adjusted to 5.0 to 7.0 scope at last.Another embodiment (B) is that soluble thorium salt and precipitation agent are placed on is in the solution of no copper basically, make the thoride precipitation, then in the presence of sedimentary thorium compound, put into soluble copper salt and precipitant solution, make insoluble heat decomposable compound precipitation, pH value is adjusted to 5.0 to 7.0 scope at last, said be deposited in to be lower than under 50 ℃ of temperature carry out, said precipitation agent comprises the carbonate and/or the supercarbonate of basic metal and/or ammonium.After the thoride precipitation, soluble copper salt can suitably be added in the sedimentary thorium compound, and need not to carry out other processing, for example filters before the precipitated copper compound.Another kind method is to separate before the precipitated copper compound, washing and the sedimentary thorium compound of redispersion.Also can change to above-mentioned embodiment (A) with (B), for example, salt be added in the precipitation agent, rather than precipitation agent is added in the salt.

When using any soluble copper salt and thorium salt, carboxylate salt for example, acetylacetonate compound, naphthenate, muriate and analogue preferably use nitrate.

Preferably use the aqueous solution of this type of salt, but if desired, also can use as aqueous alcohol solutions.

In basic metal, sodium and potassium suit, and this mainly is the reason owing to source and cost.The example of suitable precipitation agent has yellow soda ash, sodium bicarbonate, salt of wormwood, saleratus, volatile salt and bicarbonate of ammonia.When adopting an alkali metal salt to make precipitation agent, the catalyst Precursors composition that obtains almost contains alkali metal cation certainly, and its amount can reduce by washing, or increases by further adding alkali metal cation.But we find that the catalyzer of alkali-free metal (b in the formula I equals 0) is active best, therefore, as precipitation agent, use volatile salt or bicarbonate of ammonia better, preferably bicarbonate of ammonia.The form of suitable volatile salt during with merchandise sales used, and it is the mixture that contains bicarbonate of ammonia and volatile salt.Use bicarbonate of ammonia as precipitation agent, provide beyond thought maximum activity the catalyzer in the scope of the invention.

Precipitation suits to carry out being lower than under 30 ℃ of temperature, is more preferably the temperature range at 0 to 25 ℃.At room temperature precipitation generally will be a most convenient.

Use the amount of soluble copper salt and thorium salt should be able to satisfy a value and b value in the formula I.

In order to improve the homogeneity of catalyzer, stir the mixture when being preferably in precipitation, suit with mechanical stirring.

Adding precipitation agent raises initial low pH value.Generally speaking, be about at 4 o'clock at pH value, the precipitation that will find thorium compound is completely basically.Importantly, during copper component in this type of catalyzer precipitation, last pH value will better be 5.5 to 6.5 in 5.0 to 7.0 scope, is more preferably 5.9 to 6.3.Step before reaching last pH value can have big change.Therefore, before reaching, above-mentioned pH value scope can add precipitation agent, adding precipitation agent again can be intermittently, prevent that thus pH value from raising, and in addition, further adds precipitation agent pH value is raise continuously, until 9 to 10 the scope of reaching (in this scope, precipitation generally is found to be completely), add acid then, the pH value of regulating mixture reaches above-mentioned scope at last.Another kind method is by adding suitable buffer reagent, and the pH value of mixture is remained on the numerical value of above-mentioned scope.

By being lower than under 50 ℃ of temperature, particularly be lower than under 30 ℃ of temperature, precipitate throw out obtained by the method for the present invention from metal nitrate and be considered to contain the crystalline phase that comprises copper, copper is that the form with basic carbonate exists, and in the sedimentary crystalline phase that precipitation obtains under top temperature, its copper contains copper, hydroxy nitrate.

Step (I) had better be carried out in the atmosphere of carbonic acid gas.Although we do not wish to be fettered by any way by theory, can believe that the existence of carbonic acid gas can make in the composition any carbonate facics stable, and can improve the wherein deployment conditions of metallographic phase.

The step of the inventive method (II) is the throw out that recycling step (I) obtains.This suits to be finished by filter method, but also can use other method of separate solid from liquid, as centrifugation.After the recovery, last washing precipitate, it is more suitable to wash with water, to remove unwanted solubility remnant.Then, can dry sediment, suitable temperature is to be lower than 150 ℃ high temperature, for example about 120 ℃.

According to the step (III) of the inventive method, contained heat decomposable compound in the throw out of step (II) recovery is carried out thermolysis.The top temperature of using in the thermolysis necessarily can not surpass 300 to 600 ℃ temperature range, is no more than 400 to 500 ℃ better, be no more than 440 to 460 ℃ best.Heat-up rate can change in a wide scope.Be preferably in one long during in, for example keep throw out within 1 to 200 hour under best temperature.And be preferably in the non-reduced atmosphere and decompose, suit in inert gas such as nitrogen, or in oxygen flow such as air, decompose.

After the decomposition, product contains metal oxide component, and it can be converted into the catalyzer that is used for synthetic gas is converted into methyl alcohol by reduction activation.

The catalyst Precursors composition (composition of formula I, wherein b=0) of doing the precipitation agent acquisition with bicarbonate of ammonia can carry out reduction activation with the reducing gas that contains carbon monoxide (for example mixture of carbon monoxide/hydrogen).The advantage of doing like this is, thus obtained precursor compositions can carry out reduction activation in the reactor of producing methyl alcohol, and the reaction conditions of use can be with to produce the reaction conditions that adopts in the methanol technics identical or different.

For the catalyst Precursors composition, except above-mentioned mention, promptly the b value in the formula I is greater than zero, preferably carrying out reduction activation initial with the reducing gas that does not contain carbon monoxide substantially (for example preferably by the hydrogen of inert gas dilution) at least.Extremely suitable gaseous mixture is to contain 5% hydrogen in nitrogen.Carry out after the initial reduction with reducing gas (not being carbon monoxide), following reduction is carried out in containing the gas of carbon monoxide, for example carbon monoxide/hydrogen mixture.Reduction activation in the method suited before being used as the catalyzer of producing methyl alcohol, perhaps pack into produce methanol reactor before or producing in the methanol reactor, carry out as an independent step.

The convenient pressure scope of carrying out the reduction activation employing is 1 to 100 crust, and suitable temperature range is 170 to 250 ℃, and the time is 24 hours or longer.

We have found that the feature of active catalyst contains higher proportion, specification is less than or equal to the elemental copper particle of 20 dusts.

Therefore, the present invention comprises the catalyst composition that is used for synthetic gas changing into methanol on the other hand, and said composition contains the oxide compound of elemental copper and thorium by the following formula atomic ratio:

Cua Th Ox （Ⅱ）

X satisfies the number that oxygen requires the valence mumber of Th in the formula,

A is from 0.1 to 4 value,

And wherein at least 30% elemental copper particulate granularity is less than or equal to 20 dusts.

Therefore activity of such catalysts is related to the elemental copper particulate absolute magnitude that granularity is less than or equal to 20 dusts, all requires a high proportion ofly as far as possible for any special composition, and granularity is less than or equal to the elemental copper of 20 dusts.

Better at least 50%, better at least 90% elemental copper particle is less than or equal to 20 dusts.

In the formula II a value preferably scope be 0.5 to 3, be more preferably 0.7 to 2.

Provide a kind of method by synthesis gas preparation methyl alcohol as another aspect of the present invention, this method comprises synthetic gas and above-mentioned catalyzer is contacted in 80 to 300 ℃ temperature range with under the pressure of 0 to 100 crust.

Synthetic gas mainly contains carbon monoxide and hydrogen, according to its source and purity, may also contain amounts of carbon dioxide, nitrogen and other rare gas element, and this is knowing in the art.Set up many methods that prepare synthetic gas in the art, these methods relate to the partial oxidation of carbonaceous material (for example coal) usually, and synthetic gas also can be prepared by the water vapor catalytic reforming of for example methane in addition.For purpose of the present invention, the ratio of carbon monoxide and hydrogen is adapted in 2: 1 to 1: 8 the scope, better is 1: 1 to 1: 3, is more preferably 1: 2.In view of the ratio by carbon monoxide in the synthetic gas of aforesaid method production and hydrogen is different from these scopes, can add carbon monoxide or hydrogen appropriate change ratio, perhaps the so-called shift reaction of being known by technician is in the art regulated ratio.Be preferably in synthetic gas with before catalyzer contacts, remove the carbonic acid gas of synthetic gas, suitable method is a washing method.

Synthetic gas contacts with catalyzer in 80 to 300 ℃ temperature range.Be higher than 300 ℃ of processing eases and produce a large amount of higher alcoholss except that the gas product, therefore reduced selectivity methyl alcohol.In order to obtain the highest selectivity, working pressure is preferably within the scope of 20 to 100 crust for methyl alcohol.The variation range of gas hourly space velocity (GHSV) is very wide, for example from 1000 to 350,000 hours ^-1

This process is suitable for operating on thermopnore or Solid Bed, perhaps intermittently carries out, and perhaps carries out continuously, preferably carries out continuously.

This catalyzer can also add other material, for example aluminum oxide or chromic oxide, and the general purpose that adds is in order to dilute, the control pellet density, and satisfy other mechanical requirement, shrink and anti scuffing as anti-.These materials can add according to convenient in arbitrary stage of preparation catalyzer.

The present invention now further describes with reference to following example.

For example 21 to 23,31 to 38 and comparison test 4,6,7, use tubular reactor shown in Figure 1.With reference to Fig. 1, the 1st, the stainless steel tube of 8mm internal diameter, in around the slotted ring around the reactor, register thermopair 2 and controller thermopair 3 are housed, are used to control and monitor the temperature of carbolite type CJT1/1000 decomposing furnace with the thermopair that the CRL controller links to each other with Honey well-Brown register (all not shown).The synthetic gas that enters tubular reactor at first contacts with the silicon oxide ball that is used as preheater, and then by catalyzer 6, pottery hair plug 7 by stainless (steel) wire 8, is gone out from reactor at last.

Mode shown in the reactor map interlinking 2 is arranged in the equipment flowsheet of Fig. 2.See also Fig. 2, main devices has Brooks mass flow controller 9, hydrogen bypass 10, the reactor assembly of Fig. 1, gas separate pot 11 and 12, T-valve 13 and pressure controller 14.

For example 24 to 30,39 to 44 and comparison test 5, use different reactor and equipment flowsheet, as shown in Figure 3 and Figure 4.Fig. 3 represents the reactor that adopts, and Fig. 4 represents to comprise the equipment flowsheet of Fig. 3 reactor.

Referring to Fig. 3, the 15th, the stainless steel tube of 7mm internal diameter, the 16th, the stainless steel thermowell of 2.5mm internal diameter, register thermopair 17 are inserted in wherein folder.Controller thermopair 18 is placed in the slotted ring that is parallel to reaction tubes.These thermopairs in succession eurotherm controller and CRL register (all not shown) are used for control and monitoring Stanton Redcroft lightweight horizontal stove 19(low mass hor izontal furnace) temperature.The synthetic gas that enters tubular reactor at first meets with pottery hair plug 20, then by catalyzer 21, by another pottery hair plug 22, goes out from reactor at last.

The reactor apparatus of Fig. 3 is arranged in the equipment flowsheet of Fig. 4 by way of illustration.Referring to Fig. 4, from the gas tank access arrangement, the needle valve 24 behind the reactor and 25 is controlled flow velocitys to gas by pressure regulator valve 23.Fluid is by the note bubble instrumentation amount in reactor outlet and G.C. exit.If desired, establish a jar of holding back of getting the product sample.

The preparation of catalyst Precursors

Example 1-catalyst Precursors A(precipitates at low temperatures)

With cupric nitrate, Cu(NO ₃) ₂3H ₂O(120 restrains) and thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄4H ₂The O(180 gram) is dissolved in 3000 ml distilled waters.Salt of wormwood (207.3 grams, anhydrous) is dissolved in 1500 ml distilled waters, and the solution of generation is added drop-wise in copper-thorium solution under stirring and room temperature (about 20 ℃).Make the last pH value of this mixture reach 6 with 1150 cubic centimetres of carbonate solutions.The suspension that filtration obtains, filter cake is by the washing that suspends once more in distilled water (3 * 300 milliliters).At 120 ℃ of down dry these solids, roasting is 6 hours in 450 ℃ of following air then, and temperature rises to 450 ℃ from 20 ℃ in 60 minutes.To the analysis revealed cupric 19% of catalyst Precursors, thorium 44%, potassium 1.37%(b/w).

Comparison test 1-catalyst Precursors B(precipitates down at 80 ℃ to 90 ℃)

The preparation method is with the preparation method who describes catalyst Precursors A in the example 1, and different is that cupric nitrate/thorium nitrate 99.99004323A8urity solution and solution of potassium carbonate were heated to 80～90 ℃ before mixing.After the roasting, to the analysis revealed cupric 22% of catalyst Precursors, thorium 44%, potassium 1.18%(are by weight).

This is not an example of the present invention, because precipitation is to carry out under 80 ℃ to 90 ℃ temperature.

Example 2-catalyst Precursors C(changes in order to add precipitation agent)

Gerhardite (20 gram) is dissolved in 250 ml distilled waters, stirs and slowly add 1 mole of solution of potassium carbonate down, reach 6.0 until the pH value of mixture.Six nitric hydrate thoriums (30 gram) are dissolved in 250 ml distilled waters, and the solution that obtains is joined in the above-mentioned copper suspension.Stir the slow down 1 mole of solution of potassium carbonate that adds then, make pH value reach 6.0.Filtering mixt, and by resuspending (3 * 500 milliliters) washing leaching cake in distilled water, following dry 6 hours at 120 ℃ at last.

This solid carries out thermolysis in the air under 450 ℃.Earlier temperature is raised to 50 ℃ rapidly, carries out temperature programming up to 450 ℃ and 450 ℃ of following maintenances 6 hours with 30 ℃/hour then.

Example 3-catalyst Precursors D(precipitates with saleratus)

Repetition example 1(catalyst Precursors A) program, different is to have replaced salt of wormwood with saleratus, and after the drying, solid is 450 ℃ of following thermolysiss, and temperature is brought up to 50 ℃ at first rapidly, carries out temperature programming with 30 ℃/hour, up to 450 ℃, kept 6 hours down at 450 ℃.

Example 4-catalyst Precursors E(ammonium bicarbonate precipitation)

Repetition example 1(catalyst Precursors A) program, different is to have replaced salt of wormwood with bicarbonate of ammonia.

Example 5-catalyst Precursors F(is 5 o'clock precipitations at pH value)

Repetition example 1(catalyst Precursors A) program, different is to add wet chemical only to make PH reach 5, prepares scaled, the exsiccant solid carries out thermolysis under 450 ℃, temperature is brought up to 50 ℃ at first rapidly, carries out temperature programming up to 450 ℃ with 30 ℃/hour then,

Example 6-catalyst Precursors G(is 6 o'clock precipitations at pH value)

Example 5(catalyst Precursors F) program is repeated, and difference is to add wet chemical to reach 6 up to pH value.

Example 7-catalyst Precursors H(is 7 o'clock precipitations at pH value)

Repetition example 5(catalyst Precursors F) program, difference is to add wet chemical to reach 7 up to pH value.

Comparison test 2-catalyst Precursors I(is 8 o'clock precipitations at pH value)

Repetition example 5(catalyst Precursors F) program, difference is to add wet chemical to reach 8 up to pH value.

This is not an example of the present invention, because last pH value is not in the scope between 5 to 7.

Example 8-catalyst Precursors I ' (the order precipitation of embodiment B)

With cupric nitrate, Cu(NO ₃) ₂3H ₂O(24.0 gram, 99.3 mmoles) solution forms solution X in 20 ml deionized water; With thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄6H ₂The O(36.0 gram, 61.2 mmoles) be dissolved in 600 ml deionized water, form solution Y; With bicarbonate of ammonia, NH ₄HCO ₃(47.6 gram, 598.0 mmoles) solution in 300 ml deionized water, and with this solution stir and room temperature under, be added drop-wise among the solution Y with the speed of 5 ml/min, reach 4 up to pH value, stop dropping.Continuously stirring is 15 minutes again, then filtering suspension liquid.Filter cake washs by being immersed in 300 ml deionized water, stirs 15 minutes, filters.Washed filter cake is redispersion in 680 ml deionized water, after solution X is added in the dispersion liquid.Suggestion adds bicarbonate of ammonia as stated above and reaches 6 up to pH value.Continuously stirring is 15 minutes again, filtering suspension liquid.Its filter cake washs three times as stated above.Then 110 ℃ of following drying products 17 hours, pulverize the back and form particle, but can not pass through 30 sieve meshes (B.S. specification) by 16 sieve meshes.

Product is decomposed by programme controlled thermal treatment in nitrogen gas stream.Temperature is raised to 450 ℃ with 120 ℃/hour with room temperature, before cooling, remain on then 450 ℃ following 6 hours.

Example 9-catalyst Precursors J

Repeat example 8, difference is that composition changes to some extent, and the amount of cupric nitrate is reduced to 14.8 grams (61.3 mmole).

Example 10-catalyst Precursors K:

With cupric nitrate, Cu(NO ₃) ₂3H ₂O(14.8 gram, 61.3 mmoles) solution in 20 ml deionized water to form solution X; With thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄6H ₂The O(36.0 gram, 61.2 mmoles) be dissolved in 600 ml deionized water to form solution Y; With bicarbonate of ammonia, NH ₄HCO ₃(47.6 gram, 598.0 mmoles) are dissolved in 300 ml deionized water, and this solution in room temperature with under stirring, is added drop-wise among the solution Y with the speed of 5 ml/min, reach 4 up to pH value, stop to add bicarbonate of ammonia.Continuously stirring is 15 minutes again, then solution X is joined in the suspension.In mixture, add ammonium bicarbonate soln again, reach 6 up to pH value by aforementioned manner.Continuously stirring is 15 minutes again, then filtering suspension liquid.

According to the described mode decomposed product of example 8 preparation catalyst Precursors I '.

This example is different from example 9 parts, before adding compound nantokite solution and therefrom precipitating copper.Sedimentary thorium compound does not separate, washing and dispersion.

Comparison test 3-catalyst Precursors L

With thorium nitrate 99.99004323A8urity, Th(NO) ₄6H ₂The O(36.0 gram, 61.2 mmoles) be dissolved in 600 ml deionized water, form solution Y; With bicarbonate of ammonia, NH ₄HCO ₃(47.6 gram, 598.0 mmoles) solution in 300 ml deionized water, and with it with 5 ml/min clock rate, be added drop-wise among the solution Y in room temperature with under stirring, reach 4 up to pH value.Continuously stirring is 15 minutes then, filtering suspension liquid.Filter cake is immersed in 300 ml deionized water and washs, and stirs 15 minutes, filters.This washing operation carries out 3 times altogether.Drying products 17 hours under 110 ℃ of temperature then.

The product (15 gram) that obtains is above ground to form fine powder, be added in 10 ml deionized water.With cupric nitrate, Cu(NO ₃) ₂3H ₂The O(10.3 gram, 42.7 mmoles) under agitation be dissolved in the suspension of thorium compound, suspension is evaporated 6 hours to dry on the placement vaporizer.The finished product are following dry 7 hours at 110 ℃ then.

Products obtained therefrom decomposes by example 8 preparation catalyst Precursors I ' described methods after dry.

This is not an example of the present invention, because copper does not precipitate.

Example 11-catalyst Precursors M:

With cupric nitrate, Cu(NO ₃) ₂3H ₂The O(24.0 gram, 99.3 mmoles) and thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄6H ₂The O(36.0 gram, 61.2 mmoles) be dissolved in 600 ml deionized water to form solution W; With bicarbonate of ammonia (NH ₄HCO ₃, 47.6 grams, 598.0 mmoles) be dissolved in 300 ml deionized water, with the speed of this solution, be added drop-wise in the solution W in room temperature with under stirring with 5 ml/min, reach 6 until pH value.Continuously stirring is 15 minutes again, filtering suspension liquid.Filter cake is immersed in 300 ml deionized water to wash, stir 15 minutes after-filtration.This washing operation carries out altogether 3 times.Product is drying products 17 hours under 110 ℃ of temperature then.

The final drying product decomposes by the method for preparing catalyst Precursors I ' that example 8 is introduced.

Thorium is not to precipitate under the situation of not having copper substantially, and this point is different from example 8.

Example 12-catalyst Precursors N

Repeat example 11, difference is that composition changes to some extent: the amount of cupric nitrate is reduced to 14.8 grams (61.3 mmole).

Thorium is not to precipitate under the situation of not having copper substantially, and this point is different from example 9.

Example 13-catalyst Precursors O(ammonium bicarbonate precipitation)

With cupric nitrate, Cu(NO ₃) ₂3H ₂The O(14.8 gram, 61.3 mmoles) and thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄6H ₂The O(36.0 gram, 61.2 mmoles) be dissolved in 600 ml deionized water to form solution X; With bicarbonate of ammonia, NH ₄HCO ₃(47.6 grams, 600 mmoles) are dissolved in (solution Y) in the deionized water.Solution Y is added drop-wise among the solution X under room temperature and strong mixing, reaches 6.0 until pH value.Continuously stirring 15 minutes, filtering suspension liquid.Filter cake washs by being immersed in 600 moles of deionized waters.This washing operation carries out 3 times altogether.Final solids cake compresses is following dry 17 hours at 110 ℃.Milling product makes it pass through 16 sieve meshes, but can not pass through 30(BSS then) (B.S. specification).

This product innovation decomposes by program thermal treatment in nitrogen gas stream then.Temperature is brought up to 450 ℃ with 120 ℃/hour from room temperature, and keeps 6 hours down in 450 ℃.

Example 14-catalyst Precursors P

This catalyst Precursors is pressed the same manner preparation of catalyst Precursors O in the example 13, and the mixture of using nitrate is as solution X:Cu(NO ₃) ₂3H ₂The O(24.0 gram, 99.3 mmoles), Ce(NO ₃) ₃6H ₂The O(1.3 gram, 3.1 mmoles) and Th(NO ₃) ₄6H ₂The O(36.0 gram, 61.2 mmoles).

Example 15-catalyst Precursors Q(is 300 ℃ of following thermolysiss)

Repeat example 1(catalyst Precursors A) program, difference is after the drying, a part of drying solid carries out thermolysis in air, its temperature is raised to 50 ℃ rapidly earlier, with 30 ℃ of/hour temperature programmings to 300 ℃, keeps 6 hours under 300 ℃ of temperature then.

Example 16-catalyst Precursors R(is 400 ℃ of following thermolysiss)

Another part drying solid that obtains in example 15 carries out thermolysis by the mode that example 15 is described, and difference is that outlet temperature is 400 ℃ rather than 300 ℃.

Example 17-catalyst Precursors S(is 450 ℃ of following thermolysiss)

Another part drying solid that obtains in example 15 carries out thermolysis by the mode that example 15 is described, and difference is that outlet temperature is 450 ℃, is not 300 ℃.

Example 18-catalyst Precursors T(is 500 ℃ of following thermolysiss)

The last part drying solid that will obtain in example 15 carries out thermolysis by example 15 describing modes, and not existing together is that outlet temperature is 500 ℃, is not 300 ℃.

Example 19-catalyst Precursors U

Adopt example 1(catalyst Precursors A) program, not existing together is that the solid thermolysis of dry back is to carry out under 450 ℃, temperature is raised to 50 ℃ rapidly earlier, keeps 6 hours down then with 30 ℃ of/hour temperature programmings to 450 ℃, and at 450 ℃.

Example 20-catalyst Precursors V

With cupric nitrate, Cu(NO ₃) ₂3H ₂O(48.0 gram, 198.6 mmoles) solution to form solution, is represented with X in 40 ml deionized water.With thorium nitrate 99.99004323A8urity, Th(NO ₃) ₄6H ₂O(72.0 gram, 122.4 mmoles) be dissolved in 120 ml deionized water to form solution, represent with Y.This solution keeps it saturated with carbon dioxide in whole process of preparation.With bicarbonate of ammonia, NH ₄HCO ₃(95.2 gram, 1196 mmoles) solution in 600 ml deionized water, and with this solution in room temperature with under stirring, be added drop-wise among the solution Y with the speed of 10 ml/min, reach at 4 o'clock up to pH value, adding stops.Continuously stirring is 15 minutes again, then solution X is added in the suspension.In this solution, add ammonium bicarbonate soln by aforementioned again with quadrat method, reach 6 up to pH value.Continuously stirring is 15 minutes again, filters this suspension then.Filter cake is pressed preceding method washing three times.Product decomposes by the method that example 8 is described then.

Catalyst Precursors changes the check of catalyzer and gained catalyzer into

(A) effect that the inventive method step (I) is carried out various changes

Example 21-catalyst A

Referring to Fig. 1 and Fig. 2, with the catalyst Precursors A reactor shown in Figure 1 of packing into, and feed the nitrogen that contain 5% hydrogen down at 170 ℃ and carried out reduction activation 16 hours, temperature is to rise to 170 ℃ within an hour.

Afterwards, stop to feed H ₂/ N ₂Air-flow comes out from gas tank, by pressure controlled valve and Brook caloic-fluid control 9, with CO: H=1: the ratio 2(mole) feed carbon monoxide and hydrogen to reaction.Intake pressure is indicated by tensimeter, and protects equipment with rupture disk, prevents its superpressure.In 30 minutes, make system be forced into 50 crust.Under this pressure, the gas hourly space velocity of stabilized fluid (GHSV) was at 7000 hours ^-1

The gaseous product that flows out from reactor by heating pipeline and selector valve 13 enter be arranged in parallel hold back jars 11 or 12.Hold back jar for these two and be cooled to-5 to-10 ℃ in solidified carbon dioxide (Cardice)/acetone, hold back jar for one and be used for trial trip, another is used for equilbrium running.Leave the gas of holding back jar and be introduced into pressure controller 14, wherein pressure is reduced to normal atmosphere, and by gasometer, sampling spot is gone out at last then.

After one hour, when reaching stable trial trip condition, open selector valve 13, and between 1 hour on-stream period, with product liquid be collected in beginning not the cold of usefulness hold back in the jar.Exit gas is measured by gasometer, and takes out the gas sample in the running.By gas chromatographic analysis liquids and gases product.With the results are shown in the table 1 that methanol yield is represented.

Comparison test 4-catalyst B

Repeat the program of example 21, difference is to replace catalyst Precursors A with catalyst Precursors B.

Table 1

Example catalyst methanol yield mol/hour/rise catalyzer

21 A 43

Comparative experiments 4 B 25

Result in the table 1 clearly demonstrates the catalyzer by sedimentary parent preparation at room temperature, and its specific activity wants big at the catalyzer of 80 to 90 ℃ of down sedimentary catalyst Precursors preparations.

Example 22

Repeat the program of example 21, difference is that catalyst Precursors A is replaced by catalyst Precursors C.The result who represents with methanol yield is listed in the table 2 together.

Table 2

Example catalyst methanol yield mol/hour/rise catalyzer

21 A 43

22 C 46

Example 23

Repeat the program of example 21, difference is that catalyst Precursors A is replaced by catalyst Precursors D.The result who represents with methanol yield is listed in the table 3 together with the result of catalyst A.

Table 3

Example catalyst precipitation agent methanol productive rate

Mol/hour/rise catalyzer

21 A salt of wormwood 43

23 D saleratus 53

Example 24

Referring to Fig. 4, catalyst Precursors E(1 milliliter) be diluted to 4 milliliters with inertia silicon carbide, be placed in the reactor, bed is long to be 5 centimetres, thinner is used for controlling reaction heat.

Feeding contains the nitrogen of 5% hydrogen, and 170 ℃ of following reduction activation catalyzer 6 hours, temperature was to bring up to 170 ℃ during 1 hour.

After the reduction activation, stop to feed H ₂/ N ₂Stream is with CO: H ₂The mixture that is the carbon monoxide of 1: 2 mol ratio and hydrogen was with 100,000 hours ^-1GHSV feeds reactor, and keeping temperature of reactor is 200 ℃, and absolute pressure is 50 crust.

Eluting gas enters the Pye Unicam gas chromatogram detector that has 2 milliliters of stopple coupons by heating pipeline (200 ℃).Hydrogen is as carrier gas, with 2 meters Porapak Q posts at 112 ℃ of following separated products.This post is separation of C O well, CO ₂, H ₂O and Me OH.Injecting 0.5 microliter methanol liquid of five equilibrium calibrates.Pye Unicam D4810 totalizing instrument is used for measuring peak area.Typical retention time than methyl alcohol in the post is 250s.With the results are shown in the table 4 that methanol yield is represented.

Example 25

Repeat the program of example 24, the same quadrat method that has been to use example 1 to describe preparation catalyst Precursors A that do not exist together prepares catalyst Precursors, promptly uses salt of wormwood as precipitation agent, and without catalyst Precursors E.With the results are shown in the table 4 that methanol yield is represented.

Table 4

The precipitation agent methanol productive rate that example catalyst is used

Mol/hour/rise catalyzer

24 E bicarbonate of ammonia 87

25 A salt of wormwood 15

Presentation of results in the table 4 does not use salt of wormwood in preparation process, and uses bicarbonate of ammonia can produce more activated catalyzer.

Example 26 to 30

Referring to Fig. 3 and Fig. 4, the sample of catalyst Precursors I ' is contained in the reactor shown in Figure 3.At room temperature synthetic gas is fed reactor, temperature is raised to 180 ℃ in then during 1 hour, before measuring catalyst activity, it was stablized 24 hours.In example 27 to 30, use catalyst Precursors J respectively, K, M and N repeat said procedure.

Underlying condition and press Me OH% and CH in the product stream ₄The % result calculated is listed in the following table 5.

Comparison test 5

Repeat the program of example 26 to 30 with catalyst Precursors L.

Table 5

Example catalyst pressure GHSV temperature Me OH** CH ₄*

Parent (absolute pressure) (hour ^-1) (℃)

26 example 8(I ') 9.3 3,600 180 3.16 *

27 example 9(J) 9.3 3,600 181 2.11 *

28 example 10(K) 9.3 3,600 180 3.14 0.02

Relatively comparison test 9.3 3,600 180 do not examine-

Test 53(L) measures

29 example 11(M) 9.3 3,600 181 2.50 0.02

28 example 12(N) 9.3 3,600 180 2.26 0.03

* do not find

* presses the percent by volume of exit gas and calculates.

Example 31

Repeat the program of example 21, difference is that catalyst Precursors A is replaced by catalyst Precursors F.With the results are shown in the table 6 that methanol yield is represented.

Example 32

Repeat the program of example 31, difference is that catalyst Precursors G replaces catalyst Precursors F.

Example 33

Repeat the program of example 31, but replace catalyst Precursors F with catalyst Precursors H.

Ratio test 6

Repeat the program of example 31, but replace catalyst Precursors F with catalyst Precursors I.

Table 6

The sedimentary pH value methanol yield of example catalyst

Mol/hour/rise catalyzer

31 F 5 24

32 G 6 43

33 H 7 27

Comparison test I 8 21

6

Catalyst activity depends on pH value final when catalyst Precursors precipitates as can be seen from Table 6.

(B) influence of various variablees in the inventive method step (III)

Example 34

Repeat the program of example 21, but replace catalyst Precursors A with catalyst Precursors Q.Represent that by methanol yield the results are shown in Table 7.

Example 35

Repeat the program of example 34, but replace catalyst Precursors Q with catalyst Precursors R.

Example 36

Repeat the program of example 34, but use catalyst Precursors S, replace catalyst Precursors Q.

Example 37

Repeat the program of example 34, but use catalyst Precursors T, replace catalyst Precursors Q

Table 7

The example catalyst heat decomposition temperature (℃) methanol yield

Mol/hour/rise catalyzer

34 Q 300 21

35 R 400 38

36 S 450 43

37 T 500 33

(C) influence of reduction activation step

Example 38

Repeat the program of example 21, not existing together is to replace catalyst Precursors A with part catalyst Precursors U.The results are shown in table 8 with what methanol yield was represented.

Comparison test 7

Repeat the program of example 21, but replace catalyst Precursors A, and save reduction activation and handle with another part catalyst Precursors U.The results are shown in table 8 with what methanol yield was represented

Table 8

Example catalyst reduction activation methanol yield

Mol/hour/rise catalyzer

38 U have 43

Comparison test 7 U do not have 6

The presentation of results reduction activation of table 8 is necessary for improving catalyst activity.

Example 39

Referring to Fig. 3 and Fig. 4, the sample of catalyst Precursors O is contained in the reactor shown in Figure 3, and under the pressure of 170 ℃ and 7 crust (definitely), carried out pre-treatment and activation 17 hours with helium (containing 5% hydrogen), GHSV is 10,000.

After the pre-treatment, stop the H/He air-flow, feed synthetic gas, and be adjusted to the required condition of catalyst test rapidly, shown in following table 9.After 24 hours product gas flow is taken a sample.

Example 40

Repeat example 39, but replace catalyst Precursors O with catalyst Precursors P.

Example 41

Referring to Fig. 3 and Fig. 4, with the catalyst Precursors sample O reactor shown in Figure 3 of packing into.(H: CO equals 2: 1) presses flow velocity shown in the table 9 and pressure wash catalyzer with synthetic gas.Temperature rises to 180 ℃ from room temperature in during 1 hour.Assay products air-flow after 24 hours.

Example 42

Repeat example 41, but replace catalyst Precursors O with catalyst Precursors P.

To example 39 to 42 resulting product gas flow analytical resultss under tabulate and provide in 9.

Table 9

Catalyzer example pressure GHSV temperature MeOH*

Parent (crust A) (hour ^-1) (℃)

O example 39 9.3 3,600 180 2.17

Example 41 9.3 3,600 180 2.26

P example 40 9.3 3,600 180 1.91

Example 42 9.3 3,600 180 2.02

* pressing exit gas volume % calculates.

The presentation of results of table 9 is under the methanol production condition, and the catalyst activity that obtains with synthetic gas reduction is used H at least with under different conditions ₂/ He gas mixture the activity of such catalysts that obtains of reduction of going ahead of the rest is equally high.

Example 43

Repeat example 26, but usefulness catalyst Precursors V replacement catalyst Precursors I '.

Example 44

Repeat example 43, but replace catalyst Precursors V with the catalyst Precursors for preparing the same method of catalyst V (but without carbonic acid gas) preparation.Reactant composition is represented by catalyst Precursors W.

Underlying condition and in product stream with Me OH% and CH ₄The result that % represents provides in following table 10.

Table 10

Example catalyst pressure GHSV temperature Me OH** CH ₄*

(absolute pressure) (hour) (℃)

43 V 9.3 3，600 180 3.18 0.04

44 W 9.3 3，600 180 2.92 0.04

* presses exit gas volume % and calculates

Catalyst characteristics

X-ray diffraction (XRD)

A series of catalyzer with following formula are prepared by aforementioned low temperature (being lower than 50 ℃) technology

Cua Th Ox

The a value from 0.1 to 4 in the formula, and the X value is that oxygen satisfies the number that the valence mumber of Th requires.With Cu K alpha-ray powder diffractometer, carry out the indirect measurement of standard X-ray diffraction analysis granularity be less than or equal to the elemental copper proportion of particles of 20 dusts.In fact, measurement be the elemental copper particulate amount of granularity greater than 20 dusts, from known total copper amount, deduct the value of mensuration again, then obtain the elemental copper particulate numerical value that granularity is less than or equal to 20 dusts.

The analytical results that carries out X-ray diffraction (XRD) for the catalyzer that will synthesize gas changing into methanol and catalyst activity provides in table 11, and this result is painted among Fig. 5 with the form of scheming.

In this table neutralization figure:

R represents the total copper amount in the catalyzer and the mol ratio of total Thorotrast amount;

%Cu represents that grain graininess is less than or equal to the percentage ratio of the elemental copper of 20 dusts,

A is illustrated under the standard test condition, the percentage ratio of the sample synthesizing methanol of every gram Thorotrast in the sample.

G represents that the granularity of share with a gram Thorotrast is less than or equal to the gram number of the copper of 20 dusts

Table 11

R %Cu A G

0.10 100 0.12 0.024

0.25 100 0.28 0.060

1.60 33 0.55 0.125

1.60 42 0.98 0.162

1.40 77 1.35 0.259

1.00 100 1.48 0.241

1.60 74 1.67 0.285

From table II and Fig. 5 as can be seen, produce in the present invention methyl alcohol catalyzer (A) activity with and 1 restrain between the gram number of copper that granularity that Thorotrast G share is less than or equal to 20 dusts direct relation arranged.Within the range of compositions of being studied, A is directly proportional with G in the testing error scope.

Claims (27)

1, a kind of method of preparation catalyst Precursors, this parent is used for after reduction activation synthetic gas changing into methanol, and has following formula:

Cua?Th?Ab?Ox(Ⅰ)

A is a basic metal in the formula,

A is from 0.1 to 4,

B is from 0 to 0.5,

X is the number that oxygen satisfies other element valence mumber requirement,

This method comprises the steps:

(I) is precipitation agent being lower than under 50 ℃ the temperature with the carbonate and/or the supercarbonate that contain basic metal and/or ammonium, and metallic copper and thorium is insoluble with it, and heat decomposable compound form is precipitated out, and last pH value is adjusted to 5.0 to 7.0 scope.

The throw out that makes in (II) recycling step (I),

(III) to step (II) but the heat-decomposing compound that contains in the throw out that reclaims carries out thermolysis, the pyrolysated maximum temperature range is 300 to 600 ℃.

2, according to the method for claim 1, a value scope from 0.5 to 3 in the formula I, b is zero.

3, according to the method for claim 1 or 2, wherein step (I) comprising: be lower than under 50 ℃ the temperature, to be that the carbonate of the soluble salt of metallic copper and thorium and alkali metal containing and/or ammonium and/or supercarbonate precipitation agent close and be placed in the solution, final pH value be adjusted to 5.0 to 7.0.

4, method according to claim 1 or 2, wherein step (I) comprising: solubility thorium salt and precipitation agent are closed be placed in the solution that is substantially free of copper, so that be settled out insoluble heat decomposable thorium compound, afterwards in the presence of sedimentary thorium compound, the solution and the precipitation agent of soluble copper salt are put together, so that be settled out insoluble heat decomposable copper compound, regulate last pH value within 5.0 to 7.0 scope, said precipitation is to carry out being lower than under 50 ℃ the temperature, and said precipitation agent contains the carbonate and/or the supercarbonate of basic metal and/or ammonium.

5, according to the method for claim 4, after the thorium compound precipitation, the solution of soluble copper salt before the precipitated copper compound, is not carried out any processing, join in the thorium compound that is settled out.

6, according to the method for claim 4, before the precipitated copper compound, the thorium compound that is settled out is separated washing and redispersion.

7, according to the process of claim 1 wherein that copper and thorium are that form with the aqueous solution of its nitrate exists.

8, according to the process of claim 1 wherein precipitation agent or volatile salt or bicarbonate of ammonia.

9, according to the process of claim 1 wherein that precipitation is to carry out being lower than under 30 ℃ the temperature.

10, according to the process of claim 1 wherein that temperature range is 0 to 25 ℃.

11, according to the method for claim 1, in step (I), the scope of final pH value is 5.5 to 6.5.

12, according to the process of claim 1 wherein that precipitation is to carry out under the atmosphere of carbonic acid gas.

13, according to the process of claim 1 wherein the throw out that reclaims in the washing step (II) and carry out drying being lower than under 150 ℃ the temperature.

14, according to the method for claim 1, from 400 to 500 ℃ of the maximum temperature range of in step (III), using.

15, according to the method for claim 1, the thermolysis in step (III) is to carry out in nitrogen gas stream or airflow.

16, according to the method for claim 1, the b in the formula I is zero and said composition is to carry out reduction activation in containing the reducing gas of carbon monoxide.

17, according to the method for claim 16, composition wherein carries out reduction activation in containing the mixture of carbon monoxide/hydrogen.

18, according to the method for claim 1, the b in the formula I is greater than zero, and said composition is to carry out reduction activation initial using in the reducing gas that is substantially free of carbon monoxide at least.

19, produce the method for methyl alcohol from synthetic gas, this method comprises: reduction activation is contacted with synthetic gas in 80 to 300 ℃ of temperature ranges with under 0 to 100 pressure that clings to the reduction activation catalyzer by the catalyst Precursors of the method preparation of claim 1 to 15.

20, according to the method for claim 19, catalyst Precursors wherein is the formula I of b=zero, and under the condition of producing methyl alcohol, realizes reduction activation with synthetic gas.

21, according to the method for claim 19, catalyst Precursors wherein is the formula I of b=zero, and before producing methyl alcohol, with the reducing gas that does not contain carbon monoxide substantially, realizes reduction activation with an independent step.

22, according to the method for arbitrary claim in the claim 19 to 21, its synthesis gas contacts with the catalyzer of reduction activation in 180 to 250 ℃ temperature range.

The catalyst composition that 23, will synthesize gas changing into methanol, said composition contain the elemental copper of following formula atomic ratio and the oxide compound of thorium:

Cua Th Ox

Wherein x is that oxygen satisfies the number that the valence mumber of Th requires,

A is from 0.1 to 4 value,

And wherein at least 30% elemental copper particulate granularity is less than or equal to 20 dusts.

24, according to the composition of claim 23, wherein at least 50% elemental copper particulate granularity is less than or equal to 20 dusts.

25, according to the composition of claim 23, wherein at least 90% elemental copper particulate granularity is less than or equal to 20 dusts.

26, according to the composition of arbitrary claim in the claim 23 to 25, a value scope in the formula II is 0.5 to 3.

27, according to the composition of claim 26, wherein a value scope is 0.7 to 2.

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