CN1141366C - Method for preparing noble metal and asistant carried acid resin catalyst - Google Patents
Method for preparing noble metal and asistant carried acid resin catalyst Download PDFInfo
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- CN1141366C CN1141366C CNB011161302A CN01116130A CN1141366C CN 1141366 C CN1141366 C CN 1141366C CN B011161302 A CNB011161302 A CN B011161302A CN 01116130 A CN01116130 A CN 01116130A CN 1141366 C CN1141366 C CN 1141366C
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- precious metal
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Abstract
The present invention relates to a preparation method of a hydroetherification catalyst capable of improving hydroisomerization activity, double bond isomerization activity and etherification activity, which comprises the following processes: water soluble salt of noble metal and an auxiliary agent are dissolved with a polar organic solvent to prepare impregnating liquid, and a coating layer hydrogen type carrier of macropore strong acidic cation-exchange resin is impregnated or modified with the impregnating liquid. The preparation method can be used for avoiding catalyst etherification activity reduction caused when the auxiliary agent is loaded, and simultaneously, the hydroisomerization activity and the double bond isomerization activity of the catalyst can be improved.
Description
Technical field
The present invention relates to Preparation of catalysts, relate in particular to a kind of ether hydro-etherification Preparation of catalysts method that can improve hydrogenation and double-bond isomerism and etherification activity.
Background technology
Containing cracking light gasoline fraction of isomeric olefine (do, or less than 100 ℃) and C thereof less than 75 ℃
5The precious metal resin catalyst that is loaded with that uses in cut and methyl alcohol or the ethanol generation etherification reaction process has three kinds of katalysis under methyltertiarvbutyl ether reactor and hydro condition, the one, the etherificate katalysis of active olefin, next is the selection hydrogenation catalyst effect of diolefin, the 3rd, and the double-bond isomerization katalysis.
C in catalytic cracking petroleum naphtha, pyrolysis gasoline and the pressure gasoline
5Cut is under the effect of an acidic catalyst, its tertiary olefin is (as 2-methyl-1-butene alkene, 2-methyl-2-butene, 2-Methyl-1-pentene, 2-methyl-2-amylene, 2-methyl-2-amylene, 3-methyl-2-amylene, 2,3-dimethyl-1-butylene, 2,3-dimethyl-2 butylene, methyl cyclopentene-1, Deng) can generate tert amyl methyl ether(TAME) (TAME) and methyl-tert hexyl ether with methyl alcohol or ethanol synthesis, this process is called as the etherification technology process.This etherification procedure can reduce vapour pressure, the olefin(e) centent of motor spirit, and can improve gasoline octane rating, reduces environmental pollution, is the significant process of improving the motor spirit quality.The wherein employed strongly acidic macroporous cation exchange resin catalyzer that is loaded with precious metal, under hydro condition, not only can select hydrogenation to objectionable constituent conjugation, diene, acetylene hydrocarbon compound in the reaction raw materials, and active olefin and methyl alcohol, alcoholic acid etherification reaction and double-bond isomerism reaction simultaneously.
Result of study shows that the etherification activity of an acidic catalyst is to be directly proportional with its strength of acid, acid amount, and hydrogenation activity and double-bond isomerism are active to be directly proportional with the noble metal support amount.Preparation method at the acid macroporous cation exchange resin catalyst that is loaded with precious metal and auxiliary agent thereof, in the open report before the present invention, for example, US4330679, US5141525, US4950820, EP490571, US4695556, CN1146927, all be to adopt aqueous solution ion exchange method and aqueous solution pickling process that reactive metal element and auxiliary element are stated from the carrier, wherein, the reactive metal element comprises Pd, Pt, and auxiliary agent comprises elements such as Si, Al, Ga, B, Ge, Sn.As everyone knows, in the aqueous solution of reactive metal element and auxiliary element, metallic element exists with the metal ion form, and this just makes in preparation process, metal ion can with the gegenion H in the storng-acid cation exchange resin
+Exchange, even pass through the reduction of hydrogen or formic acid, auxiliary element still can not be metallic state, thereby reduces the acid amount on the acid resin catalyst, and the result causes the etherification activity of catalyzer to descend.Its chemical reaction process is as follows:
A) ion-exchange
B) reduction
Expression macropore strong acid cation exchange resin
M
N+: Al
3+Sn
4+B
3+Deng
Summary of the invention
The object of the present invention is to provide a kind of above-mentioned method that is loaded with the acid resin catalyst of precious metal and auxiliary agent for preparing, cause the catalyzer etherification activity to reduce in the time of can avoiding the load auxiliary agent, can improve the hydrogenation and the double-bond isomerism activity of this class catalyzer simultaneously.
Preparation method provided by the invention comprises the water-soluble salt that adopts polar organic solvent dissolving precious metal and auxiliary agent and is mixed with steeping fluid and floods or the process of modified coating Hydrogen macropore strong acid cation exchange resin carrier with this steeping fluid.
Catalyst according to the invention preparation method is a carrier with Hydrogen macropore strong acid cation exchange resin, as domestic resin S
54, D
005, D
001, D
72Deng, use anhydrous polar organic solvent, for example Virahol, propyl alcohol, acetate, formic acid, methyl alcohol, ethanol etc., be preferably polar organic solvent ethanol, methyl alcohol or propyl alcohol, the water soluble salt of dissolving precious metal and auxiliary agent, for example, nitrate, acetate, oxymuriate etc., be made into organic solution, by co-impregnation or step impregnation method precious metal and auxiliary agent are carried on the Hydrogen macropore strong acid cation exchange resin surface, after 30-110 ℃ of following drying, reduce again, can be prepared into catalyzer of the present invention.
In the chemical fundamentals theory, described precious metal comprises the stable gold and silver of chemical property, platinum family element (platinum, iridium, osmium, ruthenium, palladium, rhodium), according to the preferred embodiment of the invention, described solubility precious metal is palladium or platinum, and to make its content in catalyzer be 0.05-9wt%, and preferred content is 0.1-1.0wt%.Auxiliary agent of the present invention is selected from IIIA, IVA main group element or transition element for example Zr, Ti, Ni, Cu, Ag etc., and its content is every liter dry resin 0-10 gram, and preferred every liter dry resin contains the 0.1-6 gram.
Preferred a kind of preparation method according to the present invention, its operating process can comprise the steps:
(1) water-soluble salt that dissolves precious metal and auxiliary agent respectively with anhydrous polar organic solvent is made into organic solution;
(2) mix as steeping fluid according to the organic solution of the salt that will ask for above-mentioned precious metal and auxiliary agent of catalyst loadings, dipping Hydrogen macropore strong acid cation exchange resin carrier, dry down in 30-110 ℃;
(3) catalyzer that with hydrogen or formic acid step (2) is obtained under 30-110 ℃ reduced 0-24 hour.
The preferred another kind of preparation method according to the present invention, its operating process can comprise the steps:
(1) water-soluble salt that dissolves precious metal and auxiliary agent respectively with anhydrous polar organic solvent is made into organic solution;
(2) get the organic solution dipping Hydrogen macropore strong acid cation exchange resin carrier that is dissolved with precious metal salt in above-mentioned (1), dry down in 30-110 ℃;
(3) get the resin catalyst for etherification that contains precious metal that the organic solution impregnation steps (2) that is dissolved with builder salts in above-mentioned (1) obtains, dry down in 30-110 ℃;
(4) catalyzer that with hydrogen or formic acid step (3) is obtained under 30-110 ℃ reduced 0-24 hour.
The preferred another kind of preparation method according to the present invention, its operating process can comprise the steps:
(1) water-soluble salt with anhydrous polar organic solvent dissolving precious metal and auxiliary agent is made into organic solution;
(2) organic solution that is dissolved with builder salts of getting in above-mentioned (1) is flooded Hydrogen macropore strong acid cation exchange resin carrier, and is dry down in 30-110 ℃;
(3) get the resin catalyst for etherification that contains auxiliary agent that the organic solution impregnation steps (2) that is dissolved with precious metal salt in above-mentioned (1) obtains, dry down in 30-110 ℃;
(4) catalyzer that with hydrogen or formic acid step (3) is obtained under 30-110 ℃ reduced 0-24 hour.
In above-mentioned preparation method, (constant temperature) exsiccant process comprises reactant stirred down constantly prior to 30-50 ℃ and carries out preliminarily dried under the 30-110 that is set forth in ℃ of the institute, then 90-110 ℃ of following constant temperature vacuum-drying 0-24 hour.Or according to actual needs only with reactant seasoning at room temperature.
Preparation in accordance with the present invention can be reduced according to ordinary method after precious metal and auxiliary agent are impregnated on the resin carrier, also can catalyzer is reduced simultaneously.I.e. reduction realizes in reaction process that generally that is to say, when reacting, catalyzer is reduced by hydrogen or formic acid as reaction raw materials in reactor.
Compare with the prior art before the present invention, the characteristics of method provided by the invention are to adopt organic solvent dissolution reactive metal and promoter metal salt, be made into organic solution, weaken the trend that metallic element exists with ionic species, thereby in the time of on impregnated in the storng-acid cation exchange resin carrier, be difficult for storng-acid cation exchange resin in gegenion H
+Carry out ion-exchange, reduce the loss of acidic resins carrier acid amount, also help reactive metal and the distribution of auxiliary agent on carrier surface simultaneously, consequently improved etherification activity, hydrogenation activity and the double-bond isomerism activity of catalyzer.
Embodiment
Describe the beneficial effect of enforcement of the present invention and generation by the following examples in detail, but should not constitute any qualification practical range of the present invention.
Embodiment 1
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 1.334 gram aluminum nitrate Al (NO
3)
39H
2O is dissolved in 46 ml distilled waters, is made into mixed aqueous solution.
Under constantly stirring, above-mentioned mixed aqueous solution is immersed in 48 milliliters of Hydrogen macropore strong acid cation exchange resin D
005On, behind 30-50 ℃ of following preliminarily dried, vacuumized dry 6 hours in 100 ℃ of following thermostat(t)ed waters again, can obtain the Pd metal content is the precious metal etherificate resin contrast medium A that contains the Al auxiliary agent of 0.36%wt.
Embodiment 2
Take by weighing 300 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 1.667 gram aluminum nitrate Al (NO
3)
39H
2O is dissolved in 57 ml methanol, is made into mixed organic solvents.
Under constantly stirring, above-mentioned mixed organic solvents is immersed in 60 milliliters of Hydrogen macropore strong acid cation exchange resin D
005On, at room temperature behind the preliminarily dried, vacuumized dry 6 hours in 100 ℃ of following thermostat(t)ed waters again, can obtain the Pd metal content is the precious metal etherificate resin catalyst B that contains the Al auxiliary agent of 0.36%wt.
Embodiment 3
Take by weighing 4 gram aluminum nitrate Al (NO
3)
39H
2O is dissolved in 46 ml methanol, is made into the methanol solution of aluminum nitrate.Under constantly stirring, this methanol solution is immersed in 48 milliliters Hydrogen macropore strong acid cation exchange resin D
005On, at room temperature behind the preliminarily dried, again in 100 ℃ of following constant temperature vacuum-dryings 6 hours, obtaining aluminium element content is the surface modified coat carrier of every liter dry resin 6 grams.
Above-mentioned modified coating carrier is dissolved with 240 milligrams of Palladous nitrate Pd (NO with 46 milliliters
3)
22H
2The methanol solution of O floods, and at room temperature behind the preliminarily dried, in 100 ℃ of following constant temperature vacuum-dryings 6 hours, obtaining the Pd metal content was 0.36%wt again, and contains the precious metal etherificate resin catalyst C of aluminium auxiliary agent.
Embodiment 4
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of nitric acid nickel (No
3)
26H
2O is dissolved in 46 ml distilled waters, is made into mixed aqueous solution.
Prepare the precious metal etherificate resin contrast medium D that contains the Ni auxiliary agent that the Pd metal content is 0.36%wt according to the method for embodiment 1.
Embodiment 5
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of nitric acid nickel (NO
3)
36H
2O is dissolved in 46 ml methanol, is made into the mixing methanol solution.Then undertaken by embodiment 2 steps, can prepare the Pd metal content is the precious metal etherificate resin catalyst E that contains the Ni auxiliary agent of 0.36%wt.
Embodiment 6
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of aluminum nitrate Ni (NO
3)
36H
2O is dissolved in 46 milliliters of ethanol, is made into mixed ethanol solution.Then undertaken by embodiment 2 steps, can prepare the Pd metal content is the precious metal etherificate resin catalyst F that contains the Ni auxiliary agent of 0.36%wt.
Embodiment 7
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of nitric acid nickel (NO
3)
36H
2O is dissolved in 46 milliliters of formic acid, is made into the mixing formic acid solution.Then undertaken by embodiment 2 steps, can prepare the Pd metal content is the precious metal etherificate resin catalyst G that contains the Ni auxiliary agent of 0.36%wt.
Embodiment 8
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of cupric nitrate Cu (NO
3)
36H
2O is dissolved in 46 ml methanol, is made into the mixing methanol solution.Then undertaken by embodiment 2 steps, can prepare the Pd metal content is the precious metal etherificate resin catalyst H that contains the Cu auxiliary agent of 0.36%wt.
Embodiment 9
Take by weighing 240 milligrams of Palladous nitrate Pd (NO
3)
22H
2O and 476 milligrams of neutralized verdigris Cu (NO
3)
36H
2O is dissolved in 46 ml methanol, is made into the mixing methanol solution.Then undertaken by embodiment 2 steps, can prepare the Pd metal content is the precious metal etherificate resin catalyst I that contains the Cu auxiliary agent of 0.36%wt.
Embodiment 10
In the small pressurized fixed-bed reactor, estimate above-mentioned etherificate, hydrogenation and the isomerization activity stability that contains the catalyst for etherification A-I of precious metal and auxiliary agent, the results are shown in following table.
The etherification reaction of hydro-refining condition is: contain 1 milliliter of the catalyst for etherification of precious metal and auxiliary agent, and 70 ℃ of temperature of reaction, reactive hydrogen dividing potential drop 1.0Mpa, liquid amasss air speed 36.0h-1,4.0～5.0 milliliters of hydrogen exhaust flows.The content of main component is in the reaction raw materials liquid: 3-methyl-1-butene 0.96%wt, activity isomerism alkene (2-methyl-1-butene alkene and 2-methyl-2-butene) 19.08%wt, pentadiene 0.52%wt, methyl alcohol 11.32%wt.
Can see from table, compare that by the catalyst B of method for making preparation of the present invention, the etherification activity that E～I can improve catalyzer, wherein catalyst B, E, F can also improve the activity of diolefin hydrogenation or double-bond isomerism with contrast medium A, D.
The diolefin hydrogenation, double-bond isomerism and the etherificate transformation efficiency (%) that contain the resin catalyst for etherification of precious metal and auxiliary agent:
3-methyl-1-butene activity isomerism alkene diolefine
Contrast medium A 32.9 15.9 100
Catalyst B 34.0 17.4 100
Catalyzer C 14.8 16.6 97.8
Contrast medium D 15.8 14.2 98.3
Catalyzer E 37.5 17.3 100
Catalyzer F 18.3 17.7 100
Catalyzer G 0.7 21.4 53.34
Catalyzer H 0.0 17.9 24.2
Catalyst I 0.0 20.3 33.0 is annotated: catalyst A～F is the result of reaction after 12 hours.
Catalyzer G～I is the result of reaction after 6 hours.
Claims (11)
1, is loaded with the preparation method of the acid resin catalyst of precious metal and auxiliary agent, it comprises the water-soluble salt that adopts polar organic solvent dissolving precious metal and auxiliary agent and is mixed with steeping fluid, with process with this steeping fluid dipping Hydrogen macropore strong acid cation exchange resin carrier, described steeping process is the common dipping that adopts the steeping fluid impregnated carrier of the water-soluble salt that is dissolved with precious metal and auxiliary agent, or adopt the step impregnation of the steeping fluid impregnated carrier of the water-soluble salt be dissolved with precious metal and auxiliary agent respectively, and each soaked carrier is all dry down in 30-110 ℃.
2, preparation method according to claim 1, it comprises the steps:
(1) water-soluble salt that dissolves precious metal and auxiliary agent respectively with anhydrous polar organic solvent is made into organic solution;
(2) mix as steeping fluid according to the above-mentioned organic solution that is dissolved with precious metal and builder salts of will asking for of catalyst loadings, dipping Hydrogen macropore strong acid cation exchange resin carrier, dry down in 30-110 ℃;
(3) under 30-110 ℃, step (2) is obtained catalyst reduction 0-24 hour with hydrogen or formic acid.
3, preparation method according to claim 1, it comprises the steps:
(1) water-soluble salt that dissolves precious metal and auxiliary agent respectively with anhydrous polar organic solvent is made into organic solution respectively;
(2) get the organic solution dipping Hydrogen macropore strong acid cation exchange resin carrier that is dissolved with precious metal salt in above-mentioned (1), dry down in 30-110 ℃;
(3) get the resin catalyst for etherification that contains precious metal that the organic solution impregnation steps (2) that is dissolved with builder salts in above-mentioned (1) obtains, dry down in 30-110 ℃;
(4) under 30-110 ℃, step (3) is obtained catalyst reduction 0-24 hour with hydrogen or formic acid.
4, preparation method according to claim 1, it comprises the steps:
(1) water-soluble salt with anhydrous polar organic solvent dissolving precious metal and auxiliary agent is made into organic solution respectively;
(2) organic solution that is dissolved with builder salts of getting in above-mentioned (1) is flooded Hydrogen macropore strong acid cation exchange resin carrier, and is dry down in 30-110 ℃;
(3) get the resin catalyst for etherification that contains auxiliary agent that the organic solution impregnation steps (2) that is dissolved with precious metal salt in above-mentioned (1) obtains, dry down in 30-110 ℃;
(4) under 30-110 ℃, step (3) is obtained catalyst reduction 0-24 hour with hydrogen or formic acid.
5, according to claim 2,3,4 described preparation methods, carry out preliminarily dried wherein said comprising prior to constantly stirring under 30-50 ℃ or the room temperature in 30-110 ℃ of following exsiccant process, then 90-110 ℃ of following constant temperature vacuum-drying 0-24 hour.
6, according to the described preparation method of claim 1-4, wherein, described polar organic solvent comprises propyl alcohol, Virahol, methyl alcohol, ethanol, acetate, formic acid.
7, according to the described preparation method of claim 1-4, wherein, the water-soluble salt of described precious metal and auxiliary agent is nitrate, acetate or oxymuriate.
8, preparation method according to claim 7, wherein, described precious metal is palladium or platinum, its content is 0.05-9wt%.
9, preparation method according to claim 8, wherein, the content of described precious metal is 0.1-1.0wt%.
10, preparation method according to claim 7, wherein, described auxiliary agent is selected from IIIA, IVA main group element or transition element, and its content is every liter dry resin 0-10 gram.
11, preparation method according to claim 10, wherein, described auxiliary agent content is every liter dry resin 0.1-6 gram.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011161302A CN1141366C (en) | 2001-05-11 | 2001-05-11 | Method for preparing noble metal and asistant carried acid resin catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011161302A CN1141366C (en) | 2001-05-11 | 2001-05-11 | Method for preparing noble metal and asistant carried acid resin catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1385497A CN1385497A (en) | 2002-12-18 |
| CN1141366C true CN1141366C (en) | 2004-03-10 |
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|---|---|---|---|
| CNB011161302A Expired - Fee Related CN1141366C (en) | 2001-05-11 | 2001-05-11 | Method for preparing noble metal and asistant carried acid resin catalyst |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101884920B (en) * | 2009-05-13 | 2012-05-09 | 中国石油化工股份有限公司 | Preparation method for fluid catalyst used for preparing vinyl acetate |
| CN102909077B (en) * | 2011-08-01 | 2015-04-15 | 中国石油化工股份有限公司 | Metal-modified cation exchange resin catalyst, preparation method and application thereof |
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