CN1216694C - Preparation of catalyst for hydrogen etherified resin - Google Patents
Preparation of catalyst for hydrogen etherified resin Download PDFInfo
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- CN1216694C CN1216694C CN 02157391 CN02157391A CN1216694C CN 1216694 C CN1216694 C CN 1216694C CN 02157391 CN02157391 CN 02157391 CN 02157391 A CN02157391 A CN 02157391A CN 1216694 C CN1216694 C CN 1216694C
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Abstract
The present invention discloses a method for preparing strong acidic macroporous cation exchange resin catalysts supported with noble metal and additives. An aqueous solution or organic solution of soluble active metal and/or additive salts having a catalytic function is used for supporting strong acidic cation exchange resin, and subsequently, and the obtained resin supporters are reduced by reducing gas containing CO. The present invention can improve the capacity for resisting impurities of the catalysts and increase the activity and the stability of hydrogenation and double bond isomerization by a reducing method different from the publicly known technology.
Description
Invention field
The present invention relates to a kind of preparation of hydrogenation catalyst, especially relate to and to improve hydrogenation and the active ether hydro-etherification Preparation of catalysts of double-bond isomerism method.
Background of invention
Containing cracking light gasoline fraction of isomeric olefine (do, or less than 100 ℃) and C thereof less than 75 ℃
5What use in cut and methyl alcohol or the ethanol generation etherification reaction process is to be loaded with the precious metal resin catalyst.The resin catalyst of this carried noble metal has three kinds of katalysis under methyltertiarvbutyl ether reactor and hydro condition, and the one, secondly the etherificate katalysis of active olefin is the selection hydrogenation catalyst effect of diolefin, the 3rd, 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, the 2-methyl-2-butene, the 2-Methyl-1-pentene, 2-methyl-2-amylene, 3-methyl-2-amylene, 2,3-dimethyl-1-butylene, 2,3-dimethyl-2-butylene, methyl cyclopentene-1 etc.) can generate tert amyl methyl ether(TAME) (TAME) and methyl-tert hexyl ether with methyl alcohol or ethanol synthesis, this process is referred to as the etherification technology process, it can reduce the vapour pressure of motor spirit, olefin(e) centent, and can improve gasoline octane rating, reducing 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 conjugated diolefine, acetylene hydrocarbon compound in the reaction raw materials, and carry out active olefin and methyl alcohol simultaneously, the reaction of alcoholic acid etherification reaction and double-bond isomerism.
Had much for this research that is loaded with the acid macroporous cation exchange resin catalyst of precious metal and auxiliary agent, the preparation method adopts aqueous solution ion exchange method or aqueous solution pickling process or organic solution pickling process that reactive metal element and auxiliary element are carried on the carrier, then again at H
2Or reduce in the atmosphere such as formic acid, wherein the reactive metal element comprises Pd, Pt, auxiliary agent includes elements such as Si, Al, Ga, B, Ge, Sn, as publication US 4,330,679; US 5,141, and 525; US4,950,820; EP 490,571; US 4,695, and 556; CN 1,146,927, Chinese patent application 01116131 etc.
According to the instruction of theory and above-mentioned prior art usually, those skilled in the art knows, load the acid resin catalyst of reactive metal element and auxiliary element have only reduction by hydrogen or formic acid or organic reaction raw material, make active ingredient become metallic state, just can have hydrogenation and double-bond isomerization catalytic activity.Yet, the catalytic cracking light gasoline fraction (do less than 75 ℃, or less than 100 ℃) and C
5Contain impurity such as organic sulfide, nitride and superoxide in the cut, these impurity can be adsorbed on the surface of metallic state active ingredient by force in the etherification reaction process, thereby cause the hydrogenation and the active reduction of double-bond isomerization of catalyzer, even inactivation, life of catalyst is shortened, and the cost of etherification reaction increases.
Summary of the invention
Purpose of the present invention just is to provide the method for the strongly acidic macroporous cation exchange resin catalyzer that a kind of preparation is loaded with precious metal and auxiliary agent thereof, by being different from the method for reducing of known technology, can strengthen the anti-impurity ability of catalyzer, it is active and stable to improve its hydrogenation and double-bond isomerism.
The invention provides a kind of preparation method who is loaded with the acid resin catalyst of hydrogenation activity component, it is characterized in that adopting the aqueous solution or organic solution solubility and active metal salt that have katalysis, the perhaps aqueous solution of active metal salt and builder salts or organic solution, storng-acid cation exchange resin is carried out load, then reduce with the resin of the reducing gas that contains CO after to resulting load.
The present invention has proposed on the basis of like product characteristic in the prior art having analyzed and researched, and is characterized in adopting the reducing gas that contains CO gas that the acid resin catalyst of carrying active metal and promoter metal is reduced.Research and experimental result prove; the method of reducing that adopts the present invention to propose; CO has strengthened the reductive action of reducing gas to reactive metal on the one hand; make it become metallic state; CO also is adsorbed on the as-reduced reactive metal surface on the other hand, and the provide protection that this has just played reactive metal has weakened the adsorption of impurity to reactive metal; consequently improved the anti-poisoning capability of catalyzer, and hydrogenation, double-bond isomerization are active and stable.
According to preferred version of the present invention, in reduction process, describedly contain CO volume content 10～100% in the CO reducing gas to catalyzer, preferably 30～100%, remaining gas is nitrogen and/or hydrogen.20～100 ℃ of the reduction temperatures of catalyzer, 0.5～24 hour recovery time, reduction pressure is that normal pressure is to 2.0MPa; Preferably, the reduction temperature of catalyzer is 40～80 ℃, and 1～12 hour recovery time, reduction pressure is 0.5～1.5MPa.
Preparation in accordance with the present invention can adopt method commonly used at present fully for the selection of acidic resins and active ingredient and carrying method.Can Hydrogen macropore strong acid cation exchange resin be carrier, as domestic resin S
54, D
005, D
001, D
72Deng, water or anhydrous polar organic solvent, be generally alcohol or the carboxylic acid of C1～C4, as propyl alcohol, Virahol, methyl alcohol, ethanol, formic acid, acetate etc., be preferably ethanol, methyl alcohol and propyl alcohol, dissolving water-soluble precious metal and auxiliary agent salt, as nitrate, acetate, oxymuriates etc. are made into the aqueous solution or organic solution, are carried on the Hydrogen macropore strong acid cation exchange resin surface by co-impregnation or step impregnation method, the content of its reactive metal element in catalyzer is 0.05～9%, 0.1～1.0%wt preferably, assistant metal element content are every liter dry resin 0～10 gram, and preferably every liter dry resin contains 0.1～6 gram, resin after the load is dry under 30 ℃～110 ℃, reduces in containing the atmosphere of CO again.
Active ingredient of the present invention can be the precious metal that defines in the element chemistry, is preferably palladium or platinum.Described auxiliary agent is selected from IIIA in the periodictable, IVA main group element such as B, Al, Ga, Si, Ge, Sn, or transition metal such as Zr, Ti, Ni, Cu, Ag etc.
Preparation method's specified operational procedure of the present invention is:
(1), salt such as dissolving water-soluble active metal Pd, Pt salt and water-soluble III, IV main group element or transition metal such as water or anhydrous polar organic solvent such as propyl alcohol, Virahol, methyl alcohol, ethanol, acetate, formic acid such as Zr, Ti, Ni, Cu, Ag is made into the aqueous solution or organic solution.
(2), to ask for the solution that a certain amount of above-mentioned (1) step is made into according to charge capacity, Hydrogen macropore strong acid resin carrier is carried out substep ion-exchange or hybrid infusion or step impregnation, in 30～110 ℃ of dryings, obtain the dry sample of the Hydrogen macropore strong acid resin catalyst of carrying active component and auxiliary agent.
(3), under 20～100 ℃, the catalyzer that step (2) is obtained with the reducing gas that contains CO concentration 10～100v% reduced 0.5～24 hour.
The load that obtains according to preparation method of the present invention the acid resin catalyst of hydrogenation activity component in process, have very high activity to hydrogenation catalyst, double-bond isomerism and the etherification of olefine of diene, show the raising of transformation efficiency and actively in the longer reaction times obviously do not reduce.Relevant test-results can be referring to the embodiment and the accompanying drawing of back.
Description of drawings
Fig. 1 is that the Pd-Ni/ resin catalyst for etherification of the embodiment of the invention 3 preparations amasss air speed 12h at liquid
-1Under the active change curve of pentadiene hydrogenation, double-bond isomerism.
Fig. 2 is that the Pd-Ni/ resin catalyst for etherification of the embodiment of the invention 3 preparations amasss air speed 12h at liquid
-1Under uncle's amylene, the change curve of uncle's hexene etherification activity.
Specific embodiments
Below describe the beneficial effect of implementation process of the present invention and generation in detail by specific embodiment, be intended to help the reader to understand essence of the present invention and spiritual place better, but should do not constitute any qualification practical range of the present invention.
Embodiment 1
Take by weighing Palladous nitrate Pd (NO
3)
22H
2240 milligrams of O and nitric acid nickel (NO
3)
26H
2O is dissolved in 46 ml methanol for 476 milligrams, is mixed with the mixing methanol solution.Under constantly stirring, above-mentioned mixed organic solvents is immersed on 48 milliliters the Hydrogen macropore strong acid cation exchange resin, behind the room temperature preliminarily dried, again 100 ℃ of following constant temperature vacuum-dryings 6 hours.Can prepare the Pd metal content is the precious metal etherificate resin catalyst A that contains the Ni auxiliary agent of 0.36%wt.
Embodiment 2
The precious metal etherificate resin catalyst A that embodiment 1 is prepared, under 70 ℃, 1.0MPa with containing H
2Reductase 12 hour in the reducing gas of 100v%.Promptly get through H
2Pd-Ni/ resin catalyst for etherification B after the reduction.
Embodiment 3
The precious metal etherificate resin catalyst A that embodiment 1 is prepared, under 70 ℃, 1.0MPa with the reducing gas reductase 12 that contains CO 100v% (volume content) hour.Promptly get the Pd-Ni/ resin catalyst for etherification C after the CO reduction.
Embodiment 4
The precious metal etherificate resin catalyst A that embodiment 1 is prepared, under 70 ℃, 1.0MPa with the reducing gas (CO and the N that contain CO 50v%
2Gas mixture) reductase 12 hour.Promptly get through CO and N
2Pd-Ni/ resin catalyst for etherification D after the gas mixture reduction.
Embodiment 5
The precious metal etherificate resin catalyst A that embodiment 1 is prepared, under 40 ℃, 1.0MPa with the reducing gas reductase 12 that contains CO 100v% hour.Promptly get the Pd-Ni/ resin catalyst for etherification E after the CO reduction.
Embodiment 6
Take by weighing Palladous nitrate Pd (NO
3)
22H
2300 milligrams of O and aluminum nitrate Al (NO
3)
39H
2O 1.667 grams are dissolved in 57 ml methanol, are made into mixed organic solvents.Under constantly stirring, above-mentioned mixed organic solvents is immersed on 60 milliliters the Hydrogen macropore strong acid cation exchange resin, behind the room temperature preliminarily dried, again 100 ℃ of following constant temperature vacuum-dryings 6 hours.Promptly getting the Pd metal content is the precious metal etherificate resin catalyst F that contains the Al auxiliary agent of 0.36%wt.
Embodiment 7
The precious metal etherificate resin catalyst F that embodiment 6 is prepared, under 70 ℃, 1.0MPa with the reducing gas reductase 12 that contains CO 100v% hour.Promptly get the Pd-Al/ resin catalyst for etherification G after the CO reduction.
Embodiment 8
Take by weighing Palladous nitrate Pd (NO
3)
22H
2O is dissolved in 57 ml methanol for 150 milligrams.Under constantly stirring, above-mentioned organic solution is immersed on 60 milliliters the Hydrogen macropore strong acid cation exchange resin, behind the room temperature preliminarily dried, again 100 ℃ of following constant temperature vacuum-dryings 6 hours.Promptly getting the Pd metal content is the precious metal etherificate resin catalyst H of 0.18%wt.
Embodiment 9
The precious metal etherificate resin catalyst H that embodiment 8 is prepared, under 70 ℃, 1.0MPa with the reducing gas reductase 12 that contains CO 100v% hour.Promptly get the Pd/ resin catalyst for etherification I after the CO reduction.
Experimental example 1
In the small pressurized fixed-bed reactor, estimated above-mentioned hydrogenation activity and the stability that contains the catalyst for etherification A～I of precious metal and auxiliary agent.The etherification reaction of hydro-refining condition is: contain 0.5 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 72.0h
-1, 10.0～11.0 milliliters of hydrogen exhaust flows.The content of main component is in the catalytic cracking petroleum naphtha reaction raw materials liquid: 3-methyl isophthalic acid butylene 0.62% (wt), activity isomerism carbon pentaene hydrocarbon (2-methyl-1-butene alkene and 2-methyl-2-butene) 12.72% (wt), pentadiene 0.538% (wt), activity isomerism C 6 olefin total amount 11.48% (wt), methyl alcohol 9.32% (wt), total sulfur 187.4 μ g/g, total nitrogen 8.4 μ g/g.The results are shown in following table 1.
The diolefin hydrogenation transformation efficiency (%) of table 1 catalyst for etherification
Experimental example 2
With above-mentioned catalytic cracking petroleum naphtha is raw material, the catalyst for etherification C that contains precious metal and auxiliary agent has been carried out 100 hours long-term operation in the small pressurized fixed-bed reactor.The etherification reaction of hydro-refining condition is: contain 3.0 milliliters 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 12.0h
-1, 10.0～11.0 milliliters of hydrogen exhaust flows.Pentadiene hydrogenation conversion, 3-methyl-1-butene double-bond isomerism transformation efficiency, activity isomerism carbon pentaene hydrocarbyl ether transformation efficiency and activity isomerism C 6 olefin etherificate transformation efficiency are with the Changing Pattern in reaction times as shown in Figure 1, 2.
Claims (9)
1, a kind of preparation method of ether hydro-etherification acid resin catalyst, it is characterized in that adopting the aqueous solution or organic solution solubility and active metal salt that have katalysis, the perhaps aqueous solution of active metal salt and builder salts or organic solution, storng-acid cation exchange resin is carried out load, then reduce with the storng-acid cation exchange resin of the reducing gas that contains CO after to resulting load, describedly contain CO volume content 10～100% in the CO reducing gas, remaining gas is nitrogen and/or hydrogen, 20～100 ℃ of reduction temperatures, 0.5～24 hour recovery time, reduction pressure be normal pressure to 2.0Mpa, and used organic solvent is alcohol or the carboxylic acid of C1～C4 in the described organic solution.
2, the described preparation method of claim 1, wherein, the volume content of CO in described reducing gas is 30～100%.
3, the described preparation method of claim 1, wherein, reduction temperature is 40～80 ℃, 1～12 hour recovery time, reduction pressure is 0.5～1.5MPa.
4, the described preparation method of claim 1, wherein, described reactive metal is precious metals pd or Pt, its content in catalyzer is 0.05～9wt.%.
5, the described preparation method of claim 4, wherein, the content of described precious metal in catalyzer is 0.1～1.0wt.%.
6, the described preparation method of claim 1, wherein, described auxiliary agent is III, IV main group element or transition metal, its content is every liter dry resin 0～10 gram.
7, the described preparation method of claim 6, wherein, the content of described auxiliary element is every liter dry resin 0.1～6 gram.
8, each described preparation method of claim 1～3, comprise water or described organic solvent dissolution water-soluble precious metal salt and builder salts, be made into the aqueous solution or organic solution, this solution is carried on the Hydrogen macropore strong acid cation exchange resin by co-impregnation or step impregnation method, after 30 ℃～110 ℃ following dryings, reduce with the reducing gas that contains CO again.
9, a kind of load has the acid resin catalyst of hydrogenation activity component, is to adopt the described method preparation of aforementioned each claim.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 02157391 CN1216694C (en) | 2002-12-23 | 2002-12-23 | Preparation of catalyst for hydrogen etherified resin |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 02157391 CN1216694C (en) | 2002-12-23 | 2002-12-23 | Preparation of catalyst for hydrogen etherified resin |
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| CN1509817A CN1509817A (en) | 2004-07-07 |
| CN1216694C true CN1216694C (en) | 2005-08-31 |
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