CN1141365C - Hydrotherifying catalyst and preparation method thereof - Google Patents
Hydrotherifying catalyst and preparation method thereof Download PDFInfo
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- CN1141365C CN1141365C CNB011161310A CN01116131A CN1141365C CN 1141365 C CN1141365 C CN 1141365C CN B011161310 A CNB011161310 A CN B011161310A CN 01116131 A CN01116131 A CN 01116131A CN 1141365 C CN1141365 C CN 1141365C
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- etherification
- auxiliary agent
- catalyzer
- metal
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Abstract
The present invention relates to a hydroetherifying catalyst and a preparation method thereof. The catalyst is prepared from active metal constituents and an auxiliary agent constituent which are combined with hydrogen type macropore strong acidic cation-exchange resin, wherein the auxiliary agent constituent comprises one or more than one transitional metal, or a mixed constituent of transition metal elements and main group elements. A resin etherifying catalyst containing noble metals and an auxiliary agent is obtained by loading the transition metal elements of the auxiliary agent and the active constituents on the strong acidic macropore cation-exchange resin as a carrier. The dispersivity and the impurity adsorbility of the active constituents are improved by utilizing the auxiliary agent so that the hydroisomerization activity, the double bond isomerization activity and the stability of the catalyst are obviously improved.
Description
Technical field
The present invention relates to a kind of ether hydro-etherification Catalysts and its preparation method, specifically, the present invention relates under hydro condition, contain the cracking light gasoline fraction (do, or less than 100 ℃) and the C thereof of isomeric olefine less than 75 ℃
5The resin catalyst for etherification that is loaded with precious metal and auxiliary agent and this Preparation of catalysts method used in cut and methyl alcohol or the ethanol generation etherification reaction process.
Background technology
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.The resin catalyst for etherification of carried noble metal and auxiliary agent has three kinds of katalysis in methyltertiarvbutyl ether reactor and under the hydro condition, i.e. the selection hydrogenation and the double-bond isomerization of the etherificate of active olefin, diolefin.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.At the strongly acidic macroporous cation exchange resin catalyzer that is loaded with precious metal and auxiliary agent thereof, the publication before the present invention (US4,330,679; US 5,141, and 525; US 4,950, and 820; EP 490,571; US 4,695, and 556; CN 1,146,927) have in and adopt aqueous solution ion exchange method and aqueous solution pickling process and reactive metal element and auxiliary element are carried on record on the carrier, wherein reactive metal unit have Pd, Pt, and auxiliary agent is elements such as Si, Al, Ga, B, Ge, Sn.But, adopting this method, the catalyzer that obtains is unsatisfactory aspect stable.
Summary of the invention
The object of the present invention is to provide a kind of ether hydro-etherification catalyzer, this catalyzer adopts the blending ingredients of transition metal or transition metal and main group element to make auxiliary agent, can provide higher stability in reaction.
In addition, the present invention also aims to provide this ether hydro-etherification Preparation of catalysts method.
Ether hydro-etherification catalyzer provided by the invention, by load on the Hydrogen macropore strong acid cation exchange resin reactive metal component and auxiliary agent component form, wherein said auxiliary agent component comprises the blending ingredients of one or more transition metal or transition metal and main group element.
In the catalyzer provided by the invention, transition metal can be selected from nickel (Ni), copper (Cu), zirconium (Zr), titanium (Ti) or silver (Ag) etc., main group element can be aluminium (Al) or tin (Sn) etc., and the mass ratio of main group element and transition metal is 0～4: 1, preferred 0～1: 1.The content of adjuvant component is/1 liter of dry resin of 0～10 gram ,/1 liter of dry resin of preferred 0.1～6 gram.When adjuvant component was two kinds of transition metal, their content sum was not particularly limited as long as in above-mentioned scope, and the mass ratio of preferred two kinds of transition metal can be about 1: 1.
The content of reactive metal is 0.05～9%wt in the catalyzer, preferred 0.1～1.0%wt.The preferred palladium of described reactive metal component etc.
Ether hydro-etherification Preparation of catalysts method of the present invention, be that the soluble salt of reactive metal and auxiliary agent component is made organic solution with anhydrous polar organic solvent, adopt co-impregnation or step impregnation method to load on Hydrogen macropore strong acid cation exchange resin surface, the reduction of dry back.
Ether hydro-etherification catalyzer of the present invention is a carrier with Hydrogen macropore strong acid cation exchange resin, for example can use domestic resin S
54, D
005, D
001, D
72Deng, the water-soluble salt that adopts the water-soluble salt of reactive metal and above-mentioned auxiliary agent is as auxiliary agent or as the coating and the surface-modifying agent of carrier, this water-soluble salt such as nitrate, acetate, oxymuriates etc. are used anhydrous polar organic solvent, dissolve the water-soluble salt of precious metal and auxiliary agent as Virahol, acetate, methyl alcohol, ethanol etc., make organic solution, adopt co-impregnation or step impregnation method to load on the surface of Hydrogen macropore strong acid cation exchange resin.Wherein, the reactive metal constituent content is 0.05～9%, preferred 0.1～1.0%Wt; Adjuvant component content is every liter dry resin 0～10 gram, preferred 0.1～6 gram; The mass ratio of main group element Al, Sn and transition metal is 0～4: 1 in the adjuvant component, preferred 0～1: 1, and the catalyzer after the load is after 30～110 ℃ of following dryings, and reduction gets final product.
Ether hydro-etherification Preparation of catalysts method of the present invention can comprise the steps:
(1) with the soluble salt of anhydrous polar organic solvent lytic activity metal and adjuvant component, makes organic mixing solutions;
(2) with this mixing solutions dipping Hydrogen macropore strong acid resin carrier, and dry down at 30～110 ℃;
Reduced 0～24 hour with hydrogen or formic acid under (3) 30～110 ℃.
According to embodiment of the present invention, this ether hydro-etherification Preparation of catalysts method also can comprise the steps:
(1) with anhydrous polar organic solvent lytic activity metal soluble salt, makes organic solution;
(2) with this organic solution dipping Hydrogen macropore strong acid resin carrier, dry down at 30～110 ℃;
(3) with the soluble salt of anhydrous polar organic solvent dissolution aids component, make organic solution;
(4) with the catalyzer that obtains in this organic solution dipping (2), dry down at 30～110 ℃;
Reduced 0～24 hour with hydrogen or formic acid under (5) 30～110 ℃.
In addition, ether hydro-etherification Preparation of catalysts method of the present invention also can comprise the steps:
(1) with the soluble salt of anhydrous polar organic solvent dissolution aids component, makes organic solution;
(2) with this organic solution dipping Hydrogen macropore strong acid resin carrier, dry down at 30～110 ℃;
(3) with anhydrous polar organic solvent lytic activity metal soluble salt, make organic solution;
(4) with the catalyzer that obtains in this organic solution dipping (2), dry down at 30～110 ℃;
Reduced 0～24 hour with hydrogen or formic acid under (5) 30～110 ℃.
30～110 ℃ of following drying operationes being adopted in the above-mentioned preparation process, can adopt natural air drying, also can adopt other drying means, preferably 30～50 ℃, constantly carry out preliminarily dried earlier under the agitation condition, then 90～110 ℃ of following constant temperature vacuum-dryings 0～24 hour.
Restoring operation in the above-mentioned preparation process generally realizes in reaction process, that is to say, when reacting, passes through hydrogen or formic acid reducing catalyst as reaction raw materials in reactor.
The present invention with auxiliary agent transition metal and active constituent noble metal support on the strongly acidic macroporous cation exchange resin carrier, make the resin catalyst for etherification that contains precious metal and auxiliary agent, utilize auxiliary agent to improve the dispersed of active constituent precious metal and absorption impurity, the hydrogenation of this catalyzer and double-bond isomerization activity, stability are improved significantly.
Promoter effect by transition metal and main group element, as nickel (Ni), copper (Cu), zirconium (Zr), titanium (Ti) or silver (Ag) and aluminium (Al), tin (Sn) etc., adopt the salt of polar organic solvent lytic activity metal and above-mentioned main group metal, make organic steeping fluid, reactive metal Pd is disperseed on the storng-acid cation exchange resin carrier more and stablize, the existence of auxiliary agent has simultaneously also improved the anti-impurity stability of noble metal catalyst, thereby makes the hydrogenation of catalyzer of the present invention and double-bond isomerization is active and stability is further improved and improve.
Embodiment
Further describe the present invention below by embodiment, but practical range of the present invention has more than and is limited to these embodiment.
Embodiment 1
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams are dissolved in 46 ml methanol, make methanol solution.Under continuous stirring condition, above-mentioned methanol solution is immersed on 48 milliliters of Hydrogen macropore strong acid cation exchange resins, behind the 30-50 ℃ of following preliminarily dried, took out constant temperature vacuum-drying 6 hours with water again under 100 ℃, obtaining the Pd metal content is the precious metal etherificate resin contrast medium A of 0.36%wt.
Embodiment 2
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams and nickelous nitrate (Ni (NO
3)
26H
2O) 476 milligrams are dissolved in 46 ml distilled waters, make mixed aqueous solution.Then, according to the method operation identical with embodiment 1, obtaining the Pd metal content is the precious metal etherificate resin contrast medium B of nickeliferous (Ni) auxiliary agent of 0.36%Wt.
Embodiment 3
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams and nickelous nitrate (Ni (NO
3)
26H
2O) 476 milligrams are dissolved in 46 ml methanol, make the mixing methanol solution.Under continuous stirring condition, above-mentioned mixing methanol solution is immersed on 48 milliliters of Hydrogen macropore strong acid cation exchange resins, under the room temperature behind the preliminarily dried, 100 ℃ of following constant temperature vacuum-dryings 6 hours, obtaining the Pd metal content was the precious metal etherificate resin catalyst C that contains the Ni auxiliary agent of 0.36%Wt again.
Embodiment 4
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams and nickelous nitrate (Ni (NO
3)
26H
2O) 1.666 grams are dissolved in 46 ml methanol, make the mixing methanol solution.Then, be the precious metal etherificate resin catalyst D that contains the Ni auxiliary agent of 0.36%wt according to carrying out with embodiment 2 identical operations, obtaining the Pd metal content.
Embodiment 5
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams and nickelous nitrate (Ni (NO
3)
26H
2O) 476 milligrams are dissolved in 46 milliliters of ethanol, make mixed ethanol solution.Then, be the precious metal etherificate resin catalyst E that contains the Ni auxiliary agent of 0.36%wt according to carrying out with embodiment 2 identical operations, obtaining the Pd metal content.
Embodiment 6
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams, nickelous nitrate (Ni (NO
3)
26H
2O) 476 milligrams and aluminum nitrate (Al (NO
3)
39H
2O) 1.334 grams are dissolved in 46 ml methanol, make the mixing methanol solution.Then, be the precious metal etherificate resin catalyst F that contains Ni, Al auxiliary agent of 0.36%Wt according to carrying out with embodiment 2 identical operations, obtaining the Pd metal content.
Embodiment 7
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams, nickelous nitrate (Ni (NO
3)
26H
2O) 476 milligrams and Silver Nitrate (Ag (NO
3) 9H
2O) 1.434 grams are dissolved in 46 ml methanol, make the mixing methanol solution.Then, be the precious metal etherificate resin catalyst G that contains Ni, Ag auxiliary agent of 0.36%Wt according to carrying out with embodiment 2 identical operations, obtaining the Pd metal content.
Embodiment 8
With Palladous nitrate (Pd (NO
3)
22H
2O) 240 milligrams and cupric nitrate (Cu (NO
3)
26H
2O) 476 milligrams are dissolved in 46 ml methanol, make the mixing methanol solution.Then, be the precious metal etherificate resin catalyst H that contains the Cu auxiliary agent of 0.36%Wt according to carrying out with embodiment 2 identical operations, obtaining the Pd metal content.
Experimental example
Estimate above-mentioned etherificate, hydrogenation and isomerization activity, the stability that contains the catalyst for etherification A～H of precious metal and auxiliary agent with the small pressurized fixed-bed reactor.
The reaction conditions of ether hydro-etherification 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, hydrogen exhaust flow 4.0～5.0ml (STP).
The content of main component is in the reaction raw materials liquid: 3-methyl-1-butene 0.96wt%, activity isomerism alkene (2-methyl-1-butene alkene and 2-methyl-2-butene) 19.08wt%, pentadiene 0.52wt%, methyl alcohol 11.32wt%.
Experimental result is as shown in the table.
Contain the resin catalyst for etherification of precious metal and auxiliary agent
Diolefin hydrogenation, double-bond isomerism and etherificate transformation efficiency (%)
3-methyl-1-butene activity isomerism alkene alkadienes contrast medium A 29.3 18.3 97.3 contrast medium B 15.8 14.2 98.3 catalyst C 37.5 17.3 100 catalyst D 27.4 12.1 100 catalyst E 30.3 17.7 100 catalyst F 29.4 17.4 99.4 catalyst G 28.7 16.4 98.3 catalyst H 0.0 17.9 24.2 notes: catalyst A～G is the analysis result of reaction after 12 hours.
Catalyzer H is the analytical results of reaction after 6 hours.
Can see that A compares with contrast medium from table, the catalyzer C～G that adds the transition metal auxiliary agent can improve the diolefin hydrogenation or the double-bond isomerism activity of catalyzer.B compares with contrast medium, adopts polar organic solvent to prepare the preparation method of steeping fluid, can improve the etherification activity that contains the auxiliary agent catalyzer.
Claims (13)
1, a kind of ether hydro-etherification catalyzer, be made up of the reactive metal component and the auxiliary agent component that are combined on the Hydrogen macropore strong acid cation exchange resin, wherein said auxiliary agent component comprises the blending ingredients of one or more transition metal or transition metal and main group element; Wherein, the charge capacity of described reactive metal component in catalyzer is 0.05～9%wt, and the content of described auxiliary agent is/1 liter of dry resin of 0～10 gram, and the mass ratio of main group element and transition metal is 0～4: 1 in the auxiliary agent component.
2, ether hydro-etherification catalyzer as claimed in claim 1, wherein said transition metal is nickel, copper, zirconium, titanium or silver.
3, ether hydro-etherification catalyzer as claimed in claim 1, wherein said main group element is aluminium or tin.
4, ether hydro-etherification catalyzer as claimed in claim 1, the content of wherein said auxiliary agent are/1 liter of dry resin of 0.1～6 gram.
5, ether hydro-etherification catalyzer as claimed in claim 1, wherein the mass ratio of main group element and transition metal is 0～1: 1 in the auxiliary agent component.
6, ether hydro-etherification catalyzer as claimed in claim 1, wherein said reactive metal is a palladium.
7, as claim 1 or 6 described ether hydro-etherification catalyzer, the charge capacity of wherein said reactive metal in catalyzer is 0.1～1.0%wt.
8, ether hydro-etherification Preparation of catalysts method according to claim 1, comprise the soluble salt of reactive metal and auxiliary agent component is made organic solution with anhydrous polar organic solvent, adopt co-impregnation or step impregnation method to load on Hydrogen macropore strong acid cation exchange resin surface, the reduction of dry back.
9, ether hydro-etherification Preparation of catalysts method as claimed in claim 8 comprises the steps:
(1) with the soluble salt of anhydrous polar organic solvent lytic activity metal and adjuvant component, makes organic mixing solutions;
(2) with this mixing solutions dipping Hydrogen macropore strong acid resin carrier, and dry down at 30～110 ℃;
Reduced 0～24 hour with hydrogen or formic acid under (3) 30～110 ℃.
10, ether hydro-etherification Preparation of catalysts method as claimed in claim 8 comprises the steps:
(1) with anhydrous polar organic solvent lytic activity metal soluble salt, makes organic solution;
(2) with this organic solution dipping Hydrogen macropore strong acid resin carrier, dry down at 30～110 ℃;
(3) with the soluble salt of anhydrous polar organic solvent dissolution aids component, make organic solution;
(4), dry down at 30～110 ℃ with the catalyzer that obtains in this organic solution impregnation steps (2);
Reduced 0～24 hour with hydrogen or formic acid under (5) 30～110 ℃.
11, ether hydro-etherification Preparation of catalysts method as claimed in claim 8 comprises the steps:
(1) with the soluble salt of anhydrous polar organic solvent dissolution aids component, makes organic solution;
(2) with this organic solution dipping Hydrogen macropore strong acid resin carrier, dry down at 30～110 ℃;
(3) with anhydrous polar organic solvent lytic activity metal soluble salt, make organic solution;
(4), dry down at 30～110 ℃ with the catalyzer that obtains in this organic solution impregnation steps (2);
Reduced 0～24 hour with hydrogen or formic acid under (5) 30～110 ℃.
12, ether hydro-etherification Preparation of catalysts method as claimed in claim 8, wherein said polar organic solvent comprises propyl alcohol, Virahol, methyl alcohol, ethanol, acetate, formic acid.
13, ether hydro-etherification Preparation of catalysts method as claimed in claim 8, wherein said soluble salt is nitrate, acetate or oxymuriate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011161310A CN1141365C (en) | 2001-05-11 | 2001-05-11 | Hydrotherifying catalyst and preparation method thereof |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011161310A CN1141365C (en) | 2001-05-11 | 2001-05-11 | Hydrotherifying catalyst and preparation method thereof |
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|---|---|
| CN1385496A CN1385496A (en) | 2002-12-18 |
| CN1141365C true CN1141365C (en) | 2004-03-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335599B (en) * | 2010-07-14 | 2013-04-24 | 中国石油天然气股份有限公司 | Olefin etherification catalyst and its preparation and use |
| CN105413732B (en) * | 2015-12-14 | 2018-03-30 | 夏百庆 | A kind of composite catalyst for gasoline etherification |
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Granted publication date: 20040310 |