CN1082943A - The heterogeneous Raney nickel and the method for making thereof of ether produced in carbonylation of methanol - Google Patents
The heterogeneous Raney nickel and the method for making thereof of ether produced in carbonylation of methanol Download PDFInfo
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- CN1082943A CN1082943A CN 92109044 CN92109044A CN1082943A CN 1082943 A CN1082943 A CN 1082943A CN 92109044 CN92109044 CN 92109044 CN 92109044 A CN92109044 A CN 92109044A CN 1082943 A CN1082943 A CN 1082943A
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Abstract
The present invention initiative with the vinylidene chloride homopolymers and (or) its copolymer add with quantitative ceramic clay mix and mechanical-moulded after, through the high temperature cabonization cracking, formation is the high-ratio surface carbon molecular sieve PT carrier of skeleton with the pottery, catalyst P TNi with nickel strong bonded formation carbonylation of methanol gas-phase reaction, be aided with the co-catalyst iodomethane, under gentle relatively condition, make methanol carbonyl turn to acetate and methyl acetate, and need not to add other any solvent.Its activity is higher than all reported in literature values at present.
Description
The invention belongs to the nickel heterogeneous catalyst.
Carbonylation of methanol prepares the catalyst and the technology thereof of acetate, soluble rhodium catalyst and the low pressure homogeneous phase method synthetic route thereof that will count the employing of U.S. Monsanto company at present are the most ripe, have technology economy advantage preferably, set up the process units that is on a grand scale in many countries.But shortcoming such as poor heat stability, equipment are perishable, catalyst and product separating technique complexity, operating condition is restive, the used metal rhodium of what is more important costs an arm and a leg that this method exists.
People wish to adopt heterogeneous catalyst cheap and easy to get to replace present industrial process always for many years.This heterogeneous catalyst should possess two characteristics, that is: (1) uses cheap transition metal, and replacing expensive metal rhodium, (2) have and are similar to the such low pressure process flow process of rhodium catalyst and sufficiently high catalytic activity and selectivity.For reaching this purpose, a lot of experimental studies has been carried out in many in the world laboratories, does not find desirable heterogeneous catalyst so far as yet.Studying carefully its cause, mainly is to have the problem of three aspects not to be resolved.The one, do not find a kind of ideal activity high and selectivity is good, mechanical strength and the also high catalyst carrier of heat endurance.Though being arranged, many work adopt polymer supports (patent: SN 1108088 in 1985), absorbent charcoal carrier (patent in 1988: J63233936), silica supports (patent: EP276 in 1988,049) and metal (comprising rare earth metal) oxide carrier (patent in 1981: J56104839), and zeolite and other inorganic salt carrier (patent in 1987: DE3606169) etc., but adopt the overall targets such as its activity of catalyst, selectivity, mechanical strength and heat endurance of these preparing carriers all can not satisfy industrial requirement.The 2nd, do not solve reactive metal coming off and running off from carrier surface.Because metal has not only shortened the service life of catalyst from catalyst surface losss that come off in course of reaction, and brings difficulty to the recycling of product separation and metal, increased the complexity and the production investment cost of equipment.The 3rd, present employed gas phase catalysis agent carrier can not realize simultaneously all that high-ratio surface and hole aperture evenly distribute and be incorporated into one or optimal compromise is unified, promptly can not reach to help methanol carbonylation most and carry out desired best hole and pore-size distribution.
The present invention is directed to the above-mentioned shortcoming that existing heterogeneous catalyst exists, what be developed into a kind of novel high mechanical properties and high thermal stability is the high-ratio surface porous material catalyst carrier of skeleton structure with the pottery, and adopt special process method that the catalyst of appendix nickel compound is handled, making performance far away than existing similar catalyst is superior nickel heterogeneous catalyst, has solved a unsolved for a long time above-mentioned difficult problem.
Catalyst technology of the present invention constitute comprise a kind of carrier that to be the polymer of skeleton such as polyvinylidene chloride with the pottery form through carbonization and with the nickel strong bonded be the methanol carbonylation nickel heterogeneous catalyst of architectural feature, a kind of special catalyst high-temperature heat treatment preparation technology's method and the purposes and using method of catalyst of designing.Said catalyst has following architectural feature:
(1) with the ceramic skeleton of ad hoc structure and polyvinylidene chloride as catalyst support substrate.After for example selecting for use an amount of ceramic clay of polyvinylidene chloride adding fully to mix, make the carrier matrix of required form and granularity through machining.Said polyvinylidene chloride is meant the vinylidene chloride homopolymers that adopts polymerisation in solution to obtain.Said ceramic clay is to select commercially available kaolin for use.Said shape and granularity are that diameter is that ball-type or the diameter of 1-5mm is the column of 2-4mm.
(2) with above-mentioned be matrix through mechanical-moulded ceramic clay and polyvinylidene chloride mixture, adopt the carbonization technique of particular design, make this matrix at high temperature sintering and carbonization, the structure that reaches the phase of giving changes, form the catalyst carrier of a kind of porous and high-ratio surface, its pore-size distribution is 8-12A, and specific area is 600-800m
2/ g is the catalyst carrier with high mechanical properties and high thermal stability of a kind of even pore distribution, pore size homogeneous.
(3) carrier and active material nickel (accounting for the 1-2.5% of catalyst weight) form the catalyst of strong bonded, have been about to adsorb the carrier of nickel compound, handle through certain high temperature, make nickel be incorporated into carrier surface securely, and difficult drop-off.This catalyst has high activity and good selectivity to carbon monoxide and methyl alcohol prepared in reaction acetate and methyl acetate.At a diameter is that 0.6cm, length are to carry out the reaction of methyl alcohol catalyzed carbonylation in the reaction column of 32cm, catalytic rate be higher than 500 gram acetate/gram nickel/hour, the actual analysis calibration value be 582 restrain acetate/gram nickel/hour.Conversion of methanol is 60-67%, and the yield of primary product acetate is 40-41%, and the yield of methyl acetate is 18-19%.
The further technical characterictic of catalyst of the present invention is its novel preparation method, comprises the method for making of catalyst carrier method for making and catalyst.The method for making of carrier and catalyst is that (1) adopts free radical initiation carrying out polymerisation in solution with common commercially available high polymer monomer vinylidene chloride.Polymeric reaction temperature is 30-50 ℃, and the best is 40 ℃ of stopped reactions after 24 hours.In gained vinylidene chloride homopolymers viscous fluid, add the ceramic clay of weight 10-50%, mix after mechanical-moulded; (2) will put into quartz ampoule after the above-mentioned matrix drying after mechanical-moulded, under inert gas such as argon shield, be warming up to 160-170 ℃ gradually, make progressively cracking of polyvinylidene chloride, discharge hydrogen chloride etc., be warming up to 800-1100 ℃ then, calcination 2-3 hour, become standby catalyst carrier; (3) preparation catalyst: nickel salt is dissolved in ethanol or other alcohol or the ketones solvent; then carrier is immersed; with vacuum pump solvent is taken away; nickel promptly is adsorbed on carrier surface; the carrier that has adsorbed nickel compound is put into quartz ampoule; under inert gas shieldings such as argon gas, be warmed up to 600-800 ℃ gradually, sintering 1-2 hour, promptly become finished catalyst PTNi.Said nickel compound is NiCl
2
The further feature of catalyst of the present invention is that also its using method is easy, and the Catalytic processes device therefor is simple: (1) has higher activity owing to it, thus in reaction system, need not to add entry and strong proton solvent, as hydroiodic acid and acetate etc.; (2) PTNi is that a kind of methanol carbonylation that is used for is the catalyst of main synthetic product with acetate, can (carbon monoxide pressure of tension is 10kg/cm in low pressure
2) and the effective methanol carbonylation of the following realization of comparatively gentle reaction temperature condition (200-220 ℃); (3) only use co-catalyst iodomethane and simple fixed bed type reactor or column reactor, can produce.
PTNi catalyst of the present invention is used for carbonylation of methanol and produces acetate, obtains following outstanding effect: (1) has replaced the present industrial expensive metal rhodium that generally uses with the metallic nickel of cheapness; (2) obtain higher acetic acid yield under gentle relatively reaction condition, this is never to see the result that report is arranged in heterogeneous catalyst; (3) by electron probe catalyst is used the relatively proof of front and back, nickel does not have difference before and after being distributed in of carrier surface used, thereby has prolonged the service life of catalyst; (4) has selectivity preferably.In experiment, primary product is an acetate, secondly is methyl acetate, a small amount of dimethyl ether, and the latter proceeds with carbonylation and changes acetate or methyl acetate into, and other accessory substance (as methane, formaldehyde etc.) is trace; (5) in reaction system, need not to add other polar solvent, promptly directly under catalyst and the effect of co-catalyst iodomethane, produce acetate by methyl alcohol and carbon monoxide; (6) owing to need not to add entry in the reaction, reduced since the hydrogen that water gas reaction is emitted to the corrosion of equipment.
Example:
Preparation of catalysts: (1) is caused vinylidene chloride and is carried out polymerisation in solution with free radical.Polymeric reaction temperature is 40 ℃, through 24 hours stopped reactions, makes vinylidene chloride homopolymers thick liquid, again to the ceramic clay that wherein adds weight 10%, mixing and mechanical-moulded be the spherolite of diameter 3mm; (2) will put into quartz ampoule after the matrix drying after the moulding, under argon shield, be warming up to 165 ℃ gradually, make vinylidene chloride progressively cracking discharge hydrogen chloride, be warming up to 1000 ℃ of calcinations 2 hours then, obtain catalyst carrier; (3) with nickel salt (NiCl
2) be dissolved in the ethanol, again carrier is immersed, make nickel compound be adsorbed on carrier surface, the carrier that has adsorbed nickel compound is put into quartz, under argon shield, be warmed up to 750 ℃ gradually, sintering 1 hour promptly becomes finished catalyst PTNi.
Getting above-mentioned PTNi catalyst (nickel content 1%, ceramic clay content are 10%) the 4.2g diameter of packing into is that 0.6cm, length are in the reaction column of 32cm, feeds carbon monoxide and removes air in the post.Carbon monoxide pressure is risen to 10kg/cm
2, be warming up to 200 ℃ and kept 1 hour, make the abundant carbonylation of nickel of catalyst surface.With compression pump the mixed liquor of methyl alcohol and iodomethane (10/1mol than) is injected reaction column with the speed of 1 milliliter of per minute then, collect cooled product from the reaction column outlet.Through gas chromatographic analysis, acetic acid content is 41% in the product, methyl acetate 19%, methyl alcohol 33%, dimethyl ether 7%.
Claims (10)
1, the heterogeneous Raney nickel of acetate is produced in a kind of carbonylation of methanol, it is characterized in that the porous carrier that structure is formed by the organic polymer carbonization of skeleton by pottery and the active material nickel of strong bonded are formed.
2, the heterogeneous Raney nickel of carbonylation of methanol as claimed in claim 1, it is characterized in that said ceramic skeleton is to select ceramic clay for use, be preferably kaolin, its shape and granularity are that ball-type or the diameter of diameter 1-5mm is the column of 2-4mm, and its consumption is the 10-50% of catalyst carrier weight.
3, the heterogeneous Raney nickel of carbonylation of methanol as claimed in claim 1, the polymer substrate that it is characterized in that producing the carbonization porous carrier is the polyvinylidene chloride of ad hoc structure.
4, as claim 1,2, the heterogeneous Raney nickel of 3 described carbonylations of methanol, the high-specific surface area that it is characterized in that polymer carbonization porous carrier is 600-800m
2/ g, its pore-size distribution are 8-12A, even pore distribution.
5, the heterogeneous Raney nickel of carbonylation of methanol as claimed in claim 4 is characterized in that the content of catalytic active substance nickel accounts for the 1-2.5% of catalyst weight.
6, the manufacture method of the heterogeneous Raney nickel of acetate is produced in a kind of carbonylation of methanol, it is characterized in that the preparation of catalyst carrier and the method for making of catalyst adopt three-procedure: the preparation of (1) carrier matrix, in the sticky polymers solution that solution polymerization makes, adding ceramic clay, the mixing and mechanical-moulded that weight is 10-50% with high polymer monomer; (2) catalyst carrier preparation, the forming matrix that is about to ceramic clay and macromolecular compound mixture are made high mechanical properties and high thermal stability catalyst carrier through high temperature cabonization processing and high temperature sintering under inert gas shielding; (3) producing of finished catalyst PTNi is about to nickel salt and is dissolved in alcohols or the ketone solution, then carrier immersed, and the carrier that will adsorb nickel compound is again put into quartz ampoule, handles through high temperature sintering under inert gas shielding.
7, the method for making of heterogeneous Raney nickel as claimed in claim 6; the used high polymer monomer of preparation that it is characterized in that (1) carrier matrix is the vinylidene chloride of ad hoc structure; it is used free radical polymerization; at 30-50 ℃, be preferably 40 ℃, reacted 24 hours; make vinylidene chloride homopolymers viscous solution; again to the potter's clay that wherein adds weight 10-50%, kaolin preferably, making spherolite or the diameter that viscosity is 1-5mm is the column of 2-4mm.
8, as claim 6; the method for making of 7 described heterogeneous Raney nickels; the high temperature cabonization that it is characterized in that forming matrix in the preparation of (2) catalyst carrier is handled and high temperature sintering; be to put into quartz ampoule after the matrix drying after the moulding; under argon shield; be warming up to 160-170 ℃ gradually and make progressively cracking carbonization of polyvinylidene chloride, be warming up to 800-1100 ℃ then, calcination 2-3 hour.
9, the method for making of heterogeneous Raney nickel as claimed in claim 6 is characterized in that in the producing of (3) finished catalyst that said nickel salt or nickel compound are NiCl
2, said inert gas is an argon, it is that the catalyst carrier of will adsorb nickel compound is warmed up to 600-800 ℃, sintering 1-2 hour gradually in quartz ampoule that said high temperature sintering is handled.
10, the using method of the heterogeneous Raney nickel of acetate is produced in carbonylation of methanol as claimed in claim 1, it is characterized in that only using co-catalyst iodomethane and simple fixed bed type reactor or column reactor, need not to add entry and strong proton solvent, can (carbon monoxide pressure of tension be 10kg/cm in low pressure
2) and comparatively gentle reaction temperature (200-220 ℃) under realize methanol carbonylation effectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109044A CN1039884C (en) | 1992-08-10 | 1992-08-10 | Heterogeneous Ni catalyst for producing ethyl ether by carbonylation of methyl alcohol and producing process thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN92109044A CN1039884C (en) | 1992-08-10 | 1992-08-10 | Heterogeneous Ni catalyst for producing ethyl ether by carbonylation of methyl alcohol and producing process thereof |
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| Publication Number | Publication Date |
|---|---|
| CN1082943A true CN1082943A (en) | 1994-03-02 |
| CN1039884C CN1039884C (en) | 1998-09-23 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN92109044A Expired - Fee Related CN1039884C (en) | 1992-08-10 | 1992-08-10 | Heterogeneous Ni catalyst for producing ethyl ether by carbonylation of methyl alcohol and producing process thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037585C (en) * | 1995-03-31 | 1998-03-04 | 中国科学院化学研究所 | Gas-solid phase carbonylation catalyst and its prepn |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4990481A (en) * | 1988-05-20 | 1991-02-05 | Toyo Engineering Corporation | Catalyst for steam reforming |
| GB2222963B (en) * | 1988-09-23 | 1992-01-02 | British Gas Plc | Catalysts |
-
1992
- 1992-08-10 CN CN92109044A patent/CN1039884C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1037585C (en) * | 1995-03-31 | 1998-03-04 | 中国科学院化学研究所 | Gas-solid phase carbonylation catalyst and its prepn |
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| CN1039884C (en) | 1998-09-23 |
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