CN102266795A - Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof - Google Patents
Catalyst used for low water acetic acid synthetic technology and preparation and application method thereof Download PDFInfo
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Abstract
The invention provides a catalyst used for low water acetic acid synthetic technology, wherein the characteristic is the catalyst is a double-metal complex; the double metal complex is H[RhM(CO)4(N)4], wherein M is one of Ir and Co, N is one of Cl, Br and I. The catalyst provided by the invention used for low water acetic acid synthetic technology is the double metal complex which uses a collaborative catalytic effect between the two metals and has a relatively high catalytic efficiency. Meanwhile, the catalyst provided by the invention also has advantages of less material categories for preparative reaction and simple route of the preparative technology to effectively reduce preparative cost of the double metal catalyst and improve economic benefit of the technology used for low water acetic acid synthetic technology.
Description
Technical field
The invention belongs to chemical industry catalytic reaction engineering technical field, relate to a kind of composition and application technology that is used for the effective catalyst of low water acetic acid synthesis technique.
Background technology
Acetic acid is a kind of important Organic Chemicals, is mainly used in chemical products such as producing VAM (VAM), cellulose acetate, terephthalic acid (TPA) (PTA), polyvinyl alcohol, acetates.Has extensive use in industries such as chemical industry, light textile, medicine, dyestuff and organic syntheses.In recent years, because the development of PTA and acetic acid downstream product, impelled acetic acid to become one of minority petroleum chemicals that output and demand all increase rapidly.
The synthesis technique of acetic acid is main in the prior art: methanol carbonyl synthetic method, acetaldehyde oxidation, direct oxidation of ethylene to method and light oil (butane or naphtha).Wherein, acetic acid synthesis from methanol carbonylation technology is little with its energy consumption, cost is low, be easy to characteristics such as suitability for industrialized production and gain great popularity.In the acetic acid synthesis from methanol carbonylation process, be accompanied by following two side reactions: the hydrogenation reaction (CH of methyl alcohol
3OH+H
2← → CH
4+ H
2O) and water gas shift reaction (CO+H
2O ← → CO
2+ H
2).Because the speed of water gas shift reaction is greater than the speed of methyl alcohol hydrogenation reaction, so the carbonylation system the variation that must be accompanied by water content, gather what of water content according to reaction system, can be with acetic acid synthesized high water conservancy project skill (water content is 14wt-15wt%) and low water conservancy project (water content be lower than 14wt%) two kinds of planting that be divided into of carbonyl process.
Traditional acetic acid synthesis from methanol carbonylation technology is representative with Monsanto/BP technology, and this technology is major catalyst with the rhodium, and iodide are co-catalyst, and it is acetic acid synthesized to utilize methyl alcohol and CO that carbonylation takes place.Above-mentioned Meng Shan all/BP technology in, in order to make catalyst have sufficiently high activity and to keep enough stability, water in the reaction system must maintain about 14-15%, belong to a kind of high water conservancy project skill, and the defective that high water conservancy project skill exists is, in order to obtain comparatively pure acetic acid, the moisture fractionation must be removed after reaction is finished, and fractionation water is the process of a highly energy-consuming, has increased the operating cost of technology greatly.
In order to solve the problems of the technologies described above, those skilled in the art have developed some gradually and still possessed the catalyst system of efficient carbonylation rate under low water contents, as disclosing the carbonylation method of a kind of C1 among the Chinese patent literature CN1129690 to C4 alkylol and/or its derivative, this method is carried out haptoreaction with C1 in C4 alkylol and/or its reactive derivative and the liquid phase reactor composition of carbon monoxide in carbonylation reactor, this liquid phase reactor composition comprises: a) a kind of rhodium catalyst, b) a kind of alkyl halide and c) at least a as in the ruthenium of co-catalyst and the osmium, wherein said rhodium catalyst and ruthenium, the osmium co-catalyst successively adds with the form of DDGS.Water concentration in the above-mentioned liquid phase reactor composition is 0.1-15wt%, and is preferred below 7%.
The using method of the catalyst system in the above-mentioned technology is: earlier autoclave is washed once with twice of nitrogen wash and with carbon monoxide, under stirring (1000 rev/mins), be heated to 185 ℃ then, when system after stablizing 30 minutes under the self-generated pressure, under carbon monoxide pressure, in described autoclave, add the rhodium catalyst solution that is dissolved in the acetate, as required feed carbon monoxide from gas pressurizer to autoclave by liquid feeding device and make the pressure of autoclave maintain 27 crust (2.7MPa) substantially.When having used the ruthenium catalyst aid, before adding rhodium catalyst solution, in autoclave, add earlier RuI
3
Yet the defective of above-mentioned prior art is, through facts have proved RuI
3Only under the condition of high temperature, high pressure and feeding carbon monoxide, can be dissolved in preferably in the acetate equal solvent, and above-mentioned technology adds RuI when beginning in autoclave
3, owing to do not possess the condition that makes its dissolving in the autoclave, so the RuI of this moment
3Still be that form with solid exists, this just causes described RuI
3Distribution in liquid-phase reaction system is also inhomogeneous, and the carbonylation that causes the initial stage is a kind of heterogeneous reaction, and reaction rate is lower and reaction conversion ratio is also very low.In addition, when described carbonylation at RuI
3Carried out in described reaction system, adding rhodium catalyst again a period of time of after under the condition that catalyst exists, this moment, rhodium and ruthenium were because residing reaction environment temperature is 185 ℃, pressure is 27 crust, so can only carry out catalysis to carbonylation as monomer catalyst independently between the two, between above-mentioned two catalyst is to form complex, and the catalytic efficiency of rhodium catalyst that exists with monomeric form and ruthenium catalyst is lower, thereby has influenced the efficient of carbonylation.
Summary of the invention
For the bimetallic catalyst that solves in the prior art can't form complex compound, can only exist with the form of two kinds of monomers, cause the lower problem of carbonylation catalytic efficiency, the invention provides a kind of catalyst and preparation and using method that is used for low water acetic acid synthesis technique.
The technical scheme of catalyst of the present invention and preparation thereof and using method is:
A kind of catalyst that is used for low water acetic acid synthesis technique, described catalyst is a bimetal complexes, described bimetal complexes is
H[RhM(CO)
4(N)
4]，
Wherein, M is a kind of among Ir, the Co; N is a kind of among cl, Br, the I.
Described bimetal complexes is H[RhIr (CO)
4I
4].
The using method of described catalyst comprises the steps:
(1) in reactor, add the methyl acetate of methyl alcohol, 8-10 weight portion of 52-63 weight portion and 0.2-0.25 weight portion catalyst, 3-5 weight portion water and stir;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 160-190 ℃, is to carry out carbonylation under the 3.0-3.5MPa condition at pressure.
In described step (1), also in described reactor, add at least a in the alkali halide of the alkyl halide of 14-17 weight portion and 12-15 weight portion.
Described alkyl halide is an iodomethane, and alkali halide is a lithium iodide.
Reaction time in the described step (2) is 10-15min, and reaction temperature is 180-185 ℃.
Bimetal complexes H[RhM (CO)
4(N)
4] be used as the purposes of the catalyst of low water acetic acid synthesis technique, wherein, M is a kind of among Ir, the Co; N is a kind of among cl, Br, the I.
Bimetal complexes H[RhIr (CO)
4I
4] be used as the purposes of the catalyst of low water acetic acid synthesis technique.
Step described in the using method of the catalyst described in the present invention (2) adds the methyl alcohol of 52-63 weight portion, the methyl acetate of 8-10 weight portion and the catalyst of 0.2-0.25 weight portion, the water of 3-5 weight portion in reactor; It is the 0.2-0.25 weight portion that described catalyst consumption here is set, and very few if reason is catalyst consumption, then the reaction rate of described carbonylation can reduce significantly; And catalyst consumption is crossed the operating cost that conference increases substantially the synthetic technology of carbonylation, reduces the economic benefit of whole technology.In addition, the present invention also further is arranged in the described step (1) at least a in the alkali halide of the alkyl halide that also adds the 14-17 weight portion in described reactor and 12-15 weight portion.When the water content in the reaction system was lower than 14%, deposited phenomenon took place in rhodium catalyst easily, directly had influence on the integrality of carbonylation rate and entire reaction.So in reactor, added iodomethane, lithium iodide co-catalyst, strengthened the stability of catalyst as the synthetic acetic acid of catalysis methanol carbonylation.Wherein, the existence of an amount of alkyl halide can strengthen the catalytic activity of catalyst and accelerate reaction rate, but halide ion can have side effects to carbonylation during the alkyl halide excessive concentration, can reduce the yield of described product on the contrary.The dissolubility of alkali halide in reaction system is higher, the alkali halide of high degree of dispersion has stabilization to activity of such catalysts, the methyl acetate that esterification is generated also has stabilization, overall reaction had the effect that improves reaction stability and product yield, but the excessive concentration of alkali halide, can in reaction system, introduce alkali halides in a large number, separate for later stage catalyst activity component recovery and bring difficulty.The present invention limits by the consumption to described alkyl halide and alkali halide, has effectively avoided above-mentioned situation.
Described step (2) feeds hydrogen and carbon monoxide in described reactor, wherein said hydrogen effect be that in the rhodium metal activity unit in described bimetallic catalyst, rhodium mainly is with Rh
+Form exists, can generation Rh after reacting when contact with oxide
3+, and the trivalent rhodium does not have catalytic activity; The present invention is by feeding H
2, make to remain under the reducing atmosphere in the described reactor, can effectively prevent Rh
+Be oxidized to Rh
3+Thereby, avoided the phenomenon of the catalyst precipitation that causes owing to separating out of trivalent rhodium compound.
Described step stirs the mixture in the described reactor in (2), and the effect of Jiao Baning here is to make the reactant that adds in the reactor to mix.
It is 110-185 ℃ that the present invention also is provided with described reaction temperature, pressure is 2.0-3.5MPa, temperature and pressure is the key factor that influences carbonylation, temperature and pressure is crossed low then carbonylation and can't be carried out, can cause the catalyst in the reaction system to precipitate and temperature and pressure is too high, the present invention limits by the temperature and pressure to reaction, is guaranteeing also to have avoided catalyst that the phenomenon of precipitation takes place when described carbonylation can efficiently carry out as far as possible.
The reaction time that the present invention also limits the carbonylation in the described step (2) is 10-15min, and reason is, if the described reaction time is too short, then reaction carry out insufficient, thereby cause the productive rate that reacts lower; If the reaction time is long, then can cause carbonylation to generate a large amount of accessory substances, thereby the difficulty that causes the later stage Dichlorodiphenyl Acetate to separate strengthens, produce tar with the long reaction system that also can cause of the reaction time, described tar covers the phenomenon that causes catalysqt deactivation on the surface of catalyst easily, described catalyst can't be regenerated, and the present invention is 10-15min by limiting the described reaction time, has effectively avoided above-mentioned situation.
The catalyst that is used for low water acetic acid synthesis technique of the present invention, advantage is:
(1) catalyst that is used for low water acetic acid synthesis technique of the present invention is bimetal complexes, can produce two catalytic active centers simultaneously in described complex, and has utilized the concerted catalysis effect between two kinds of metals, has higher catalytic efficiency.Simultaneously, it is less that catalyst of the present invention also has the material classification of participating in preparation feedback, the simple advantage of preparation were established, thus effectively reduce the preparation cost of described bimetallic catalyst, improved the described economic benefit that is used for the technology of low water acetic acid synthesis technique.
(2) catalyst that is used for low water acetic acid synthesis technique of the present invention, it is H[RhIr (CO) that described catalyst further is set
4I
4], I in the described catalyst and CO are the raw material in the carbonylation reaction system, do not introduce reaction system material in addition in course of reaction, the material or the ion that are present in the reaction system all can access good utilization, and conversion between the material and utilization rate are very high.Simultaneously, owing to do not introduce other materials, also significantly reduced the difficulty that product is separated with accessory substance.It is rhodium-iridium catalyst that the present invention further limits described catalyst here, has that reaction selectivity is higher, stability is stronger, temperature required low, the advantage that accessory substance is few of reaction.
In order to make content of the present invention be convenient to more understand, below in conjunction with the specific embodiment to of the present invention be used for low water acetic acid synthesis technique catalyst and preparation and using method further set forth.
The specific embodiment
Embodiment 1
Catalyst described in the present embodiment is H[RhCo (CO)
4I
4], described Preparation of catalysts method comprises:
(1) with RhI
3With CoI
2Add to and obtain mixture in the methanol solvate, described RhI
3Consumption count 400ppm with rhodium, described CoI
2Consumption count 200ppm with Co;
(2) said mixture being sent in the reactor, is 185 ℃ in temperature, and pressure is to react 3h under the condition of 3.5MPa, promptly obtains described catalyst.
The using method of above-mentioned catalyst comprises:
(1) in reactor, adds the water of the catalyst of methyl acetate, 0.25 weight portion of methyl alcohol, 10 weight portions of 63 weight portions and 3 weight portions and stirring;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 190 ℃, is to carry out carbonylation under the 3.5MPa condition at pressure, and the reaction time is 9min;
The dividing potential drop of wherein said hydrogen is 0.07MPa.
Embodiment 2
Catalyst described in the present embodiment is H[RhIr (CO)
4I
4], described Preparation of catalysts method comprises:
(1) with RhI
3With IrI
3Add to and obtain mixture in the acetate solvate, described RhI
3Consumption count 400ppm with rhodium, described IrI
3Consumption count 180ppm with Ir;
(2) be 165 ℃ in temperature, carbon monoxide pressure of tension is to react 2.5h under the condition of 3MPa, promptly obtains described catalyst.
The using method of above-mentioned catalyst comprises:
(1) in reactor, add the methyl acetate of methyl alcohol, 8 weight portions of 52 weight portions and 0.2 weight portion catalyst, 5 weight portions water and stir;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 160 ℃, is to carry out carbonylation under the 3MPa condition at pressure, and the reaction time is 10min;
The dividing potential drop of wherein said hydrogen is 0.07MPa.
Embodiment 3
Catalyst described in the present embodiment is H[RhIr (CO)
4I
4], described Preparation of catalysts method comprises:
(1) with RhI
3With IrI
3Add to and obtain mixture in the acetate solvate, described RhI
3Consumption count 400ppm with rhodium, described IrI
3Consumption count 180ppm with Ir;
(2) be 165 ℃ in temperature, carbon monoxide pressure of tension is to react 2.5h under the condition of 3MPa, promptly obtains described catalyst.
The using method of above-mentioned catalyst comprises:
(1) in reactor, add the methyl acetate of methyl alcohol, 9 weight portions of 55 weight portions and 0.2 weight portion catalyst, 4 weight portions water and stir;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 180 ℃, is to carry out carbonylation under the 3MPa condition at pressure, and the reaction time is 15min;
The dividing potential drop of wherein said hydrogen is 0.075MPa.
Embodiment 4
Catalyst described in the present embodiment is H[RhIr (CO)
4I
4], described Preparation of catalysts method comprises:
(1) with RhI
3With IrI
3Add to and obtain mixture in the acetate solvate, described RhI
3Consumption count 400ppm with rhodium, described IrI
3Consumption count 180ppm with Ir;
(2) be 165 ℃ in temperature, carbon monoxide pressure of tension is to react 2.5h under the condition of 3MPa, promptly obtains described catalyst.
The using method of above-mentioned catalyst comprises:
(1) in reactor, add the methyl acetate of methyl alcohol, 9 weight portions of 57 weight portions and 0.23 weight portion catalyst, 4 weight portions water and stir;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 185 ℃, is to carry out carbonylation under the 3.5MPa condition at pressure, and the reaction time is 15min;
The dividing potential drop of wherein said hydrogen is 0.075MPa.
Present embodiment also comprises the step of using air in the carbon monoxide replacement reaction kettle between described step (1) and step (2), in described displacement step, use the interior air of carbon monoxide replacement reaction kettle 3 times.
As selectable embodiment, in the above-described embodiments, also can use the chloride of described rhodium and M, bromide band to react for its iodide.
Experimental example 1
In order to prove that catalyst of the present invention has substantial technique effect, below in conjunction with the result of actual experiment to being further detailed below in conjunction with the technique effect of Comparative Examples to catalyst of the present invention.
This experimental example is set after described reaction is carried out 15 minutes, measures the catalytic efficiency of described catalytic reaction, and it is as shown in the table to obtain the result:
Experimental example 2
In order to verify the molecular formula in the foregoing description, the present invention adopts the method for nuclear magnetic resonance that the catalyst that generates is characterized, and it is AvanceIII that the present invention adopts its model of NMR of Bruker brand, and concrete technical indicator is as follows;
Magnetic field intensity: 9.39T, proton resonance frequency: 400MHz; Two irradiation passages, two probes (5mm BBFO broadband and PADUL H-C double-core probe).
5mm BBFO broadband probe: multinuclear (31P-15N); Extent of alternating temperature :-150 ~+180 ℃; 1H resolution ratio ﹤ 0.3Hz, sensitivity (s/n) ﹥ 300:1; 13C resolution ratio ﹤ 0.2Hz, sensitivity (s/n) ﹥ 180:1; Z direction gradient unit.
5mm PADUL H-C double-core probe: 1H resolution ratio ﹤ 0.2Hz, sensitivity (s/n) ﹥ 290:1; 13C resolution ratio ﹤ 0.1Hz, sensitivity (s/n) ﹥ 178:1; Z direction gradient unit.
Requirement to sample during experiment is:
When test purpose was the authenticating compound structure, sample was pure one-component, and dry, no ferromagnetism pollutant or filter paper bits; Sample must have fine solubility in organic solvent or water.
Except the method for above-mentioned nuclear magnetic resonance, also can be by the XRD(X x ray diffraction), XPS(X ray electron spectrum) characterize.
Comparative Examples
In order to prove that catalyst of the present invention has substantial technique effect than catalyst of the prior art, below will be by comparing with Comparative Examples, the technique effect of catalyst of the present invention is further detailed.
In described Comparative Examples, in described autoclave, add methyl alcohol, the methyl acetate of 9 weight portions and the water of 4 weight portions of 53 weight portions earlier; Again autoclave is heated to 185 ℃ stirring under (1000 rev/mins), when system after stablizing 30 minutes under the self-generated pressure, under carbon monoxide pressure, in described autoclave, add RuI earlier
3, add the rhodium chloride solution that is dissolved in the acetate after 30 seconds again, as required feed carbon monoxide from gas pressurizer to autoclave by liquid feeding device and make the pressure of autoclave maintain 2.7MPa substantially.
Treat above-mentioned reaction carry out after 15 minutes measuring described acetic acid yield be 40% from The above results as can be known the acetic acid yield 40% the Comparative Examples to be lower than the acetic acid yield of catalyst of the present invention.Therefore catalyst of the present invention has substantial technique effect than catalyst of the prior art.
Obviously, the foregoing description only is for example clearly is described, and is not the qualification to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here need not also can't give to all embodiments exhaustive, and the conspicuous variation of being extended out thus or the change still be among the protection domain of the invention.
Claims (8)
1. a catalyst that is used for low water acetic acid synthesis technique is characterized in that described catalyst is a bimetal complexes, and described bimetal complexes is
H[RhM(CO)
4(N)
4]，
Wherein, M is a kind of among Ir, the Co; N is a kind of among cl, Br, the I.
2. catalyst according to claim 1 is characterized in that described bimetal complexes is
H[RhIr?(CO)
4I
4]。
3. the using method of claim 1 or 2 described catalyst comprises the steps:
(1) in reactor, add the methyl acetate of methyl alcohol, 8-10 weight portion of 52-63 weight portion and 0.2-0.25 weight portion catalyst, 3-5 weight portion water and stir;
(2) feeding hydrogen and carbon monoxide in described reactor, the temperature in the described autoclave is heated to 160-190 ℃, is to carry out carbonylation under the 3.0-3.5MPa condition at pressure.
4. the using method of catalyst according to claim 3 is characterized in that, also adds at least a in the alkali halide of the alkyl halide of 14-17 weight portion and 12-15 weight portion in described step (1) in described reactor.
5. according to the using method of the described catalyst of claim 4, it is characterized in that described alkyl halide is an iodomethane, alkali halide is a lithium iodide.
6. according to the using method of claim 3 or 4 described catalyst, it is characterized in that the reaction time in the described step (2) is 10-15min, reaction temperature is 180-185 ℃.
7. bimetal complexes H[RhM (CO)
4(N)
4] as the purposes of the catalyst of low water acetic acid synthesis technique, wherein, M is a kind of among Ir, the Co; N is a kind of among cl, Br, the I.
8. bimetal complexes H[RhIr (CO)
4I
4] as the purposes of the catalyst of low water acetic acid synthesis technique.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129690A (en) * | 1995-02-21 | 1996-08-28 | 英国石油化学品有限公司 | Process for the carbonylation of an alcohol |
| CN1986053A (en) * | 2006-12-28 | 2007-06-27 | 山东华鲁恒升集团德化设计研究有限公司 | Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process |
| CN101182340A (en) * | 2007-12-20 | 2008-05-21 | 中国科学院化学研究所 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
-
2011
- 2011-06-15 CN CN 201110159875 patent/CN102266795B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1129690A (en) * | 1995-02-21 | 1996-08-28 | 英国石油化学品有限公司 | Process for the carbonylation of an alcohol |
| CN1986053A (en) * | 2006-12-28 | 2007-06-27 | 山东华鲁恒升集团德化设计研究有限公司 | Liquid phase reaction process of methyl acetate and CO to produce acetic anhydride and its catalyst preparing process |
| CN101182340A (en) * | 2007-12-20 | 2008-05-21 | 中国科学院化学研究所 | Method for producing acetic acid by carbonylation of methanol as well as special catalyst and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 张抒峰等: "螯合型羰基铑配合物催化甲醇羰基化反应的机理研究", 《化学学报》, vol. 67, no. 01, 31 December 2009 (2009-12-31), pages 59 - 64 * |
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