CN1309114A - Process for synthesizing acetic acid in heterogeneous catalysis system - Google Patents
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- CN1309114A CN1309114A CN00126596A CN00126596A CN1309114A CN 1309114 A CN1309114 A CN 1309114A CN 00126596 A CN00126596 A CN 00126596A CN 00126596 A CN00126596 A CN 00126596A CN 1309114 A CN1309114 A CN 1309114A
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- heterogeneous catalysis
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Abstract
A process for synthesizing acetic acid from methane (CH4) and CO2 in heterogeneous catalysis system features that CH4 and CO2 (or CO2/H2) are alteratively fed. Its advantages are simple process, low cost, less exhaust of CO2 and no secondary pollution.
Description
The present invention is a kind of new method of synthesis of acetic acid, belongs to organic chemical industry's category.Specifically be a kind of method that in heterogeneous catalysis system, prepares acetate.It is characterized in that with CH
4And CO
2Be raw material, on solid heterogeneous catalyst, neither need through CH
4With CO
2The process of high temperature preparing synthetic gas by reforming, do not need through methyl alcohol yet and use expensive oxygen, but adopt CH
4And CO
2Or CH
4And CO
2/ H
2The mode of alternate feed promptly at first makes CH
4In the catalyst surface activation, and then and CO
2Or CO
2/ H
2Reaction is carried out, so repeatedly finally by CH
4And CO
2Direct synthesis of acetic acid (
)。Owing to H is arranged in the first step
2Emit, H is arranged in second step
2Benefit is gone into, and therefore can break through the thermodynamical restriction of total reaction, directly by methane and carbonic acid gas synthesis of acetic acid.This technology is simple, and spending is saved; Can reduce Carbon emission, alleviate Greenhouse effect; Also avoided simultaneously danger and secondary pollution in the existing technology, using value and economic benefit are considerable.
Acetate claims acetic acid again, is important Organic Chemicals, can produce vinylacetate, diacetyl oxide, cellulose acetate, multiple synthetic plastics, synthon, esters solvent and many Organic Chemicals from the it.Acetate is widely used in foodstuffs industry, printing and dyeing industry, pharmaceutical industry, is the organic acid of industrial output maximum, the status of similar sulfuric acid in inorganic industry, its status in organic chemistry.
The initial industrial preparation of acetate is to adopt fermentation method, then mainly adopts methanol carbonylation modern age.Though by CH
4Or the technology that other alkane prepares acetate indirectly or directly exists, but up to now, on solid heterogeneous catalyst, adopts two-step reaction process with CH
4And CO
2The technology that directly changes into acetate is not seen any report as yet.
United States Patent (USP) has been described a kind of by CH No. 5659077
4Produce the indirect method of acetate.This method is with CH
4Be raw material, with O
2, air or other can make CH
4The gas that partial oxidation takes place is oxygenant, and reaction is controlled in the quite high temperature and pressure scope, makes CH earlier
4Partial oxidation generates methyl alcohol, CO, CO
2, CH
4And mixture of steam, adding some methyl alcohol again after removing water vapour, the methyl alcohol that initiate methyl alcohol and partial oxidation generate carries out oxonation with CO together and generates acetate and/or methyl acetate under quite high temperature and pressure.Unnecessary CH
4, CO
2Can be recycled with methyl alcohol, acetate and methyl acetate reclaim as product.The essence of this process is CH
4At first generated methyl alcohol by partial oxidation, then methyl alcohol again carbonylation generate acetate.Be that with difference of the present invention this method needs the O of consume expensive
2, and having generated independently intermediate product methyl alcohol, methyl alcohol must be with generating final product acetate behind traditional method carbonylation
United States Patent (USP) has been described another kind of method with two above carboxylic acids of carbon of lower carbon number hydrocarbons direct oxidation carbonylation generation for No. 5510525, and this method had both needed to use CO, also needed to use O
2Make reagent.Being reflected in the homogeneous phase metal-salt catalyst system and carrying out, is auxiliary agent with the halogen ion.Removing needs to use CO and O
2Outside making reagent and the present invention being different, be that the catalyst system of this technology is a homogeneous, and makes auxiliary agent with the halogen ion with another essential distinction of the present invention.
Another is about with hydro carbons, especially C
1-C
6The method that the direct Catalytic Oxygen of hydrocarbon and mononuclear aromatics changes into carboxylic acid is with H
2O
2For oxygenant (United States Patent (USP) 5399922), utilize soluble metal complex compound or metal-salt to be catalyzer, temperature of reaction is between 70～200 ℃.Identical with patent 5510525, reaction still needs CO and oxygenant (H
2O
2) participate in.And acetate is only generated by ethane in this method, CH
4Only generate formic acid, that is to say the generation that does not contain the C-C key.And the present invention is with CH
4And CO
2Change into acetate (CH
3COOH), contain the generation of C-C key.
No. the 9605163rd, world patent that close with the present invention is and No. 9959952.The two has all described a kind of on solid heterogeneous catalyst, does not need the pilot process through generation synthetic gas or methyl alcohol, and by CH
4With CO
2Directly carboxylation generates the method for acetate.Different with the present invention is that the two all adopts conventional feeding manner, i.e. CH
4, CO
2The single step reaction of parallel feeding.Owing to be subjected to thermodynamical restriction, in fact can not produce acetate effectively according to the method for describing on this two patent specification.Therefore, all do not provide the example that generates free acetic acid in two patents.And the first CH that the present invention adopts
4Activation, back CO
2The substep feeding manner of reaction is owing to have H in the first step
2Release, and H arranged in second step
2Replenish, can overcome thermodynamical restriction, obtain tangible acetic acid product.
To sum up, patent 5659077 and 5510525 is not all considered CO
2Utilization, and need O
2Participation; Patent 551052 and 5399922 all is a homogeneous system, does not contain the generation of C-C simultaneously among the latter reaction; Patent 9605163 and 9959952 all is the disadvantageous process of thermodynamics; They all are essentially different with the present invention.
Existing business-likely produce the lipid acid operational path by alkane and comprise a series of independently processes, each process all needs to carry out under oneself specific reactor and specific catalytic condition:
Ni etc. (1)
Cu etc. (2)
Rh etc. (3)
In the first step, CH
4Be converted to synthetic gas on nickel catalyzator, this synthetic gas also can be got with traditional method gasification by coal or other carbonaceous material.Synthetic gas also can be used for production number of chemical product, comprising the methyl alcohol that generates in second step.At last, CH in the 3rd step
3OH produces acetate with the CO reaction on homogeneous phase Rh catalyzer.At present, 98% acetate is all produced by this three-step approach on the market, wherein expensive more than 60% of acetic acid production total cost that accounts for of synthetic gas production process.Clearly, improve the economic benefit of acetic acid production cost, it is the most key saving the gas making process.
In addition, in the 3rd step, the reaction needed of methyl alcohol and CO is used the solubility Rh catalyzer of costliness, and to be aided with iodide be auxiliary agent, so its economic benefit depends on the recycling of catalyzer.Because the costliness of Rh, iodide (are generally CH
3I) toxic and corrodibility, these have all increased the investment of production process, thereby total cost is improved.
In theory, methyl alcohol (is generally Al at heterogeneous catalyzer in vapor phase
2O
3, SiO
2Or the RhCl that supports of the mixture of the two
3, Ni also has katalysis to this reaction, but is easy to inactivation) on also can become acetate by carbonylation, this reaction has obtained broad research in laboratory scope.But the still untapped catalyzer that goes out to have industrial value up to now.Even develop such catalyzer, this technology is still indirect, because it needs the preparation process of synthetic gas and the generative process of methyl alcohol.Therefore, seek a kind of CH of heterogeneous catalysis
4, CO
2The method that directly changes into acetate necessitates.
Be necessary to mention the research work that some are relevant here.The most important thing is that wherein M.Kurioka etc. once used Pd (OAc)
2/ Cu (OAc)
2Be catalyzer, at K
2S
2O
8/ CF
380 ℃ of following homogeneous catalysis CH4-CO in the COOH system
2Synthesized acetate, this is CH
4-CO
2Directly the first of synthesis of acetic acid is reported (1995).Yet because this reaction is a homogeneous, the acetate of generation dissolves in CF
3Among the COOH, thereby increase isolating expense, and increased the complicacy of whole process of production.In addition, this reaction times of 20 to 40 hours of process need, this make this technology commercial be unpractical.Simultaneously, it is a homogeneous, is different from and heterogeneous catalysis process of the present invention, and is also different with the present invention on feeding manner.
Other relates to CH
4CO and/or O have all been used in the research (Nishiguchi et al., 1992, Kurioka et al., 1995, Lin et al., 1997, Lin and Sen, 1994 and Senand Lin, 1996) that is converted into acetate
2, and in homogeneous system, carry out, they all have the difference of essence with the present invention.
In a word, before the present invention, on heterogeneous catalyst, it is unfavorable to adopt two-step reaction to overcome the thermodynamics of total reaction, by CH
4And CO
2The method of synthesis of acetic acid is not appeared in the newspapers expeditiously.
The object of the present invention is to provide the method for synthesis of acetic acid in a kind of heterogeneous catalysis system, it is characterized in that be a kind of be raw material with methane and carbonic acid gas, it is unfavorable to adopt the process of two substeps to overcome the thermodynamics of total reaction, and then the direct method of synthesis of acetic acid.It is to carry out in nonhomogeneous system, is included on the solid heterogeneous catalyst, adopts the mode synthesis of acetic acid with methane, carbonic acid gas alternate feed.Its reaction process is carried out in two steps, and the first step as catalyzer, feeds methane with transition metal, makes it generate the carbide surface kind in the catalyst surface activation; Logical carbon dioxide gas of second step makes itself and the carbide surface kind reaction that generates generate acetate.The raw material of the first step reaction is a methane gas, and it comprises that Sweet natural gas, coal-seam gas and other are rich in the gas of methane, or the gas mixture of methane and rare gas element; The raw material of second step reaction is a carbon dioxide gas, and it comprises Natural carbon dioxide gas, various burning and exhausting gas, synthetic-ammonia transformation gas, fermentation gas, coal and other carbonaceous material gasification gas, or the gas mixture of carbonic acid gas and hydrogen.
The used catalyzer of the present invention comes from the transition metal of I B and VII family, and top-priority in the metal of indication is metals such as Cu, Co, Ni, Pd, Rh, Pt, Ru, Re.Catalyzer is single, double or multi-metal system, is simple substance, compound type, mechanically mixing or is supported on inert, tart or the basic supports.Its carrier comes from oxide compound, molecular sieve and the activated carbon etc. of various forms of aluminum oxide, silicon-dioxide, rare earth oxide, alkaline-earth metal and III B～VII B family.The reactive metal charge capacity is 0.1%～30%, and auxiliary agent is basic metal, alkaline-earth metal, rare earth metal, zinc, IV B～VII B family element and their compound.
Temperature of reaction of the present invention is at 100～600 ℃, and reaction pressure is at normal pressure～20Mpa, and the temperature and pressure of two-step reaction can carry out under identical or different condition.The first step reaction raw materials adopts pure CH
4Gas or use rare gas element, for example Ar, N
2Deng the methane gas of dilution, preferably Xi Shi methane gas.Gas flow rate is controlled at every liter of catalyzer per hour in 500～5000 liters the scope.Aeration time maintains in 0.01～30min, preferably 0.5～10min.The raw material of second step reaction adopts pure CO
2Gas or CO
2/ H
2Gas mixture, CO preferably
2/ H
2Gas mixture, preferred ratio is 0.5～3, flow velocity can be controlled in the scope identical with the first step, aeration time is 0.01～60min, preferably 0.5～20min.
Another notable feature of the inventive method is that also it also is applicable to other low-carbon (LC) carboxylic acid and C
2+Synthesizing of chemical such as hydrocarbon, methylene acetone or aldehyde, methyltetrahydrofuran and pentamethylene acetylene.
The present invention is applicable to the various CH of containing
4Or CO
2Source of the gas, for example Sweet natural gas (comprises natural CO
2Gas), stack gas, fermentation gas and the synthetic-ammonia transformation gas etc. in coal-seam gas, refinery gas, fuel-burning power plant are raw material, synthetic high value added product acetate and other oxygenatedchemicals, the product net added value is more than 10 times.The invention has the advantages that:
(1) do not need expensive and the huge CH that consumes energy
4Reforming step, expensive more than 60% of existing acetic acid production process total cost that accounts at least of this step.
(2) the employed Rh base of carbonylation of methanol homogeneous catalyst is replaced by the solid heterogeneous catalyzer, no longer needs to generate the methyl alcohol intermediate and carries out carbonylation of methanol, production technique and product separation is oversimplified, thereby saved spending.
(3) carbonylation of methanol need use poisonous, be corrosive and the iodine compound that contains of potentially dangerous (is generally CH
3I) make auxiliary agent, and the present invention can avoid this point.
(4) the present invention is that greenhouse gases with two kinds of maximums are raw material, and is environmentally friendly.
What (5) the present invention used is heterogeneous catalyst, can adjust the streams flux significantly in Industrial processes, separates simply, can save cost relatively.
(6) the present invention utilizes resourceful CH
4With CO
2Effect can reduce CO on a large scale
2To atmospheric discharging, alleviate Greenhouse effect.
(7) with respect to existing or at process of grinding and existing patent report, another environmental advantage of the present invention is to have reduced danger and secondary pollution.
(8) technology of the present invention can overcome the thermodynamical restriction of total reaction.Its reaction process can be represented by following two equations:
(low dividing potential drop) (x=0～3) (1)
(2) total reaction:
(3) therefore, the Δ G=of total reaction
), i.e. Δ G=Δ G
1+ (4-x) RTln (H
2(low dividing potential drop)/H
2(high partial pressures)).Obviously, owing to H in the two-step reaction
2The difference of dividing potential drop makes the Δ G of total reaction reduce greatly, and Δ G can be negative value under proper condition, because after the first step reaction, remains in the H of catalyst surface
2Dividing potential drop is generally 10
-4Bar (M.Belgued, 1996).
(9) technology of the present invention can (be carried out under the normal pressure～20Mpa) at low relatively temperature (100～600 ℃) and pressure.
(10) the present invention goes back by-product C
2The utmost points such as hydrocarbon, formic acid, methylene acetone or aldehyde, methyltetrahydrofuran and pentamethylene acetylene have the chemical of using value.
Embodiment 12.0g places reactor by Cu-Co (Cu/Co=3) catalyzer of coprecipitation method preparation, uses 10%H
2/ N
2(or Ar) gas mixture reduces in heating schedule, then at N
2Drop to temperature of reaction in (or Ar) air-flow.Under 3MPa, with the logical 20%CH of 50ml/min
4H
2/ N
2(or Ar) 5min is then with the logical CO of 75ml/min
2/ H
2(1:1) 10min, the two hockets and finishes until reaction.In the time of 250 ℃, acetic acid yield 0.020g/gcat.h; In the time of 300 ℃, acetic acid yield 0.023g/gcat.h.
Embodiment 22.0g by the Cu-Co-Zr of coprecipitation method preparation (Cu/Co=5,10%ZrOCl) catalyzer places reactor, with top identical condition under react.In the time of 250 ℃, acetic acid yield 0.037g/gcat.h, formic acid yield 0.024g/gcat.h; In the time of 300 ℃, acetic acid yield 0.048g/gcat.h, formic acid yield 0.053g/gcat.h.
Embodiment 30.5g is by the Pd/SiO of immersion process for preparing
2(containing Pd1%), catalyzer placed reactor, with top identical condition under react.In the time of 250 ℃, acetic acid yield 0.096g/gcat.h, formic acid yield 0.025g/gcat.h; In the time of 300 ℃, acetic acid yield 0.070g/gcat.h.
Embodiment 40.5g is by the ultra-fine SiO of the Pd/ of immersion process for preparing
2(containing Pd1%), catalyzer placed reactor, with top identical condition under react.In the time of 250 ℃, acetic acid yield 0.135g/gcat.h, formic acid yield 0.040g/gcat.h; In the time of 300 ℃, acetic acid yield 0.137g/gcat.h.
Embodiment 52.2g is by the Pd/TiO of immersion process for preparing
2(containing Pd2%), catalyzer placed reactor, with top identical condition under react.In the time of 250 ℃, acetic acid yield 0.016g/gcat.h, formic acid yield 0.020g/gcat.h; In the time of 300 ℃, acetic acid yield 0.037g/gcat.h, formic acid yield 0.026g/gcat.h.
Embodiment 61.8g places reactor by Pd/ molecular sieve (the containing Pd2%) catalyzer of immersion process for preparing, with top identical condition under react.In the time of 250 ℃, acetic acid yield 0.029g/gcat.h, formic acid yield 0.032g/gcat.h; In the time of 300 ℃, acetic acid yield 0.025g/gcat.h, formic acid yield 0.031g/gcat.h.
Claims (8)
1. the method for synthesis of acetic acid in the heterogeneous catalysis system, it is characterized in that be a kind of be raw material with methane and carbonic acid gas, it is unfavorable to adopt the process of two substeps to overcome the thermodynamics of total reaction, and then the method for direct synthesis of acetic acid, it is to carry out in nonhomogeneous system, be included on the heterogeneous catalyst, employing is with the mode synthesis of acetic acid of methane, carbonic acid gas alternate feed, its reaction process is carried out in two steps, the first step with transition metal as catalyzer, feed methane, make it generate the carbide surface kind in the catalyst surface activation; Logical carbon dioxide gas of second step makes itself and the carbide surface kind reaction that generates generate acetate.
2. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1, it is characterized in that the first step reaction raw materials is a methane gas, it comprises that Sweet natural gas, coal-seam gas and other are rich in the gas of methane, or the gas mixture of methane and rare gas element.
3. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1, it is characterized in that the second step reaction raw materials is a carbon dioxide gas, it comprises Natural carbon dioxide gas, various burning and exhausting gas, synthetic-ammonia transformation gas, fermentation gas, coal or other carbonaceous material gasification gas, or the gas mixture of carbonic acid gas and hydrogen.
4. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1, it is characterized in that described catalyzer comes from the transition metal of I B and VIII family, top-priority in the metal of indication is metals such as Cu, Co, Ni, Pd, Rh, Pt, Ru, Re.
5. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1, it is characterized in that described catalyzer is single, double or multi-metal system, be simple substance, compound type or be supported on inert, tart or the basic supports.
6. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 5, it is characterized in that described support of the catalyst comes from oxide compound, molecular sieve and the activated carbon etc. of various forms of aluminum oxide, silicon-dioxide, rare earth oxide, alkaline-earth metal and III B～VII B family.The reactive metal charge capacity is 0.1%～30%, and auxiliary agent is basic metal, alkaline-earth metal, rare earth metal, zinc, VII B～VII B family element and their compound.
7. the method according to synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1 is characterized in that, temperature of reaction is at 100～600 ℃, and reaction pressure is at normal pressure～20Mpa, and the two-step reaction temperature and pressure can carry out under identical or different condition.
8. according to the method for synthesis of acetic acid in the described a kind of heterogeneous catalysis system of claim 1, it is characterized in that this method also is applicable to other low-carbon (LC) carboxylic acid and C
2Synthesizing of chemical such as+hydrocarbon, methylene acetone or aldehyde, methyltetrahydrofuran and pentamethylene acetylene.
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|---|---|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016113399A (en) * | 2014-12-15 | 2016-06-23 | 旭化成ケミカルズ株式会社 | Method for producing organic acid |
| JP2016155775A (en) * | 2015-02-24 | 2016-09-01 | 旭化成株式会社 | Organic acid production method |
| CN111675609A (en) * | 2020-06-10 | 2020-09-18 | 大连海事大学 | Low-temperature plasma and supported copper-based catalyst synergetic one-step CH conversion4And CO2Method for preparing acetic acid |
| CN111672543A (en) * | 2020-06-10 | 2020-09-18 | 大连海事大学 | Low-temperature plasma and modified molecular sieve catalyst synergetic one-step CH conversion4And CO2Method for preparing acetic acid |
| CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
| CN115806479A (en) * | 2022-11-18 | 2023-03-17 | 南京工业大学 | Conversion of CH 4 And CO 2 Method for directly preparing acetic acid |
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| CN101357313B (en) * | 2008-05-21 | 2011-12-07 | 太原理工大学 | Serialization two-step reaction technique and device thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1996005163A1 (en) * | 1994-08-12 | 1996-02-22 | Hoechst Aktiengesellschaft | Method of manufacturing acetic acid |
| WO1999059952A1 (en) * | 1998-05-15 | 1999-11-25 | Research Triangle Institute | Method of preparing alkyl carboxylic acids by carboxylation of lower alkanes methane |
-
2000
- 2000-09-30 CN CN00126596A patent/CN1103330C/en not_active Expired - Fee Related
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2016113399A (en) * | 2014-12-15 | 2016-06-23 | 旭化成ケミカルズ株式会社 | Method for producing organic acid |
| JP2016155775A (en) * | 2015-02-24 | 2016-09-01 | 旭化成株式会社 | Organic acid production method |
| CN111675609A (en) * | 2020-06-10 | 2020-09-18 | 大连海事大学 | Low-temperature plasma and supported copper-based catalyst synergetic one-step CH conversion4And CO2Method for preparing acetic acid |
| CN111672543A (en) * | 2020-06-10 | 2020-09-18 | 大连海事大学 | Low-temperature plasma and modified molecular sieve catalyst synergetic one-step CH conversion4And CO2Method for preparing acetic acid |
| CN111675609B (en) * | 2020-06-10 | 2023-03-24 | 大连海事大学 | Low-temperature plasma and supported copper-based catalyst synergetic one-step CH conversion 4 And CO 2 Method for preparing acetic acid |
| CN115069285A (en) * | 2022-06-14 | 2022-09-20 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane, and preparation method and application thereof |
| CN115069285B (en) * | 2022-06-14 | 2024-01-16 | 太原理工大学 | Photo-thermal catalyst for directly preparing methanol from methane and preparation method and application thereof |
| CN115806479A (en) * | 2022-11-18 | 2023-03-17 | 南京工业大学 | Conversion of CH 4 And CO 2 Method for directly preparing acetic acid |
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| CN1103330C (en) | 2003-03-19 |
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