CN114515605A - Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation - Google Patents
Preparation and application of ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation Download PDFInfo
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- CN114515605A CN114515605A CN202210140810.1A CN202210140810A CN114515605A CN 114515605 A CN114515605 A CN 114515605A CN 202210140810 A CN202210140810 A CN 202210140810A CN 114515605 A CN114515605 A CN 114515605A
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- ruthenium
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- acetic acid
- palladium
- carbonylation
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 151
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 239000003054 catalyst Substances 0.000 title claims abstract description 113
- WFDIJRYMOXRFFG-UHFFFAOYSA-N acetic acid anhydride Natural products CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 79
- 238000005810 carbonylation reaction Methods 0.000 title claims abstract description 27
- 230000006315 carbonylation Effects 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000002194 synthesizing effect Effects 0.000 title claims description 10
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims abstract description 97
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 96
- 230000003197 catalytic effect Effects 0.000 claims abstract description 28
- 239000003446 ligand Substances 0.000 claims abstract description 22
- 230000000694 effects Effects 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 14
- 239000002184 metal Substances 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 8
- -1 palladium ions Chemical class 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 115
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 93
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 51
- 238000003756 stirring Methods 0.000 claims description 35
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 25
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 25
- 239000000178 monomer Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 229920000642 polymer Polymers 0.000 claims description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 18
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 17
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 17
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 239000003431 cross linking reagent Substances 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 239000002244 precipitate Substances 0.000 claims description 11
- 239000000047 product Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000001556 precipitation Methods 0.000 claims description 10
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 8
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 7
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- VMDTXBZDEOAFQF-UHFFFAOYSA-N formaldehyde;ruthenium Chemical compound [Ru].O=C VMDTXBZDEOAFQF-UHFFFAOYSA-N 0.000 claims description 5
- 239000003999 initiator Substances 0.000 claims description 5
- 239000012046 mixed solvent Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 4
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 4
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical group CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 2
- SUPCQIBBMFXVTL-UHFFFAOYSA-N ethyl 2-methylprop-2-enoate Chemical compound CCOC(=O)C(C)=C SUPCQIBBMFXVTL-UHFFFAOYSA-N 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 claims description 2
- 238000006116 polymerization reaction Methods 0.000 claims description 2
- 230000009977 dual effect Effects 0.000 claims 2
- MTJGVAJYTOXFJH-UHFFFAOYSA-N 3-aminonaphthalene-1,5-disulfonic acid Chemical compound C1=CC=C(S(O)(=O)=O)C2=CC(N)=CC(S(O)(=O)=O)=C21 MTJGVAJYTOXFJH-UHFFFAOYSA-N 0.000 claims 1
- 239000012752 auxiliary agent Substances 0.000 claims 1
- 239000010948 rhodium Substances 0.000 abstract description 25
- 229910052703 rhodium Inorganic materials 0.000 abstract description 23
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract description 23
- 230000009471 action Effects 0.000 abstract description 2
- 229920001477 hydrophilic polymer Polymers 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000000034 method Methods 0.000 description 22
- 230000008569 process Effects 0.000 description 19
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 17
- 238000006555 catalytic reaction Methods 0.000 description 10
- 238000001704 evaporation Methods 0.000 description 9
- 230000008020 evaporation Effects 0.000 description 9
- 238000010998 test method Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 5
- 230000006872 improvement Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000011160 research Methods 0.000 description 5
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 description 4
- 238000004088 simulation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000012327 Ruthenium complex Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229920013683 Celanese Polymers 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- NQZFAUXPNWSLBI-UHFFFAOYSA-N carbon monoxide;ruthenium Chemical group [Ru].[Ru].[Ru].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] NQZFAUXPNWSLBI-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- UZUODNWWWUQRIR-UHFFFAOYSA-L disodium;3-aminonaphthalene-1,5-disulfonate Chemical compound [Na+].[Na+].C1=CC=C(S([O-])(=O)=O)C2=CC(N)=CC(S([O-])(=O)=O)=C21 UZUODNWWWUQRIR-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002496 iodine Chemical class 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- KXAHUXSHRWNTOD-UHFFFAOYSA-K rhodium(3+);triiodide Chemical compound [Rh+3].[I-].[I-].[I-] KXAHUXSHRWNTOD-UHFFFAOYSA-K 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/10—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide
- C07C51/12—Preparation of carboxylic acids or their salts, halides or anhydrides by reaction with carbon monoxide on an oxygen-containing group in organic compounds, e.g. alcohols
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention belongs to the field of synthesis of acetic acid and acetic anhydride by carbonylation, and discloses preparation and application of a ruthenium-palladium double-active-center catalyst for synthesis of acetic acid or acetic anhydride by carbonylation. The invention prepares a micro-crosslinked hydrophilic polymer as a metal ruthenium ligand, simultaneously introduces palladium ions as a cocatalyst, and the system expands to a cage-shaped structure in reaction liquid. Compared with the conventional rhodium catalyst for preparing acetic acid by carbonylation, the metal ruthenium has low price, can effectively reduce the catalyst cost, and has the characteristics of low cost and long service life due to good stability and high selectivity of a catalytic system under the comprehensive action of the system although the activity of the catalytic system is lower than that of a rhodium-based catalyst system.
Description
Technical Field
The invention belongs to the field of synthesis of acetic acid and acetic anhydride by carbonylation, and particularly relates to preparation and application of a ruthenium-palladium double-active-center catalyst for synthesis of acetic acid or acetic anhydride by carbonylation.
Background
The invention of Paulik et al (US3769329) of Monsanto company in the early 70 th century is that methanol and carbon monoxide are carbonylated under the action of homogeneous rhodium catalyst to prepare acetic acid, and this invention opens up a new important technological route for the oxo synthesis of methanol. On this basis, the subsequent work by Halcon (BE819455) Ealtman, Ajinamoto (Japan Kokai50/30,820), Showa Denko (Japan Kokai50/47,922), BP (B.Von Schlotheim, chem.Industrie1994, 9/89.80) and Hoechst (DE 24560965) has made a breakthrough in the study of the same [ Rh (CO)2I2] -negative ion structure for the carbonylation of methyl acetate to produce acetic anhydride.
With continued improvement and sophistication, the use of homogeneous rhodium as a catalyst for the carbonylation of methanol and methyl acetate has become the world's most important process route for the production of acetic acid and acetic anhydride. The catalyst has high activity and good selectivity, and is an obvious advantage of the catalyst; however, the instability of such catalysts, which tend to form precipitates of trivalent rhodium, especially at higher temperatures which favor the reaction, or even when the partial carbon monoxide pressure in the flash-separated part is reduced, is well recognized. The design of catalyst structures and the improvement of reaction systems have been the subject of intense research for a long time, and a large number of research papers and patent patents are published every year.
The most successful example is hoechst celanese, which developed a low water content oxo process in the beginning of the 80 s of the 20 th century by improving the Monsanto process, and which is characterized by adding a relatively high content of inorganic iodine salt to the reaction system, and the technical advantages of the process are very obvious, and the patent application is US5001259 and EP 055618. Lithium iodide is also the most important catalyst promoter in the reaction system for preparing acetic anhydride by carbonylation of methyl acetate. Joseph r, zoeller etalcatal, today, 1992, 13.73-91 et al reported the acetic anhydride catalytic system of Eastman corporation, discussed the role of lithium iodide in the reaction, and proposed the reaction mechanism of methyl acetate carbonylation catalyzed by the Li-Rh co-catalytic system.
In the process of the industrial development of acetic acid in China, how to improve the stability of the rhodium catalyst is a hotspot of constant research. In the process, many enterprises try to introduce a ruthenium compound or a ruthenium carbonyl compound as a reaction promoter or stabilizer (publication numbers CN103012103A, CN1656053B, and CN108097319A) into a catalytic system, and by adding a ruthenium complex, the partial pressure of CO in the reaction system can be controlled, and dissociation of lithium polyiodide is promoted, so that RhI can be inhibited to some extent3And the activity and stability of the catalytic system are improved.
These efforts have all effectively improved the catalyst life and reduced the reaction cost, making acetic acid and acetic anhydride important chemical products worldwide. However, in recent years, particularly after 2020, the price of noble metals has risen, particularly the price of rhodium metal has risen by nearly 10 times and exceeds 4000 yuan/g, and as a main catalytic system for domestic acetic acid production, the expensive price of rhodium catalysts is a weight that cannot be borne by acetic anhydride production enterprises. The search for low-cost catalytic systems becomes a hotspot of various enterprise researches.
In view of this, the somep group has also performed many studies as an important domestic acetic acid production enterprise. In the process, the ruthenium complex not only has the function of improving the stability of a catalytic system, but also has certain catalytic activity. Meanwhile, it is well known that palladium ions have good catalytic activity in carbonylation reactions, but are easily inactivated due to carbon monoxide reduction, and further research is needed to meet production requirements.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method and application of a ruthenium-palladium double-activity center catalyst for synthesizing acetic acid or acetic anhydride by carbonylation, wherein a double-activity center cage-shaped catalyst is formed by adopting metal ruthenium and palladium and a polymer ligand, a large amount of ruthenium is introduced into a palladium catalytic system to effectively inhibit the reduction inactivation of palladium and maintain the high activity of the catalyst, the price of the metal ruthenium is relatively stable and better in economy, the price of the palladium is lower than that of the rhodium, and the expensive rhodium catalyst is replaced, so that the economic carbonylation catalyst is provided, and the catalytic system is applied to synthesizing the acetic acid or the acetic anhydride by carbonylation.
In order to solve the problems of the prior art, the invention adopts the technical scheme that:
preparing a ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride by carbonylation, wherein a micro-crosslinked cage-shaped polymer is taken as a ligand, metal ruthenium is taken as an active center, metal palladium is taken as a cocatalyst, and lithium ions are introduced as a catalytic assistant to form a cage-shaped catalytic system; the caged polymer is a ligand, and is a copolymer of 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate monomers which are lightly crosslinked by a crosslinking agent; the light crosslinking means that the crosslinking agent is 0.2-0.8% of the total molar amount of the monomers; the preparation method comprises the following steps:
step 1, dissolving 0.03g of lithium hydroxide and 2g of polymer ligand in a 95% ethanol-water mixed solvent, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
step 2, 0.02-0.04g of PdCl2Dispersing in ethanol, adding diluted hydrochloric acid dropwise to dissolve completely, adding product A, stirring at 30 deg.C for 4 hr, cooling in ice water bath, and adding excessive diethyl etherPrecipitating, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate obtained in the step 2 in acetone, stirring in an ice bath, adding 0.55g of dodecacarbonyl triruthenium, continuously stirring for 1-2h, adding excessive diethyl ether for precipitation, and filtering to obtain the ruthenium-palladium double-activity center catalyst.
The improvement is that when the cage polymer is used as a ligand, the using amount of the 2-vinylpyridine is 15 to 30 percent of the total molar amount of the polymerized monomers, and the using amount of the acrylic acid or the methacrylic acid is 20 to 30 percent of the total molar amount of the polymerized monomers; the dosage of the acrylate monomer is 40-65% of the total molar amount of the polymerized monomer.
The improvement is that the crosslinking agent is trimethylolpropane trimethacrylate or divinylbenzene.
The acrylate monomer is one or a mixture of methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate.
The preparation method of the caged polymer serving as the ligand comprises the following steps: mixing 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate monomers with a cross-linking agent, adding the mixture into a benzene solvent, stirring, slowly adding azodiisobutyronitrile with the mole number of 1% of a polymerization monomer as an initiator, reacting at 65 ℃ for 1h, cooling the solution, precipitating and filtering by using diethyl ether, dissolving by using acetone, repeatedly dissolving and precipitating for 3-4 times, and putting the solution under vacuum and reducing the pressure to constant weight.
The application of any one of the ruthenium-palladium double-active-center catalysts in the synthesis of acetic acid by methanol carbonylation.
The improvement is that the ruthenium palladium double-active center catalyst, methanol and methyl iodide are added into a pressure kettle, carbon monoxide is introduced, the pressure of the carbon monoxide is kept at 3-4 MPa, the reaction temperature is 150-200 ℃, and acetic acid is obtained after stirring reaction, wherein the dosage of the polymer ligand multi-metal cage-shaped catalyst in a reaction system is calculated by ruthenium, and the content of ruthenium is 2000-6000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-3 mol/L.
The ruthenium palladium double-active center catalyst is applied to catalyzing carbonylation of methyl acetate to synthesize acetic anhydride.
Adding a ruthenium-palladium double-activity center catalyst, methyl acetate, methyl iodide and an acetic acid solvent into a pressure kettle, introducing carbon monoxide to replace air in the pressure kettle, continuously introducing the carbon monoxide and adding hydrogen at the reaction temperature of 165-200 ℃, stirring and reacting to obtain acetic anhydride, wherein the amount of the ruthenium-palladium double-activity center catalyst in a reaction system is calculated by ruthenium, and the content of ruthenium is 2000-5000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-2 mol/L; the pressure of the mixed gas of the carbon monoxide and the hydrogen is 3.5-4.5 MPa, wherein the volume content of the hydrogen in the mixed gas is 1-10%.
Has the advantages that:
compared with the prior art, the preparation and the application of the ruthenium-palladium double-active-center catalyst for synthesizing acetic acid or acetic anhydride by carbonylation have the following advantages:
the invention adopts metal ruthenium, palladium and polymer ligand to form double-active center cage catalyst to replace expensive rhodium catalyst, and applies the catalyst system to carbonylation synthesis of acetic acid or acetic anhydride. By preparing a micro-crosslinked hydrophilic polymer rich in nitrogen-oxygen coordination atoms as a metal ruthenium and palladium ligand, a catalyst system expands to a cage-shaped structure in a reaction solution, and because the crosslinking degree is extremely low, the solution can be communicated without obstruction inside and outside the system in the reaction process.
Ruthenium and a small amount of palladium are used as active centers, so that the cost of the catalyst is greatly reduced, and meanwhile, under the catalysis of the palladium active centers, the selectivity of a catalytic system is better, although the activity of the catalyst is slightly lower compared with that of a rhodium catalytic system, the catalytic system has the comprehensive advantages of low cost and good stability, so that a good economical choice can be provided for enterprises under the condition that the price of the existing metal rhodium is high.
Detailed Description
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
Example 1
Mixing 0.25mol of 2-vinylpyridine, 0.25mol of acrylic acid, 0.5 mol of methyl acrylate and a trace amount of cross-linking agent (the content of the cross-linking agent monomer is 0.3 percent of the total mole amount of the monomer), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1 percent of the monomer as an initiator, reacting for 1 hour at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 1.
Dissolving 0.03g of lithium hydroxide and 2g of polymer ligand 1 in a mixed solvent of ethanol and water with volume fraction of 95%, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
0.03g of PdCl2Dispersing in ethanol, dropwise adding dilute hydrochloric acid to fully dissolve, adding product A, refluxing at 30 deg.C for 4 hr, cooling in ice water bath to room temperature, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
dissolving the precipitate in acetone, stirring in an ice bath, adding 0.55g of dodecacarbonyl triruthenium, continuously stirring for 1-2h, adding excessive diethyl ether for precipitation, and filtering to obtain the ruthenium-palladium double-activity center catalyst 1.
Example 2
2.75g of ruthenium palladium double-active center catalyst 1 (the system contains about 2500ppm of ruthenium and about 190ppm of palladium), 1.1mol of methanol, 0.2mol of methyl iodide (a cocatalyst) and 0.75mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process, the reaction can be carried out without adding, but a certain amount of acetic acid is usually reserved in the continuous circulation process); after carbon monoxide is introduced, the temperature is raised to 150 ℃, the stirring speed is 500 r/min, the reaction pressure is controlled to be 3.5MPa, and the reaction time is 30 min, so that the acetic acid is obtained.
The conversion frequency of the catalyst calculated by ruthenium is 478.8/h, the conversion rate of methanol is 51.4%, the catalyst is reused for catalytic reaction by simulating a flash evaporation process in a laboratory, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 461.8/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 49.7%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.3% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.7% of ruthenium was lost, and about 4.8% of palladium was lost, the palladium content was 95.2% of the initial state.
Example 3
5.47g of ruthenium palladium double-active center catalyst 1 (the system contains about 5000ppm of ruthenium and about 380ppm of palladium), 1.1mol of methanol, 0.2mol of methyl iodide (a promoter) and 0.75mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process, the reaction can be carried out without adding, but a certain amount of acetic acid is usually reserved in the continuous circulation process); after carbon monoxide is introduced, the temperature is raised to 150 ℃, the stirring speed is 500 r/min, the reaction pressure is controlled to be 3.5MPa, and the reaction time is 30 min, so that the acetic acid is obtained.
The conversion frequency of the catalyst calculated by ruthenium is 392.0/h, the conversion rate of methanol is 84.1%, the catalyst is reused for catalytic reaction by simulating a flash evaporation process in a laboratory, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 389.1/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 84.0%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.7% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.3% of ruthenium was lost, and about 4.7% of palladium was lost, the palladium content was 95.3% of the initial state.
Comparative example 1
Adding a traditional industrial rhodium catalytic system (namely 0.51g of rhodium triiodide and 0.03g of lithium hydroxide) into a 250ml pressure kettle, wherein the content of rhodium in a solution is 1000ppm), 1.1mol of methanol, 0.2mol of methyl iodide and 0.75mol of acetic acid (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process, the reaction can be carried out without adding, but a certain amount of acetic acid is usually reserved in the continuous circulation process); after carbon monoxide is introduced, the temperature is raised to 150 ℃, the stirring speed is 500rpm, the reaction pressure is controlled to be 3.5MPa, and the reaction time is 30 minutes, so that the acetic acid is obtained.
The conversion frequency of the catalyst calculated by rhodium is 2131/h, the conversion rate of methanol is 89.7%, the catalyst is reused for catalytic reaction by simulating a flash evaporation process in a laboratory, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by rhodium is 1665/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 70.1%, and the attenuation is obvious. The rhodium content in the reaction solution after the initial and the 50 times of circulation tests by atomic absorption spectroscopy, and the rhodium content still reaches 78.3% of that in the initial state after the 50 times of circulation, and about 21.7% of rhodium is precipitated and lost.
As can be seen from example 2, example 3 and comparative example 1: the catalytic conversion frequency of ruthenium metal is far lower than that of rhodium, even if double active centers are formed with palladium, the activity is still lower, but the catalytic system is more stable, the catalytic system still has better stability under higher concentration, the insufficient catalytic activity can be improved by increasing the concentration of the catalyst, and the reaction efficiency is improved.
It can be seen from example 3 and comparative example 1 that when the ruthenium concentration is increased by a factor of 5 times that of rhodium, the methanol conversion at the same time is already close to that of the rhodium-based catalyst, and after many cycles, the catalytic system is still relatively stable. Therefore, compared with the lower price of ruthenium, the catalytic system is a novel catalytic system which is more stable and economical.
Example 4
2.15g ruthenium palladium double active center catalyst 1 (system contains about 2000ppm ruthenium, about 152ppm palladium), 1.1mol methanol, 0.022mol methyl iodide, 1.12mol acetic acid (in continuous reaction process usually a certain amount of acetic acid is retained as solvent to maintain the catalyst stable) are added into a 250ml pressure kettle; introducing carbon monoxide, heating to 170 ℃, stirring at 500 r/min, controlling the reaction pressure to be 4.0MPa, and reacting for 30 min to obtain the acetic acid.
The conversion frequency of the catalyst calculated by ruthenium is 402.7/h, the conversion rate of methanol is 43.2%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 385.0/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 41.3%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.5% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.5% of ruthenium was lost, and about 5.1% of palladium was lost, the palladium content was 94.9% of the initial state.
Example 5
5.07g of ruthenium palladium double-active center catalyst 1 (the system contains about 4000ppm of ruthenium and about 304ppm of palladium), 1.1mol of methanol, 0.3mol of methyl iodide and 0.78mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually kept as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, reacting at 200 deg.C under 3.0MPa for 30 min at a stirring speed of 500rpm to obtain acetic acid.
The conversion frequency of the catalyst calculated by ruthenium is 346.5/h, the conversion rate of methanol is 81.3%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 335.7/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 78.8%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.2% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.8% of ruthenium was lost, and about 5.6% of palladium was lost, the palladium content was 94.4% of the initial state.
Example 6
5.95g of ruthenium palladium double-active center catalyst 1 (the system contains about 6000ppm of ruthenium and about 456ppm of palladium), 1.1mol of methanol, 0.1mol of methyl iodide and 0.8mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); introducing carbon monoxide, reacting at 175 deg.C under 4.0MPa for 30 min at a stirring speed of 500rpm to obtain acetic acid.
The conversion frequency of the catalyst calculated by ruthenium is 338.0/h, the conversion rate of methanol is 90.2%, the catalyst is reused for catalytic reaction by simulating a flash evaporation process in a laboratory, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 337.2/h after the catalyst is recycled for 50 times, the conversion rate of methanol is 90.0%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial cycle and the 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content after the 50 cycles still reached 98.7% of the initial state (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.3% of ruthenium was lost, and about 4.9% of palladium was lost, the palladium content was 95.1% of the initial state.
Example 7
1.55g of ruthenium palladium double-active center catalyst 1 (the system contains about 2000ppm of ruthenium and about 152ppm of palladium), 0.80mol of methyl acetate, 0.02mol of methyl iodide (a cocatalyst) and 0.25mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); replacing air in the pressure kettle with carbon monoxide, continuously introducing carbon monoxide, adding hydrogen, heating to 185 ℃ under 0.1MPa and 4.0MPa, stirring at 500 r/min under constant reaction pressure of 4.2MPa for 30 min, and obtaining acetic anhydride.
The conversion frequency of the catalyst calculated by ruthenium is 391.5/h, the conversion rate of methyl acetate is 39.7%, the catalyst is reused for catalytic reaction by simulating a flash evaporation process in a laboratory, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 378.7/h and the conversion rate of methyl acetate is 38.4% after the catalyst is recycled for 50 times, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.8% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.2% of ruthenium was lost, and about 5.9% of palladium was lost, the palladium content was 94.1% of the initial state.
Example 8
3.92g of ruthenium palladium double-active center catalyst 1 (the system contains about 3500ppm of ruthenium and about 266ppm of palladium), 0.55mol of methyl acetate, 0.17mol of methyl iodide and 0.55mol of acetic acid are added into a 250ml pressure kettle (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process); replacing air in the reaction kettle with carbon monoxide, introducing hydrogen at 0.2MPa, introducing carbon monoxide to control the reaction temperature at 190 ℃, the total reaction pressure at 4.5MPa, the stirring speed at 500 r/min, and the reaction time at 30 minutes to obtain acetic anhydride.
The conversion frequency of the catalyst is calculated to be 210.1/h by ruthenium, the conversion rate of methyl acetate is 64.8%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion frequency of the catalyst is calculated to be 209.5/h by ruthenium after the catalyst is recycled for 50 times, the conversion rate of methyl acetate is 64.6%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.6% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.4% of ruthenium was lost, and about 5.8% of palladium was lost, the palladium content was 94.2% of the initial state.
Example 9
5.06g of ruthenium palladium double-active center catalyst 1 (the system contains about 5000ppm of ruthenium and about 380ppm of palladium), 0.65mol of methyl acetate, 0.08mol of methyl iodide and 0.67mol of acetic acid (a certain amount of acetic acid is usually reserved as a solvent to maintain the stability of the catalyst in the continuous reaction process) are added into a 250ml pressure kettle, the air in the reaction kettle is replaced by carbon monoxide, hydrogen is introduced into the reaction kettle under 0.3MPa, the carbon monoxide is added to keep the total reaction pressure of 3.5MPa, the reaction temperature is 165 ℃, the stirring speed is 500 r/min, and the reaction time is 25 min, so that the acetic anhydride is obtained.
The conversion frequency of the catalyst calculated by ruthenium is 212.2/h, the conversion rate of methyl acetate is 67.2%, the catalyst is reused for catalytic reaction through a laboratory simulation flash evaporation process, the reaction condition is unchanged, the conversion frequency of the catalyst calculated by ruthenium is 210.0/h after the catalyst is recycled for 50 times, the conversion rate of methyl acetate is 66.5%, and the attenuation is not obvious. The contents of ruthenium and palladium in the reaction solution after the initial and 50 cycles were measured by atomic absorption spectroscopy, and it was found that the ruthenium content still reached 98.6% of the initial state after 50 cycles (the test method was to measure the amount of ruthenium in the reaction solution by atomic absorption spectroscopy, divided by the amount added), about 1.4% of ruthenium was lost, and about 5.1% of palladium was lost, the palladium content was 94.9% of the initial state.
Example 10
Mixing 0.15 mol of 2-vinylpyridine, 0.2mol of methacrylic acid, 0.65mol of methyl methacrylate and a trace amount of cross-linking agent (wherein the cross-linking agent is 0.2 percent of the total mole amount of the monomers), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1 percent of the monomers as an initiator, reacting for 1 hour at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 2.
Dissolving 0.03g of lithium hydroxide and 2g of polymer ligand 2 in a mixed solvent of ethanol and water with the volume fraction of 95%, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A1;
0.02gPdCl2Dispersing in ethanol, dropwise adding dilute hydrochloric acid to fully dissolve, adding product A1, refluxing at 30 deg.C for 4 hr, cooling to room temperature, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate obtained in the step 2 in acetone, stirring in an ice bath, adding 0.55g of dodecacarbonyl triruthenium, continuously stirring for 2 hours, adding excessive diethyl ether for precipitation, and filtering to obtain the ruthenium-palladium double-activity center catalyst 2.
Example 11
Mixing 0.3mol of 2-vinylpyridine, 0.3mol of methacrylic acid, 0.4 mol of methyl methacrylate and a trace amount of cross-linking agent (wherein the cross-linking agent is 0.8 percent of the total mole amount of the monomers), adding the mixture into a benzene solvent, stirring, slowly adding azobisisobutyronitrile with the mole number of 1 percent of the monomers as an initiator, reacting for 1 hour at 65 ℃, cooling the solution, precipitating and filtering by diethyl ether, dissolving by acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution in vacuum and reducing the pressure to constant weight to obtain the polymer ligand 3.
Dissolving 0.03g of lithium hydroxide and 2g of polymer ligand 3 in a mixed solvent of ethanol and water with the volume fraction of 95%, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A2;
0.04g of PdCl2Dispersing in ethanol, dropwise adding dilute hydrochloric acid to fully dissolve, adding product A2, refluxing at 30 deg.C for 4 hr, cooling to room temperature, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate obtained in the step 2 in acetone, stirring in an ice bath, adding 0.55g of dodecacarbonyl triruthenium, continuously stirring for 1 hour, adding excessive diethyl ether for precipitation, and filtering to obtain the ruthenium-palladium double-activity center catalyst 3.
The above description is only a preferred embodiment of the present invention, and the scope of the present invention is not limited thereto, and any simple modifications or equivalent substitutions of the technical solutions that can be obviously obtained by those skilled in the art within the technical scope of the present invention are within the scope of the present invention.
Claims (9)
1. The preparation method of the ruthenium palladium double-active center catalyst for synthesizing acetic acid or acetic anhydride by carbonylation is characterized in that a cage-shaped catalytic system is formed by taking a micro-crosslinked cage-shaped polymer as a ligand, taking metal ruthenium as an active center, taking a metal target as a cocatalyst and simultaneously introducing lithium ions as a catalytic auxiliary agent; the caged polymer is a ligand, and is a copolymer of 2-vinylpyridine, acrylic acid or methacrylic acid and acrylate monomers which are lightly crosslinked by a crosslinking agent; the light crosslinking means that the crosslinking agent is 0.2 to 0.8 percent of the total molar amount of the polymerized monomers; the preparation method comprises the following steps:
step 1, dissolving 0.03g of lithium hydroxide and 2g of polymer ligand in a 95% ethanol-water mixed solvent, stirring at normal temperature for 1h, adding excessive ether for precipitation, and placing in vacuum and reducing pressure to constant weight to obtain a product A;
step 2, 0.02-0.04g of PdCl2Dispersing in ethanol, dropwise adding dilute hydrochloric acid to fully dissolve, adding product A, stirring at 30 deg.C for 4 hr, cooling in ice water bath, precipitating with excessive diethyl ether, washing the precipitate with 0 deg.C methanol for several times, and vacuum drying to constant weight;
and 3, dissolving the precipitate obtained in the step 2 in acetone, stirring in an ice bath, adding 0.55g of dodecacarbonyl triruthenium, continuously stirring for 1-2h, adding excessive diethyl ether for precipitation, and filtering to obtain the ruthenium-palladium double-activity center catalyst.
2. The preparation method of the ruthenium palladium double-active center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation according to claim 1, wherein when the cage-shaped polymer is used as the ligand, the dosage of the 2-vinylpyridine is 15 to 30 percent of the total molar amount of the polymerized monomer, and the dosage of the acrylic acid or the methacrylic acid is 20 to 30 percent of the total molar amount of the polymerized monomer; the dosage of the acrylate monomer is 40-65% of the total molar amount of the polymerized monomer.
3. The preparation of the ruthenium palladium dual active site catalyst for the carbonylation synthesis of acetic acid or acetic anhydride according to claim 1 wherein the cross-linking agent is trimethylolpropane trimethacrylate or divinylbenzene.
4. The preparation method of the ruthenium palladium double-active center catalyst for synthesizing acetic acid or acetic anhydride through carbonylation according to claim 1, wherein the acrylic ester monomer is one or a mixture of methyl methacrylate, ethyl methacrylate, methyl acrylate or ethyl acrylate.
5. The preparation method of the ruthenium palladium double-active center catalyst for synthesizing acetic acid or acetic anhydride by carbonylation according to claim 1, wherein the preparation method of the cage polymer as the ligand is as follows: mixing 2-vinylpyridine, acrylic acid or methacrylic acid, acrylate monomer and a cross-linking agent, adding the mixture into a benzene solvent, stirring, slowly adding azodiisobutyronitrile with the molar number of 1% of the polymerization monomer as an initiator, reacting at 65 ℃ for 1h, cooling the solution, precipitating and filtering by using ether, dissolving by using acetone, repeatedly dissolving and precipitating for 3-4 times, and placing the solution under vacuum and reducing the pressure to constant weight.
6. Use of a ruthenium palladium dual active site catalyst according to any one of claims 1 to 5 for the carbonylation of methanol to acetic acid.
7. The application of the catalyst as claimed in claim 6, wherein the ruthenium palladium double-activity center catalyst, methanol and methyl iodide are added into a pressure kettle, carbon monoxide is introduced, the pressure of the carbon monoxide is kept to be 3-4 MPa, the reaction temperature is 150-200 ℃, and acetic acid is obtained after stirring reaction, wherein the dosage of the polymer ligand multi-metal cage system catalyst in a reaction system is calculated by ruthenium, and the content of ruthenium is 2000-6000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-3 mol/L.
8. Use of a ruthenium palladium double active site catalyst according to any one of claims 1 to 5 for the catalytic carbonylation of methyl acetate to acetic anhydride.
9. The application of the catalyst as claimed in claim 8, wherein the ruthenium palladium double-active center catalyst, methyl acetate, methyl iodide and acetic acid solvent are added into a pressure kettle, carbon monoxide is introduced to replace air in the pressure kettle, carbon monoxide is continuously introduced and hydrogen is added, the reaction temperature is 165-200 ℃, acetic anhydride is obtained after stirring reaction, the amount of the ruthenium palladium double-active center catalyst in the reaction system is calculated by ruthenium, and the content of ruthenium is 2000-5000 PPm; the usage amount of the catalyst promoter methyl iodide in the reaction system is 0.2-2 mol/L; the pressure of the mixed gas of carbon monoxide and hydrogen is 3.5-4.5 MPa, wherein the volume content of the hydrogen in the mixed gas is 1-10%.
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