CN109970815A - Pyridyl rhodium catalyst and its preparation method and application - Google Patents
Pyridyl rhodium catalyst and its preparation method and application Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 109
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- -1 Pyridyl rhodium Chemical compound 0.000 title abstract description 45
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 96
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 77
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- 239000002994 raw material Substances 0.000 claims abstract description 35
- 125000004076 pyridyl group Chemical group 0.000 claims abstract description 34
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000005810 carbonylation reaction Methods 0.000 claims abstract description 21
- 150000001875 compounds Chemical class 0.000 claims abstract description 21
- 230000006315 carbonylation Effects 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 13
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 37
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 21
- LMHIBYREWJHKNZ-UHFFFAOYSA-N 3-methylpyridine-2-carboxylic acid Chemical compound CC1=CC=CN=C1C(O)=O LMHIBYREWJHKNZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 6
- NMMIHXMBOZYNET-UHFFFAOYSA-N Methyl picolinate Chemical class COC(=O)C1=CC=CC=N1 NMMIHXMBOZYNET-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 4
- 238000004458 analytical method Methods 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- KNVZVRWMLMPTTJ-UHFFFAOYSA-N 2-(3-carboxy-2-pyridinyl)-3-pyridinecarboxylic acid Chemical class OC(=O)C1=CC=CN=C1C1=NC=CC=C1C(O)=O KNVZVRWMLMPTTJ-UHFFFAOYSA-N 0.000 claims 2
- 238000001816 cooling Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 238000011017 operating method Methods 0.000 claims 1
- 239000000052 vinegar Substances 0.000 claims 1
- 235000021419 vinegar Nutrition 0.000 claims 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000006227 byproduct Substances 0.000 abstract description 2
- 230000009849 deactivation Effects 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- GNPXKHTZVDUNOY-UHFFFAOYSA-N oxomethylidenerhodium Chemical compound O=C=[Rh] GNPXKHTZVDUNOY-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 51
- 230000003197 catalytic effect Effects 0.000 description 18
- 239000011259 mixed solution Substances 0.000 description 16
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 13
- POYRLWQLOUUKAY-UHFFFAOYSA-N 6,7,8,9-tetrahydro-5h-carbazol-3-amine Chemical compound C1CCCC2=C1NC1=CC=C(N)C=C12 POYRLWQLOUUKAY-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000004868 gas analysis Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012803 optimization experiment Methods 0.000 description 2
- 238000006464 oxidative addition reaction Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- MYSWGLZTUMZAAS-UHFFFAOYSA-N [Rh].[I] Chemical compound [Rh].[I] MYSWGLZTUMZAAS-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000013441 quality evaluation Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- 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
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
-
- 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
- B01J31/20—Carbonyls
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
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- 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
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
-
- 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
- B01J2531/822—Rhodium
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- Chemical & Material Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
一种吡啶基铑催化剂，所述吡啶基铑催化剂由含吡啶基的化合物与Rh2(CO)4X2配位形成，其中，X为Cl或I。本发明以Rh2(CO)4X2与含吡啶基团的化合物原料，在羰基铑与含吡啶基团的化合物之间，形成Rh‑N与Rh‑O配位键，使得铑与含吡啶基的化合物相配位，得到结构稳定的吡啶基铑催化剂。该吡啶基铑催化剂，通过含吡啶基团维持催化剂的稳定性，使得催化剂不易分解沉淀造成失活，通过在铑基催化剂的基础上通过添加配体来提高催化剂的稳定性，保持其活性。另外，该反应中原料采用甲醇和CO来合成醋酸，反应中不仅甲醇的转化率高，而且选择性专一只生成醋酸，解决了羰化过程中副产物多以及醋酸的选择性不高等问题。本发明还提供了该吡啶基铑催化剂的制备方法和应用。
A pyridyl rhodium catalyst, wherein the pyridyl rhodium catalyst is formed by the coordination of a pyridyl-containing compound and Rh 2 (CO) 4 X 2 , wherein X is Cl or I. The present invention uses Rh 2 (CO) 4 X 2 and the compound raw material containing the pyridine group, between the carbonyl rhodium and the compound containing the pyridine group, forms Rh-N and Rh-O coordination bonds, so that the rhodium and the pyridine group-containing compound form Rh-N and Rh-O coordination bonds. The pyridyl rhodium catalyst is obtained by coordinating with the compound of the base. The pyridyl rhodium catalyst maintains the stability of the catalyst by containing a pyridine group, so that the catalyst is not easily decomposed and precipitated to cause deactivation, and the stability of the catalyst is improved by adding ligands on the basis of the rhodium-based catalyst to maintain its activity. In addition, in this reaction, methanol and CO are used as raw materials to synthesize acetic acid. In the reaction, not only the conversion rate of methanol is high, but also only acetic acid is selectively generated, which solves the problems of many by-products and low selectivity of acetic acid in the carbonylation process. The invention also provides the preparation method and application of the pyridyl rhodium catalyst.
Description
技术领域：Technical field:
本发明涉及羰基化制备醋酸技术领域，具体地说，涉及一种吡啶基铑催化剂及其制备方法和应用。The invention relates to the technical field of carbonylation to prepare acetic acid, in particular to a pyridyl rhodium catalyst and a preparation method and application thereof.
背景技术：Background technique:
醋酸是一种重要的基本有机化工产品，作为重要有机原料和一种优良的有机溶剂广泛应用于化工、轻纺、塑料、医药、橡胶以及染料等行业。Acetic acid is an important basic organic chemical product. As an important organic raw material and an excellent organic solvent, it is widely used in chemical, textile, plastic, pharmaceutical, rubber and dye industries.
目前就全世界的醋酸生产工艺来说，甲醇羰基化制醋酸生产工艺已经成为全球醋酸生产工艺，而Monsanto生产技术也成为其醋酸生产的主流工艺。 Monsanto生产工艺以[Rh(CO)2I2]–为催化活性中心，反应条件在150-200℃，压力在3-6MPa，反应条件较为温和。但是Monsanto工艺中铑碘催化剂也存在一些问题，催化剂活性中心[Rh(CO)2I2]–与体系中HI作用会形成[Rh(CO)2I3H]–， [Rh(CO)2I3H]–进而与HI作用形成[Rh(CO)2I4]–造成催化剂活性中心的变价。因此在铑基催化剂反应体系中一般需要添加质量分数14-16％的水来加速[Rh(CO)2I4]–向[Rh(CO)2I2]–的转化，提高催化剂的稳定性及保持其催化剂的活性，但是，高含量的水会导致反应体系中间水煤气变换副反应的发生，转化率降低，在后期产物分离过程中提高成本。As far as the acetic acid production process in the world is concerned, the methanol carbonylation to acetic acid production process has become the global acetic acid production process, and the Monsanto production technology has also become the mainstream process of its acetic acid production. The production process of Monsanto takes [Rh(CO) 2 I 2 ] - as the catalytic active center, the reaction conditions are 150-200℃, the pressure is 3-6MPa, and the reaction conditions are relatively mild. However, the rhodium iodine catalyst in the Monsanto process also has some problems. The catalyst active center [Rh(CO) 2 I 2 ] – interacts with HI in the system to form [Rh(CO) 2 I 3 H] – , [Rh(CO) 2 I 3 H] - which in turn reacts with HI to form [Rh(CO) 2 I 4 ] - causes a change in the valence of the catalyst's active site. Therefore, it is generally necessary to add 14-16% water by mass in the rhodium-based catalyst reaction system to accelerate the conversion of [Rh(CO) 2 I 4 ] – to [Rh(CO) 2 I 2 ] – and improve the stability of the catalyst and maintain the activity of its catalyst, but high content of water will lead to the occurrence of water-gas shift side reactions in the reaction system, the conversion rate will be reduced, and the cost will be increased in the later product separation process.
因此，需要对以铑为活性中心的催化剂体系进行改性，以提高催化剂的稳定性以保持其催化剂的活性，避免因水含量高导致反应体系中间水煤气变换副反应的发生，提高转化率降，降低后期产物分离过程中的成本。Therefore, it is necessary to modify the catalyst system with rhodium as the active center in order to improve the stability of the catalyst to maintain the activity of the catalyst, avoid the occurrence of the water-gas shift side reaction in the reaction system due to high water content, and improve the conversion rate. Reduce costs in later product separation processes.
发明内容：Invention content:
本发明的目的之一是提供一种吡啶基铑催化剂，以含吡啶基团作为催化剂的稳定剂，以提高催化剂的稳定性以保持其催化剂的活性，避免因水含量高导致反应体系中间水煤气变换副反应的发生，提高转化率降，降低后期产物分离过程中的成本。One of the objectives of the present invention is to provide a pyridyl rhodium catalyst, which uses a pyridine group as a stabilizer for the catalyst, so as to improve the stability of the catalyst to maintain the activity of the catalyst, and avoid water-gas shift in the middle of the reaction system due to high water content. The occurrence of side reactions increases the conversion rate and reduces the cost in the later product separation process.
本发明的目的之二是提供一种吡啶基铑催化剂的制备方法。The second object of the present invention is to provide a preparation method of a pyridyl rhodium catalyst.
本发明的目的之三是提供一种吡啶基铑催化剂的应用。The third object of the present invention is to provide an application of a pyridyl rhodium catalyst.
一种吡啶基铑催化剂，所述吡啶基铑催化剂由含吡啶基的化合物与 Rh2(CO)4X2配位形成，其中，X为Cl或I，吡啶基铑催化剂的结构式如下：A pyridyl rhodium catalyst, the pyridyl rhodium catalyst is formed by the pyridyl-containing compound and Rh 2 (CO) 4 X 2 coordination, wherein, X is Cl or I, and the structural formula of the pyridyl rhodium catalyst is as follows:
优选的，所述含吡啶基的化合物为3-甲基-2-吡啶甲酸、2-吡啶甲酸甲酯及 2,2'-联吡啶-3,3'-二羧酸中的一种。Preferably, the pyridyl-containing compound is one of 3-methyl-2-picolinic acid, methyl 2-picolinate and 2,2'-bipyridine-3,3'-dicarboxylic acid.
一种如权利要求1所述吡啶基铑催化剂的制备方法，包括以下步骤：A preparation method of a pyridyl rhodium catalyst as claimed in claim 1, comprising the following steps:
(1)称取Rh2(CO)4X2溶于CH3OH溶液中得到溶液A，溶液A中Rh2(CO)4X2的摩尔浓度为0.004～0.01mol/L；(1) Weighing Rh 2 (CO) 4 X 2 and dissolving it in CH 3 OH solution to obtain solution A, the molar concentration of Rh 2 (CO) 4 X 2 in solution A is 0.004～0.01mol/L;
(2)按照摩尔比Rh2(CO)4X2：含吡啶基的化合物＝1：2称取含吡啶基的化合物，溶于CH3OH中得到溶液B，溶液B中含吡啶基的化合物的摩尔浓度与溶液A中Rh2(CO)4X2的摩尔浓度相同；(2) According to the molar ratio Rh 2 (CO) 4 X 2 : pyridyl-containing compound=1:2, weigh the pyridyl-containing compound, dissolve it in CH 3 OH to obtain solution B, and the pyridyl-containing compound in solution B The molar concentration of is the same as the molar concentration of Rh 2 (CO) 4 X 2 in solution A;
(3)按照摩尔比Rh2(CO)4X2：NaBPh4＝1：2称取NaBPh4，溶于CH3OH中得到溶液C，溶液C中NaBPh4的摩尔浓度为溶液A中Rh2(CO)4X2的摩尔浓度的2倍；(3) Weigh NaBPh 4 according to the molar ratio Rh 2 (CO) 4 X 2 : NaBPh 4 =1:2, dissolve it in CH 3 OH to obtain solution C, the molar concentration of NaBPh 4 in solution C is Rh 2 in solution A 2 times the molar concentration of (CO) 4 X 2 ;
(4)在搅拌状态下，将溶液B逐滴滴入溶液A中，待溶液B滴完后，在室温下继续搅拌20～60min，得到混合液；(4) under stirring state, drop solution B into solution A dropwise, after the solution B is dropped, continue stirring at room temperature for 20-60 min to obtain a mixed solution;
(5)将溶液C逐滴滴入步骤(3)的混合液中，待溶液C滴完后，在室温下继续搅拌20～60min；(5) drop the solution C into the mixed solution of step (3) dropwise, after the solution C is dropped, continue stirring at room temperature for 20-60 min;
(6)继续搅拌混合溶液，并在搅拌状态下逐滴加入无水乙醚，搅拌均匀后静置20～30min后过滤，将过滤得到的固体用乙醚洗涤至少三次，然后真空干燥至溶剂完全挥发，得到吡啶基铑催化剂。(6) Continue to stir the mixed solution, and add anhydrous ether dropwise under stirring state, stir evenly, let stand for 20～30min and then filter, wash the solid obtained by filtration with ether at least three times, and then vacuum dry until the solvent is completely volatilized, A pyridyl rhodium catalyst is obtained.
优选的，所述含吡啶基的化合物为3-甲基-2-吡啶甲酸、2-吡啶甲酸甲酯及2,2'-联吡啶-3,3'-二羧酸中的一种。Preferably, the pyridyl-containing compound is one of 3-methyl-2-picolinic acid, methyl 2-picolinate and 2,2'-bipyridine-3,3'-dicarboxylic acid.
优选的，所述步骤(1)溶液A中Rh2(CO)4X2的摩尔浓度为0.006mol/L。Preferably, the molar concentration of Rh 2 (CO) 4 X 2 in the solution A of the step (1) is 0.006 mol/L.
优选的，所述步骤(5)中无水乙醚的加入量为混合液总体积的20～30％。Preferably, the amount of anhydrous ether added in the step (5) is 20-30% of the total volume of the mixed solution.
一种如权利要求1所述吡啶基铑催化剂的应用，将吡啶基铑催化剂用作甲醇羰基化制备醋酸过程中的催化剂。A kind of application of the pyridyl rhodium catalyst as claimed in claim 1, the pyridyl rhodium catalyst is used as the catalyst in the methanol carbonylation to prepare the acetic acid process.
优选的，将吡啶基铑催化剂应用于甲醇羰基化制备醋酸的操作步骤为，按照各原料分别占原料总重量的百分比为：w(H2O)0～8％、w(CH3COOH)30～60％、 w(CH3I)8～16％、w(LiI)4％，w(CH3OH)18～48％称取各原料，将全部原料加入反应釜并搅拌均匀并加入0.07～0.1mmol吡啶基铑催化剂，设置反应釜搅拌转速 500rpm、温度170～210℃，通过CO进行三次置换反应釜内空气，最后通入2～4 MPa CO压力进行羰基化反应，反应60min后，待温度冷却，取样，进行气质分析。Preferably, the operation steps of applying the pyridyl rhodium catalyst to the carbonylation of methanol to prepare acetic acid are as follows, according to the percentage of each raw material in the total weight of the raw materials: w(H 2 O) 0-8%, w(CH 3 COOH) 30% ～60%, w(CH 3 I) 8～16%, w(LiI) 4%, w(CH 3 OH) 18～48% Weigh each raw material, add all the raw materials into the reaction kettle and stir evenly and add 0.07～ 0.1 mmol of pyridyl rhodium catalyst, set the stirring speed of the reactor at 500 rpm and the temperature at 170-210 ° C, replace the air in the reactor three times with CO, and finally introduce 2-4 MPa CO pressure to carry out the carbonylation reaction. After the reaction for 60 min, wait for the temperature Cool, sample, and perform gas analysis.
优选的，各原料添加顺序为：先将H2O、CH3COOH、CH3OH加入反应釜中，再添加LiI、CH3I，最后将吡啶基铑催化剂加入反应釜中。Preferably, the order of adding each raw material is as follows: first add H 2 O, CH 3 COOH and CH 3 OH into the reaction kettle, then add LiI and CH 3 I, and finally add the pyridyl rhodium catalyst into the reaction kettle.
优选的，所述甲醇羰基化制备醋酸过程，反应条件为：温度200℃、3.5MPa CO反应压力；各原料占原料总重量的百分比分别为：w(H2O)6％、w(CH3COOH) 54％、w(CH3I)12％、w(LiI)4％、w(CH3OH)24％。Preferably, in the process of preparing acetic acid by methanol carbonylation, the reaction conditions are: temperature 200°C, CO reaction pressure 3.5MPa; the percentages of each raw material in the total weight of the raw materials are: w(H 2 O) 6%, w(CH 3 COOH) 54%, w( CH3I ) 12%, w(LiI) 4 %, w(CH3OH) 24%.
本发明有益效果如下：本发明以Rh2(CO)4X2与含吡啶基团的化合物原料，在羰基铑与含吡啶基团的化合物之间，形成Rh-N与Rh-O配位键，使得铑与含吡啶基的化合物相配位，得到结构稳定的吡啶基铑催化剂。该吡啶基铑催化剂，通过含吡啶基团维持催化剂的稳定性，使得催化剂不易分解沉淀造成失活，通过在铑基催化剂的基础上通过添加配体来提高催化剂的稳定性，保持其活性。另外，该反应中原料采用甲醇和CO来合成醋酸，反应中不仅甲醇的转化率高，而且选择性专一只生成醋酸，解决了羰化过程中副产物多以及醋酸的选择性不高等问题。The beneficial effects of the present invention are as follows: the present invention uses Rh 2 (CO) 4 X 2 and the compound raw material containing a pyridine group to form Rh-N and Rh-O coordination bonds between the carbonyl rhodium and the compound containing a pyridine group. , so that rhodium is coordinated with the pyridyl-containing compound to obtain a structurally stable pyridyl-rhodium catalyst. The pyridyl rhodium catalyst maintains the stability of the catalyst by containing a pyridine group, so that the catalyst is not easily decomposed and precipitated to cause deactivation, and the stability of the catalyst is improved by adding ligands on the basis of the rhodium-based catalyst to maintain its activity. In addition, in this reaction, methanol and CO are used as raw materials to synthesize acetic acid. In the reaction, not only the conversion rate of methanol is high, but also only acetic acid is selectively generated, which solves the problems of many by-products and low selectivity of acetic acid in the carbonylation process.
附图说明：Description of drawings:
图1是不同醋酸浓度下Rh-L1催化甲醇羰基化反应的催化活性；Fig. 1 is the catalytic activity of Rh-L1 catalyzing methanol carbonylation under different acetic acid concentrations;
图2是不同气压下Rh-L1催化甲醇羰基化反应的催化活性。Figure 2 shows the catalytic activity of Rh-L1 for methanol carbonylation at different pressures.
具体实施方式：Detailed ways:
实施例1：Example 1:
本实施例的吡啶基铑催化剂，由含吡啶基的化合物2,2'-联吡啶-3,3'-二羧酸与Rh2(CO)4Cl2配位形成，吡啶基铑催化剂的结构式如下：The pyridyl rhodium catalyst of this embodiment is formed by the coordination of a pyridyl-containing compound 2,2'-bipyridine-3,3'-dicarboxylic acid and Rh 2 (CO) 4 Cl 2 , and the structural formula of the pyridyl rhodium catalyst is as follows:
上述吡啶基铑催化剂的制备方法，包括以下步骤：The preparation method of above-mentioned pyridyl rhodium catalyst, comprises the following steps:
(1)称取Rh2(CO)4Cl2溶于CH3OH溶液中得到溶液A，溶液A中Rh2(CO)4Cl2的摩尔浓度为0.006mol/L；(1) Weigh Rh 2 (CO) 4 Cl 2 and dissolve it in CH 3 OH solution to obtain solution A, the molar concentration of Rh 2 (CO) 4 Cl 2 in solution A is 0.006mol/L;
(2)按照摩尔比Rh2(CO)4Cl2：2,2'-联吡啶-3,3'-二羧酸＝1：2称取2,2'-联吡啶-3,3'-二羧酸，溶于CH3OH中得到溶液B，溶液B中2,2'-联吡啶-3,3'-二羧酸的摩尔浓度为0.006mol/L；(2) According to the molar ratio Rh 2 (CO) 4 Cl 2 : 2,2'-bipyridine-3,3'-dicarboxylic acid=1:2, 2,2'-bipyridine-3,3'- Dicarboxylic acid, dissolved in CH 3 OH to obtain solution B, the molar concentration of 2,2'-bipyridine-3,3'-dicarboxylic acid in solution B is 0.006mol/L;
(3)按照摩尔比Rh2(CO)4X2：NaBPh4＝1：2称取NaBPh4，溶于CH3OH中得到溶液C，溶液C中NaBPh4的摩尔浓度为0.012mol/L；(3) Weigh NaBPh 4 according to the molar ratio Rh 2 (CO) 4 X 2 : NaBPh 4 =1:2, dissolve it in CH 3 OH to obtain solution C, and the molar concentration of NaBPh 4 in solution C is 0.012mol/L;
(4)在搅拌状态下，将溶液B逐滴滴入溶液A中，待溶液B滴完后，在室温下继续搅拌30min，得到混合液；(4) in a state of stirring, drop solution B into solution A dropwise, after the solution B is dropped, continue stirring at room temperature for 30min to obtain a mixed solution;
(5)将溶液C逐滴滴入步骤(3)的混合液中，待溶液C滴完后，在室温下继续搅拌30min；(5) dropwise dropwise solution C into the mixed solution of step (3), after the solution C is dropped, continue stirring for 30min at room temperature;
(6)继续搅拌混合溶液，并在搅拌状态下逐滴加入混合液总体积的25％的无水乙醚，搅拌均匀后静置20～30min后过滤，将过滤得到的固体用乙醚洗涤至少三次，然后真空干燥至溶剂完全挥发，得到吡啶基铑催化剂Rh-L1，即土黄色固体Rh-2,2'-联吡啶-3,3'-二羧酸配合物。(6) Continue to stir the mixed solution, and dropwise add 25% of the total volume of the mixed solution with anhydrous diethyl ether in a state of stirring, stir evenly, let stand for 20 to 30 min and then filter, and wash the solid obtained by filtration with diethyl ether at least three times, Then vacuum-drying until the solvent is completely evaporated to obtain the pyridyl rhodium catalyst Rh-L1, that is, a khaki solid Rh-2,2'-bipyridine-3,3'-dicarboxylic acid complex.
上述吡啶基铑催化剂的应用，将吡啶基铑催化剂应用于甲醇羰基化制备醋酸的操作步骤为，按照各原料分别占原料总重量的百分比为：w(H2O)6％、 w(CH3COOH)54％、w(CH3I)12％、w(LiI)4％，w(CH3OH)24％称取各原料，先将H2O、CH3COOH、CH3OH加入反应釜中，再添加LiI、CH3I，将全部原料加入反应釜并搅拌均匀，然后加入0.07～0.1mmol吡啶基铑催化剂，设置反应釜搅拌转速500rpm、温度200℃，通过CO进行三次置换反应釜内空气，最后通入 3.5MPa CO压力进行羰基化反应，反应60min后，待温度冷却，取样，进行气质分析。The application of the above-mentioned pyridyl rhodium catalyst, the operation steps of applying the pyridyl rhodium catalyst to methanol carbonylation to prepare acetic acid are as follows, according to the percentage of the total weight of the raw materials respectively accounted for by each raw material: w(H 2 O) 6%, w(CH 3 COOH) 54%, w(CH 3 I) 12%, w(LiI) 4%, w(CH 3 OH) 24% Weigh each raw material, first add H 2 O, CH 3 COOH and CH 3 OH to the reaction kettle Add LiI and CH 3 I again, add all the raw materials into the reactor and stir evenly, then add 0.07-0.1 mmol pyridyl rhodium catalyst, set the stirring speed of the reactor at 500 rpm and the temperature at 200 ° C, and replace the inside of the reactor with CO three times. Air, and finally introduced 3.5MPa CO pressure to carry out carbonylation reaction. After 60min of reaction, the temperature was cooled, sampling was carried out, and gas quality analysis was carried out.
所述吡啶基铑催化剂在甲醇羰基化制备醋酸的催化循环过程分四步进行：The catalytic cycle process of the pyridyl rhodium catalyst for preparing acetic acid by methanol carbonylation is carried out in four steps:
a、碘甲烷的氧化加成过程：配合物催化剂与CH3I通过氧化加成反应生成中间体TN1；a. Oxidative addition process of methyl iodide: the complex catalyst reacts with CH 3 I to generate intermediate TN1 through oxidative addition reaction;
b、甲基迁移：中间体TN1中，甲基不断向羰基趋近，进而完成迁移形成中间体TN2完成重排；b. Methyl migration: In the intermediate TN1, the methyl group continues to approach the carbonyl group, and then completes the migration to form the intermediate TN2 to complete the rearrangement;
c、羰基配位：羰基与中间体TN2相互作用形成下一中间产物TN3；c. Carbonyl coordination: the carbonyl interacts with the intermediate TN2 to form the next intermediate TN3;
d、CH3COI还原消除：中间体TN3还原消除形成CH3COI，进而水解生成产物CH3COOH，而催化剂又恢复到最开始状态，进而进行下一催化循环过程。催化循环过程示意如下：d. Reduction and elimination of CH 3 COI: the intermediate TN3 is reduced and eliminated to form CH 3 COI, which is then hydrolyzed to produce CH 3 COOH, and the catalyst returns to the original state, and the next catalytic cycle is carried out. The catalytic cycle process is illustrated as follows:
例2：Example 2:
本实施例的吡啶基铑催化剂，由含吡啶基的化合物3-甲基-2-吡啶甲酸与 Rh2(CO)4Cl2配位形成，吡啶基铑催化剂的结构式如下：The pyridyl rhodium catalyst of the present embodiment is formed by the coordination of the pyridyl-containing compound 3-methyl-2-picolinic acid and Rh 2 (CO) 4 Cl 2 , and the structural formula of the pyridyl rhodium catalyst is as follows:
上述吡啶基铑催化剂的制备方法，包括以下步骤：The preparation method of above-mentioned pyridyl rhodium catalyst, comprises the following steps:
(1)称取Rh2(CO)4Cl2溶于CH3OH溶液中得到溶液A，溶液A中Rh2(CO)4Cl2的摩尔浓度为0.004mol/L；(1) Weigh Rh 2 (CO) 4 Cl 2 and dissolve it in CH 3 OH solution to obtain solution A, the molar concentration of Rh 2 (CO) 4 Cl 2 in solution A is 0.004mol/L;
(2)按照摩尔比Rh2(CO)4Cl2：3-甲基-2-吡啶甲酸＝1：2称取3-甲基-2-吡啶甲酸，溶于CH3OH中得到溶液B，溶液B中3-甲基-2-吡啶甲酸的摩尔浓度为0.004mol/L；(2) According to the molar ratio Rh 2 (CO) 4 Cl 2 : 3-methyl-2-picolinic acid=1:2, 3-methyl-2-picolinic acid was weighed, dissolved in CH 3 OH to obtain solution B, The molar concentration of 3-methyl-2-picolinic acid in solution B is 0.004mol/L;
(3)按照摩尔比Rh2(CO)4Cl2：NaBPh4＝1：2称取NaBPh4，溶于CH3OH 中得到溶液C，溶液C中NaBPh4的摩尔浓度为0.008mol/L；(3) Weigh NaBPh 4 according to the molar ratio Rh 2 (CO) 4 Cl 2 : NaBPh 4 =1:2, dissolve it in CH 3 OH to obtain solution C, and the molar concentration of NaBPh 4 in solution C is 0.008mol/L;
(4)在搅拌状态下，将溶液B逐滴滴入溶液A中，待溶液B滴完后，在室温下继续搅拌20min，得到混合液；(4) under stirring state, drop solution B into solution A dropwise, after the solution B is dropped, continue stirring for 20min at room temperature to obtain a mixed solution;
(5)将溶液C逐滴滴入步骤(3)的混合液中，待溶液C滴完后，在室温下继续搅拌20min；(5) dropwise solution C into the mixed solution of step (3), after the solution C is dropped, continue stirring for 20min at room temperature;
(6)继续搅拌混合溶液，并在搅拌状态下逐滴加入混合液总体积的20％的无水乙醚，搅拌均匀后静置25min后过滤，将过滤得到的固体用乙醚洗涤至少三次，然后真空干燥至溶剂完全挥发，得到吡啶基铑催化剂Rh-L2，即土黄色固体Rh-3-甲基-2-吡啶甲酸配合物。(6) Continue to stir the mixed solution, and dropwise add 20% of the total volume of the mixed solution with anhydrous ether under stirring, stir evenly, leave it to stand for 25 min and then filter, wash the solid obtained by filtration with ether for at least three times, and then vacuum It is dried until the solvent is completely evaporated to obtain the pyridyl rhodium catalyst Rh-L2, which is a khaki solid Rh-3-methyl-2-picolinic acid complex.
上述吡啶基铑催化剂的应用，将吡啶基铑催化剂应用于甲醇羰基化制备醋酸的操作步骤为，按照各原料分别占原料总重量的百分比为：w(H2O)4％、 w(CH3COOH)45％、w(CH3I)15％、w(LiI)4％，w(CH3OH)32％称取各原料，先将H2O、CH3COOH、CH3OH加入反应釜中，再添加LiI、CH3I，将全部原料加入反应釜并搅拌均匀，然后加入0.1mmol吡啶基铑催化剂，设置反应釜搅拌转速500rpm、温度180℃，通过CO进行三次置换反应釜内空气，最后通入3MPa CO压力进行羰基化反应，反应60min后，待温度冷却，取样，进行气质分析。其催化过程与实施例1相同。In the application of the above-mentioned pyridyl rhodium catalyst, the operation steps of applying the pyridyl rhodium catalyst to methanol carbonylation to prepare acetic acid are as follows, according to the percentages of the raw materials in the total weight of the raw materials: w(H 2 O) 4%, w(CH 3 COOH) 45%, w(CH 3 I) 15%, w(LiI) 4%, w(CH 3 OH) 32% Weigh each raw material, first add H 2 O, CH 3 COOH and CH 3 OH to the reaction kettle Then, add LiI and CH 3 I, add all the raw materials into the reaction kettle and stir evenly, then add 0.1 mmol pyridyl rhodium catalyst, set the stirring speed of the reaction kettle to 500 rpm and the temperature to 180 ° C, and replace the air in the reaction kettle three times by CO, Finally, the pressure of 3MPa CO was introduced to carry out the carbonylation reaction. After the reaction for 60min, the temperature was cooled, and sampling was carried out for gas analysis. The catalytic process is the same as that of Example 1.
实施例3：Example 3:
本实施例的吡啶基铑催化剂，由含吡啶基的化合物吡啶甲酸甲酯与 Rh2(CO)4I2配位形成，吡啶基铑催化剂的结构式如下：The pyridyl rhodium catalyst of the present embodiment is formed by the coordination of the pyridyl-containing compound methyl picolinate and Rh 2 (CO) 4 I , and the structural formula of the pyridyl rhodium catalyst is as follows:
上述吡啶基铑催化剂的制备方法，包括以下步骤：The preparation method of above-mentioned pyridyl rhodium catalyst, comprises the following steps:
(1)称取Rh2(CO)4I2溶于CH3OH溶液中得到溶液A，溶液A中Rh2(CO)4I2的摩尔浓度为0.008mol/L；(1) take by weighing Rh 2 (CO) 4 I 2 and dissolve it in CH 3 OH solution to obtain solution A, and the molar concentration of Rh 2 (CO) 4 I 2 in solution A is 0.008mol/L;
(2)按照摩尔比Rh2(CO)4I2：2,2'-联吡啶-3,3'-二羧酸＝1：2称取2,2'-联吡啶-3,3'-二羧酸，溶于CH3OH中得到溶液B，溶液B中2,2'-联吡啶-3,3'-二羧酸的摩尔浓度为0.008mol/L；(2) According to the molar ratio Rh 2 (CO) 4 I 2 : 2,2'-bipyridine-3,3'-dicarboxylic acid=1:2, 2,2'-bipyridine-3,3'- Dicarboxylic acid, dissolved in CH 3 OH to obtain solution B, the molar concentration of 2,2'-bipyridine-3,3'-dicarboxylic acid in solution B is 0.008mol/L;
(3)按照摩尔比Rh2(CO)4I2：NaBPh4＝1：2称取NaBPh4，溶于CH3OH中得到溶液C，溶液C中NaBPh4的摩尔浓度为0.016mol/L；(3) Weigh NaBPh 4 according to the molar ratio Rh 2 (CO) 4 I 2 : NaBPh 4 =1:2, dissolve it in CH 3 OH to obtain solution C, and the molar concentration of NaBPh 4 in solution C is 0.016mol/L;
(4)在搅拌状态下，将溶液B逐滴滴入溶液A中，待溶液B滴完后，在室温下继续搅拌50min，得到混合液；(4) under stirring state, drop solution B into solution A dropwise, after the solution B is dropped, continue stirring for 50min at room temperature to obtain a mixed solution;
(5)将溶液C逐滴滴入步骤(3)的混合液中，待溶液C滴完后，在室温下继续搅拌40min；(5) dropwise solution C into the mixed solution of step (3), after the solution C is dropped, continue stirring for 40min at room temperature;
(6)继续搅拌混合溶液，并在搅拌状态下逐滴加入混合液总体积的28％的无水乙醚，搅拌均匀后静置28min后过滤，将过滤得到的固体用乙醚洗涤至少三次，然后真空干燥至溶剂完全挥发，得到吡啶基铑催化剂Rh-L3，即黑色固体 Rh-吡啶甲酸甲酯配合物。(6) Continue to stir the mixed solution, and add dropwise 28% anhydrous ether of the total volume of the mixed solution under agitation, stir evenly, let stand for 28 min and filter, wash the solid obtained by filtration with ether at least three times, then vacuum It is dried until the solvent is completely evaporated to obtain a pyridyl rhodium catalyst Rh-L3, namely a black solid Rh-methyl picolinate complex.
上述吡啶基铑催化剂的应用，将吡啶基铑催化剂应用于甲醇羰基化制备醋酸的操作步骤为，按照各原料分别占原料总重量的百分比为：w(H2O)2％、 w(CH3COOH)38％、w(CH3I)10％、w(LiI)4％，w(CH3OH)46％称取各原料，先将H2O、CH3COOH、CH3OH加入反应釜中，再添加LiI、CH3I，将全部原料加入反应釜并搅拌均匀，然后加入0.08mmol吡啶基铑催化剂，设置反应釜搅拌转速500rpm、温度185℃，通过CO进行三次置换反应釜内空气，最后通入4MPa CO压力进行羰基化反应，反应60min后，待温度冷却，取样，进行气质分析。其催化过程与实施例1相同。In the application of the above-mentioned pyridyl rhodium catalyst, the operation steps of applying the pyridyl rhodium catalyst to methanol carbonylation to prepare acetic acid are as follows, according to the percentage of the total raw material weight of each raw material: w(H 2 O) 2%, w(CH 3 COOH) 38%, w(CH 3 I) 10%, w(LiI) 4%, w(CH 3 OH) 46% Weigh each raw material, first add H 2 O, CH 3 COOH and CH 3 OH to the reaction kettle Then, add LiI and CH 3 I, add all the raw materials into the reactor and stir evenly, then add 0.08mmol pyridyl rhodium catalyst, set the stirring speed of the reactor to 500rpm and the temperature to 185°C, and replace the air in the reactor three times by CO, Finally, the pressure of 4MPa CO was introduced to carry out the carbonylation reaction. After the reaction for 60min, the temperature was cooled, and the samples were taken for gas analysis. The catalytic process is the same as that of Example 1.
转化性能测量与分析：Conversion performance measurement and analysis:
气质评价条件：采用气相色谱仪(GC-2014)对产物进行定性及定量分析，气相检测程序为：检测器及气化室温度分别为230℃和220℃，分流比为10，进样量为1μL，色谱柱起始温度为32℃，保留时间为2min，以5℃/min升温至60℃，保留2min，再以10℃/min升温至150℃，保留2min。采用外标法测定产物中出现物质的标准曲线，每个样平行测定3次，取平均值，得到相应标准曲线方程，根据标准曲线方程对实验产品进行定量分析：对产品进行GC分析，通过GC结果谱图中对应物质的面积带入相应标准曲线方程式，得到其质量分数。Gas quality evaluation conditions: use gas chromatograph (GC-2014) to carry out qualitative and quantitative analysis of the product. The gas phase detection program is: the temperature of the detector and the gasification chamber are 230 °C and 220 °C, respectively, the split ratio is 10, and the injection volume is 1 μL, the initial temperature of the chromatographic column is 32 °C, the retention time is 2 min, the temperature is increased to 60 °C at 5 °C/min, and the retention is 2 min, and then the temperature is increased to 150 °C at 10 °C/min, and the retention time is 2 min. The external standard method was used to determine the standard curve of the substances in the product. Each sample was measured three times in parallel, and the average value was taken to obtain the corresponding standard curve equation. Quantitative analysis of the experimental product was carried out according to the standard curve equation. The area of the corresponding substance in the resulting spectrum was brought into the corresponding standard curve equation to obtain its mass fraction.
表1：各物质标准曲线方程式Table 1: Standard curve equation of each substance
表1中：aMi为i物质的质量分数，Ai为i物质的峰面积In Table 1: a M i is the mass fraction of i species, A i is the peak area of i species
以甲醇转化率(x，％)、醋酸选择性(sHAc，％)、醋酸甲酯选择性(sMeOAc，％)、醋酸收率(yHAc，％)、醋酸甲酯收率(yMeOAc，％)为其催化性能评价指标。In methanol conversion (x, %), acetic acid selectivity (s HAc , %), methyl acetate selectivity (s MeOAc , %), acetic acid yield (y HAc , %), methyl acetate yield (y MeOAc ) , %) as its catalytic performance evaluation index.
yHAc＝x×sHAc×100％ (4)y HAc = x × s HAc × 100% (4)
yMeOAc＝x×sMeOAc×100％ (5)y MeOAc = x × s MeOAc × 100% (5)
式(1)～(5)为其计算公式，式中，n1、n2、n3、n4分别为反应过程中甲醇添加量、甲醇消耗量、醋酸生成量、醋酸甲酯生成量，单位均为mol。Formulas (1) to (5) are their calculation formulas, where n 1 , n 2 , n 3 , and n 4 are the methanol addition, methanol consumption, acetic acid production, and methyl acetate production in the reaction process, respectively, The unit is mol.
将实施例1-3中制备所得的催化剂进行催化反应试验得到表2中的性能对比数据。The catalysts prepared in Examples 1-3 were subjected to a catalytic reaction test to obtain the performance comparison data in Table 2.
表2：不同催化剂催化性能对比Table 2: Comparison of catalytic performance of different catalysts
表2中，L1：2，2’-联吡啶-3，3’-二羧酸，L2：3-甲基-2-吡啶甲酸，L3：吡啶甲酸甲酯In Table 2, L1: 2,2'-bipyridine-3,3'-dicarboxylic acid, L2: 3-methyl-2-picolinic acid, L3: methyl picolinate
从表2可以看出，在各实施例限定的催化反应条件下，Rh-L1配合物相较 Rh-L2、Rh-L3配合物催化剂表现出优越的催化性能，甲醇转化率达100％，醋酸选择性在96％以上，无二甲醚产物产生，同样其催化性能明显优越于 Rh2(CO)4Cl2。It can be seen from Table 2 that under the catalytic reaction conditions defined in each example, the Rh-L1 complex exhibits superior catalytic performance compared to the Rh-L2 and Rh-L3 complex catalysts, the methanol conversion rate reaches 100%, and the acetic acid The selectivity is above 96%, no dimethyl ether product is produced, and its catalytic performance is obviously superior to that of Rh 2 (CO) 4 Cl 2 .
Rh-L1催化条件优化实验：Rh-L1 catalytic conditions optimization experiment:
对具体实施例1中制备所得的催化剂Rh-L1进行催化条件优化实验，在反应条件为“温度200℃、3.5MPa CO反应压力；各原料占原料总重量的百分比分别为：w(H2O)6％、w(CH3COOH)为54％、w(CH3I)为12％”的基础上，改变任意参数，进行对比，得到表3至5及图1和图2。The catalyst Rh-L1 prepared in the specific example 1 was subjected to a catalytic condition optimization experiment, and the reaction conditions were "temperature 200 ° C, 3.5 MPa CO reaction pressure; the percentages of each raw material in the total weight of the raw materials were: w(H 2 O ) 6%, w(CH 3 COOH) is 54%, w(CH 3 I) is 12%”, any parameters are changed, and comparisons are made to obtain Tables 3 to 5 and FIGS. 1 and 2 .
表3：不同温度下Rh-1L催化甲醇羰基化反应的催化活性Table 3: Catalytic activity of Rh-1L for methanol carbonylation at different temperatures
表4：不同水含量w(H2O)下Rh-L1催化甲醇羰基化反应的催化活性Table 4: Catalytic activity of Rh-L1 for methanol carbonylation under different water content w(H 2 O)
表5：不同温度下Rh-L1催化甲醇羰基化反应的催化活性Table 5: Catalytic activity of Rh-L1 for methanol carbonylation at different temperatures
从表3至5及图1和图2可以看出，Rh-L1在温度200℃、3.5MPa CO反应压力、水含量w(H2O)为6％、醋酸含量w(CH3COOH)为54％、CH3I含量w(CH3I) 控制在12％时，醋酸转化率高达100％，醋酸选择性达到最高为96.73％。From Tables 3 to 5 and Figures 1 and 2, it can be seen that Rh-L1 at a temperature of 200°C, a CO reaction pressure of 3.5MPa, a water content w(H 2 O) of 6%, and an acetic acid content w(CH 3 COOH) of When the CH 3 I content w(CH 3 I) was controlled at 54% and 12%, the conversion rate of acetic acid was as high as 100%, and the selectivity of acetic acid was up to 96.73%.
此外，将上述得到的Rh-L1催化优化条件(反应条件为：温度200℃、3.5MPa CO反应压力；各原料占原料总重量的百分比分别为：w(H2O)6％、w(CH3COOH) 54％、w(CH3I)12％、w(LiI)4％、w(CH3OH)24％。)，应用于Rh-L2及Rh-L3配合物进行实验，甲醇转化率达100％，醋酸选择性在96％以上，且无二甲醚产物产生。In addition, the above-obtained Rh-L1 catalytic optimization conditions (reaction conditions are: temperature 200 ° C, 3.5 MPa CO reaction pressure; the percentages of each raw material in the total weight of the raw materials are: w(H 2 O) 6%, w(CH 3 COOH) 54%, w(CH 3 I) 12%, w(LiI) 4%, w(CH 3 OH) 24%.), applied to Rh-L2 and Rh-L3 complexes for experiments, methanol conversion rate 100%, the selectivity of acetic acid is above 96%, and no dimethyl ether product is produced.
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