CN109970815A - Pyridyl group rhodium catalyst and its preparation method and application - Google Patents
Pyridyl group rhodium catalyst and its preparation method and application Download PDFInfo
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- 239000010948 rhodium Substances 0.000 title claims abstract description 112
- 239000003054 catalyst Substances 0.000 title claims abstract description 89
- 125000004076 pyridyl group Chemical group 0.000 title claims abstract description 80
- 229910052703 rhodium Inorganic materials 0.000 title claims abstract description 71
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 110
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 55
- 239000002994 raw material Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 15
- 230000006315 carbonylation Effects 0.000 claims abstract description 14
- 238000005810 carbonylation reaction 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 23
- 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
- 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 description 7
- 238000004458 analytical method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 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
- 238000002156 mixing Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005070 sampling Methods 0.000 claims description 4
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims description 3
- 238000011017 operating method Methods 0.000 claims description 2
- 239000000052 vinegar Substances 0.000 claims description 2
- 235000021419 vinegar Nutrition 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000006227 byproduct Substances 0.000 abstract description 2
- 239000003446 ligand Substances 0.000 abstract description 2
- 230000001376 precipitating effect Effects 0.000 abstract description 2
- 229960000583 acetic acid Drugs 0.000 description 23
- 230000003197 catalytic effect Effects 0.000 description 17
- 239000000047 product Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 4
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 238000012803 optimization experiment Methods 0.000 description 2
- 238000004445 quantitative analysis Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- MYSWGLZTUMZAAS-UHFFFAOYSA-N [Rh].[I] Chemical compound [Rh].[I] MYSWGLZTUMZAAS-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 229940125782 compound 2 Drugs 0.000 description 1
- -1 compound pyridine carboxylic acid methyl esters Chemical class 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000006464 oxidative addition reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 239000005060 rubber 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
-
- 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
-
- 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)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Pyridine Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
A kind of pyridyl group rhodium catalyst, the pyridyl group rhodium catalyst is by compound and Rh containing pyridyl group2(CO)4X2Coordination is formed, wherein X is Cl or I.The present invention is with Rh2(CO)4X2Rh-N and Rh-O coordinate bond are formed so that rhodium is mutually coordinated with the compound containing pyridyl group and obtains the pyridyl group rhodium catalyst of stable structure between rhodium carbonyl and compound containing pyridine groups with the raw materials of compound containing pyridine groups.The pyridyl group rhodium catalyst, so that catalyst is not easily decomposed precipitating and causes to inactivate, by improving the stability of catalyst by addition ligand on the basis of rhodium base catalyst, keeps its activity by maintaining the stability of catalyst containing pyridine groups.In addition, raw material synthesizes acetic acid using methanol and CO in the reaction, the not only high conversion rate of methanol in reaction, but also selectivity is single-minded only generates acetic acid solves the problems such as by-product in CARBONYLATION PROCESSES is more and the selectivity of acetic acid is not high.The present invention also provides the preparation method and application of the pyridyl group rhodium catalyst.
Description
Technical field:
The present invention relates to carbonylations to prepare acetic acid technical field, specifically, be related to a kind of pyridyl group rhodium catalyst and its
Preparation method and application.
Background technique:
Acetic acid is a kind of important basic organic chemical industry product, as important Organic Ingredients and a kind of excellent organic solvent
It is widely used in the industries such as chemical industry, light textile, plastics, medicine, rubber and dyestuff.
At present for global Processes for Producing Acetic Acid, Production of Acetic Acid by Methanol Carbonylation production technology has become global vinegar
Acid production process, and Monsanto production technology also becomes the prevailing technology of its production of acetic acid.Monsanto production technology with
[Rh(CO)2I2]–For catalytic active center, reaction condition is at 150-200 DEG C, and for pressure in 3-6MPa, reaction condition is more mild.
But there is also some problems, catalyst active center [Rh (CO) for rhodium iodine catalyst in Monsanto technique2I2]–In system
HI effect will form [Rh (CO)2I3H]–, [Rh (CO)2I3H]–And then it acts on forming [Rh (CO) with HI2I4]–Cause catalyst living
It appraises at the current rate at property center.Therefore the water of addition mass fraction 14-16% is generally required in rhodium base catalyst reaction system to accelerate
[Rh(CO)2I4]–To [Rh (CO)2I2]–Conversion, improve the stability of catalyst and keep the activity of its catalyst, it is still, high
The water of content will lead to the generation of Water gas shift/WGS side reaction among reaction system, and conversion ratio is reduced, separated in late-stage products
Cost is improved in journey.
Therefore, it is necessary to be modified to by the catalyst system in activated centre of rhodium, with improve the stability of catalyst with
The activity for keeping its catalyst avoids the generation for leading to Water gas shift/WGS side reaction among reaction system because of water content height, improves
Conversion ratio drop, reduces the cost in late-stage products separation process.
Summary of the invention:
An object of the present invention is to provide a kind of pyridyl group rhodium catalyst, using the stabilization containing pyridine groups as catalyst
Agent avoids leading to water among reaction system because of water content height to improve the stability of catalyst to keep the activity of its catalyst
The generation of gas conversion side reaction improves conversion ratio drop, reduces the cost in late-stage products separation process.
The second object of the present invention is to provide a kind of preparation method of pyridyl group rhodium catalyst.
The third object of the present invention is to provide a kind of application of pyridyl group rhodium catalyst.
A kind of pyridyl group rhodium catalyst, the pyridyl group rhodium catalyst is by compound and Rh containing pyridyl group2(CO)4X2Match
Position is formed, wherein X is Cl or I, and the structural formula of pyridyl group rhodium catalyst is as follows:
Preferably, the compound containing pyridyl group is 3- methyl -2- pyridine carboxylic acid, 2- pyridine carboxylic acid methyl esters and 2,2'-
One of bipyridyl -3,3'- dicarboxylic acids.
A kind of preparation method of pyridyl group rhodium catalyst as described in claim 1, comprising the following steps:
(1) Rh is weighed2(CO)4X2It is dissolved in CH3Solution A, Rh in solution A are obtained in OH solution2(CO)4X2Molar concentration be
0.004~0.01mol/L；
(2) according to molar ratio Rh2(CO)4X2: compound=1:2 containing pyridyl group weighs the compound containing pyridyl group, is dissolved in
CH3Solution B is obtained in OH, Rh in the molar concentration and solution A of the compound containing pyridyl group in solution B2(CO)4X2It is mole dense
It spends identical；
(3) according to molar ratio Rh2(CO)4X2: NaBPh4=1:2 weighs NaBPh4, it is dissolved in CH3Solution C, solution are obtained in OH
NaBPh in C4Molar concentration be solution A in Rh2(CO)4X22 times of molar concentration；
(4) under stirring, solution B is instilled in solution A dropwise, after solution B drips off, continues to stir at room temperature
20~60min obtains mixed liquor；
(5) solution C is instilled in the mixed liquor of step (3) dropwise, after solution C drips off, continues stirring 20 at room temperature
~60min；
(6) continue to be stirred solution, and anhydrous ether be added dropwise under stirring, after mixing evenly stand 20~
It is filtered after 30min, the solid being obtained by filtration is washed at least three times with ether, solvent is then dried under vacuum to and volatilizees completely, obtain
To pyridyl group rhodium catalyst.
Preferably, the compound containing pyridyl group is 3- methyl -2- pyridine carboxylic acid, 2- pyridine carboxylic acid methyl esters and 2,2'-
One of bipyridyl -3,3'- dicarboxylic acids.
Preferably, Rh in step (1) solution A2(CO)4X2Molar concentration be 0.006mol/L.
Preferably, the additional amount of anhydrous ether is the 20~30% of mixed liquor total volume in the step (5).
Pyridyl group rhodium catalyst is used as methanol carbonyl by a kind of application of pyridyl group rhodium catalyst as described in claim 1
Change prepares the catalyst in process of acetic acid.
Preferably, it is by the operating procedure that pyridyl group rhodium catalyst prepares acetic acid applied to methanol carbonyl, according to each original
Material accounts for the percentage of raw material gross weight respectively are as follows: w (H2O) 0~8%, w (CH3COOH) 30~60%, w (CH3I) 8~16%, w
(LiI) 4%, w (CH3OH) 18~48% each raw material is weighed, reaction kettle is added in whole raw materials and stirs evenly and is added 0.07
Reaction kettle speed of agitator 500rpm, 170~210 DEG C of temperature is arranged in~0.1mmol pyridyl group rhodium catalyst, carries out three by CO
Air in secondary replacement reaction kettle is finally passed through 2~4 MPa CO pressure and carries out carbonylation, cold to temperature after reacting 60min
But, it samples, carries out makings analysis.
Preferably, each raw material order of addition are as follows: first by H2O、CH3COOH、CH3OH be added reaction kettle in, then add LiI,
CH3Finally pyridyl group rhodium catalyst is added in reaction kettle by I.
Preferably, the methanol carbonyl prepares process of acetic acid, reaction condition are as follows: 200 DEG C of temperature, 3.5MPa CO reaction
Pressure；The percentage that each raw material accounts for raw material gross weight is respectively as follows: w (H2O) 6%, w (CH3COOH) 54%, w (CH3I) 12%, w
(LiI) 4%, w (CH3OH) 24%.
The present invention has the beneficial effect that: the present invention is with Rh2(CO)4X2With the raw materials of compound containing pyridine groups, in rhodium carbonyl
Between the compound containing pyridine groups, Rh-N and Rh-O coordinate bond are formed, so that rhodium is mutually coordinated with the compound containing pyridyl group,
Obtain the pyridyl group rhodium catalyst of stable structure.The pyridyl group rhodium catalyst, by the stabilization for maintaining catalyst containing pyridine groups
Property, so that catalyst is not easily decomposed precipitating and causes to inactivate, by being improved on the basis of rhodium base catalyst by addition ligand
The stability of catalyst keeps its activity.In addition, raw material synthesizes acetic acid using methanol and CO in the reaction, in reaction not only
The high conversion rate of methanol, and selectivity is single-minded only generates acetic acid, solves that by-product in CARBONYLATION PROCESSES is more and the choosing of acetic acid
The problems such as selecting property is not high.
Detailed description of the invention:
Fig. 1 is the catalytic activity of Rh-L1 catalysis methanol carbonylation under different acetate concentrations；
Fig. 2 is the catalytic activity of Rh-L1 catalysis methanol carbonylation under different air pressures.
Specific embodiment:
Embodiment 1:
The pyridyl group rhodium catalyst of the present embodiment, by the compound 2 containing pyridyl group, 2'- bipyridyl -3,3'- dicarboxylic acids with
Rh2(CO)4Cl2Coordination is formed, and the structural formula of pyridyl group rhodium catalyst is as follows:
The preparation method of above-mentioned pyridyl group rhodium catalyst, comprising the following steps:
(1) Rh is weighed2(CO)4Cl2It is dissolved in CH3Solution A, Rh in solution A are obtained in OH solution2(CO)4Cl2Molar concentration
For 0.006mol/L；
(2) according to molar ratio Rh2(CO)4Cl2: 2,2'- bipyridyl -3,3'- dicarboxylic acids=1:2 weighs 2,2'- bipyridyl -
3,3'- dicarboxylic acids, are dissolved in CH3Solution B is obtained in OH, the molar concentration of 2,2'- bipyridyl -3,3'- dicarboxylic acids is in solution B
0.006mol/L；
(3) according to molar ratio Rh2(CO)4X2: NaBPh4=1:2 weighs NaBPh4, it is dissolved in CH3Solution C, solution are obtained in OH
NaBPh in C4Molar concentration be 0.012mol/L；
(4) under stirring, solution B is instilled in solution A dropwise, after solution B drips off, continues to stir at room temperature
30min obtains mixed liquor；
(5) solution C is instilled in the mixed liquor of step (3) dropwise, after solution C drips off, continues to stir at room temperature
30min；
(6) continue to be stirred solution, and 25% anhydrous second of mixed liquor total volume is added dropwise under stirring
Ether is filtered after standing 20~30min after mixing evenly, the solid being obtained by filtration is washed at least three times with ether, then vacuum
Drying is volatilized completely to solvent, obtains pyridyl group rhodium catalyst Rh-L1, i.e. khaki solid Rh-2,2'- bipyridyl -3,3'- bis-
Carboxylates.
Pyridyl group rhodium catalyst is applied to the behaviour that methanol carbonyl prepares acetic acid by the application of above-mentioned pyridyl group rhodium catalyst
It is to account for the percentage of raw material gross weight respectively according to each raw material as step are as follows: w (H2O) 6%, w (CH3COOH) 54%, w
(CH3I) 12%, w (LiI) 4%, w (CH3OH) 24% each raw material is weighed, first by H2O、CH3COOH、CH3OH is added in reaction kettle,
LiI, CH are added again3Whole raw materials are added reaction kettle and stirred evenly by I, and 0.07~0.1mmol pyridyl group rhodium is then added and urges
Reaction kettle speed of agitator 500rpm, 200 DEG C of temperature is arranged in agent, carries out air in replacement reaction kettle three times by CO, finally leads to
Enter 3.5MPa CO pressure and carry out carbonylation, cooling to temperature after reacting 60min, sampling carries out makings analysis.
The pyridyl group rhodium catalyst is carried out in four steps in the catalytic cycle process that methanol carbonyl prepares acetic acid:
A, the oxidation addition process of iodomethane: composition catalyst and CH3I generates intermediate by oxidative addition
TN1；
B, methyl migrates: in intermediate TN1, methyl is constantly approached to carbonyl, and then completes migration to form intermediate TN2 complete
At rearrangement；
C, carbonyl is coordinated: carbonyl and intermediate TN2 interact to form next intermediate product TN3；
d、CH3COI reduction is eliminated: intermediate TN3 reduction, which is eliminated, forms CH3COI, and then hydrolyze and generate product CH3COOH,
And catalyst is restored to and most starts state, and then carries out next catalytic cycle process.Catalytic cycle process is schematically as follows:
Example 2:
The pyridyl group rhodium catalyst of the present embodiment, by compound 3- methyl -2- pyridine carboxylic acid and Rh containing pyridyl group2
(CO)4Cl2Coordination is formed, and the structural formula of pyridyl group rhodium catalyst is as follows:
The preparation method of above-mentioned pyridyl group rhodium catalyst, comprising the following steps:
(1) Rh is weighed2(CO)4Cl2It is dissolved in CH3Solution A, Rh in solution A are obtained in OH solution2(CO)4Cl2Molar concentration
For 0.004mol/L；
(2) according to molar ratio Rh2(CO)4Cl2: 3- methyl -2- pyridine carboxylic acid=1:2 weighs 3- methyl -2- pyridine carboxylic acid,
It is dissolved in CH3Solution B is obtained in OH, the molar concentration of 3- methyl -2- pyridine carboxylic acid is 0.004mol/L in solution B；
(3) according to molar ratio Rh2(CO)4Cl2: NaBPh4=1:2 weighs NaBPh4, it is dissolved in CH3Solution C is obtained in OH, it is molten
NaBPh in liquid C4Molar concentration be 0.008mol/L；
(4) under stirring, solution B is instilled in solution A dropwise, after solution B drips off, continues to stir at room temperature
20min obtains mixed liquor；
(5) solution C is instilled in the mixed liquor of step (3) dropwise, after solution C drips off, continues to stir at room temperature
20min；
(6) continue to be stirred solution, and 20% anhydrous second of mixed liquor total volume is added dropwise under stirring
Ether filters after standing 25min after mixing evenly, the solid being obtained by filtration is washed at least three times with ether, is then dried in vacuo
It volatilizees completely to solvent, obtains pyridyl group rhodium catalyst Rh-L2, is i.e. khaki solid Rh-3- methyl -2- pyridine carboxylic acid cooperates
Object.
Pyridyl group rhodium catalyst is applied to the behaviour that methanol carbonyl prepares acetic acid by the application of above-mentioned pyridyl group rhodium catalyst
It is to account for the percentage of raw material gross weight respectively according to each raw material as step are as follows: w (H2O) 4%, w (CH3COOH) 45%, w
(CH3I) 15%, w (LiI) 4%, w (CH3OH) 32% each raw material is weighed, first by H2O、CH3COOH、CH3OH is added in reaction kettle,
LiI, CH are added again3Whole raw materials are added reaction kettle and stirred evenly, 0.1mmol pyridyl group rhodium catalyst is then added by I,
Reaction kettle speed of agitator 500rpm, 180 DEG C of temperature are set, air in replacement reaction kettle three times is carried out by CO, is finally passed through
3MPa CO pressure carries out carbonylation, cooling to temperature after reacting 60min, and sampling carries out makings analysis.Its catalytic process
It is same as Example 1.
Embodiment 3:
The pyridyl group rhodium catalyst of the present embodiment, by compound pyridine carboxylic acid methyl esters and Rh containing pyridyl group2(CO)4I2Match
Position is formed, and the structural formula of pyridyl group rhodium catalyst is as follows:
The preparation method of above-mentioned pyridyl group rhodium catalyst, comprising the following steps:
(1) Rh is weighed2(CO)4I2It is dissolved in CH3Solution A, Rh in solution A are obtained in OH solution2(CO)4I2Molar concentration be
0.008mol/L；
(2) according to molar ratio Rh2(CO)4I2: 2,2'- bipyridyl -3,3'- dicarboxylic acids=1:2 weighs bipyridyl -3 2,2'-,
3'- dicarboxylic acids, is dissolved in CH3Solution B is obtained in OH, the molar concentration of 2,2'- bipyridyl -3,3'- dicarboxylic acids is in solution B
0.008mol/L；
(3) according to molar ratio Rh2(CO)4I2: NaBPh4=1:2 weighs NaBPh4, it is dissolved in CH3Solution C, solution are obtained in OH
NaBPh in C4Molar concentration be 0.016mol/L；
(4) under stirring, solution B is instilled in solution A dropwise, after solution B drips off, continues to stir at room temperature
50min obtains mixed liquor；
(5) solution C is instilled in the mixed liquor of step (3) dropwise, after solution C drips off, continues to stir at room temperature
40min；
(6) continue to be stirred solution, and 28% anhydrous second of mixed liquor total volume is added dropwise under stirring
Ether filters after standing 28min after mixing evenly, the solid being obtained by filtration is washed at least three times with ether, is then dried in vacuo
It volatilizees completely to solvent, obtains pyridyl group rhodium catalyst Rh-L3, i.e. black solid Rh- pyridine carboxylic acid methyl esters complex.
Pyridyl group rhodium catalyst is applied to the behaviour that methanol carbonyl prepares acetic acid by the application of above-mentioned pyridyl group rhodium catalyst
It is to account for the percentage of raw material gross weight respectively according to each raw material as step are as follows: w (H2O) 2%, w (CH3COOH) 38%, w
(CH3I) 10%, w (LiI) 4%, w (CH3OH) 46% each raw material is weighed, first by H2O、CH3COOH、CH3OH is added in reaction kettle,
LiI, CH are added again3Whole raw materials are added reaction kettle and stirred evenly, 0.08mmol pyridyl group rhodium catalyst is then added by I,
Reaction kettle speed of agitator 500rpm, 185 DEG C of temperature are set, air in replacement reaction kettle three times is carried out by CO, is finally passed through
4MPa CO pressure carries out carbonylation, cooling to temperature after reacting 60min, and sampling carries out makings analysis.Its catalytic process
It is same as Example 1.
Conversion performance measurement and analysis:
Makings evaluation condition: carrying out qualitative and quantitative analysis to product using gas chromatograph (GC-2014), vapor detection
Program are as follows: detector and gasification room temperature are respectively 230 DEG C and 220 DEG C, and split ratio 10, sample volume is 1 μ L, and chromatographic column originates
Temperature is 32 DEG C, retention time 2min, is warming up to 60 DEG C with 5 DEG C/min, retains 2min, then be warming up to 150 with 10 DEG C/min
DEG C, retain 2min.Using occurring the standard curve of substance in external standard method product, each sample is measured in parallel 3 times, is averaged
Value, obtains respective standard curvilinear equation, carries out quantitative analysis to experimental products according to calibration curve equation: carrying out GC to product
Analysis, brings respective standard fitting equation by the area of tie substance in GC result spectrogram, obtains its mass fraction.
Table 1: each standard of physical fitting equation
In table 1:aMiFor the mass fraction of i substance, AiFor the peak area of i substance
With methanol conversion (x, %), acetic acid selectivity (sHAc, %), methyl acetate selectivity (sMeOAc, %), acetic acid receive
Rate (yHAc, %), methyl acetate yield (yMeOAc, %) and it is its catalytic performance test index.
yHAc=x × sHAc× 100% (4)
yMeOAc=x × sMeOAc× 100% (5)
Formula (1)~(5) are its calculation formula, in formula, n1、n2、n3、n4Methanol additive amount, methanol respectively in reaction process
Consumption, acetic acid production quantity, methyl acetate production quantity, unit are mol.
To be prepared in embodiment 1-3 resulting catalyst carry out catalysis reaction test obtain the performance comparison data in table 2.
Table 2: different catalysts catalytic performance comparison
In table 2, L1:2,2 '-bipyridyl -3,3 '-dicarboxylic acids, L2:3- methyl -2- pyridine carboxylic acid, L3: pyridine carboxylic acid methyl esters
From table 2 it can be seen that each embodiment limit catalytic reaction condition under, Rh-L1 complex compare Rh-L2,
Rh-L3 composition catalyst shows superior catalytic performance, methanol conversion up to 100%, acetic acid selectivity 96% or more,
No product dimethyl ether generates, its same catalytic performance is obviously superior to Rh2(CO)4Cl2。
The optimization experiment of Rh-L1 catalytic condition:
Catalytic condition optimization experiment is carried out to resulting catalyst Rh-L1 is prepared in specific embodiment 1, is in reaction condition
" 200 DEG C of temperature, 3.5MPa CO reaction pressure；The percentage that each raw material accounts for raw material gross weight is respectively as follows: w (H2O) 6%, w
(CH3It COOH) is 54%, w (CH3I) to change arbitrary parameter, compare on the basis of 12% ", obtain table 3 to 5 and Fig. 1 and
Fig. 2.
Table 3: the catalytic activity of Rh-1L catalysis methanol carbonylation under different temperatures
Table 4: different water content w (H2O the catalytic activity of Rh-L1 catalysis methanol carbonylation under)
Table 5: the catalytic activity of Rh-L1 catalysis methanol carbonylation under different temperatures
It can be seen that Rh-L1 in 200 DEG C of temperature, 3.5MPa CO reaction pressure, water content w from table 3 to 5 and Fig. 1 and Fig. 2
(H2It O) is 6%, acetic acid content w (CH3It COOH) is 54%, CH3I content w (CH3I) control is at 12%, acetic acid high conversion rate
Up to 100%, acetic acid selectively reaches up to 96.73%.
In addition, by Rh-L1 optimized for catalysis condition obtained above (reaction condition are as follows: 200 DEG C of temperature, 3.5MPa CO reaction
Pressure；The percentage that each raw material accounts for raw material gross weight is respectively as follows: w (H2O) 6%, w (CH3COOH) 54%, w (CH3I) 12%, w
(LiI) 4%, w (CH3OH) 24%.), it is tested applied to Rh-L2 and Rh-L3 complex, methanol conversion is up to 100%, vinegar
Sour selectivity is generated 96% or more, and without product dimethyl ether.
Claims (10)
1. a kind of pyridyl group rhodium catalyst, which is characterized in that the pyridyl group rhodium catalyst is by compound and Rh containing pyridyl group2
(CO)4X2Coordination is formed, wherein X is Cl or I, and the structural formula of pyridyl group rhodium catalyst is as follows:
。
2. pyridyl group rhodium catalyst as described in claim 1, which is characterized in that the compound containing pyridyl group is 3- first
One of base -2- pyridine carboxylic acid, 2- pyridine carboxylic acid methyl esters and 2,2'- bipyridyl -3,3'- dicarboxylic acids.
3. a kind of preparation method of pyridyl group rhodium catalyst as described in claim 1, which comprises the following steps:
(1) Rh is weighed2(CO)4X2It is dissolved in CH3Solution A, Rh in solution A are obtained in OH solution2(CO)4X2Molar concentration be 0.004
~0.01mol/L；
(2) according to molar ratio Rh2(CO)4X2: compound=1:2 containing pyridyl group weighs the compound containing pyridyl group, is dissolved in CH3OH
In obtain solution B, Rh in the molar concentration and solution A of the compound containing pyridyl group in solution B2(CO)4X2Molar concentration phase
Together；
(3) according to molar ratio Rh2(CO)4X2: NaBPh4=1:2 weighs NaBPh4, it is dissolved in CH3Solution C is obtained in OH, in solution C
NaBPh4Molar concentration be solution A in Rh2(CO)4X22 times of molar concentration；
(4) under stirring, solution B is instilled in solution A dropwise, after solution B drips off, continue at room temperature stirring 20~
60min obtains mixed liquor；
(5) solution C is instilled dropwise in the mixed liquor of step (3), after solution C drips off, continue at room temperature stirring 20~
60min；
(6) continue to be stirred solution, and anhydrous ether be added dropwise under stirring, after mixing evenly stand 20~
It is filtered after 30min, the solid being obtained by filtration is washed at least three times with ether, solvent is then dried under vacuum to and volatilizees completely, obtain
To pyridyl group rhodium catalyst.
4. the preparation method of pyridyl group rhodium catalyst as claimed in claim 3, which is characterized in that the chemical combination containing pyridyl group
Object is one of 3- methyl -2- pyridine carboxylic acid, 2- pyridine carboxylic acid methyl esters and 2,2'- bipyridyl -3,3'- dicarboxylic acids.
5. the preparation method of pyridyl group rhodium catalyst as claimed in claim 3, which is characterized in that in step (1) solution A
Rh2(CO)4X2Molar concentration be 0.006mol/L.
6. the preparation method of pyridyl group rhodium catalyst as claimed in claim 3, which is characterized in that anhydrous in the step (5)
The additional amount of ether is the 20~30% of mixed liquor total volume.
7. a kind of application of pyridyl group rhodium catalyst as described in claim 1, which is characterized in that pyridyl group rhodium catalyst to be used as
Methanol carbonyl prepares the catalyst in process of acetic acid.
8. the application of pyridyl group rhodium catalyst as claimed in claim 7, which is characterized in that pyridyl group rhodium catalyst to be applied to
The operating procedure that methanol carbonyl prepares acetic acid is to account for the percentage of raw material gross weight respectively according to each raw material are as follows: w (H2) 0 O~
8%, w (CH3COOH) 30~60%, w (CH3I) 8~16%, w (LiI) 4%, w (CH3OH) 18~48% each raw material is weighed, it will
Whole raw materials are added reaction kettle and stir evenly and be added 0.07~0.1mmol pyridyl group rhodium catalyst, and setting reaction kettle stirs
170~210 DEG C of revolving speed 500rpm, temperature carry out air in replacement reaction kettle three times by CO, are finally passed through 2~4MPa CO pressure
Power carries out carbonylation, cooling to temperature after reacting 60min, and sampling carries out makings analysis.
9. the application of pyridyl group rhodium catalyst as claimed in claim 8, which is characterized in that each raw material order of addition are as follows: first will
H2O、CH3COOH、CH3OH is added in reaction kettle, then adds LiI, CH3Finally pyridyl group rhodium catalyst is added in reaction kettle by I.
10. the application of pyridyl group rhodium catalyst as claimed in claim 8, which is characterized in that the methanol carbonyl prepares vinegar
Sour process, reaction condition are as follows: 200 DEG C of temperature, 3.5MPa CO reaction pressure；Each raw material accounts for the percentage difference of raw material gross weight
Are as follows: w (H2O) 6%, w (CH3COOH) 54%, w (CH3I) 12%, w (LiI) 4%, w (CH3OH) 24%.
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