WO2014101901A1 - 一种二甲醚羰基化制备乙酸甲酯的方法 - Google Patents

一种二甲醚羰基化制备乙酸甲酯的方法 Download PDF

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WO2014101901A1
WO2014101901A1 PCT/CN2014/000128 CN2014000128W WO2014101901A1 WO 2014101901 A1 WO2014101901 A1 WO 2014101901A1 CN 2014000128 W CN2014000128 W CN 2014000128W WO 2014101901 A1 WO2014101901 A1 WO 2014101901A1
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dimethyl ether
catalyst
reactor
reaction
mordenite
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PCT/CN2014/000128
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English (en)
French (fr)
Chinese (zh)
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朱文良
刘红超
刘勇
倪友明
刘中民
孟霜鹤
李利娜
刘世平
周慧
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中国科学院大连化学物理研究所
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Publication of WO2014101901A1 publication Critical patent/WO2014101901A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/36—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates
    • C07C67/37—Preparation of carboxylic acid esters by reaction with carbon monoxide or formates by reaction of ethers with carbon monoxide

Definitions

  • the invention belongs to the field of catalytic chemistry, and particularly relates to a method for preparing methyl acetate.
  • the raw material dimethyl ether enters the catalyst bed through a gas distributor and undergoes carbonylation reaction to synthesize methyl acetate. Background technique
  • ethanol has good mutual solubility. It can be blended into gasoline as a blending component, partially replaces gasoline, and increases the Xinxin value and oxygen content of gasoline, effectively promoting the full combustion of gasoline and reducing The emission of CO and HC in automobile exhaust.
  • ethanol can make China's vehicle fuels have diverse structural characteristics. At present, China mainly develops fuel ethanol from grain, especially corn. It has become the third largest producer and consumer of fuel ethanol in Brazil and the United States. However, according to China's national conditions, there are many unfavorable factors for ethanol production from grain. In the future, the development of fuel ethanol in China is more than a non-food route.
  • the process route of coal-to-ethanol is mainly divided into two types: one is that the synthesis gas directly produces ethanol, but the noble metal ruthenium catalyst is required, the cost of the catalyst is high and the yield of ruthenium is limited; the second is that the synthesis gas is hydrogenated by acetic acid to produce ethanol.
  • the synthesis gas is first subjected to liquid phase carbonylation of methanol to acetic acid, and then hydrogenated to synthesize ethanol. This route is mature, but the equipment needs special alloys that are resistant to corrosion and costly.
  • the temperature of the catalyst bed of the adiabatic bed reactor can be as high as 100 ° C or even higher.
  • the following fixed bed reactors are generally employed for the strong exothermic reaction: adiabatic reactor; internal heat exchanger reactor; tubular reactor; gas phase cold reactor; gas phase quench reactor.
  • the temperature distribution of the catalyst bed is uneven and difficult to control, and it is difficult to carry out large-scale industrial production. Summary of the invention
  • Those skilled in the art can select the appropriate number and type of reactors and the connection between the reactors according to the needs of actual industrial production.
  • a gas distributor is disposed in the middle of the reactor, and a catalyst bed is disposed between the distributor and the inner wall of the reactor, and the dimethyl ether gas in the raw material gas or the raw material gas enters the distributor axially. , uniformly distributed radially to each catalyst bed through small holes in the wall of the distributor.
  • the reactor is a fixed bed reactor.
  • the number of catalyst beds in the reactor is 2 to 20, and a further preferred number is 2 to 6.
  • the reactor may be a single reactor or a plurality of reactors connected in series.
  • the reaction zone comprises 2 to 20 reactors. In a further preferred embodiment, the reaction zone contains from 2 to 6 reactors in series.
  • the reaction temperature is 220 to 280 °C.
  • reaction pressure is 2.0 to 10.0 MPa.
  • the gas volumetric space velocity is 100 SOOOO'.
  • the molar ratio of dimethyl ether to carbon monoxide is DME/COl/2 ⁇ 0.
  • the ferrierite is a hydrogen type ferrierite having a silicon to aluminum atomic ratio of 5 to 100.
  • the mordenite molecular sieve skeleton contains hetero atom iron and/or gallium.
  • the ferrierite molecular sieve skeleton contains hetero atom iron and/or gallium.
  • the mordenite molecular sieve is supported by iron, copper, An oxide of a metal of one or more of silver, iridium, platinum, palladium, cobalt, or ruthenium.
  • the ferrierite molecular sieve supports an oxide of a metal selected from one or more of iron, copper, silver, ruthenium, platinum, palladium, cobalt, and rhodium.
  • the mordenite may be adsorbed by a pyridine and/or pyridine substituent prior to the reaction.
  • the pyridine substituent is one, two or three of the five H on the pyridine ring independently selected from the group consisting of F, Cl, Br, I, CH 3 , CF 3 , CH 3 CH Substituted by a substituent in 2 or N0 2 .
  • the process of adsorbing the mordenite catalyst by the pyridine and/or pyridine substitution is: filling the hydrogen type mordenite into the reactor, and introducing pyridine at an adsorption temperature of 90 to 420 ° C a mixture of an organic amine and any one or more gases selected from the group consisting of carbon monoxide, hydrogen, air, nitrogen, helium and argon, adsorbed for 0.5 to 48 hours, and then at a temperature selected from the group consisting of carbon monoxide, hydrogen, A mixture of air, nitrogen, helium and argon or a mixture of a plurality of gases is purged for 0.5 to 6 hours to obtain a hydrogenated mordenite adsorbed by a pyridine organic amine.
  • the adsorption temperature is 160 to 320 °C.
  • the pyridine organic amine adsorbed in the catalyst is pyridine and/or 2-methylpyridine
  • the pyridine organic amine in the raw material gas is pyridine and/or 2-methylpyridine
  • the pyridine organic amine can also be expressed as a pyridine compound, including aminopyridine, bromopyridine, picoline, iodopyridine, chloropyridine, nitropyridine, hydroxypyridine, benzylpyridine, ethylpyridine, Cyanopyridine, fluoropyridine, dihydropyridine and other alkylpyridines and halopyridines, and the like.
  • the bromopyridine such as 2-fluoro-5-bromopyridine, 2-amino-3-iodo-5-bromopyridine, 4-bromopyridine hydrochloride, 2-chloro-4-bromopyridine, 4-amino-3-bromopyridine, 2-indolyl-5-bromopyridine, 2-fluoro-3-bromopyridine, 2,3,5-tribromopyridine, methyl 5-bromopyridine-2-carboxylate, 2-fluoro-4-methyl-5-bromopyridine, 2-acetyl-5-bromopyridine, 3,5-dibromopyridine, 2,3-dibromopyridine, 2-hydroxymethyl-4-bromopyridine, 2,4-dibromopyridine, 2,6-dimethyl-3-bromopyridine, 2,6-dibromopyridine, 2,5-dichloro-3-bromopyridine, and the like.
  • the iodopyridine such as 4-(BOC-amino)-3-iodopyridine, 2-ammonia Yl --3-methyl _ _ _ 5-iodopyridine, 2-bromo-5-iodopyridine, 5-bromo-2-iodopyridine, 2-amino-5-chloro-3-iodopyridine, 2-chloro-4-iodo Pyridine-3-carbaldehyde, 3-amino-4-iodopyridine, 2-fluoro-3-aldehyde-4-iodopyridine, 3-fluoro-4-iodopyridine, 2,6-dichloro-4-iodopyridine, 2-iodopyridine, 2-chloro-5-trifluoromethyl-4-iodopyridine, 3-bromo-5-iodopyridine, 2,5-diiodopyridine, 2-bromo-4-iodopyridine
  • the nitropyridine such as 2-amino-4-methyl-5-nitropyridine, 2,4-dichloro-6-methyl-3-nitropyridine, 3-chloro-2 -nitropyridine, 2-fluoro-3-nitropyridine, 2,4-dichloro-5-nitropyridine, 2-methoxy-4-methyl-5-nitropyridine, dichloro-3- Nitropyridine, 4-chloro-3-nitropyridine, 3-ethoxy-2-nitropyridine, 3,5-dimethyl-4-nitropyridine-2-methanol, 2,6-dibromo 3-nitropyridine, 1-(5-nitropyridin-2-yl)piperazine, 4-methoxy-3-nitropyridine, 3-bromo-4-nitropyridine-N-oxide, 5-bromo-2-nitropyridine, 2,5-dibromo-3-nitropyridine, 3-amino-2-nitropyridine, 5-methyl-2-amino-3-nitropyridine, and the like.
  • the picoline such as 2,5-dibromo-3-methylpyridine, 2-fluoro-6-methylpyridine, 2-(chloromethyl)-4-methoxy-3 , 5-dimethylpyridine, 2-amino-3-bromo-6-methylpyridine, 2-methyl-6-trifluoromethylpyridine-3-carbonyl chloride 6-bromo-3-hydroxymethylpyridine, 2-bromo-4-methylpyridine, 2-(chloromethyl)-4-(3-methoxypropoxy)-3-methylpyridine, 3-chloromethylpyridine hydrochloride, 2-amino • 5-Bromo-4-methylpyridine, 2-methoxy-5-trifluoromethylpyridine, 5-cyano-2-methylpyridine, 3-aldehyde-6-methylpyridine, 2,5- Dibromo-6-methylpyridine, 5-bromo-2-hydroxymethylpyridine, 3-amino-2-methylpyridine, 2-fluoro-6-trifluoromethylpyridine, 3-trifluoromethylpyr
  • the ethyl pyridine such as 1-ethyl-1,2-dihydro-6-light-4-methyl-2-oxo-3-pyridinecarboxamide, 3-(2- Aminoethyl)pyridine, 3-(2-chloroethyl)-6,7,8,9-tetrahydro-2-methyl-4H-pyrido[l,2-a]pyrimidin-4-one, 2 -bromo-4-ethylpyridine, 2-(2-aminoethyl)pyridine, 2-amino-4-ethylpyridine, diethyl(3-pyridyl)-boronium 5- ⁇ 4-[2- (5-ethyl-2-pyridyl)-ethoxy]-benzyl ⁇ -2-imino-4-thiazolonesone, 1-ethylbromide pyridine, 1-ethylchloropyridine 6- ( Tert-butyl)-3-ethyl-2-amino
  • aminopyridine such as 2,6-diaminopyridine, 2-chloro-4-aminopyridine, 2-acetamidopyridine, 3-chloro-2-aminopyridine, 4-methylaminopyridine, 2 ,6-dichloro-3-ammonia Pyridine, 4-(3-methylphenyl)aminopyridine-3-sulfonamide 2-chloro-5-aminopyridine, methyl 6-aminopicolinate, 2-methoxy-6-methylaminopyridine, 2 ,4-diaminopyridine, 6-methoxy-2,3-diaminopyridine dihydrochloride, 2-benzylaminopyridine, 3-aminopyridine-4-carboxylic acid ethyl ester, 3-methyl-4- Aminopyridine, 2,6-dibromo-3-aminopyridine, 2-bromo-3-aminopyridine, 2-acetamido-5-aminopyridine,
  • the fluoropyridine such as 2-fluoropyridine-5-formaldehyde, 2,6-difluoropyridine-3-boronic acid, 2-chloro-3-fluoropyridine-4-boronic acid, 2-methoxyl 3-bromo-5-fluoropyridine, 2-fluoropyridine-6-carboxylic acid, 5-chloro-2-fluoropyridine 2-bromo-4-fluoropyridine, 3,5-dichloro-2,4,6- Trifluoropyridine, 4-amino-3,5-dichloro-2,6-difluoropyridine, 2-amino-3-fluoropyridine, 2-fluoropyridine, 2-chloro-3-fluoropyridine, 2-chloro- 3-nitro-5-fluoropyridine, 3-fluoropyridine-2-carboxylic acid, 3-chloro-2,4,5,6-tetrafluoropyridine, 4-bromo-2-fluoropyridine,
  • the chloropyridine such as 2-amino-6-chloropyridine, 2-[N, n-bis(trifluoromethanesulfonyl)amino]-5-chloropyridine, 2-amino-3-nitrate 5--6-chloropyridine, 5-amino-2,3-dichloropyridine, 2-chloropyridine-4-boronic acid pinacol ester, 2,3-diamino-5-chloropyridine, 2-amino-3, 5 dichloropyridine, 2-chloropyridine oxide, 2-methoxy-3-bromo-5-chloropyridine, 2-amino-5-chloropyridine,
  • the hydroxypyridine such as 4-hydroxy-6-methyl-3-nitro-2-pyridinol, 3-bromo-2-hydroxy-5-methylpyridine, 6-methyl-2 -hydroxypyridine, 1,2-dimethyl-3-hydroxy-4-pyridone, 2-amino-3-hydroxypyridine, 2-hydroxy-4-(trifluoromethyl)pyridine, 2-hydroxy-5- Iodopyridine, 2-hydroxy-4-methylpyridine, 2-hydroxy-5-methyl-3-nitropyridine, 2-hydroxy-6-methyl-5-nitropyridine, 2,6-dihydroxy- 3,4-dimethylpyridine, 3-amino-4-hydroxypyridine, 2-hydroxy-3-nitropyridine, 2-hydroxypyridine, 5-nitro-2-hydroxy-3-chloropyridine, 2-hydroxyl Pyridine-N-oxide, 4-hydroxy-3-methylpyridine, 2-bromo-6-hydroxypyridine, and the like.
  • the cyanopyridine such as 3-cyano-6-trifluoromethylpyridine, 5-bromo-2-cyano-3-nitropyridine, 2-amino-3-cyanopyridine , 3-nitro-2-cyanopyridine, 4-cyanopyridine, 3-cyano-2-fluoropyridine, 3-cyano-6-hydroxypyridine, 4-chloro-3-cyanopyridine, 3- Cyano-4-methylpyridine, 3-amino-6-cyanopyridine, 2-cyano-5-hydroxypyridine, 2-cyano-3-fluoropyridine, 3-chloro-4-cyanopyridine, 4 -cyanopyridine, N-oxide, 2-chloro-3-cyanopyridine, 3-amino-4-cyanopyridine, 2-cyanopyridine-5-boronic acid pinamate 5-bromo-2-cyano Pyridine, etc.
  • the dihydropyridine such as 2,3-dihydropyrido[2,3-d][l,3]oxazol-2-one, 4-oxo-1,4-dihydrogen -2,6-pyridinedicarboxylic acid, 6,7-dihydro-5H-pyrrolo[3,4-b]pyridine, 5-bromo-2,3-dihydro-1H-pyrrolyl [2,3-B Pyridine, methyl 2-oxo-1,2-dihydro-3-pyridinecarboxylate, 2,4-dichloro-5,6-dihydropyrido[3,4-D]pyrimidine-7 (8H )-tert-butyl formate, 2,3-dihydro-1,4-di[2,3-b]pyridine, 9-methyl-3,4-dihydro-2H-pyridopyrimidin-2-one , N-benzyloxycarbonyl-3,6-dihydro-2H
  • the benzylpyridine such as 2-benzylpyridine, 4-(4-nitrobenzyl)pyridine, 2-p-chlorobenzylpyridine, 4-benzylpyridine, 1-benzylpyridine 3-carboxylate, 6-benzyl-2,4-dichloro-5,6,7,8-tetrahydropyrido[4,3-D]pyrimidine, 7-benzyl-4-chloro-5 ,6,7,8-tetrahydropyridine
  • [3,4B]pyridine (4-chlorobenzyl)pyridin-3-ylmethylamine, (4-fluorobenzyl)pyridine-3-methylamine, 7-benzyl-5,6,7,8-tetra Hydropyrido[3,4-D]pyrimidine-2,4(1H,3H)-dione, 1-(4-nitrobenzyl)-4-(4-diethylamine phenylazo)bromopyridine, 2-amino-3-nitro-6-(4-fluorobenzylamino)pyridine, benzylpyridin-2-ylmethylamine and the like.
  • the outstanding advantage of the invention is that the raw material dimethyl ether uniformly enters the catalyst bed through the gas distributor, can effectively control the temperature distribution of the catalyst bed, avoid hot spots, thereby reducing side reactions, improving the selectivity of the target product, and prolonging the life of the catalyst. . DRAWINGS
  • FIG. 1 (a) Schematic diagram of the gas distributor
  • Figure 1 (b) Schematic diagram of the reactor containing the gas distributor
  • FIG. 5 Schematic diagram of multiple fixed bed reactors in series feeding
  • Dimethyl ether conversion [(mole of dimethyl ether in feed gas) - (molar of dimethyl ether in product)] ⁇ (mole of dimethyl ether in feed gas) ⁇ ( ⁇ %)
  • Methyl acetate selectivity (2/3) X (methyl moles of methyl acetate in the product) ⁇ [(mole of dimethyl ether carbon in the feed gas) - (molar mole of dimethyl ether in the product) X (100 %)
  • the catalyst is represented by 11%] ⁇ /8, wherein:
  • n mass percentage of metal based on the total weight of the catalyst X 100; the metal in the supported catalyst is in an oxidized state, and the content is represented by a simple metal.
  • the MOR molecular sieve support was subjected to a calcination purification treatment at a temperature of 550 °C. After cooling, an equal volume of impregnation was carried out. 1.8875 g of ⁇ ( ⁇ 0 3)3 ⁇ 3 ⁇ 2 0 was dissolved in 6 ml of deionized water, and the mixed aqueous solution was impregnated onto an 9.5 g MOR molecular sieve support by an equal volume impregnation method, and excess solvent was evaporated in an 80 ° C water bath. The obtained sample was dried in a 120-inch oven for 12 h.
  • the sample was placed in a muffle furnace, and the temperature was raised to 350 ° C at a heating rate of 2 ° C/min, and calcined for 3 hours.
  • the mordenite catalyst supported on the metal copper oxide obtained after calcination is represented by the mass percentage of metallic copper: 5 wt% Cu/MOR.
  • the ferrierite molecular sieve carrier was subjected to a calcination purification treatment at a temperature of 550 °C. After cooling, an equal volume of impregnation was carried out. 1.8875 g of Cu(N0 3) 3 , 3H 2 0 was dissolved in 6 ml of deionized water, and the mixed aqueous solution was impregnated onto an 9.5 g of magnesium-based molecular sieve support by an equal volume impregnation method, and excess solvent was evaporated in an 80-inch water bath. The obtained sample was dried in a 120-inch oven for 12 hours.
  • the ferrobase catalyst supported on the copper oxide supported after calcination is represented by the mass percentage of metallic copper: 5 wt% Cu/FER.
  • the prepared sodium mordenite Na-MOR or Na-FER and Y-A1 2 0 3 are based on dry weight
  • the ratio of 80:20 was uniformly mixed, and an appropriate amount of nitric acid solution was added for extrusion molding.
  • the strip catalyst was 02.0 mm in diameter, dried at room temperature, dried at 120 ° C for 4 hours, and calcined at 550 ° C for 4 hours in a muffle furnace. Then, it was ion-exchanged three times with a 0.8 M ammonium nitrate solution at 80 ° C, washed three times with deionized water, then dried at 120 ° C for 4 hours, and calcined at 550 ° C for 4 hours to obtain a desired catalyst.
  • the strip catalyst which was broken to about 3 mm during the reaction was charged.
  • the catalyst was activated at 550 Torr for 4 hours in a nitrogen atmosphere, and then the temperature of the bed was lowered to the reaction temperature, and a certain proportion of dimethyl ether, a mixture of carbon monoxide and hydrogen was introduced to raise and react.
  • the reactor is heated by an electric furnace and the reaction temperature is determined by the thermocouple inserted into the catalyst bed.
  • the catalyst can be subjected to adsorption pretreatment of pyridine before the reaction.
  • the catalyst was activated at 550 ° C for 4 hours in a nitrogen atmosphere, and then the temperature of the bed was lowered to 300 ° C, and gaseous pyridine diluted with nitrogen was introduced for adsorption. After adsorption for 1 hour, pure nitrogen was purged at the same temperature for 30 min.
  • the temperature of the catalyst bed is lowered to the reaction temperature, and a certain proportion of dimethyl ether is introduced, and a mixture of carbon monoxide and hydrogen is pressurized and reacted.
  • the reactor is heated by an electric heating furnace and the reaction temperature is determined by a thermocouple inserted into the catalyst bed.
  • Example 3 Analytical method of product
  • the starting materials and the resulting product were analyzed on an Agilent 7890A gas chromatograph.
  • the chromatograph is equipped with dual detectors FID and TCD, and has a ten-way valve that allows the product to enter the packed column and capillary column separately.
  • a hydrogen flame detector detects hydrocarbons, alcohols, ethers, and a thermal conductivity detector to detect carbon monoxide and hydrogen in the feedstock and product. Data was processed using Agilent's Chemstation software.
  • FID column HP-PLOT-Q 19091S-001, 50m x 0.2 ⁇ (inside diameter), 0.5 Ym film thickness
  • Carrier gas helium, 2.5 ml/min
  • TCD column carbon molecular sieve column, Porapak-Q 2m x 2mm (inside diameter)
  • Carrier gas helium, 20ml/min
  • Gas distributors are conventional distributors in the industry.
  • the metal tube used for the design of this experiment is closed at one end, and the wall is opened, as shown in Figure 1 (a).
  • the diameter, height, aperture, and amount of the distributor are determined by the size of the device.
  • the reactor with the gas distributor inside is shown in Figure 1 (b).
  • 500 ml of the shaped catalyst was packed into a fixed bed reactor having an inner diameter of 036 mm.
  • the inside of the reactor was 015 mm of a dimethyl ether gas distributor, and the catalyst was packed outside the gas distributor.
  • Dimethyl ether was uniformly distributed into the catalyst bed through a gas distributor; the reacted materials were subjected to on-line analysis of the chromatographic components. There is a thermocouple reaction temperature in the catalyst bed.
  • the dimethyl ether carbonylation reaction was carried out using dimethyl ether having a purity of 99.5%, 99.99%-carbon monoxide, and 99.99% hydrogen as a reaction raw material.
  • the results are shown in Table 5 below.
  • the results of the stability of this experiment are shown in Figure 4.
  • the catalytic performance of carrying different metal oxide mordenite was investigated.
  • the dimethyl ether feed enters the catalyst bed through a gas distributor.
  • Table 8 The results are shown in Table 8 below :
  • the catalyst is a ferrierite containing iron heteroatoms in the framework.
  • the results are shown in Table 10:
  • the catalytic performance of ferrierite supporting different metal oxides was investigated.
  • the catalyst was packed as in Example 4.
  • the methyl ether feed enters the catalyst bed through a gas distributor.
  • Table 13 The results for each ferrierite are shown in Table 13 below:

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PCT/CN2014/000128 2012-12-25 2014-01-28 一种二甲醚羰基化制备乙酸甲酯的方法 WO2014101901A1 (zh)

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