CN104725229B - The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate - Google Patents

The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate Download PDF

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CN104725229B
CN104725229B CN201310723379.4A CN201310723379A CN104725229B CN 104725229 B CN104725229 B CN 104725229B CN 201310723379 A CN201310723379 A CN 201310723379A CN 104725229 B CN104725229 B CN 104725229B
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acid
reaction
dimethyl ether
embodiment
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CN104725229A (en
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倪友明
朱文良
刘勇
刘红超
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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    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals
    • Y02P20/52Improvements relating to the production of products other than chlorine, adipic acid, caprolactam, or chlorodifluoromethane, e.g. bulk or fine chemicals or pharmaceuticals using catalysts, e.g. selective catalysts

Abstract

The present invention provides a kind of method of the polymethoxy dimethyl ether carbonyl compound and/or methoxy menthyl acetate for preparing the intermediate as production ethylene glycol, including by raw material polymethoxy dimethyl ether or dimethoxym ethane together with carbon monoxide and hydrogen by being loaded with the reactor of the acid molecular sieve catalyst of Dealumination, reaction prepares corresponding product under the conditions of the appropriate reaction without other solvents, and wherein course of reaction is gas-liquid-solid phase reaction.The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the inventive method, the selectivity of each product is high, and catalyst life is long, it is not necessary to use plus solvent, and reaction condition is gentleer, can continuously produce, and possesses industrial applications potentiality.And, the product for being obtained can produce ethylene glycol by being hydrolyzed after hydrogenation or hydrolyzing back end hydrogenation.

Description

The method for preparing polymethoxy dimethyl ether carbonyl compound and methoxy menthyl acetate

Technical field

The present invention relates to the polymethoxy dimethyl ether carbonyl compound and methoxyl group second of a kind of intermediate as production ethylene glycol The preparation method of sour methyl esters.

Background technology

Ethylene glycol is the important industrial chemicals of country and strategic materials, for manufacture polyester (can further produce terylene, PET bottle, film), explosive, glyoxal, and can be used as antifreezing agent, plasticizer, hydraulic fluid and solvent etc..China in 2009 Ethylene glycol import volume is more than 5,800,000 tons, it is contemplated that China's ethylene glycol demand is up to 11,200,000 tons, production capacity about 500 within 2015 Ten thousand tons, insufficiency of supply-demand still up to 6,200,000 tons, therefore, before the development and application of China's ethylene glycol production new technology have good market Scape.The main ethene using petroleum cracking is oxidized in the world obtains oxirane, and ethylene oxide hydration obtains ethylene glycol.In view of The energy resources structure of China's " few gas of rich coal oil starvation " maintains the present situations such as run at high level for a long time with crude oil price, and coal-ethylene glycol is new Moulded coal Chemical Engineering Technology can ensure the energy security of country, and the coal resources of China are taken full advantage of again, be that following Coal Chemical Industry is produced The most real selection of industry.

At present, the ripe technology of domestic contrast is " the CO gas phase catalytic synthesis developed by Chinese Academy of Sciences's Fujian thing structure Oxalate and oxalate catalytic hydrogenation synthesizing glycol packaged process." in early December, 2009, what is attracted much industry attention is complete The first set industrialization demonstration plant of ball-Tongliao, Inner Mongolia gold Coal Chemical Industry company " coal-ethylene glycol project " first stage of the project, annual output 200000 Ton coal-ethylene glycol project smoothly gets through all fronts technological process, produces qualified ethylene glycol product.But technique unit is more, work The requirement of industry gas purity is high, needs to use noble metal catalyst during oxidative coupling, it is necessary to using latency environment pollution Economy, the feature of environmental protection, energy saving and the further engineering that oxynitrides etc. can restrict the flow are amplified.

Polymethoxy dimethyl ether (or polymethoxy methylal is, English entitled Polyoxymethylene dimethyl Ethers molecular formula) is CH3O(CH2O)nCH3, wherein n >=2, commonly abbreviated as DMMn(or PODEn).Preparing polymethoxy During dimethyl ether, the product irrational distribution of its generation, dimethoxym ethane and DMM2It is higher, and can serve as diesel fuel additives DMM3~4Selectivity is relatively low, as a result, it is often necessary to the accessory substance in its preparation process is separated repeatedly react again, this Sample energy consumption is larger, and economy is poor.Therefore, if can be using as the DMM of accessory substance2Directly it is processed into economic worth product higher Product will improve the economy of this process.

In recent years, the Alexis T.Bell professors seminar of U.S. UC, Berkeley proposes to utilize dimethoxym ethane gas phase carbonyl Change method prepares methoxy menthyl acetate, and then hydrogenation hydrolyzation obtains a variation route of ethylene glycol, and a step of wherein most critical is Gas carbonylation.But catalyst life is short, dimethoxym ethane concentration is low in unstripped gas, dimethoxym ethane conversion ratio and methoxyacetic acid first Ester selectivity it is all not ideal enough, from industrialization also have it is considerably long with a distance from [Angew.Chem.Iht.Ed., 2009,48,4813~ 4815;J.Catal., 2010,270,185~195;J.Catal., 2010,274,150~162;WO2010/048300A1].

The content of the invention

It is an object of the invention to provide a kind of poly- methoxy that the intermediate as production ethylene glycol is prepared by being carbonylated The method of base dimethyl ether carbonyl compound and methoxy menthyl acetate.

Therefore, the invention provides a kind of polymethoxy two that the intermediate as production ethylene glycol is prepared by being carbonylated The method of methyl ether carbonyl compound, it is characterised in that by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3Together with carbon monoxide and hydrogen Gas by being loaded with the reactor of the acid molecular sieve catalyst of Dealumination, 60~140 DEG C of reaction temperature, reaction pressure 2~ 10MPa, polymethoxy dimethyl ether mass space velocity are 0.2~10.0h-1And prepare product without reaction under conditions of other solvents Polymethoxy dimethyl ether carbonyl compound, wherein under the cited reaction conditions, the raw material is liquid with least one in the product Phase, the acid molecular sieve catalyst of the Dealumination is solid phase, and carbon monoxide and hydrogen are gas phase so that course of reaction is gas Liquid solid phase reaction, and the mol ratio of carbon monoxide and the raw material is 2: 1~20: 1, the mol ratio of hydrogen and the raw material It is 1: 1~5: 1, wherein n >=2 and be integer.

Present invention also offers a kind of by the way that the intermediate methoxy menthyl acetate prepared as production ethylene glycol is carbonylated And the method for polymethoxy dimethyl ether carbonyl compound, it is characterised in that by raw material dimethoxym ethane CH3O-CH2-OCH3Together with carbon monoxide With hydrogen by being loaded with the reactor of the acid molecular sieve catalyst of Dealumination, in 60~140 DEG C of reaction temperature, reaction pressure 2~10MPa, dimethoxym ethane mass space velocity are 0.2~10.0h-1And prepare product methoxy without reaction under conditions of other solvents Acetic acid methyl ester and polymethoxy dimethyl ether carbonyl compound, wherein under the cited reaction conditions, in the raw material and the product At least one is liquid phase, and the acid molecular sieve catalyst of the Dealumination is solid phase, carbon monoxide and hydrogen be gas phase so that Course of reaction is gas-liquid-solid phase reaction, and the mol ratio of carbon monoxide and the raw material is 2: 1~20: 1, hydrogen with it is described The mol ratio of raw material is 1: 1~5: 1.

In a preferred embodiment, the product polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether CH3O(CH2O)nCH3- the O-CH of strand2Inserted on-O- construction units formed after one or more carbonyls-CO- with-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, wherein n >=2.

In a preferred embodiment, the polymethoxy dimethyl ether is two polymethoxy dimethyl ether CH3O(CH2O)2CH3

In a preferred embodiment, the polymethoxy dimethyl ether carbonyl compound be it is following in one or more:

CH3-O-(CO)-CH2-O-CH2-O-CH3,

CH3-O-CH2-(CO)-O-CH2-O-CH3,

CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3, and

CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3

In a preferred embodiment, the acid molecular sieve catalyst of the Dealumination is urged by making acidic molecular sieve Agent is passed through includes that steam treatment is prepared with the Dealumination of acid treatment.

In a preferred embodiment, the temperature of the steam treatment is 400~700 DEG C, and the time is 1~8h;Institute It is 0.03~3.0mol/L selected from hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid to state the acid used in acid treatment Plant or various acid, and the temperature of the acid treatment is 15~95 DEG C, and the time is 1~24h.

In a preferred embodiment, the structure type of the acid molecular sieve catalyst of the Dealumination be MWW, FER, MFI, MOR, FAU or BEA.

In a preferred embodiment, the acid molecular sieve catalyst of the Dealumination is MCM-22 molecular sieves, magnesium One or more in alkali zeolite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta molecular sieves.

In a preferred embodiment, reaction temperature is 60~120 DEG C, and reaction pressure is 4~10MPa, the raw material Mass space velocity be 0.5~3.0h-1, the mol ratio of carbon monoxide and the raw material is 2: 1~15: 1, hydrogen and the raw material Mol ratio is 1: 1~3: 1.

In a preferred embodiment, reaction temperature is 60~90 DEG C, and reaction pressure is 5~10MPa, the raw material Mass space velocity is 0.5~1.5h-1, carbon monoxide is 2: 1~10: 1 with the mol ratio of the raw material, and hydrogen rubs with the raw material You are than being 1: 1~2: 1.

In a preferred embodiment, the reactor is fixed bed reactors, the still reaction for realizing successive reaction Device, moving-burden bed reactor or fluidized-bed reactor.

The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the inventive method, the selectivity of each product is high, urges Agent long lifespan, it is not necessary to use plus solvent, reaction condition is gentleer, can continuously produce, and possesses industrial applications and dives Power.And, the product for being obtained can produce ethylene glycol by being hydrolyzed after hydrogenation or hydrolyzing back end hydrogenation.

Specific embodiment

The present invention provides a kind of method for preparing polymethoxy dimethyl ether carbonyl compound, it is characterised in that will contain poly- methoxy Base dimethyl ether CH3O(CH2O)nCH3, carbon monoxide and hydrogen raw material by being loaded with the acid molecular sieve catalyst of Dealumination Reactor, 60~140 DEG C of reaction temperature, 2~10MPa of reaction pressure, polymethoxy dimethyl ether mass space velocity be 0.2~ 10.0h-1And reacted without under conditions of other solvents, prepare polymethoxy dimethyl ether carbonyl compound;Raw material gathers under reaction condition It is liquid phase that methoxyl group dimethyl ether is at least one with product polymethoxy dimethyl ether carbonyl compound, and catalyst is solid phase, and raw material one is aoxidized Carbon and hydrogen are gas phase, and course of reaction is gas-liquid-solid phase reaction;In raw material, carbon monoxide and polymethoxy dimethyl ether mole Than being 2: 1~20: 1, the mol ratio of hydrogen and polymethoxy dimethyl ether is 1: 1~5: 1, wherein n >=2 and be integer.

Described polymethoxy dimethyl ether is one-component or mixture, and molecular formula is CH3O(CH2O)nCH3, wherein n >=2 And be integer, preferably n=2, i.e. CH3O(CH2O)2CH3

In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~120 DEG C, instead Pressure is answered for 4~10MPa, polymethoxy dimethyl ether mass space velocity is 0.5~3.0h-1, carbon monoxide and polymethoxy dimethyl ether Mol ratio for the mol ratio of 2: 1~15: 1 preferred hydrogen and polymethoxy dimethyl ether be 1: 1~3: 1.

In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~90 DEG C, reaction Pressure is 5~10MPa, and polymethoxy dimethyl ether mass space velocity is 0.5~1.5h-1, carbon monoxide and polymethoxy dimethyl ether Mol ratio is 2: 1~10: 1, preferred hydrogen is 1: 1~2: 1 with the mol ratio of polymethoxy dimethyl ether.

In some embodiments of the invention, the choosing of the conversion ratio and polymethoxy dimethyl ether carbonyl compound of polymethoxy dimethyl ether Selecting property is all based on polymethoxy dimethyl ether carbon molal quantity and is calculated:

Polymethoxy dimethyl ether conversion ratio=[(polymethoxy dimethyl ether carbon molal quantity in charging)-(discharging polymethoxy two Methyl ether carbon molal quantity)] ÷ (polymethoxy dimethyl ether carbon molal quantity in charging) × (100%)

Polymethoxy dimethyl ether carbonyl compound selectivity=(polymethoxy dimethyl ether carbonyl compound removes the carbon after carbonyl in charging Molal quantity) ÷ [(polymethoxy dimethyl ether carbon molal quantity in charging)-(polymethoxy dimethyl ether carbon molal quantity in discharging)] × (100%)

The present invention also provides the preparation method of a kind of methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound, its feature It is that will contain dimethoxym ethane CH3O-CH2-OCH3, carbon monoxide and hydrogen raw material by being loaded with the acidic molecular of Dealumination The reactor of sieve catalyst, 60~140 DEG C of reaction temperature, reaction pressure 2~10MPa dimethoxym ethanes mass space velocity be 0.2~ 10.0h-1And reacted without under conditions of other solvents, prepare methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound; It is liquid phase that raw material dimethoxym ethane is at least one with product methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound under reaction condition, Catalyst is solid phase, and raw material carbon monoxide and hydrogen are gas phase, and course of reaction is gas-liquid-solid phase reaction;In raw material, an oxidation Carbon is 2: 1~20: 1 with the mol ratio of dimethoxym ethane, and hydrogen is 1: 1~5: 1 with the mol ratio of dimethoxym ethane.

In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~120 DEG C, instead Pressure is answered for 4~10MPa, dimethoxym ethane mass space velocity is 0.5~3.0h-1, carbon monoxide is 2: 1~15 with the mol ratio of dimethoxym ethane : 1 preferred hydrogen is 1: 1~3: 1 with the mol ratio of dimethoxym ethane.

In a preferred embodiment, course of reaction is gas-liquid-solid phase reaction, and reaction temperature is 60~90 DEG C, reaction Pressure is 5.0~10MPa, and dimethoxym ethane mass space velocity is 0.5~1.5h-1, carbon monoxide is 2: 1~10 with the mol ratio of dimethoxym ethane : 1, preferred hydrogen is 1: 1~2: 1 with the mol ratio of dimethoxym ethane.

In certain embodiments, the conversion ratio of dimethoxym ethane and the selectivity of product are all based on dimethoxym ethane carbon molal quantity and are counted Calculate:

Dimethoxym ethane conversion ratio=[(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] ÷ is (in charging Dimethoxym ethane carbon molal quantity) × (100%)

Methoxy menthyl acetate selectivity=(methoxy menthyl acetate removes the carbon molal quantity after carbonyl in discharging) ÷ [(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] × (100%)

Polymethoxy dimethyl ether carbonyl compound selectivity=(polymethoxy dimethyl ether carbonyl compound removes the carbon after carbonyl in discharging Molal quantity) ÷ [(dimethoxym ethane carbon molal quantity in charging)-(dimethoxym ethane carbon molal quantity in discharging)] × (100%)

The method of described Dealumination includes steam treatment and acid treatment.

Described steam treatment temperature is 400~700 DEG C, and preferably 550~650 DEG C, the steam treatment time does not limit, excellent Select 1~8h;The acid used in acid treatment is 0.03~3.0mol/L, the preferably hydrochloric acid of 0.1~1.0mol/L, sulfuric acid, nitric acid, vinegar One or more mixed acid in acid, oxalic acid, citric acid, acid treatment temperature is 15~95 DEG C, preferably 60~80 DEG C, acid treatment Time does not limit, preferably 1~24h.

The structure type of described acid molecular sieve catalyst is MWW, FER, MFI, MOR, FAU or BEA.Preferably, institute The acid molecular sieve catalyst stated is MCM-22 molecular sieves, ferrierite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta Any one in molecular sieve or any several mixing, sial atomic ratio is 3: 1~150: 1.

In embodiment, the S.O.P. that sodium form molecular sieve is converted into acidic molecular sieve is:By the dried Na of 50g+Type molecular sieve is put into the 0.8M NH of 400ml4NO3In solution, 12h is stirred at 80 DEG C, washed with the distillation of 800ml after filtering Wash.This ion exchange process obtains NH in triplicate4 +The molecular sieve of type.By fully dry after, be placed in Muffle furnace, with 2 DEG C/ Min is increased to 550 DEG C and keeps calcining 4h to obtain acidic molecular sieve.

Described polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether strand-O-CH2- O- construction units Formed after upper insertion carbonyl-CO- with-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, poly- methoxy Base dimethyl ether carbonyl compound contains one or more carbonyls.

In embodiment produce polymethoxy dimethyl ether carbonyl compound can be it is following in one or more:

CH3-O-(CO)-CH2-O-CH2-O-CH3Referred to as C5-1,

CH3-O-CH2-(CO)-O-CH2-O-CH3Referred to as C5-2,

CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3Referred to as C6-1,

CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3Referred to as C6-2.

Product methoxy menthyl acetate of the invention or polymethoxy dimethyl ether carbonyl compound can by hydrolysis after hydrogenation or Hydrolysis back end hydrogenation obtains ethylene glycol, additionally, the product is also used as vapour, diesel fuel additives.For example, with two polymethoxies Dimethyl ether (DMM2)CH3O(CH2O)2CH3As a example by profile up to generation ethylene glycol course of reaction be:

In a preferred embodiment, the reactor is fixed bed reactors, tank reactor, the shifting of continuous flowing Dynamic bed reactor or fluidized-bed reactor.

Below by embodiment in detail the present invention is described in detail, but the invention is not limited in these embodiments.

Embodiment 1

By 50g sodium form silica alumina ratio for 40: 1 MCM-22 molecular sieves are converted into acidic molecular sieve using S.O.P., Catalyst A is designated as, 1 is shown in Table.

Embodiment 2

By 100g sodium form silica alumina ratio for 40: 1 MCM-22 molecular sieves are passed through steam treatment 4h under the conditions of 550 DEG C, so Acidic molecular sieve is changed into using S.O.P. afterwards, catalyst B is designated as, 1 is shown in Table.

Embodiment 3

By 100g sodium form silica alumina ratio for 40: 1 MCM-22 molecular sieves under the conditions of 60 DEG C the 0.1mol/L hydrochloric acid of 500ml it is molten 1h is processed in liquid, then acidic molecular sieve is changed into using S.O.P., catalyst C is designated as, 1 is shown in Table.

Embodiment 4

By 50g sodium form silica alumina ratio for 10: 1 ferrierite is converted into acidic molecular sieve using S.O.P., it is designated as Catalyst D, is shown in Table 1.

Embodiment 5

By 100g sodium form silica alumina ratio for 10: 1 ferrierite is passed through steam treatment 1h, Ran Houli under the conditions of 700 DEG C Acidic molecular sieve is changed into S.O.P., catalyst E is designated as, 1 is shown in Table.

Embodiment 6

It is 10: 1 ferrierite under the conditions of 80 DEG C in the 0.4mol/L sulfuric acid solutions of 500ml by 100g sodium form silica alumina ratio Treatment 4h, then changes into acidic molecular sieve using S.O.P., is designated as catalyst F, is shown in Table 1.

Embodiment 7

By 50g sodium form silica alumina ratio for 150: 1 ZSM-5 molecular sieve is converted into acidic molecular sieve using S.O.P., Catalyst G is designated as, 1 is shown in Table.

Embodiment 8

By 100g sodium form silica alumina ratio for 150: 1 ZSM-5 molecular sieve is passed through steam treatment 8h under the conditions of 400 DEG C, so Acidic molecular sieve is changed into using S.O.P. afterwards, catalyst H is designated as, 1 is shown in Table.

Embodiment 9

By 100g sodium form silica alumina ratio for 150: 1 ZSM-5 molecular sieve under the conditions of 75 DEG C the 1.0mol/L acetic acid of 500ml it is molten 8h is processed in liquid, then acidic molecular sieve is changed into using S.O.P., catalyst I is designated as, 1 is shown in Table.

Embodiment 10

By 50g sodium form silica alumina ratio for 3: 1 modenite is converted into acidic molecular sieve using S.O.P., it is designated as urging Agent J, is shown in Table 1.

Embodiment 11

By 100g sodium form silica alumina ratio for 3: 1 modenite is passed through steam treatment 3h under the conditions of 650 DEG C, then utilize S.O.P. changes into acidic molecular sieve, is designated as catalyst K, is shown in Table 1.

Embodiment 12

It is the 3.0mol/L citric acid solutions of 3: 1 modenite 500ml under the conditions of 60 DEG C by 100g sodium form silica alumina ratio Middle treatment 12h, then changes into acidic molecular sieve using S.O.P., is designated as catalyst L, is shown in Table 1.

Embodiment 13

By 50g sodium form silica alumina ratio for 20: 1 Y molecular sieve is converted into acidic molecular sieve using S.O.P., it is designated as urging Agent M, is shown in Table 1.

Embodiment 14

By 100g sodium form silica alumina ratio for 20: 1 Y molecular sieve is passed through steam treatment 2h under the conditions of 500 DEG C, then utilize S.O.P. changes into acidic molecular sieve, is designated as catalyst n, is shown in Table 1.

Embodiment 15

It is 20: 1 Y molecular sieve under the conditions of 95 DEG C in the 1.5mol/L oxalic acid solutions of 500ml by 100g sodium form silica alumina ratio Treatment 5h, then changes into acidic molecular sieve using S.O.P., is designated as catalyst O, is shown in Table 1.

Embodiment 16

By 50g sodium form silica alumina ratio for 15: 1 Beta molecular sieves are converted into acidic molecular sieve using S.O.P., remember It is catalyst P, is shown in Table 1.

Embodiment 17

By 100g sodium form silica alumina ratio for 15: 1 Beta molecular sieves are passed through steam treatment 4h under the conditions of 600 DEG C, then Acidic molecular sieve is changed into using S.O.P., catalyst Q is designated as, 1 is shown in Table.

Embodiment 18

By 100g sodium form silica alumina ratio for 15: 1 Beta molecular sieves under the conditions of 15 DEG C the 0.03mol/L nitric acid of 500ml it is molten 24h is processed in liquid, then acidic molecular sieve is changed into using S.O.P., catalyst R is designated as, 1 is shown in Table.

Method for preparing catalyst in the embodiment 1~18 of table 1

Embodiment Catalyst is numbered Molecular sieve classification Silica alumina ratio Dealumination process Treatment temperature, time, concentration 1 A MCM-22 40∶1 - - 2 B MCM-22 65∶1 Vapor 550℃、4h 3 C MCM-22 50∶1 Hydrochloric acid 60 DEG C, 1h, 0.1mol/L 4 D Ferrierite 10∶1 - - 5 E Ferrierite 25∶1 Vapor 700℃、1h 6 F Ferrierite 30∶1 Sulfuric acid 80 DEG C, 4h, 0.4mol/L 7 G ZSM-5 150∶1 - - 8 H ZSM-5 170∶1 Vapor 400℃、8h 9 I ZSM-5 180∶1 Acetic acid 75 DEG C, 8h, 1.0mol/L 10 J Modenite 3∶1 - - 11 K Modenite 8∶1 Vapor 650℃、3h 12 L Modenite 10∶1 Citric acid 60 DEG C, 12h, 3.0mol/L 13 M Y 20∶1 - - 14 N Y 30∶1 Vapor 500℃、2h 15 O Y 35∶1 Oxalic acid 95 DEG C, 5h, 1.5mol/L 16 P Beta 15∶1 - - 17 Q Beta 25∶1 Vapor 600℃、4h 18 R Beta 30∶1 Nitric acid 15 DEG C, 24h, 0.03mol/L

Embodiment 19

Catalyst A sample compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst A10g is weighed, loads internal diameter In the stainless steel reaction pipe of 8.5mm, nitrogen activation to be used 4 hours at normal pressure, 550 DEG C, reaction temperature (T)=90 is then dropped to DEG C, it is passed through carbon monoxide: two polymethoxy dimethyl ethers: hydrogen (CO: DMM2∶H2)=7: 1: 1, slowly boost to reaction pressure (P)= 10MPa, two polymethoxy dimethyl ether mass space velocities (WHSV)=0.2h-1, gas chromatographic analysis product is used, after reacting basicly stable, The conversion ratio of two polymethoxy dimethyl ethers and the selectivity of polymethoxy dimethyl ether carbonyl compound are calculated, reaction result is shown in Table 2.

Embodiment 20

Change the catalyst in embodiment 19 into catalyst B, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 21

Change the catalyst in embodiment 19 into catalyst C, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 22

Change the catalyst in embodiment 19 into catalyst D, reaction condition is changed to:T=60 DEG C, CO: DMM2∶H2=13∶1∶ 3, P=4MPa, WHSV=1.5h-1, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 23

Change the catalyst in embodiment 22 into catalyst E, remaining experimental procedure is consistent with embodiment 22, and reaction result is shown in Table 2.

Embodiment 24

Change the catalyst in embodiment 22 into catalyst F, remaining experimental procedure is consistent with embodiment 22, and reaction result is shown in Table 2.

Embodiment 25

Change the catalyst in embodiment 19 into catalyst G, reaction condition is changed to:T=140 DEG C, CO: DMM2∶H2=2: 1: 5, P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 26

Change the catalyst in embodiment 25 into catalyst H, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in Table 2.

Embodiment 27

Change the catalyst in embodiment 25 into catalyst I, remaining experimental procedure is consistent with embodiment 25, and reaction result is shown in Table 2.

Embodiment 28

Change the catalyst in embodiment 19 into catalyst J, reaction condition is changed to:T=105 DEG C, CO: DMM2∶H2=20∶1∶ 1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 29

Change the catalyst in embodiment 28 into catalyst K, remaining experimental procedure is consistent with embodiment 28, and reaction result is shown in Table 2.

Embodiment 30

Change the catalyst in embodiment 28 into catalyst L, remaining experimental procedure is consistent with embodiment 28, and reaction result is shown in Table 2.

Embodiment 31

Change the catalyst in embodiment 19 into catalyst M, reaction condition is changed to:T=73 DEG C, CO: DMM2∶H2=10∶1∶ 2, P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 32

Change the catalyst in embodiment 31 into catalyst n, remaining experimental procedure is consistent with embodiment 31, and reaction result is shown in Table 2.

Embodiment 33

Change the catalyst in embodiment 31 into catalyst O, remaining experimental procedure is consistent with embodiment 31, and reaction result is shown in Table 2.

Embodiment 34

Change the catalyst in embodiment 19 into catalyst P, reaction condition is changed to:T=120 DEG C, CO: DMM2∶H2=15∶1∶ 4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 19, and reaction result is shown in Table 2.

Embodiment 35

Change the catalyst in embodiment 34 into catalyst Q, remaining experimental procedure is consistent with embodiment 34, and reaction result is shown in Table 2.

Embodiment 36

Change the catalyst in embodiment 34 into catalyst R, remaining experimental procedure is consistent with embodiment 34, and reaction result is shown in Table 2.

Embodiment 37

Catalyst G samples compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst sample 10g is weighed, loads interior Footpath in the stainless steel reaction pipe of 8.5mm, with nitrogen activation 4 hours at normal pressure, 550 DEG C, then drop to reaction temperature (T)= 88 DEG C, it is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO: DMMn∶H2)=8: 1: 1, wherein DMMnThe matter of each component Measuring ratio is:DMM2∶DMM3∶DMM4∶DMM5∶DMM6=51.2: 26.6: 12.8: 6.5: 2.9, slowly boost to reaction pressure (P)= 8MPa, polymethoxy dimethyl ether mass space velocity (WHSV)=1.5h-1, gas chromatographic analysis product is used, after reacting basicly stable, instead 2 should be the results are shown in Table.

Embodiment 38

Change the catalyst in embodiment 37 into catalyst H, other conditions are constant, and reaction result is shown in Table 2.

Embodiment 39

Change the catalyst in embodiment 37 into catalyst I, other conditions are constant, and reaction result is shown in Table 2.

Embodiment 40

Catalyst M samples compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst sample 10g is weighed, loads interior Footpath in the stainless steel reaction pipe of 8.5mm, with nitrogen activation 4 hours at normal pressure, 550 DEG C, then drop to reaction temperature (T)= 95 DEG C, it is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO: DMMn∶H2)=10: 1: 1, wherein DMMnEach component Mass ratio is:DMM2∶DMM3∶DMM4∶DMM5∶DMM6=47.7: 26.9: 14.0: 7.8: 3.6, slowly boost to reaction pressure (P)= 7MPa, polymethoxy dimethyl ether mass space velocity (WHSV)=2.0h-1, gas chromatographic analysis product is used, after reacting basicly stable, instead 2 should be the results are shown in Table.

Embodiment 41

Change the catalyst in embodiment 40 into catalyst n, other conditions are constant, and reaction result is shown in Table 2.

Embodiment 42

Change the catalyst in embodiment 40 into catalyst O, other conditions are constant, and reaction result is shown in Table 2.

Comparative example 1

Change the gas ratio in embodiment 30 into CO: DMM2∶H2=20: 1: 0, remaining experimental procedure and embodiment 30 1 Cause, reaction result is shown in Table 2.

Comparative example 2

Change the gas ratio in embodiment 32 into CO: DMM2∶H2=10: 1: 0, remaining experimental procedure and embodiment 32 1 Cause, reaction result is shown in Table 2.

Embodiment 43

Catalyst A sample compressing tablet, 20~40 mesh are ground into, for active testing.Catalyst A10g is weighed, loads internal diameter In the stainless steel reaction pipe of 8.5mm, nitrogen activation to be used 4 hours at normal pressure, 550 DEG C, reaction temperature (T)=90 is then dropped to DEG C, it is passed through carbon monoxide: dimethoxym ethane: hydrogen (CO: DMM: H2)=7: 1: 1, slowly boost to reaction pressure (P)=10MPa, control Dimethoxym ethane mass space velocity (WHSV)=0.2h-1, gas chromatographic analysis product is used, after reacting basicly stable, calculate the conversion of dimethoxym ethane The selectivity of rate and product, reaction result is shown in Table 3.

Embodiment 44

Change the catalyst in embodiment 43 into catalyst B, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 45

Change the catalyst in embodiment 43 into catalyst C, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 46

Change the catalyst in embodiment 43 into catalyst D, T=60 DEG C, CO: DMM: H2=13: 1: 3, P=4MPa, WHSV= 1.5h-1, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 47

Change the catalyst in embodiment 46 into catalyst E, remaining experimental procedure is consistent with embodiment 46, and reaction result is shown in Table 3.

Embodiment 48

Change the catalyst in embodiment 46 into catalyst F, remaining experimental procedure is consistent with embodiment 46, and reaction result is shown in Table 3.

Embodiment 49

Change the catalyst in embodiment 43 into catalyst G, reaction condition is changed to:T=140 DEG C, CO: DMM: H2=2: 1: 5, P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 50

Change the catalyst in embodiment 49 into catalyst H, remaining experimental procedure is consistent with embodiment 49, and reaction result is shown in Table 3.

Embodiment 51

Change the catalyst in embodiment 49 into catalyst I, remaining experimental procedure is consistent with embodiment 49, and reaction result is shown in Table 3.

Embodiment 52

Change the catalyst in embodiment 43 into catalyst J, reaction condition is changed to:T=105 DEG C, CO: DMM: H2=20∶1∶ 1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 53

Change the catalyst in embodiment 52 into catalyst K, remaining experimental procedure is consistent with embodiment 52, and reaction result is shown in Table 3.

Embodiment 54

Change the catalyst in embodiment 52 into catalyst L, remaining experimental procedure is consistent with embodiment 52, and reaction result is shown in Table 3.

Embodiment 55

Change the catalyst in embodiment 43 into catalyst M, reaction condition is changed to:T=73 DEG C, CO: DMM: H2=10: 1: 2, P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 56

Change the catalyst in embodiment 55 into catalyst n, remaining experimental procedure is consistent with embodiment 55, and reaction result is shown in Table 3.

Embodiment 57

Change the catalyst in embodiment 55 into catalyst O, remaining experimental procedure is consistent with embodiment 55, and reaction result is shown in Table 3.

Embodiment 58

Change the catalyst in embodiment 43 into catalyst P, reaction condition is changed to:T=120 DEG C, CO: DMM: H2=15∶1∶ 4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 43, and reaction result is shown in Table 3.

Embodiment 59

Change the catalyst in embodiment 58 into catalyst Q, remaining experimental procedure is consistent with embodiment 58, and reaction result is shown in Table 3.

Embodiment 60

Change the catalyst in embodiment 58 into catalyst R, remaining experimental procedure is consistent with embodiment 58, and reaction result is shown in Table 3.

Comparative example 3

Gas ratio in embodiment 54 is changed to CO: DMM: H2=20: 1: 0, remaining experimental procedure and embodiment 54 1 Cause, reaction result is shown in Table 3.

Comparative example 4

Gas ratio in embodiment 56 is changed to CO: DMM: H2=10: 1: 0, remaining experimental procedure and embodiment 56 1 Cause, reaction result is shown in Table 3.

Beneficial effects of the present invention are included but is not limited to:The catalyst that the method for the present invention is used is the acid of Dealumination Property molecular sieve catalyst, raw material is polymethoxy dimethyl ether or dimethoxym ethane together with carbon monoxide and the gaseous mixture of hydrogen.In this hair Under bright reaction condition, raw material by catalyst can stability and high efficiency produce as produce ethylene glycol intermediate the poly- first of product Epoxide dimethyl ether carbonyl compound or methoxy menthyl acetate, course of reaction are gas-liquid-solid phase reaction.Methoxyl group dimethyl ether or first contract Aldehyde carbonyl groupsization reaction is strong exothermal reaction, in the present invention reaction temperature than relatively low, along with liquid phase thermal capacitance greatly and latent heat of phase change, energy Enough fine controlling reaction temperatures, prevent the problem of temperature runaway in industrial processes.The gas-liquid-solid three-phase that the present invention is used simultaneously is anti- Should be able to be operated under polymethoxy dimethyl ether high or dimethoxym ethane concentration, improve one way reaction production capacity in industrial production, subtracted Lack the energy consumption in compression, circulation and separation process, improve economic performance.

The high conversion rate of raw material polymethoxy dimethyl ether or dimethoxym ethane in the present invention, product polymethoxy dimethyl ether carbonyl compound Or methoxy menthyl acetate selectivity is high, catalyst single pass life is long.Additionally, in the methods of the invention, liquid phase feed reactant Or product inherently fine solvent, it is not necessary to use plus solvent.Other liquid phase reactor thing or product can catalytic dissolution it is anti- Pre- carbon distribution material during answering, is conducive to improving the activity and stability of catalyst, and reaction condition is gentleer, can be continuous Production, possesses industrial applications potentiality.

And, carbonylation uses the gaseous mixture of carbon monoxide and hydrogen as gas phase in the present invention, relative to existing Coal Chemical Industry production ethylene glycol technology needs high-purity carbon monooxide, and the present invention does not need high-purity carbon monooxide, can be significantly Synthesis gas separating energy consumption is reduced, the economy in production process is improved.Hydrogen is added in other reaction gas can also improve poly- first Epoxide dimethyl ether or dimethoxym ethane conversion ratio and polymethoxy dimethyl ether carbonyl compound or methoxy menthyl acetate selectivity, extension catalysis Agent single pass life.

Molecular sieve Dealumination method in the present invention is simple to operation, is adapted to industrial mass production, changes by dealuminzation The enough single pass lifes by catalyst of performance extend 5~10 times, effectively reduce the number of times that annual catalyst is lived again, favorably In improve annual capacity, reduce wastage of material, reduce waste gas discharge of wastewater, reduce catalyst because pressure release and burn carbon distribution and caused by Loss, extends production equipment usage cycles, improves economic performance.

Additionally, the polymethoxy dimethyl ether carbonyl compound or methoxy menthyl acetate that are produced in the present invention can be by being hydrogenated with water Solution or hydrolysis back end hydrogenation production ethylene glycol.

Below to the present invention have been described in detail, but the invention is not limited in specific embodiment party described herein Formula.It will be appreciated by those skilled in the art that in the case without departing from the scope of the present invention, other changes can be made and deformed.This hair Bright scope is defined by the following claims.

Claims (8)

1. a kind of by the way that the method for preparing the polymethoxy dimethyl ether carbonyl compound as the intermediate for producing ethylene glycol is carbonylated, its It is characterised by, by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3Together with carbon monoxide and hydrogen by being loaded with Dealumination Acid molecular sieve catalyst reactor, in 60~90 DEG C of reaction temperature, 5~10MPa of reaction pressure, polymethoxy dimethyl ether Mass space velocity is 0.5~1.5h-1And product polymethoxy dimethyl ether carbonyl compound is prepared without reaction under conditions of other solvents, Wherein under the cited reaction conditions, the raw material and at least one in the product are liquid phase, the acidity of the Dealumination Molecular sieve catalyst is solid phase, and carbon monoxide and hydrogen are gas phase so that course of reaction is gas-liquid-solid phase reaction, and an oxygen It is 2 to change carbon with the mol ratio of the raw material:1~10:1, hydrogen is 1 with the mol ratio of the raw material:1~2:1, wherein n >=2 and It is integer, the acid molecular sieve catalyst of the Dealumination is by making acid molecular sieve catalyst by including steam treatment Prepared by the Dealumination with acid treatment, wherein the temperature of the steam treatment is 400~700 DEG C, the time is 1~8h;It is described The acid used in acid treatment is 0.03~3.0mol/L selected from the one kind in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid Or various acid, and the temperature of the acid treatment is 15~95 DEG C, the time is 1~24h.
2. a kind of by the way that the intermediate methoxy menthyl acetate and polymethoxy dimethyl ether that prepare as production ethylene glycol is carbonylated The method of carbonyl compound, it is characterised in that by raw material dimethoxym ethane CH3O-CH2-OCH3It is de- by being loaded with together with carbon monoxide and hydrogen The reactor of the modified acid molecular sieve catalyst of aluminium, in 60~90 DEG C of reaction temperature, 5~10MPa of reaction pressure, dimethoxym ethane matter Amount air speed is 0.5~1.5h-1And prepare product methoxy menthyl acetate and poly- methoxy without reaction under conditions of other solvents Base dimethyl ether carbonyl compound, wherein under the cited reaction conditions, the raw material is liquid phase with least one in the product, described The acid molecular sieve catalyst of Dealumination is solid phase, and carbon monoxide and hydrogen are gas phase so that course of reaction is gas-liquid-solid three-phase Reaction, and carbon monoxide and the mol ratio of the raw material are 2:1~10:1, hydrogen is 1 with the mol ratio of the raw material:1~ 2:1, the acid molecular sieve catalyst of the Dealumination by make acid molecular sieve catalyst by include steam treatment and Prepared by the Dealumination of acid treatment, wherein the temperature of the steam treatment is 400~700 DEG C, the time is 1~8h;The acid The acid used in treatment be 0.03~3.0mol/L selected from the one kind in hydrochloric acid, sulfuric acid, nitric acid, acetic acid, oxalic acid, citric acid or The various acid of person, and the temperature of the acid treatment is 15~95 DEG C, and the time is 1~24h.
3. method according to claim 1 and 2, it is characterised in that the product polymethoxy dimethyl ether carbonyl compound be Polymethoxy dimethyl ether CH3O(CH2O)nCH3- the O-CH of strand2After one or more carbonyls-CO- is inserted in-O- construction units Formed with-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, wherein n >=2.
4. method according to claim 1, it is characterised in that the polymethoxy dimethyl ether is two polymethoxy dimethyl ethers CH3O(CH2O)2CH3
5. method according to claim 1 and 2, it is characterised in that the polymethoxy dimethyl ether carbonyl compound is in following One or more:
CH3-O-(CO)-CH2-O-CH2-O-CH3,
CH3-O-CH2-(CO)-O-CH2-O-CH3,
CH3-O-(CO)-CH2-O-(CO)-CH2-O-CH3, and
CH3-O-(CO)-CH2-O-CH2-(CO)-O-CH3
6. method according to claim 1 and 2, it is characterised in that the acid molecular sieve catalyst of the Dealumination Structure type is MWW, FER, MFI, MOR, FAU or BEA.
7. method according to claim 6, it is characterised in that the acid molecular sieve catalyst of the Dealumination is MCM- One or more in 22 molecular sieves, ferrierite, ZSM-5 molecular sieve, modenite, Y zeolites or Beta molecular sieves.
8. method according to claim 1 and 2, it is characterised in that the reactor is the fixed bed for realizing successive reaction Reactor, tank reactor, moving-burden bed reactor or fluidized-bed reactor.
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CN106365995B (en) * 2015-07-20 2018-06-05 中国科学院大连化学物理研究所 A kind of production method of methyl acetate
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CN106513032A (en) * 2016-11-02 2017-03-22 东方红升江苏新能源有限公司 Molecular sieve catalyst for preparation of polyoxymethylene dimethyl ethers
CN108097325A (en) * 2016-11-25 2018-06-01 中国科学院大连化学物理研究所 A kind of catalyst for preparing acrylic acid and methyl acrylate and preparation method thereof
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CN107497479A (en) * 2017-07-20 2017-12-22 沈阳化工大学 A kind of cordierite is that carrier synthesis beta-molecular sieve prepares methoxy menthyl acetate method

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101903325A (en) * 2007-12-20 2010-12-01 英国石油化学品有限公司 Carbonylation process for the production of acetic acid and/or methyl acetate
CN101903099A (en) * 2007-12-19 2010-12-01 英国石油化学品有限公司 Carbonylation process for the production of methyl acetate
CN102245298A (en) * 2008-12-10 2011-11-16 英国石油化学品有限公司 Carbonylation process using bound silver and/or copper mordenite catalysts

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103172517B (en) * 2011-12-20 2015-05-27 中国科学院大连化学物理研究所 Methyl methoxyacetate preparation method

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101903099A (en) * 2007-12-19 2010-12-01 英国石油化学品有限公司 Carbonylation process for the production of methyl acetate
CN101903325A (en) * 2007-12-20 2010-12-01 英国石油化学品有限公司 Carbonylation process for the production of acetic acid and/or methyl acetate
CN102245298A (en) * 2008-12-10 2011-11-16 英国石油化学品有限公司 Carbonylation process using bound silver and/or copper mordenite catalysts

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