CN104725224B - Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate - Google Patents
Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate Download PDFInfo
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Abstract
The invention provides a method for preparing polyoxymethylene dimethyl ether carboxylate and/or methyl methoxy acetate which serves as an intermediate for producing ethylene glycol. The method comprises the step of enabling a raw material, namely polyoxymethylene dimethyl ether or methylal, together with carbon monoxide and hydrogen gas to react in an acidic molecular sieve catalyst loaded reactor under appropriate reaction conditions without adding other solvents, so as to prepare corresponding products, wherein a reaction process is of gas-liquid-solid three-phase reaction. According to the method provided by the invention, the conversion ratio of the raw material polyoxymethylene dimethyl ether or methylal is high, the selectivity of each product is high, the service life of a catalyst is long, external solvents are not required to be used, reaction conditions are relatively mild, and continuous production can be carried out, so that the method has industrial application potential. Furthermore, the obtained products can be used for producing ethylene glycol through hydrolyzing after hydrogenating or hydrogenating after hydrolyzing.
Description
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 ester.
Background technology
Ethylene glycol is the important industrial chemicals of country and strategic materials, for manufacture polyester (can further produce terylene,
PET bottle, thin film), explosive, Biformyl, 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 within 2015, production capacity about 500
Ten thousand tons, insufficiency of supply-demand still up to 6,200,000 tons, therefore, the development and application of China's ethylene glycol production new technology have before good market
Scape.In the world mainly using petroleum cracking ethylene it is oxidized obtain oxirane, ethylene oxide hydration obtains ethylene glycol.In view of
The energy resources structure of China's " few gas of rich coal oil starvation " maintains for a long time the present situations such as run at high level 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's " 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
Industry gas purity has high demands, and needs to use noble metal catalyst during oxidative coupling, needs using latency environment pollution
Oxynitride etc. can restrict economy, the feature of environmental protection, energy saving and the further engineering of the flow process and amplify.
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 products distribution that it is generated is unreasonable, 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 by-product in its preparation process is separated repeatedly react again, so
Energy consumption is larger, and economy is poor.Therefore, if can be using as the dimethoxym ethane and DMM of by-product2Directly it is processed into economic worth more
High 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 2-Methoxyacetic acid first
Ester selectivity is all not ideal enough, also have with a distance from considerably long from industrialization [Angew.Chem.Iht.Ed., 2009,48,4813～
4815；J.Catal., 2010,270,185～195；J.Catal., 2010,274,150～162；WO2010/048300 A1].
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 carbonylation
The method of base dimethyl ether carbonyl compound and methoxy menthyl acetate.
For this purpose, a kind of the invention provides intermediate polymethoxy diformazan prepared by carbonylation as production ethylene glycol
The method of ether carbonyl compound, it is characterised in that by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3Together with carbon monoxide and hydrogen
By the reactor for being loaded with acid molecular sieve catalyst, in 60～140 DEG C of reaction temperature, 2～10MPa of reaction pressure, poly- methoxy
Base dimethyl ether mass space velocity is 0.2～10.0h-1And prepare product polymethoxy diformazan without reaction under conditions of other solvents
Ether carbonyl compound, wherein under the cited reaction conditions, the raw material is liquid phase with least one in the product, described acid point
Sub- 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 oxidation
The mol ratio of carbon and the raw material is 2: 1～20: 1, and hydrogen is 1: 1～5: 1 with the mol ratio of the raw material, wherein n >=2 and is
Integer.
Present invention also offers a kind of intermediate methoxy menthyl acetate prepared by carbonylation as production ethylene glycol
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 acid molecular sieve catalyst, 60～140 DEG C of reaction temperature, 2～10MPa of reaction pressure,
Dimethoxym ethane mass space velocity is 0.2～10.0h-1And prepare product methoxy menthyl acetate without reaction under conditions of other solvents
And polymethoxy dimethyl ether carbonyl compound, wherein under the cited reaction conditions, the raw material is with least one in the product
Liquid phase, the acid molecular sieve catalyst 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: 1～20: 1, and hydrogen is 1: 1～5 with the mol ratio of the raw material
∶1。
In a preferred embodiment, the product polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether
CH3O(CH2O)nCH3- the O-CH of strand2Insert on-O- construction units after one or more carbonyls-CO- formed 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 structure type of the acid molecular sieve catalyst be MWW, FER, MFI, MOR,
FAU or BEA.
In a preferred embodiment, the acid molecular sieve catalyst is MCM-22 molecular sieves, ferrierite, ZSM-
Any one in 5 molecular sieves, modenite, Y zeolite or Beta molecular sieves or arbitrarily several mixing.
In a preferred embodiment, reaction temperature be 60～120 DEG C, reaction pressure be 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 life-span length, 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 hydrolysis or hydrolysis back end hydrogenation can produce ethylene glycol after hydrogenation.
Specific embodiment
The present invention provides a kind of method for preparing polymethoxy dimethyl ether carbonyl compound, it is characterised in that：Will be containing poly- methoxy
The raw material of base dimethyl ether, carbon monoxide and hydrogen by being loaded with the reactor of acid molecular sieve catalyst, reaction temperature 60～
140 DEG C, 2～10MPa of reaction pressure, polymethoxy dimethyl ether mass space velocity be 0.2～10.0h-1And without other solvents
Under the conditions of react, prepare polymethoxy dimethyl ether carbonyl compound；Raw material polymethoxy dimethyl ether and the poly- methoxy of product under reaction condition
It is liquid phase that base dimethyl ether carbonyl compound is at least one, and 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, the mol ratio of carbon monoxide and polymethoxy dimethyl ether is 2: 1～20: 1, hydrogen and poly- first
The mol ratio of epoxide dimethyl ether is 1: 1～5: 1.
Described polymethoxy dimethyl ether is one-component or mixture, and molecular formula is CH3O(CH2O)nCH3, wherein n >=2
And for integer, preferred 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 to be 4～10MPa, polymethoxy dimethyl ether mass space velocity is 0.5～3.0h-, carbon monoxide and polymethoxy dimethyl ether
Mol ratio be 2: 1～15: 1, the mol ratio of preferred hydrogen and polymethoxy dimethyl ether is 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 conversion ratio of polymethoxy dimethyl ether and polymethoxy dimethyl ether carbonyl compound
Selectivity 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)-(polymethoxy in discharging
Dimethyl 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 discharging
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, will be containing dimethoxym ethane CH3O-CH2-OCH3, carbon monoxide and hydrogen raw material by being loaded with acid molecular sieve catalyst
Reactor, is 0.2～10.0h in 60～140 DEG C of reaction temperature, reaction pressure 2～10MPa dimethoxym ethanes mass space velocity-1And do not add
Plus react under conditions of other solvents, prepare methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound；It is former under reaction condition
It is liquid phase that material dimethoxym ethane is at least one with product methoxy menthyl acetate and polymethoxy dimethyl ether carbonyl compound, and catalyst is solid
Phase, raw material carbon monoxide and hydrogen are gas phase, and course of reaction is gas-liquid-solid phase reaction；In raw material, carbon monoxide and dimethoxym ethane
Mol ratio be 2: 1～20: 1, the mol ratio of hydrogen and dimethoxym ethane is 1: 1～5: 1.
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 zeolite or Beta
Any one in molecular sieve or arbitrarily several mixing, sial atomic ratio is 3: 1～150: 1.
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 to be 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 5～10MPa, 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) ÷ [(enters
Dimethoxym ethane carbon molal quantity in material)-(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%)
Described polymethoxy dimethyl ether carbonyl compound is in polymethoxy dimethyl ether strand-O-CH2- O- construction units
After upper insertion carbonyl-CO- formed 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.
The present invention product methoxy menthyl acetate or polymethoxy dimethyl ether carbonyl compound can by hydrogenation after hydrolyze or
Hydrolysis back end hydrogenation obtains ethylene glycol, additionally, the product is also used as vapour, diesel fuel additives.For example, with two polymethoxies two
Methyl ether (DMM2)CH3O(CH2O)2CH3As a example by profile up to generate 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 the acid MCM-22 molecular sieve catalysts of 50g silica alumina ratios (Si: Al)=40: 1 under the air atmosphere of Muffle furnace
550 DEG C of roastings 5 hours, take a portion pressed powder pellet, 20～40 mesh are ground into, for active testing.Weigh the acid
Property MCM-22 molecular sieve catalyst sample 10g, load internal diameter for 8.5mm stainless steel reaction pipe in, use at normal pressure, 550 DEG C
Nitrogen activation 4 hours, then drops to reaction temperature (T)=90 DEG C, is passed through carbon monoxide: two polymethoxy dimethyl ethers: hydrogen (CO:
DMM2∶H2)=7: 1: 1, slowly boost to reaction pressure (P)=10MPa, and two polymethoxy dimethyl ether mass space velocities (WHSV)=
0.2h-1, gas chromatographic analysiss product is used, after reacting basicly stable, calculate the conversion ratio and poly- methoxy of two polymethoxy dimethyl ethers
The selectivity of base dimethyl ether carbonyl compound, reaction result is shown in Table 1.
Embodiment 2
Change the catalyst in embodiment 1 into acid ferrierite molecular sieve, Si: Al=10: 1, T=60 DEG C, CO: DMM2∶H2
=13: 1: 3, P=4MPa, WHSV=1.5h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 3
Change the catalyst in embodiment 1 into acid ZSM-5 molecular sieve, Si: Al=150: 1, T=140 DEG C, CO: DMM2∶H2=
2: 1: 5, P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 4
Change the catalyst in embodiment 1 into acidic mordenites molecular sieve, Si: Al=3: 1, T=105 DEG C, CO: DMM2∶H2
=20: 1: 1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 5
Change the catalyst in embodiment 1 into acid Y molecular sieve, Si: Al=20: 1, T=73 DEG C, CO: DMM2∶H2=10∶1∶
2, P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 6
Change the catalyst in embodiment 1 into acid Beta molecular sieves, Si: Al=15: 1, T=120 DEG C, CO: DMM2∶H2=15
: 1: 4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 1, and reaction result is shown in Table 1.
Embodiment 7
By the acid ZSM-5 molecular sieve catalyst of 50g silica alumina ratios (Si: Al)=40: 1 550 under the air atmosphere of Muffle furnace
DEG C roasting 5 hours, takes a portion pressed powder pellet, 20～40 mesh is ground into, for active testing.Weigh the acidity
ZSM-5 molecular sieve catalyst sample 10g, loads internal diameter in the stainless steel reaction pipe of 8.5mm, at normal pressure, 550 DEG C nitrogen to be used
Activation 4 hours, then drops to reaction temperature (T)=88 DEG C, is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO:
DMMn∶H2)=8: 1: 1, wherein DMMnThe mass ratio of each component 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, use gas phase
Chromatography product, reaction result is shown in Table 1.
Embodiment 8
By 50g silica alumina ratios (Si: Al)=23：1 acid Y molecular sieve catalyst, 550 DEG C of roastings under the air atmosphere of Muffle furnace
Burn 5 hours, take a portion pressed powder pellet, 20～40 mesh be ground into, for active testing.Weigh the acid Y molecules
Sieve catalyst sample 10g, loads internal diameter in the stainless steel reaction pipe of 8.5mm, to use nitrogen activation 4 little at normal pressure, 550 DEG C
When, reaction temperature (T)=95 DEG C is then dropped to, it is passed through raw material carbon monoxide: polymethoxy dimethyl ether: hydrogen (CO: DMMn∶H2)=
10: 1: 1, wherein DMMnThe mass ratio of each component 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, use gas chromatogram
Assay products, reaction result is shown in Table 1.
Comparative example 1
Change the gas ratio in embodiment 4 into CO: DMM2∶H2=20: 1: 0, remaining experimental procedure is consistent with embodiment 4,
Reaction result is shown in Table 1.
Comparative example 2
Change the gas ratio in embodiment 5 into CO: DMM2∶H2=10: 1: 0, remaining experimental procedure is consistent with embodiment 5,
Reaction result is shown in Table 1.
Embodiment 9
By the acid MCM-22 molecular sieve catalysts of 50g silica alumina ratios (Si: Al)=40: 1 under the air atmosphere of Muffle furnace
550 DEG C of roastings 5 hours, take a portion pressed powder pellet, 20～40 mesh are ground into, for active testing.Weigh the acid
Property MCM-22 molecular sieve catalyst sample 10g, load internal diameter for 8.5mm stainless steel reaction pipe in, use at normal pressure, 550 DEG C
Nitrogen activation 4 hours, then drops to reaction temperature (T)=90 DEG C, is passed through carbon monoxide: dimethoxym ethane: hydrogen (CO: DMM: H2)=7∶
1: 1, slowly boost to reaction pressure (P)=10MPa, dimethoxym ethane mass space velocity (WHSV)=0.2h-1, produced with gas chromatographic analysiss
Thing, after stable reaction, calculates the conversion ratio of dimethoxym ethane and the selectivity of product, and reaction result is shown in Table 2.
Embodiment 10
Change the catalyst in embodiment 9 into acid ferrierite molecular sieve, Si: Al=10: 1, T=60 DEG C, CO: DMM: H2
=13: 1: 3, P=4MPa, WHSV=i.5h-1, remaining experimental procedure is consistent with embodiment 9, and reaction result is shown in Table 2.
Embodiment 11
Change the catalyst in embodiment 9 into acid ZSM-5 molecular sieve, Si: Al=150: 1, T=140 DEG C, CO: DMM: H2=
2: 1: 5, P=6.5MPa, WHSV=3.0h-1, remaining experimental procedure is consistent with embodiment 9, and reaction result is shown in Table 2.
Embodiment 12
Change the catalyst in embodiment 9 into acidic mordenites molecular sieve, Si: Al=3: 1, T=105 DEG C, CO: DMM: H2
=20: 1: 1, P=5.0MPa, WHSV=1.0h-1, remaining experimental procedure is consistent with embodiment 9, and reaction result is shown in Table 2.
Embodiment 13
Change the catalyst in embodiment 9 into acid Y molecular sieve, Si: Al=20: 1, T=73 DEG C, CO: DMM: H2=10∶1∶
2, P=2MPa, WHSV=10.0h-1, remaining experimental procedure is consistent with embodiment 9, and reaction result is shown in Table 2.
Embodiment 14
Change the catalyst in embodiment 9 into acid Beta molecular sieves, Si: Al=15: 1, T=120 DEG C, CO: DMM: H2=15
: 1: 4, P=4.7MPa, WHSV=0.5h-1, remaining experimental procedure is consistent with embodiment 9, and reaction result is shown in Table 2.
Comparative example 3
Gas ratio in embodiment 12 is changed to into CO: DMM: H2=20: 1: 0, remaining experimental procedure and embodiment 12 1
Cause, reaction result is shown in Table 2.
Comparative example 4
Gas ratio in embodiment 13 is changed to into CO: DMM: H2=10: 1: 0, remaining experimental procedure and embodiment 13 1
Cause, reaction result is shown in Table 2.
Beneficial effects of the present invention are included but is not limited to：The catalyst that the method for the present invention is adopted for acidic molecular sieve,
Raw material is polymethoxy dimethyl ether or dimethoxym ethane together with carbon monoxide and the gaseous mixture of hydrogen.Under the reaction conditions of the present invention,
Raw material by catalyst can stability and high efficiency production as produce ethylene glycol intermediate product polymethoxy dimethyl ether carbonylation
Thing or methoxy menthyl acetate, course of reaction is gas-liquid-solid phase reaction.Polymethoxy dimethyl ether or dimethoxym ethane carbonylation
For strong exothermal reaction, reaction temperature along with liquid phase thermal capacitance greatly and latent heat of phase change, can be controlled very well anti-than relatively low in the present invention
Temperature is answered, the problem of temperature runaway in industrial processes is prevented.The gas-liquid-solid phase reaction that simultaneously present invention is adopted can be high
Operate under polymethoxy dimethyl ether or dimethoxym ethane concentration, improve one way reaction production capacity in commercial production, reduce compression, circulation
And the energy consumption in 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.In addition liquid phase reactor thing or product can catalytic dissolution it is anti-
Pre- carbon distribution material during answering, is conducive to improving the activity of catalyst and stability, and reaction condition is gentleer, can be continuous
Production, possesses industrial applications potentiality.
And, carbonylation adopts 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, the present invention not to 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 to improve poly- first in reaction gas in addition
Epoxide dimethyl ether or dimethoxym ethane conversion ratio and polymethoxy dimethyl ether carbonyl compound or methoxy menthyl acetate selectivity, extend catalysis
Agent single pass life.
Additionally, the polymethoxy dimethyl ether carbonyl compound produced in the present invention or methoxy menthyl acetate can be by being hydrogenated with water
Solution hydrolyzes 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 is deformed.This
Bright scope is defined by the following claims.
Claims (7)
1. it is a kind of by carbonylation prepare as produce ethylene glycol intermediate polymethoxy dimethyl ether carbonyl compound method, its
It is characterised by, by raw material polymethoxy dimethyl ether CH3O(CH2O)nCH3Together with carbon monoxide and hydrogen by being loaded with acidic molecular
The reactor of sieve catalyst, be in 60～90 DEG C of reaction temperature, 5～10MPa of reaction pressure, polymethoxy dimethyl ether mass space velocity
0.5～1.5h-1And product polymethoxy dimethyl ether carbonyl compound is prepared without reaction under conditions of other solvents, wherein described
Under reaction condition, at least one in the raw material and the product is liquid phase, and the acid molecular sieve catalyst is solid phase, one
Carbonoxide 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
For 2:1～10:1, hydrogen is 1 with the mol ratio of the raw material:1～2:1, wherein n >=2 and for integer.
2. method according to claim 1, it is characterised in that the product polymethoxy dimethyl ether carbonyl compound is in poly- first
Epoxide dimethyl ether CH3O(CH2O)nCH3- the O-CH of strand2Insert in-O- construction units and formed after one or more carbonyls-CO-
With-O- (CO)-CH2- O- or-O-CH2The product of-(CO)-O- construction units, wherein n >=2.
3. method according to claim 1, it is characterised in that the polymethoxy dimethyl ether is two polymethoxy dimethyl ethers
CH3O(CH2O)2CH3。
4. method according to claim 1, it is characterised in that the polymethoxy dimethyl ether carbonyl compound be it is following in one
Plant or various：
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。
5. method according to claim 1, it is characterised in that the structure type of the acid molecular sieve catalyst be MWW,
FER, MFI, MOR, FAU or BEA.
6. method according to claim 5, it is characterised in that the acid molecular sieve catalyst be MCM-22 molecular sieves,
Any one in ferrierite, ZSM-5 molecular sieve, modenite, Y zeolite or Beta molecular sieves or arbitrarily several mixing.
7. method according to claim 1, it is characterised in that the reactor is the fixed bed reaction for realizing successive reaction
Device, tank reactor, moving-burden bed reactor or fluidized-bed reactor.
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