CN105622365B - The method that carried heteropoly acid catalyst prepares diethoxymethane - Google Patents

The method that carried heteropoly acid catalyst prepares diethoxymethane Download PDF

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CN105622365B
CN105622365B CN201610121434.6A CN201610121434A CN105622365B CN 105622365 B CN105622365 B CN 105622365B CN 201610121434 A CN201610121434 A CN 201610121434A CN 105622365 B CN105622365 B CN 105622365B
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CN105622365A (en
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石磊
赵佳
姚杰
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Shenyang University of Chemical Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/48—Preparation of compounds having groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
    • B01J29/035—Microporous crystalline materials not having base exchange properties, such as silica polymorphs, e.g. silicalites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself

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Abstract

The method that carried heteropoly acid catalyst prepares diethoxymethane is related to preparing the method for diethoxymethane, and the method dimethoxymethane and ethyl alcohol are raw material, and using liquid acid and support type liquid acid as catalyst, carried heteropoly acid catalyst is with 33%H3PW12O40/SiO2For preparation method it is as follows：With the phosphotungstic acid aqueous solution of a concentration of 33 mass percent, with SiO2For carrier, maceration extract volume is close with hole appearance, and by the two, 10 h of room temperature standing obtain catalyst sample after mixing, and by 120 DEG C of drying of sample, mass fractions are made as 33%H in 350 DEG C of 4 h of roasting3PW12O40/SiO2Catalyst.Product of the present invention is more single, and high selectivity has a good application prospect.And raw material needed for this method is cheap and easy to get and whole flow process is easy to operate, while this method does not generate the chemical substance of any pollution environment, belongs to environmentally friendly processing route.

Description

The method that carried heteropoly acid catalyst prepares diethoxymethane
Technical field
The present invention relates to a kind of methods preparing diethoxymethane, more particularly to a kind of carried heteropoly acid catalyst The method for preparing diethoxymethane.
Background technology
Diethoxymethane is a kind of important industrial chemicals, English name：Diethoxymethan writes a Chinese character in simplified form DEM, structure Formula：CH3CH2OCH2OCH2CH3.Diethoxymethane is achromaticity and clarification volatile liquid, there is the smell of similar ether, fusing point -66.5 DEG C, 89 DEG C of boiling point is dissolved in benzene, ether, ethyl alcohol, is slightly soluble in water.Diethoxymethane has low toxicity, high oxygen content, existing parent It is aqueous and have that lipophile, solvability are strong, the small performances such as low with heat of evaporation of surface tension.Its application is mainly divided to two classes：One kind is As solvent, another kind of is as reaction reagent.As solvent, diethoxymethane is a kind of aprotic solvent, need not be done The dry reaction that just can be used for some to water sensitive.Diethoxymethane viscosity is low, in the big reaction of low-temp reaction and other viscosity It is easily handled in environment, diethoxy first is used in some alkylations, acylation, organolithium reaction and Grignard reactions Alkane makees solvent.Diethoxymethane is solvent very useful in anhydrous aluminum cell, with other ethers it was found that, diethoxymethane To the change very little of cell voltage, the application of electrode and electrolyte decomposed in the polymer may also suppress.It is added as fuel The Cetane number of diesel oil can be improved in agent, improves the burning quality of diesel oil, also reduces the discharge of carbon monoxide and soot.Poly- It closes in object and also plays excellent solvent action.Can be ethoxymethyl reagent, formaldehyde equivalent, carbonyl as reaction reagent The substrate of glycosylation reaction.
Synthesis and application study of the China in relation to diethoxymethane at present is less.Therefore, reinforce exploitation diethoxy first The fundamental and applied research of alkane all has a very important significance.
It is learnt through consulting literatures, the synthetic method of diethoxymethane mainly has dichloromethane method, dimethyl sulfoxide method, chlorination Calcium method, acid catalyzed process and chloramphenicol by-product method are several, are described below respectively：
(1) dichloromethane method
ClCH2CH2Cl + NaOC2H5 → CH3CH2OCH2OCH2CH3
This method is to be reacted to prepare diethoxymethane under the conditions of 50 DEG C with sodium ethoxide by dichloromethane, is synthesis diethyl Oxygroup methane method earlier, reaction not only need sodium ethoxide to make reagent, also require waterless operation, plus yield is low, and catalysis Agent is unstable thus limit its development to acid.
(2) dimethyl sulfoxide method
CH3CH2OH + (CH3)2SO → CH3CH2OCH2OCH2CH3
This method is that dimethyl sulfoxide heat resolve under acid medium effect is then formaldehyde generates diethoxy with ethanol synthesis Methylmethane.The dosage of dimethyl sulfoxide is more, catalyst is not high to sour unstable and yield, is unfavorable for mass producing.
(3) Calcium Chloride Method
HCHO + CH3CH2OH → 2CH3CH2OCH2OCH2CH3
The method is that ethyl alcohol reacts synthesis diethoxymethane with formalin under calcium chloride effect.Reaction yield compared with It is good, but the reaction time is long, and post-processing is inconvenient, is unfavorable for industrialization and generates.
(4) acid catalyzed process
HCHO + CH3CH2OH → CH3CH2OCH2OCH2CH3
The method is that ethyl alcohol reacts under using concentrated hydrochloric acid as catalyst with formalin and can prepare diethoxymethane.Operation Simply, the reaction time is short, high income, is comparatively ideal preparation method.But because using inorganic acid as catalyst, equipment corrosion tight Weight, and the waste water COD content that building-up process generates is high, and processing is difficult, and serious pollution is brought to environment.
（5）Chloramphenicol by-product method
O2NC6H10COCH2Br(CH2)6N4 → CH3CH2OCH2OCH2CH3 + O2NC6H10COCH2NH3
In the production process of chloramphenicol, there is the methenamine solution generation to nitro -2- bromoacetophenones, in this solution The middle ethanol solution that hydrochloric acid is added, obtains byproduct diethoxymethane.This method chloramphenicol by-product method is unfavorable because of limits throughput In large-scale production.
Other than above-mentioned preparation method, also dichloromethane with ethyl alcohol under elevated pressure and ethylmagnesium bromide with formaldehyde low It is anti-under temperature
Diethoxymethane should be prepared.Currently, consider the factors such as cost, operating condition and the yield of raw material, it is ideal Be acid catalyzed process and production chloramphenicol producer chloramphenicol by-product method.
Invention content
The purpose of the present invention is to provide a kind of method that carried heteropoly acid catalyst prepares diethoxymethane, we Method uses carried heteropoly acid for catalyst, and diethoxy is prepared with high selectivity as raw material using dimethoxymethane and ethyl alcohol Methylmethane organic matter.Product is simple, and side reaction is less, and the selectivity of required product diethoxymethane is good；Environment is not made At pollution.
The purpose of the present invention is what is be achieved through the following technical solutions：
The method that carried heteropoly acid catalyst prepares diethoxymethane, the method dimethoxymethane and ethyl alcohol are Raw material, using liquid acid and support type liquid acid as catalyst, in 0~160 DEG C of reaction temperature, 0.1~10.0 MPa of reaction pressure Under the conditions of react, highly selective generation diethoxymethane；Heteropolyacid catalyst is prepared using equi-volume impregnating, with activity Charcoal, TiO2、Al2O3、SiO2, at least one of SBA-15 and MCM-41 be used as carrier；Carried heteropoly acid catalyst includes miscellaneous Polyacid and carrier for carried heteropoly acid, the one kind or more of heteropoly acid in phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and silicomolybdic acid Kind；Heteropoly acid accounts for 0.1~50 % of the carried heteropoly acid catalyst total weight in carried heteropoly acid catalyst；Load It is 5~40 % that heteropoly acid, which accounts for the carried heteropoly acid catalyst total weight still more preferably, in type heteropolyacid catalyst；It is negative Load type heteropolyacid catalyst is with 33%H3PW12O40/SiO2For preparation method it is as follows：
With the phosphotungstic acid aqueous solution of a concentration of 33 mass percent, with SiO2For carrier, maceration extract volume is close with hole appearance, By the two, 10 h of room temperature standing obtain catalyst sample after mixing, and by 120 DEG C of drying of sample, 350 DEG C of 4 h of roasting are made Mass fraction is 33%H3PW12O40/SiO2Catalyst.
The method that the carried heteropoly acid catalyst prepares diethoxymethane, the reaction temperature are 0~160 DEG C, reaction pressure is 0.1~10.0 MPa；Filling gas is inert gas, is argon gas, helium, carbon dioxide or N2Gaseous mixture In one kind or gaseous mixture.
The method that the carried heteropoly acid catalyst prepares diethoxymethane, the carried heteropoly acid catalyst The method for preparing diethoxymethane, the reactor are fixed bed or tank reactor；Still more preferably still reaction Device.
The method that the carried heteropoly acid catalyst prepares diethoxymethane, the raw material dimethoxymethane and Ethyl alcohol molar ratio is 1:4~2:1, still more preferably 1:4.
Advantages of the present invention is with effect：
Product of the present invention is more single, and high selectivity has a good application prospect.And raw material needed for this method is cheap It is easy to get and whole flow process is easy to operate, while this method does not generate the chemical substance of any pollution environment, belongs to environmentally friendly Processing route.
Description of the drawings
Fig. 1 is influence curve figure of the reaction pressure to diethoxymethane selectivity.
Specific implementation mode
The following describes the present invention in detail with reference to examples.
Carried heteropoly acid catalyst is used the present invention provides a kind of, diethoxy is prepared by dimethoxymethane and ethyl alcohol The method of methylmethane.In the reaction of the present invention, following reaction occurs for raw material：
CH3OCH2OCH3 + CH3CH2OH → CH3CH2OCH2OCH3 + CH3OH……………………………… （1）
CH3OCH2OCH3 + 2CH3CH2OH → CH3CH2OCH2OCH2CH3 + 2CH3OH……………………… （2）
Specifically, as shown in above formula.Formula (1) indicates raw material dimethoxymethane and ethyl alcohol with molar ratio for 1:2 reactions, It is 1 to generate molar ratio:2 diethoxymethane and methanol, formula (2) indicate that raw material dimethoxymethane and ethyl alcohol are with molar ratio 1:1 reaction, it is 1 to generate molar ratio:1 methoxy ethoxy methane and methanol.
With gradually rising for reaction temperature, catalyst activity significantly improves.
It can be seen that from the above reaction process and be by the mixture obtained after raw material dimethoxymethane and ethanol synthesis： Diethoxymethane, methoxy ethoxy methane and methanol, also a small amount of remaining raw material dimethoxymethane and ethyl alcohol.
For the present invention, it is desirable to which dimethoxymethane and ethyl alcohol are with molar ratio 1:2 reactions completely, generating molar ratio is 1:2 diethoxymethane and methanol, without generating methoxy ethoxy methane.The selectivity of each product can be urged by changing The type of agent, the temperature of reaction, reaction contact time, the conditions such as reaction pressure change.
In the present invention, product is detected and is determined by gas-chromatography and mass spectrometer analysis.Therefore, lead to Cross gas-matter chromatography analysis detection, it is determined that the mixture composition in product is simple, only dimethoxymethane, ethyl alcohol, diethyl Oxygroup methane, methoxy ethoxy methane and methanol.
Embodiment 1
30 g dimethoxymethane, 40 g ethyl alcohol and 3 g catalyst, catalyst are added in 200 mL autoclaves Respectively mass fraction is 33%H3PW12O40/SiO2、33%H4SiW12O40/ activated carbon, 33% H3PMo12O40/SBA-15、33% H4SiMo12O40/MCM-41、33%H3PW12O40/TiO2And 33%H3PW12O40/Al2O3.The preparation method of carried heteropoly acid with 33%H3PW12O40/SiO2For preparation process it is as follows：With the phosphotungstic acid aqueous solution of a concentration of 33 mass percent, with SiO2To carry Body, maceration extract volume is close with hole appearance, and by the two, 10 h of room temperature standing obtain catalyst sample after mixing, by sample 120 DEG C drying, 350 DEG C roasting 4 h be made mass fractions be 33%H3PW12O40/SiO2Catalyst.Other Catalyst Preparation Procedures and The above process is identical, the difference is that carrier, solvent in preparation condition（Optional ethyl alcohol is as solvent）, solution concentration, roasting Burn one or more of temperature.Use N2Air under the conditions of 1.0 MPa in displacement kettle makes remaining air in kettle contain three times Amount is less than 0.1 %, and is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that the air tight heel row of device Empty gas reactor.Under the conditions of ensuring gastight, heat temperature raising reaction, 500 revs/min of reaction kettle mixing speed, reaction are carried out 120 DEG C of temperature, 3.0 MPa of reaction pressure, in 6 hours reaction time, the results are shown in Table 1 for control catalyst type.
Table 1. different loads type heteropolyacid catalyst is to dimethoxymethane and ethanol synthesis activity and selectivity of product It influences.
From table 1 it follows that in 120 DEG C of 3.0 MPa of pressure, temperature, the object of reactant dimethoxymethane and ethyl alcohol The amount of matter is than about 5：When 11, reaction is passed through 6 hours, and different carried heteropoly acid catalysts is affected to reaction, Middle carried heteropoly acid catalyst is that mass fraction is 33%H3PW12O40/SiO2When diethoxymethane selectivity be up to 86 %.Then we are 33%H with mass fraction3PW12O40/SiO2For catalyst, reaction raw materials dimethoxymethane and ethyl alcohol is not with The amount ratio of commaterial is tested, and the results are shown in Table 2.
Embodiment 2
The amount ratio that the substance of raw material dimethoxymethane and ethyl alcohol is added in 200 mL autoclaves is 2:1、1: 1、1:2、1:3、1:4 and 3 g mass fractions are 33%H3PW12O40/SiO2Carried heteropoly acid catalyst, at ambient temperature Use N2Air under the conditions of 1.0 MPa in displacement kettle three times, makes remaining air content in kettle be less than 0.1 %, and lead to again Enter 2.0 MPa N2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that empty gas reactor after device is air tight.Ensuring not Under conditions of gas leakage, heat temperature raising, 500 revs/min of reaction kettle mixing speed, 120 DEG C of reaction temperature, reaction pressure are carried out under normal pressure 3.0 MPa of power, in 6 hours reaction time, the results are shown in Table 2 for control raw material ratio.
Influence of 2. different ratios of raw materials of table to reactivity and selectivity of product.
From Table 2, it can be seen that use quality score is 33%H3PW12O40/SiO2Carried heteropoly acid catalyst is being pressed 120 DEG C of 3.0 MPa of power, temperature, reaction are passed through 6 hours, the amount of different material than reaction raw materials dimethoxymethane and ethyl alcohol Result obtained by the reaction is different, and the selectivity of the higher diethoxymethane of ethanol content is higher in raw material, ethanol content in raw material The selectivity of lower diethoxymethane is lower.Reducing the amount ratio of the substance of dimethoxymethane and ethyl alcohol in raw material can increase The selectivity of diethoxymethane.
Embodiment 3
30 g dimethoxymethane, 40 g ethyl alcohol are added in 200 mL autoclaves, 3 g mass fractions are 33% H3PW12O40/SiO2Carried heteropoly acid catalyst uses N at ambient temperature2The air in kettle is replaced under the conditions of 1.0 MPa Three times, so that remaining air content in kettle is less than 0.1 %, and be passed through 2.0 MPa N again2, 30 min are stood, reaction kettle is used for It leaks hunting, it is ensured that gas reactor is emptied after device is air tight.Under the conditions of ensuring gastight, heat temperature raising is carried out under normal pressure, instead Answer 500 revs/min of kettle mixing speed, in 6 hours reaction time, 3.0 MPa of reaction pressure, reaction temperature is respectively 25 DEG C, 40 DEG C, 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 130 DEG C, 140 DEG C, 150 DEG C, 160 DEG C, under differential responses temperature condition Reaction result is as shown in table 3.
3. 33%H of table3PW12O40/SiO2Catalyst reacts dimethoxymethane and ethyl alcohol work at a temperature of differential responses The influence of property and selectivity of product.
From table 3 it is observed that when use quality score is 33%H3PW12O40/SiO2When as catalyst, 3.0 MPa pressures It is reacted 6 hours under power, the matter ratio of reactant dimethoxymethane and ethanol material is 5：When 11, as reaction temperature is from 25 DEG C It is increased to 160 DEG C, the conversion ratio of raw material dimethoxymethane and ethyl alcohol all gradually increases, the product within the scope of 25~160 DEG C The selectivity of diethoxymethane increases with the raising of temperature.
Embodiment 4
30 g dimethoxymethane, 40 g ethyl alcohol are added in 200 mL autoclaves, 3 g mass fractions are 33% H3PW12O40/SiO2Catalyst uses N at ambient temperature2Air under the conditions of 1.0 MPa in displacement kettle three times, makes to remain in kettle Remaining air content is less than 0.1 %, and is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that device Gas reactor is emptied after air tight.Under the conditions of ensuring gastight, heat temperature raising is carried out, reaction temperature is 120 DEG C, reaction 500 revs/min of kettle mixing speed, 6 hours reaction time are respectively 0.1 MPa, 1.0 MPa, 1.5 MPa, 2.0 in pressure It is reacted under MPa, 3.0 MPa, 4.0 MPa, 6.0 MPa, 8.0 MPa, 10.0 MPa, controls reaction pressure result such as table 4 It is shown.
4.33 %H of table3PW12O40/SiO2Catalyst reacts dimethoxymethane and ethyl alcohol work under differential responses pressure The influence of property and selectivity of product
From table 4, it can be seen that when use quality score is 33%H3PW12O40/SiO2When as catalyst, 120 DEG C of reactions 6 hours time, reactant dimethoxymethane and ethyl alcohol molar ratio are 5：It is 0.1~10.0 MPa in pressure limit when 11, it is former The conversion ratio of material dimethoxymethane and ethyl alcohol is improved with the increase of pressure, and the selectivity of product diethoxymethane exists 0.1~1.5 MPa ranges are reduced with the raising of pressure, but selectivity under conditions of 1.5~10.0 MPa relatively high pressures It is increased with the raising of pressure.
Embodiment 5
30 g dimethoxymethane, 40 g ethyl alcohol are added in 200 mL autoclaves, 3 g mass fractions are 33% H3PW12O40/SiO2Catalyst uses N at ambient temperature2Air under the conditions of 1.0 MPa in displacement kettle three times, makes to remain in kettle Remaining air content is less than 0.1 %, and is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that device Gas reactor is emptied after air tight.Under the conditions of ensuring gastight, heat temperature raising is carried out under 3.0 MPa pressure, temperature is set as 120 DEG C, 500 revs/min of reaction kettle mixing speed, the reaction time is respectively 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, Controlling the reaction time, the results are shown in Table 5.
Table 5.33%H3PW12O40/SiO2Catalyst is to dimethoxymethane and ethyl alcohol in differential responses time activity and product The influence of selectivity.
As can be seen from Table 5, it is 33%H with mass fraction3PW12O40/SiO2For catalyst, reactant dimethoxymethane Amount ratio with ethanol material is 5：When 11, under the conditions of 120 DEG C, 3.0 MPa, the reaction time is shorter to make reaction insufficient, instead Longer reaction is more abundant between seasonable, and the selectivity of product is higher, but when reacted between when reaching 8 hours, reaction reaches balance, then With the increase in reaction time, the selectivity of product diethoxymethane is basically unchanged.
Embodiment 6
Be added 30 g dimethoxymethane in 200 mL autoclaves, 40 g ethyl alcohol and quality be respectively 1.0 g, 2.0 g, 3.0 g, 4.0 g, 6.0 g, 8.0 g, 9.0 g, 10.0 g mass fraction be 33%H3PW12O40/SiO2Catalyst. Use N2Air under the conditions of 1.0 MPa in displacement kettle three times, makes remaining air content in kettle be less than 0.1 %, and lead to again Enter 2.0 MPa N2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that empty gas reactor after device is air tight.Ensuring not Under conditions of gas leakage, heat temperature raising reaction, 120 DEG C of reaction temperature, reaction kettle mixing speed 500 are carried out under 3.0 MPa pressure Rev/min, in 6 hours reaction time, the results are shown in Table 6.
The 33%H of 6. different quality of table3PW12O40/SiO2Catalyst is to dimethoxymethane and ethanol synthesis activity and product The influence of selectivity.
As can be seen from Table 6, it is 33%H with mass fraction3PW12O40/SiO2For catalyst, in 3.0 MPa pressure, 120 It is reacted 6 hours under DEG C temperature condition, reactant dimethoxymethane and ethyl alcohol molar ratio are 5：When 11, when the quality of catalyst increases The conversion ratio of dimethoxymethane, ethyl alcohol is added to increase, while the selectivity of diethoxymethane also increases, when catalyst quality is big After 8 g, the selectivity variation of dimethoxymethane, the conversion ratio of ethyl alcohol and diethoxymethane is little, the reason is that catalyst Amount reaches saturation value.
Embodiment 7
30 g dimethoxymethane are added in 200 mL autoclaves, 40 g ethyl alcohol and catalyst are respectively quality Score is 33%H4SiW12O40/ activated carbon, 33% H4SiMo12O40/MCM-41、33%H3PW12O40/TiO2With 33 %H3PW12O40/ Al2O3Quality respectively be 3 g, 6 g, 8 g, 10 g.N is used at ambient temperature2The air in kettle is replaced under the conditions of 1.0 MPa Three times, so that remaining air content in kettle is less than 0.1 %, and be passed through 2.0 MPa N again2, 30 min are stood, reaction kettle is used for It leaks hunting, it is ensured that gas reactor is emptied after device is air tight.Under the conditions of ensuring gastight, heated under 3.0 MPa pressure Heating, temperature are 120 DEG C, 500 revs/min of reaction kettle mixing speed, 6 hours reaction time, controlling reaction temperature result such as table 7 It is shown.
The various catalyst of 7. different quality of table are to raw material dimethoxymethane and ethanol synthesis activity and selectivity of product Influence.
As can be seen from Table 7, it is 33%H with mass fraction3PW12O40/SiO2For catalyst, in 3.0 MPa pressure, 120 Under DEG C temperature condition, reactant dimethoxymethane and ethyl alcohol molar ratio are 5：When 11, the quality of catalyst turns reactant Rate and selectivity are influential, and influences of quality 8 g and 10 g to the conversion ratio of reactant and selectivity is added in table 7 not Greatly, i.e., saturation state has been reached when the quality of catalyst is 8 g.
Embodiment 8
30 g dimethoxymethane are added in 200 mL autoclaves, 40 g ethyl alcohol and 3 g catalyst are respectively Mass fraction is 33%H4SiW12O40/ activated carbon, 33% H4SiMo12O40/MCM-41、33%H3PW12O40/TiO2With 33% H3PW12O40/Al2O3, N is used under the conditions of temperature is respectively 70 DEG C, 90 DEG C, 120 DEG C, 140 DEG C, 160 DEG C2In 1.0 MPa Under the conditions of air in displacement kettle three times, so that remaining air content is less than 0.1 %, and be passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that empty gas reactor after device is air tight.Under the conditions of ensuring gastight, Heat temperature raising is carried out under 3.0 MPa pressure, 120 DEG C of reaction temperature, 500 revs/min of reaction kettle mixing speed, the reaction time 6 is small When, the results are shown in Table 8 for controlling reaction temperature.
8. various catalyst of table under differential responses temperature condition to raw material dimethoxymethane and ethanol synthesis activity and The influence of selectivity of product.
As can be seen from Table 8, under 3.0 MPa pressure conditions, reactant dimethoxymethane and ethyl alcohol molar ratio are 5： When 11, in 6 hours reaction time, with the raising of temperature, the conversion ratio of reactant dimethoxymethane all increases various catalyst, The selectivity of product diethoxymethane also all increases.Wherein, mass fraction 33%H3PW12O40/TiO2Catalyst is made to temperature It is more sensitive, it is big with the selective increasing degree for increasing its product diethoxymethane of temperature.
Embodiment 9
30 g dimethoxymethane are added in 200 mL autoclaves, 40 g ethyl alcohol and 3 g catalyst are respectively Mass fraction is 33%H4SiW12O40/ activated carbon, 33% H4SiMo12O40/MCM-41、33%H3PW12O40/TiO2With 33% H3PW12O40/Al2O3, N is used under the conditions of pressure is respectively 0.1 MPa, 1.5 MPa, 2.0 MPa, 6.0 MPa, 10.0 MPa2 Air under the conditions of 1.0 MPa in displacement kettle three times, makes remaining air content in kettle be less than 0.1 %, and be passed through 2.0 again MPa N2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that empty gas reactor after device is air tight.Ensure it is gastight Under the conditions of, heat temperature raising, 120 DEG C of reaction temperature, 500 revs/min of reaction kettle mixing speed, reaction are carried out under 3.0 MPa pressure 6 hours time, the results are shown in Table 9 for controlling reaction temperature.
9. various catalyst of table are under the conditions of different pressures to raw material dimethoxymethane and ethanol synthesis activity and product The influence of selectivity.
As can be seen from Table 9, at 120 DEG C, in 6 hours reaction time, reactant dimethoxymethane and ethyl alcohol molar ratio are 5：When 11, under conditions of differential pressure, reactant dimethoxy can be increased to different catalyst by increasing the various catalyst of pressure The conversion ratio of methylmethane, but the selectivity of product diethoxymethane still conforms to the liter in 0.1~1.5 MPa ranges with pressure It is high and reduce, but selectively increase with the raising of pressure under conditions of 1.5~10.0 MPa relatively high pressures.Wherein, matter Amount score is 33%H4SiW12O40/ activated-carbon catalyst when increasing pressure, product diethoxymethane selectivity increasing degree compared with Greatly.
Embodiment 10
30 g dimethoxymethane are added in 200 mL autoclaves, 40 g ethyl alcohol and 3 g catalyst are respectively Mass fraction is 33%H4SiW12O40/ activated carbon, 33% H4SiMo12O40/MCM-41、33%H3PW12O40/TiO2With 33% H3PW12O40/Al2O3, N is used in atmospheric conditions2Air under the conditions of 1.0 MPa in displacement kettle makes remaining sky in kettle three times Gas content is less than 0.1 %, and is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that device is air tight After empty gas reactor.Under the conditions of ensuring gastight, heat temperature raising is carried out under 3.0 MPa pressure, 120 DEG C of reaction temperature, 500 revs/min of reaction kettle mixing speed, reaction time are respectively 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, control reaction Temperature results are as shown in table 10.
10. various catalyst of table under differential responses time conditions to raw material dimethoxymethane and ethanol synthesis activity and The influence of selectivity of product.
As can be seen from Table 10, in 120 DEG C of 3.0 MPa of reaction pressure, reaction temperature, reaction response object dimethoxy first Alkane and ethyl alcohol molar ratio are 5：When 11, with the increase in reaction time, the conversion ratio of reactant increases for the reactions of different catalysts, The selectivity of product diethoxymethane also increases, still, when reacted between reach 8 hours, reaction reach balance, with reaction The selectivity of the increase of time, product diethoxymethane is basically unchanged.
The above is only several embodiments of the application, not does any type of limitation to the application, although this Shen Please disclosed as above with preferred embodiment, however not to limit the application, any person skilled in the art is not taking off In the range of technical scheme, makes a little variation using the technology contents of the disclosure above or modification is equal to Case study on implementation is imitated, is belonged in technical proposal scope.

Claims (3)

1. the method that carried heteropoly acid catalyst prepares diethoxymethane, which is characterized in that the method is as follows：200 The amount ratio that the substance of raw material dimethoxymethane and ethyl alcohol is added in mL autoclaves is 1:4 and 3 g mass fractions are 33%H3PW12O40/SiO2Carried heteropoly acid catalyst uses N at ambient temperature2The sky in kettle is replaced under the conditions of 1.0 MPa Gas three times, makes remaining air content in kettle be less than 0.1 %, and be passed through 2.0 MPa N again2, 30 min are stood, for reacting Kettle leaks hunting, it is ensured that gas reactor is emptied after device is air tight；Under the conditions of ensuring gastight, heat temperature raising is carried out under normal pressure, 500 revs/min of reaction kettle mixing speed, 120 DEG C of reaction temperature, 3.0 MPa of reaction pressure, 6 hours reaction time；
The 33%H3PW12O40/SiO2The preparation method of carried heteropoly acid catalyst is：With a concentration of 33 mass percent Phosphotungstic acid aqueous solution, with SiO2For carrier, maceration extract volume is close with hole appearance, and by the two, 10 h of room temperature standing are obtained after mixing To catalyst sample, by 120 DEG C of drying of sample, it is 33%H that mass fraction, which is made, in 350 DEG C of 4 h of roasting3PW12O40/SiO2Catalysis Agent.
2. the method that carried heteropoly acid catalyst prepares diethoxymethane, which is characterized in that the method is as follows：200 30 g dimethoxymethane, 40 g ethyl alcohol are added in mL autoclaves, 3 g mass fractions are 33%H3PW12O40/SiO2Load Type heteropolyacid catalyst, uses N at ambient temperature2Air under the conditions of 1.0 MPa in displacement kettle makes remaining in kettle three times Air content is less than 0.1 %, and is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that device does not leak Gas reactor is emptied after gas；Under the conditions of ensuring gastight, heat temperature raising, reaction kettle mixing speed 500 are carried out under normal pressure Rev/min, in 6 hours reaction time, 3.0 MPa of reaction pressure, reaction temperature is 160 DEG C；
The 33%H3PW12O40/SiO2The preparation method of carried heteropoly acid catalyst is：With a concentration of 33 mass percent Phosphotungstic acid aqueous solution, with SiO2For carrier, maceration extract volume is close with hole appearance, and by the two, 10 h of room temperature standing are obtained after mixing To catalyst sample, by 120 DEG C of drying of sample, it is 33%H that mass fraction, which is made, in 350 DEG C of 4 h of roasting3PW12O40/SiO2Catalysis Agent.
3. the method that carried heteropoly acid catalyst prepares diethoxymethane, which is characterized in that the method is as follows：200 30 g dimethoxymethane, 40 g ethyl alcohol are added in mL autoclaves, 3 g mass fractions are 33%H3PW12O40/SiO2Catalysis N is used in agent at ambient temperature2Air under the conditions of 1.0 MPa in displacement kettle makes remaining air content in kettle be less than three times 0.1 %, and it is passed through 2.0 MPa N again2, 30 min are stood, are leaked hunting for reaction kettle, it is ensured that after device is air tight in emptying kettle Gas；Under the conditions of ensuring gastight, heat temperature raising is carried out, reaction temperature is 120 DEG C, 500 turns of reaction kettle mixing speed/ Point, 6 hours reaction time was reacted in the case where pressure is 10.0 MPa；
The 33%H3PW12O40/SiO2The preparation method of carried heteropoly acid catalyst is：With a concentration of 33 mass percent Phosphotungstic acid aqueous solution, with SiO2For carrier, maceration extract volume is close with hole appearance, and by the two, 10 h of room temperature standing are obtained after mixing To catalyst sample, by 120 DEG C of drying of sample, it is 33%H that mass fraction, which is made, in 350 DEG C of 4 h of roasting3PW12O40/SiO2Catalysis Agent.
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