CN105801383B

CN105801383B - A method of butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol

Info

Publication number: CN105801383B
Application number: CN201610184563.XA
Authority: CN
Inventors: 石磊; 姚杰; 赵佳; 李朕权
Original assignee: Shenyang University of Chemical Technology
Current assignee: Shenyang University of Chemical Technology
Priority date: 2016-03-29
Filing date: 2016-03-29
Publication date: 2018-10-12
Anticipated expiration: 2036-03-29
Also published as: CN105801383A

Abstract

A method of butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, is related to a kind of method of synthesizing methane, including following procedure：The synthetic method of butyl glycol ether, this method include three steps, and first step dimethoxym ethane and butanol synthesize butoxymethoxy methane；Second step butoxymethoxy methane orientation carbonylation, generates butoxy acetic acid methyl esters；Third walks butoxy acetic acid methyl ester hydrogenation and generates butyl glycol ether and methanol；The method for preparing butoxymethoxy methane at temperature and pressure, with carried heteropoly acid as catalyst, prepares butoxymethoxy methane using dimethoxymethane and n-butanol as raw material.Response path product of the present invention is single, and raw material is simple and easy to get, and selectivity of product is high and can be carried out without reaction under high pressure condition, 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

A method of butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol

Technical field

The present invention relates to a kind of methods of synthesizing methane, are synthesized with dimethoxymethane and n-butanol more particularly to one kind The method of butoxymethoxy methane.

Background technology

Butyl glycol ether（HOCH₂CH₂OCH₂CH₂CH₂CH₃）, colourless flammable liquid, with moderate ether taste, boiling point 171 ℃.Due to not only containing ehter bond in its molecule but also containing hydroxyl, this unique property makes it both can dissolve organic molecule, synthesis Or natural high-molecular compound, and can dissolve each other to some extent with water or water soluble compound, thus be used as applying extensively The uses such as material, ink, cleaning agent, pharmaceutical extraction agent.According to statistics, China's coating, ink industry in 2010 about consume glycol ether 200000 tons, account for about the 80% of glycol ether aggregate consumption.Cleaning agent industry about consumes 20,000 tons of glycol ether, and it is total to account for about glycol ether The 8% of consumption figure, it can be seen that paint solvent is still the largest application areas of glycol ether.However recently some researches show that, Gylcol ether（Especially methyl ether and ether）Hematologic disease and fetal anomaly are may result in, beginning limits for developed country It makes its production and uses.But butyl glycol ether does not show similar toxicity, it is external its not as hazardous materials transportation and storage. Therefore ethylene glycol monomethyl ether and ether is replaced to use in a solvent by butyl glycol ether imperative.Currently, in China's ethylene glycol fourth Ether dosage is maximum, and dosage accounts for about the 60% of gylcol ether product consumption total amount.But since the country produces butyl glycol ether Technology it is immature, the source of China's butyl glycol ether depends on import, and import volume accounts for 90% of total amount or more, and close several Year, China grew at top speed again for the demand of butyl glycol ether with 10% average growth rate per annum, and imbalance of supply and demand phenomenon is on the rise.Cause This opens up a practicable butyl glycol ether production ways and is particularly important.

Consulting literatures and patent are it is found that the synthetic method of butyl glycol ether mainly has following two approach：

One, using ethylene oxide and butanol as raw material preparing ethylene glycol butyl ether

+ CH₃CH₂CH₂CH₂OH→ HOCH₂CH₂OCH₂CH₂CH₂CH₃....................(1)

Such as equation（1）Shown, Zhang Mu exists《Petrochemical industry》Second is prepared with the response path in supplementary issues of volume 37 in 2008 Glycol butyl ether.This method is prepared using heteropoly acid as catalyst in 70~120 DEG C of low pressure using ethylene oxide and n-butanol as raw material Butyl glycol ether, glycol product butyl ether selectively up to 75%.However the byproduct of reaction is more, and be strong exothermal reaction, instead It should be not easily controlled, a large amount of butyl, triethylene glycol butyl ether, tetraethylene glycol butyl ether, five ethylene glycol are contained in product Butyl ether, six butyl glycol ethers and corresponding bis ether, later separation is difficult, and energy consumption is higher.

Two, synthesis gas formaldehyde method preparing ethylene glycol butyl ether

CO + 2H₂+ HCHO + CH₃CH₂CH₂CH₂OH → HOCH₂CH₂OCH₂CH₂CH₂CH₃+ H₂O.....................(2)

Such as equation（2）Shown, Japanese chemists Kurashiki is in 4071568 intermediaries of United States Patent It continues using synthesis gas, formaldehyde and n-butanol as raw material, is catalyst under the conditions of 100~250 DEG C, 50 Mpa extremely high pressures using cobalt Synthesizing butyl cellosolve, wherein butyl glycol ether yield are up to 55.6%.But the disadvantages of this method is that reaction is needed in extra-high voltage Lower progress needs 500 atmospheric pressure, high to consersion unit requirement, and the preparation process of the Co catalysts reacted is cumbersome, nothing Method is reused, therefore is used without using in large-scale industrial production.

Three, ethylene glycol reacts preparing ethylene glycol butyl ether with butanol

HOCH₂CH₂OH + CH₃CH₂CH₂CH₂OH→ HOCH₂CH₂OCH₂CH₂CH₂CH₃................(3)

Such as equation（3）It is shown, using ethylene glycol and butanol as reaction raw materials, ethylene glycol fourth is prepared under acid catalysed conditions Ether, this method are the preparation methods of industrial butyl glycol ether at present.But the reaction product is more complex, there is butyl cellosolve, Butyl ether, diethanol butyl ether, dibutyl ethylene glycol ether etc., later separation is difficult, and energy consumption is higher.

Based on the above reason, we open a kind of synthesis path of completely new butyl glycol ether, the first step by dimethoxym ethane and The highly selective synthesis butoxymethoxy methane of butanol；Second step butoxymethoxy methane orientation carbonylation, generates fourth oxygen Acetic acid methyl ester；Third walks butoxy acetic acid methyl ester hydrogenation and generates butyl glycol ether and methanol.Wherein third step ester through hydrogenation reaction It is very easy to carry out, and selectivity is higher.Second step orients carbonylation, all it has been reported that crossing dimethoxym ethane in document and patent The highly selective generation methoxy menthyl acetate of carbonylation.The synthesis of first step reaction raw materials methoxybutoxy methane only, at present The report in relation to specific synthetic method and path is had no on SciFinder.

Invention content

Butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol the purpose of the present invention is to provide a kind of Method, response path product of the present invention is single, and raw material is simple and easy to get, and selectivity of product is high and can without reaction under high pressure condition Carry out, by-product is less, and target product selectivity is higher, and reaction condition is mild, and product yield is higher, required raw material dimethoxym ethane with Butanol 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 ring The processing route of border friendly.

The purpose of the present invention is what is be achieved through the following technical solutions：

One kind synthesizing butoxymethoxy methane, including following procedure with dimethoxymethane and n-butanol：

A. the synthetic method of butyl glycol ether, this method include three steps, the first step such as equation（1）It is shown, dimethoxym ethane and Butanol synthesizes butoxymethoxy methane；Second step such as equation（2）Shown, butoxymethoxy methane orientation carbonylation is raw At butoxy acetic acid methyl esters；Third step such as equation（3）Shown, butoxy acetic acid methyl ester hydrogenation generates butyl glycol ether and first Alcohol；

CH3OCH2OCH3 + CH3CH2CH2CH2OH → CH3CH2CH2CH2OCH2OCH3+CH3O.…(1)

CH3CH2CH2CH2OCH2OCH3 + CO → CH3CH2CH2CH2OCH2COOCH3............(2)

CH3CH2CH2CH2OCH2COOCH3 +H2 → HOCH2CH2OCH2CH2CH2CH3+CH3OH...(3)

B. butoxymethoxy methane is prepared, using dimethoxymethane and n-butanol as raw material, at temperature and pressure, with Carried heteropoly acid prepares butoxymethoxy methane as catalyst.

A kind of preparation method of butoxymethoxy methane, the heteropolyacid catalyst use equi-volume impregnating It prepares, with activated carbon, TiO₂、Al₂O₃、SiO₂, at least one of SBA-15 and MCM-41 be used as carrier.

A kind of method that butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, the support type Heteropolyacid catalyst includes heteropoly acid and the carrier for carried heteropoly acid, heteropoly acid be selected from phosphotungstic acid, silico-tungstic acid, phosphomolybdic acid and It is one or more in silicomolybdic acid.

A kind of method that butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, the support type Heteropoly acid accounts for the 0.1~50% of the carried heteropoly acid catalyst total weight in heteropolyacid catalyst, is still more preferably 5 ~40%.

A kind of method that butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, the support type The preparation method of heteropoly acid is 33%H with mass fraction₃PW₁₂O₄₀/ SiO₂For preparation process it is as follows：With a concentration of 33 mass hundred The phosphotungstic acid aqueous solution of score, with SiO₂For carrier, maceration extract volume is close with hole appearance, and by the two, room temperature is stood after mixing 10 h obtain catalyst sample, and 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/ SiO₂Catalyst.Other Catalyst Preparation Procedures are identical with the above process, the difference is that change preparation condition in carrier, Solvent（Ethyl alcohol can be used as solvent）, solution concentration, one or more of calcination temperature and roasting time.

A kind of method that butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, the reaction temperature Degree is 0~160 DEG C, and reaction pressure is 0.1~10.0 MPa；Filling gas is inert gas, can be argon gas, helium, titanium dioxide Carbon either one kind or gaseous mixture in nitrogen；Reactor is fixed bed or tank reactor, and still more preferably autoclave is anti- Answer device.

A kind of method that butoxymethoxy methane is synthesized with dimethoxymethane and n-butanol, the raw material two Methoxyl group methane and n-butanol molar ratio are 1:2~5:1；Still more preferably 1:1.

Advantages of the present invention is with effect：

The method of the present invention uses carried heteropoly acid for catalyst, using dimethoxymethane and n-butanol as raw material, Gao Xuan Selecting property generates butoxymethoxy methane.Entire building-up process product is simple, and side reaction is less, products therefrom butoxymethoxy The selectivity of methane is higher.

Description of the drawings

Fig. 1 is using H₃PMo₁₂O₄₀Reaction temperature and butoxymethoxy methane selectively relationship when/SBA-15 catalyst Figure.

The following describes the present invention in detail with reference to examples.

In the reaction of the present invention, raw material is it may also happen that following side reaction：

CH₃OCH₂OCH₃+2CH₃CH₂CH₂CH₂OH→CH₃CH₂CH₂CH₂OCH₂OCH₂CH₂CH₂CH₃+2CH₃OH...(7)

Actually it is by the mixture obtained after raw material dimethoxymethane and n-butanol reaction：Butoxymethoxy first Alkane, dibutoxy methane and methanol, also a small amount of remaining reaction raw materials dimethoxymethane and n-butanol.

For the present invention, it is desirable to which dimethoxymethane and n-butanol are with molar ratio 1:1 reaction completely, generates molar ratio It is 1:1 butoxymethoxy methane and methanol, without generating dibutoxy methane.The selectivity of two kinds of products can be by changing The type of change catalyzer, reaction raw materials ratio, 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.Pass through gas- Mass spectrometry analysis detection, it is determined that the mixture composition after reaction is simple, only dimethoxymethane, n-butanol, two fourth oxygen Methylmethane, butoxymethoxy methane and methanol.

Embodiment 1

38 g dimethoxymethane, 37 g n-butanols and 3 g catalyst are added in 180 mL autoclaves, are catalyzed Agent is respectively 33% H of mass fraction₃PW₁₂O₄₀/ SiO₂、33%H₄SiW₁₂O₄₀/ activated carbon, 33% H₃PMo₁₂O₄₀/SBA-15、33% H₄SiW₁₂O₄₀/MCM-41、33% H₃PW₁₂O₄₀/TiO₂With 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 SiO₂ For carrier, 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 33% H is made in 120 DEG C of drying, 350 DEG C of 4 h of roasting₃PW₁₂O₄₀/ SiO₂Catalyst.Other Catalyst Preparation Procedures and above-mentioned Process is identical, the difference is that changing the carrier in preparation condition, solvent（Optional ethyl alcohol is as solvent）, solution concentration, roasting Burn one or more of temperature and roasting time.Use N₂Air 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 reaction, reaction kettle mixing speed 500 are carried out Rev/min, reaction pressure 0.1MPa, 70 DEG C of reaction temperature, in 4 hours reaction time, reaction result is as shown in table 1.

From the response data of table 1 it is found that normal pressure, 70 DEG C, reaction raw materials dimethoxymethane and n-butanol with mole Than 1：1 reaction 4 hours, different carried heteropoly acid catalysts is affected to selectivity of product, wherein carried heteropoly acid Catalyst is 33%H₃PMo₁₂O₄₀The selective highest of butoxymethoxy methane when/SBA-15 is 87 %.

Embodiment 2

Normal pressure, under the conditions of 70 DEG C, it is 1 that molar ratio is added in 180 mL autoclaves:3、1:2、2:1、3:1、4: 1、5:1 raw material dimethoxymethane and n-butanol and 3 g mass fractions are 33%H₃PMo₁₂O₄₀/ SBA-15 support types are miscellaneous more Acid catalyst（Wherein n-butanol quality is 37 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, heat temperature raising is carried out under normal pressure, instead Answer 500 revs/min of kettle mixing speed, 4 hours reaction time, influence of the different ratios of raw materials to reactivity and selectivity of product As shown in table 2.

From Table 2, it can be seen that normal pressure, 70 DEG C, reaction pass through 4 hours, the reaction raw materials dimethoxy of different mol ratio Methylmethane and n-butanol result obtained by the reaction are different, the selectivity of the higher butoxymethoxy methane of levels of n-butanol in raw material Lower, the selectivity of the lower butoxymethoxy methane of levels of n-butanol is higher in raw material.Improve dimethoxymethane in raw material The selectivity of butoxymethoxy methane can be increased with the molar ratio of n-butanol.

Embodiment 3

38 g dimethoxymethane, 37 g n-butanols, 3 g, 33% H are added in 180 mL autoclaves₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acid catalysts, use N at ambient temperature₂Air under the conditions of 1.0 MPa in displacement kettle makes three times Remaining air content is less than 0.1% in kettle, and is passed through 2.0 MPa N again₂, 30 min are stood, are leaked hunting for reaction kettle, really Gas reactor is emptied after protection device is air tight.Under the conditions of ensuring gastight, heat temperature raising, reaction kettle mixing speed are carried out 500 revs/min, 4 hours reaction time, 0.1 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, the reaction result such as table under differential responses temperature condition Shown in 3.

From table 3 it is observed that when use quality score is 33%H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acids are used as and urge It when agent, is reacted 4 hours under normal pressure, reactant dimethoxymethane and n-butanol molar ratio are 1：When 1, with the raising fourth of temperature Oxymethoxy methane selectively reduces, the selective higher of butoxymethoxy methane within the scope of relatively low temperature.

Embodiment 4

Select mass percent for 33%H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acids are as catalyst, in 180 mL high pressures 38 g dimethoxymethane, 37 g n-butanols are added in reaction kettle, 3 g mass percents are 33%H₃PMo₁₂O₄₀/ SBA-15 is catalyzed 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, temperature is 70 DEG C, 500 revs/min of reaction kettle mixing speed, instead It is respectively 0.1 MPa, 1.0 MPa, 1.5 MPa, 2.0 MPa, 3.0 MPa, 4.0 MPa, 6.0 in pressure 4 hours between seasonable It is reacted under MPa, 8.0 MPa, 10.0 MPa, the reaction result under differential responses pressure condition is as shown in table 4.

From table 4, it can be seen that when use quality percentage is 33% H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acids are used as and urge When agent, in 70 DEG C of 4 hours reaction time, reactant dimethoxymethane and n-butanol molar ratio are 1：When 1, in pressure limit For 0.1~10.0 MPa, the conversion ratio of raw material dimethoxymethane and n-butanol is improved with the increase of pressure, product fourth oxygen The selectivity of ylmethoxy methane is increased in 0.1~1.5 MPa ranges with the raising of pressure, but in 1.5~10.0 MPa It is selectively reduced with the raising of pressure under conditions of relatively high pressure.Butoxy methoxy in the pressure limit of 0.1~1.5 MPa Methylmethane has higher selectivity.

Embodiment 5

Select mass percent for 33% H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acids are as catalyst, in 180 mL high 38 g dimethoxymethane, 37 g n-butanols are added in pressure reaction kettle, 3 g mass percents are 33% H₃PMo₁₂O₄₀/SBA-15 Carried heteropoly acid catalyst 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 normal pressure, temperature is set as 70 DEG C, instead It is respectively 2 hours, 4 hours, 6 hours, 8 hours, 10 hours to answer 500 revs/min of kettle mixing speed, reaction time, differential responses pressure Reaction result under the conditions of power is as shown in table 5.

As can be seen from Table 5, when use quality percentage is 33% H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acids are used as and urge When agent, 70 DEG C, synthesis under normal pressure, reactant dimethoxymethane and n-butanol molar ratio are 1：When 1, the reaction time is short to be conducive to The generation of butoxymethoxy methane, the reaction time is longer, and reaction is more abundant, and the selectivity of butoxymethoxy methane is lower.

Embodiment 6

It is added 38 g dimethoxymethane in 180 mL autoclaves, 37 g n-butanols and the different quality of quality Percentage is 33%H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acid catalysts, use N at ambient temperature₂Under the conditions of 1.0 MPa Air in displacement kettle three times, makes remaining air content in kettle be less than 0.1%, and be passed through 2.0 MPa N again₂, stand 30 Min leaks hunting for reaction kettle, it is ensured that gas reactor is emptied after device is air tight.Under the conditions of ensuring gastight, under normal pressure into Row heat temperature raising, 70 DEG C are reacted, 500 revs/min of reaction kettle mixing speed, 4 hours reaction time, and the 33% of different quality H₃PMo₁₂O₄₀/ SBA-15 carried heteropoly acid catalysts are to dimethoxymethane and n-butanol reactivity and selectivity of product It influences as shown in table 6.

As can be seen from Table 6, it at 70 DEG C, is reacted 4 hours under normal pressure, reactant dimethoxymethane and n-butanol mole Than being 1：When 1, when the quality of catalyst increases the conversion ratio increase of dimethoxymethane, n-butanol, while butoxymethoxy The selectivity of methane reduces, after catalyst quality is more than 7 g, dimethoxymethane, the conversion ratio of n-butanol and butoxy first The selectivity variation of oxygroup methane is little, the reason is that catalytic amount reaches saturation value.

Embodiment 7

Under condition of normal pressure, 38 g dimethoxymethane, 37 g n-butanols and 3 g are added in 180 mL autoclaves Catalyst, catalyst are respectively mass percent 33%H₃PW₁₂O₄₀/SiO₂、33%H₄SiW₁₂O₄₀/ activated carbon, 33% H₄SiMo₁₂O₄₀/MCM-41、33% H₃PW₁₂O₄₀/Ti O₂, temperature be respectively 50 DEG C, 70 DEG C, 90 DEG C, 130 DEG C, 160 N is used under the conditions of DEG C₂Air in kettle is replaced under the conditions of 1.0 MPa three times, and remaining air content is made in kettle to be less than 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 empty gas reactor after device is air tight. Ensure it is gastight under the conditions of, under normal pressure carry out heat temperature raising reaction, 500 revs/min of reaction kettle mixing speed, the reaction time 4 is small When, various carried heteropoly acid catalysts raw material dimethoxymethane and n-butanol reactivity and production under condition of different temperatures The results are shown in Table 7 for object selectivity.

As can be seen from Table 7, it reacts 4 hours in atmospheric conditions, reactant dimethoxymethane and n-butanol molar ratio It is 1：When 1, with the raising of temperature, the reaction of various catalysts, the conversion of reactant dimethoxymethane and n-butanol Rate all increases, and high temperature is unfavorable for the raising of product butoxymethoxy methane selectively.

Embodiment 8

38 g dimethoxymethane, 37 g n-butanols, 3 g catalyst, catalyst are added in 180 mL autoclaves Respectively mass percent is 33% H₃PW₁₂O₄₀/SiO₂、33%H₄SiW₁₂O₄₀/ activated carbon, 33% H₄SiMo₁₂O₄₀/MCM-41、 33% H₃PW₁₂O₄/TiO₂, N is used at ambient temperature₂Air under the conditions of 1.0 MPa in displacement kettle three times, makes remaining in kettle Air content be 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 device is not Gas reactor is emptied after gas leakage.Under the conditions of ensuring gastight, heat temperature raising is carried out, temperature is 70 DEG C, reaction kettle stirring speed 500 revs/min of degree, 4 hours reaction time are respectively 0.1 MPa, 1.5 MPa, 2.0 MPa, 6.0 MPa, 10.0 in pressure Reacted under MPa, various catalyst at various pressures under the conditions of raw material dimethoxymethane and n-butanol reactivity and Selectivity of product is as shown in table 8.

As can be seen from Table 8, it at 70 DEG C, reacts 4 hours, reactant dimethoxymethane and n-butanol molar ratio are 1：1 When, the reaction of various catalysts, the conversion ratio for increasing stress reaction object dimethoxymethane and n-butanol all increases, but produces The selectivity of object butoxymethoxy methane still conforms to the rule of embodiment 4.

Embodiment 9

38 g dimethoxymethane, 37 g n-butanols are added in 180 mL autoclaves, catalyst is respectively 3 g Mass percent is 33% H₃PW₁₂O₄₀/SiO₂、33% H₄SiW₁₂O₄₀/ activated carbon, 33% H₄SiMo₁₂O₄₀/MCM-41、33% H₃PW₁₂O₄₀//TiO₂, N is used in atmospheric conditions₂Air 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, 70 DEG C of reaction temperature, reaction kettle are carried out under normal pressure 500 revs/min of mixing speed, reaction time are respectively 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, reaction result such as table 9 It is shown.

As can be seen from Table 9, in 70 DEG C, normal pressure, reactant dimethoxymethane and n-butanol molar ratio are 1：When 1, increase The conversion ratio of reaction time reactant dimethoxymethane and n-butanol is added all to increase, but the choosing of product butoxymethoxy methane Selecting property still conforms to the rule of embodiment 5.

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

1. a kind of method of synthesizing butyl cellosolve, which is characterized in that the method includes following procedure：

A. the synthetic method of butyl glycol ether, this method include three steps, the first step such as equation（1）It is shown, dimethoxym ethane and butanol Synthesize butoxymethoxy methane；Second step such as equation（2）Shown, butoxymethoxy methane orientation carbonylation generates fourth Ethoxyacetic acid methyl esters；Third step such as equation（3）Shown, butoxy acetic acid methyl ester hydrogenation generates butyl glycol ether and methanol；

CH3OCH2OCH3 + CH3CH2CH2CH2OH → CH3CH2CH2CH2OCH2OCH3+CH3O (1)

CH3CH2CH2CH2OCH2OCH3 + CO → CH3CH2CH2CH2OCH2COOCH3 (2)

CH3CH2CH2CH2OCH2COOCH3 +H2 → HOCH2CH2OCH2CH2CH2CH3+CH3OH (3)

B. the method for preparing butoxymethoxy methane, using dimethoxymethane and n-butanol as raw material, at temperature and pressure, With carried heteropoly acid as catalyst, butoxymethoxy methane is prepared；

Heteropoly acid accounts for the 5~40% of the carried heteropoly acid catalyst total weight in the carried heteropoly acid catalyst；Load Type heteropolyacid catalyst is that mass fraction is 33%H₃PW₁₂O₄₀/SiO₂；

The reaction temperature is 0~160 DEG C, and reaction pressure is 0.1~10.0 MPa；Filling gas is inert gas, can be argon Gas, helium, carbon dioxide either one kind or gaseous mixture in nitrogen；Reactor is tank reactor；

The mass fraction is 33%H₃PW₁₂O₄₀/SiO₂The preparation method of carried heteropoly acid is as follows：With a concentration of 33 mass hundred The phosphotungstic acid aqueous solution of score, with SiO₂For carrier, maceration extract volume is close with hole appearance, and by the two, room temperature is stood after mixing 10 h obtain catalyst sample, and 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/ SiO₂Catalyst；

The raw material dimethoxymethane and n-butanol molar ratio are 1:1.