CN105367393B - By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers - Google Patents
By the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers Download PDFInfo
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Abstract
The present invention relates to a kind of method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, mainly solve that conventional catalyst reaction efficiency is low, metaformaldehyde is the problem of cost of material is higher.The present invention is by using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol：Dimethoxym ethane：The mass ratio of paraformaldehyde is (0~10): (0~10): 1, wherein the consumption of methanol and dimethoxym ethane can not be 0 simultaneously, it it is 70~200 DEG C in reaction temperature, reaction pressure is under the conditions of 0.2~6MPa, raw material is contacted with catalyst, reaction generation polyoxymethylene dimethyl ether, catalyst amount be raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction including following components：A) 30~80 parts of intrinsic microporous polymer carrier (PIMs)；B) technical scheme of 20~70 parts of solid super-strong acids, preferably solves the problem, available in the industrial production of polyoxymethylene dimethyl ether.
Description
Technical field
The present invention relates to a kind of method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, especially with regard to one kind by poly
Formaldehyde is the method for Material synthesis polyoxymethylene dimethyl ether.
Background technology
In recent years, with the industrial revolution influence increasingly deeply and China's distinctive " many coals, few oil, there is gas " resource grid
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increases.It is expected that following 10~20 years, China's oil supply rate
Only~50%.How the energy crisis for solving China using the coal resources of China's abundant becomes is badly in need of solving for researcher
Certainly the problem of.Therefore the attention that new oil product substitute is increasingly subject to people is developed by coal-based methanol.
Dimethyl ether is proposed as a kind of procetane earliest, yet with its own cold starting performance is poor, normal temperature
Lower vapour pressure is high, easily produce vapour lock causes dimethyl ether significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a class material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, with higher octane number (>30) with oxygen content (42~51%).When n value is 2~10, its thing
Rationality matter, combustibility and diesel oil closely, preferably resolve dimethyl ether as lacking that derv fuel blend component is present
Fall into.Therefore polyoxymethylene dimethyl ether can be as new cleaning diesel component, and the addition in diesel oil, can up to 30% (v/v)
To improve the combustion position of diesel oil within the engine, the particulate matter and CO in the thermal efficiency, reduction tail gas are improvedxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarge 7~10%, PM reductions by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only replace part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, danger of the reduction diesel combustion to environment
Evil, with important strategic importance and good economic value.
McKeown the and Budd groups of Univ Manchester UK have developed a kind of new organic microporous polymer, name
For intrinsic microporous polymer (PIMs).These materials are by passing through covalent bond phase comprising rigid, non-rectilinear molecule of functional group
Connect.This polymer that is rigid, reversing can not effectively occupy the space between strand, therefore these " free volumes "
Form microcellular structure.The molecule obtained after polymerization will be unable to effectively occupy the space between strand, molecule serious distortion, shape
Into intermolecular free volume, PIM-1 specific surface areas have reached 1000m2/g。
Polyoxymethylene dimethyl ether can be by oligomeric in 150~180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid in laboratory
Right paraformaldehyde or paraformaldehyde are prepared with the method that methanol reacts.In recent years, polyoxymethylene dimethyl ether synthetic technology is achieved
Progress.
CN 102040491A are described using β zeolites, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve
Deng as catalyst, pass through the method that methanol, dimethoxym ethane and paraformaldehyde are reactant synthesizing polyoxymethylene dimethyl ether.CN
102040490A, which is described, uses solid super acid catalyst, in 90~130 DEG C of reaction temperature, 0.4~4.0MPa of reaction pressure
When, conversion ratio and selectivity are all used as catalyst not as good as using intrinsic microporous polymer supported solid superacid acid.
Although it is reported above it is middle use methanol, dimethoxym ethane and paraformaldehyde for reaction raw materials, molecular sieve and solid super-strong acid
As these synthesis techniques of catalyst, but zeolite catalyst and the solid super acid catalyst separation used is difficult, raw material
Conversion ratio is low, selectivity of product is poor.Particularly, intrinsic microporous polymer carrier (PIMs) has high specific surface area and space
Rate, can be reaction product " customized " its pore passage structure, it is considered to be unformed poromerics.Most PIMs are steady to heat
It is qualitative higher, it can be used repeatedly during reaction.
The content of the invention
The technical problems to be solved by the invention are that prior art is closed by reaction raw materials of methanol, dimethoxym ethane and paraformaldehyde
Have that catalyst reaction efficiency is low, metaformaldehyde is that there is provided one for the problem of cost of material is higher into polyoxymethylene dimethyl ether technique
Plant the method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers newly and the new catalyst suitable for the technique.This method has
The advantage that catalyst low-temperature activity is high, selectivity is high, reaction condition is gentle.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：One kind synthesizes poly- first by paraformaldehyde
The method of aldehyde dimethyl ether, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein methanol: dimethoxym ethane: the quality of paraformaldehyde
Than for (0~10): (0~10): 1, the consumption of methanol and dimethoxym ethane can not be 0 simultaneously, be 70~200 DEG C in reaction temperature, instead
Pressure is answered under the conditions of 0.2~6MPa, raw material is contacted with catalyst, reaction generation polyoxymethylene dimethyl ether, catalyst amount is original
Expect weight 0.05~10%, wherein catalyst used in terms of parts by weight including following components：A) 30~80 parts of carrier,
At least one of intrinsic microporous polymers of carrier PIM-1, PIM-2, PIM-6 in PIMs；Be loaded in b thereon) 20~
70 parts are selected from SO4 2-、Cl-、S2O8 2-At least one of solid super-strong acid, preferably simultaneously including SO4 2-And S2O8 2-Two kinds of solids surpass
Strong acid.
In above-mentioned technical proposal, catalyst amount preferred scope is the 0.1~5% of raw material weight.In reactant methanol with
The consumption sum of dimethoxym ethane and the mass ratio of paraformaldehyde are preferably (0.4~5): 1；Methanol: dimethoxym ethane: the quality of paraformaldehyde
It is (0.2~10): (0.5~10): 1 than preferred scope.The preferred scope of reaction temperature is 90~130 DEG C.Reaction pressure is preferred
Scope is 0.4~4.0MPa.The degree of polymerization of the paraformaldehyde is preferably 2~8, and more preferably 4~6.Poly- first is made in catalytic reaction
Aldehyde dimethyl ether, can filter or centrifugation by way of separating catalyst and liquid phase reactor thing.
In above-mentioned technical proposal, from the invention technical problem to be solved, with prior art effect it is year-on-year for, reaction
Time is not the key point of the present invention, but is considered from operational control and time efficiency other factorses, generally by the reaction time
Control as 1 to 20 hour.The reaction time used in the embodiment of the present invention is 4~12 hour.
In above-mentioned technical proposal, SO4 2-/PIM-1、SO4 2-/PIM-2、SO4 2-/PIM-6、Cl-/PIM-1、Cl-/PIM-2、
Cl-/PIM-6、S2O8 2-/PIM-1、S2O8 2-/PIM-2、S2O8 2-/ PIM-6 is known substance, can be used for the present invention and solves
Present invention problem.The mol ratio of covalent ion and part in wherein intrinsic capillary copolymer material COFs series preferably exists
Between 1: 10 to 10: 1.
The degree of polymerization of paraformaldehyde uses Arbiso process or iodometric determination, and method comes from：Chen Yongjie, Zhao Hui, Shao Yong
The preparation of the polymerization degree measurement and low polymerization degree paraformaldehyde of the industrial paraformaldehydes of that waits so long, Shenyang Institute of Chemical Technology journal, 15 (2)：
2001。
Due to the use of intrinsic capillary copolymer material PIMs supported solid superacids acid being catalyst in the present invention, it can realize
Metaformaldehyde in methanol, dimethoxym ethane and paraformaldehyde catalytic reaction synthesizing polyoxymethylene dimethyl ether, substitution traditional raw material.Due to this
Method can be inexpensive to make production cost relatively low using paraformaldehyde as raw material, and distribution of reaction products is uniform.With intrinsic microporous polymer
Material PIMs supported solid superacids acid is catalyst, and intrinsic microporous polymer PIMs carriers can make catalyst have pole Large ratio surface
With higher heat endurance and chemical stability while product and porosity, so that the yield of polyoxymethylene dimethyl ether is improved,
Extend the service life of catalyst.Used catalyst contains extremely strong acidity, by the method for distillation from methanol and poly first
Obtain dimethoxym ethane in the reaction product of aldehyde, make accessory substance dimethoxym ethane be recycled into acid catalytic systems again with polyformaldehyde reaction,
Therefore higher reaction conversion ratio and product yield can be kept.It is 70~200 DEG C in reaction temperature using the inventive method,
Reaction pressure is under the conditions of 0.2~6MPa, using methanol, dimethoxym ethane and polyformaldehyde reaction, its result is as follows：First, production
Cost is relatively low；Second, catalyst is separated simply with reaction product, makes accessory substance circular response, therefore production using the method for distillation
The yield of thing n=2~10 is good, and selectivity of product is up to 75.1%, achieves preferable technique effect.In addition, the catalyst makes
With 10 times, its catalytic performance is not decreased obviously.
Below by embodiment, the present invention is further elaborated, the raw material paraformaldehyde used in embodiment and comparative example
The degree of polymerization be 5, selectivity of product be by 2~10 polyoxymethylene dimethyl ether of the degree of polymerization on the basis of paraformaldehyde target production
Thing is calculated.
Embodiment
【Embodiment 1】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-1
0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 20:80,100 grams of methanol and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.8MPa self-generated pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 2】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-2
0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-2 carriers is 20:80,100 grams of methanol and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 3】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-6
0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-6 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 4】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-(mol ratio of covalent groups and part is /PIM-1
0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 20:80,100 grams distillation sample (87wt% dimethoxym ethane,
Remaining is methanol) and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C, 0.7MPa self-generated pressures, is extracted after sample centrifugation
By through gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, its group are included in product
Into distribution such as table 1.
【Embodiment 5】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-(mol ratio of covalent groups and part is /PIM-2
0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-2 carriers is 20:80,100 grams of methanol and 50 grams of paraformaldehydes,
130 DEG C, 4h is reacted under 0.7MPa self-generated pressures, is extracted after sample is centrifuged by through gas chromatographic analysis.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 6】
2 grams of catalyst S are added in 300 milliliters of tank reactors2O8 2-/ PIM-6 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and PIM-6 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, reacts 4h under 130 DEG C, 0.6MPa self-generated pressures, extracts after sample is centrifuged by gas chromatographic analysis.Included in product
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 7】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-1
10), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 20:80,100 grams of methanol and 100 grams of paraformaldehydes,
12h is reacted under 130 DEG C and 2MPa self-generated pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 8】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-1
10), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 70:30,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 120 DEG C and 4MPa nitrogen pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 9】
0.5 gram of catalyst SO is added in 300 milliliters of tank reactors4 2-/ PIM-1 (the mol ratios of covalent groups and part
For 10), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, reacts 4h under 120 DEG C and 4MPa nitrogen pressures, extracts after sample is centrifuged by gas chromatographic analysis.Included in product
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 10】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-(mol ratio of covalent groups and part is /PIM-1
10), the mass fraction ratio of wherein solid super-strong acid and PIM-1 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes,
4h is reacted under 90 DEG C and 4MPa nitrogen pressures, is extracted after sample is centrifuged by gas chromatographic analysis.Poly- first is included in product
Aldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it constitutes distribution such as table 1.
【Embodiment 11】
By the catalyst SO in embodiment 14 2-/ PIM-1 takes out after the completion of reaction, according to embodiment 1 after drying process
In reaction condition carry out 9 times reuse, extract sample centrifuge after by gas chromatographic analysis.Polyformaldehyde is included in product
Dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance and chemical stability of the catalyst, its
Composition distribution such as table 2.
【Embodiment 12】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ PIM-1/SBA-15 be (metal group and part
Mol ratio is that 0.1), wherein the mass fraction ratio of solid super-strong acid and carrier is 20:80, PIM-1 and molecular sieve carrier SBA-15
Weight ratio be 50:50.100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C and 4MPa nitrogen pressures, is extracted
By gas chromatographic analysis after sample centrifugation.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane are included in product and many
Polyformaldehyde, it constitutes distribution such as table 1.
【Embodiment 13】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/S2O8 2-(covalent groups and part rub/PIM-6
You are than being 0.1；SO4 2-And S2O8 2-Mutual load is in PIM-6, SO4 2-Solid super-strong acid and S2O8 2-The mass ratio of solid super-strong acid is
50:50), the mass fraction ratio of wherein solid super-strong acid gross mass and PIM-6 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams
Paraformaldehyde, reacts 4h under 130 DEG C, 0.6MPa self-generated pressures, extracts after sample is centrifuged by gas chromatographic analysis.Production
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in thing, it constitutes distribution such as table 1.
【Comparative example 1】
According to patent《The synthetic method of polyoxymethylene dimethyl ether》(number of patent application：201210325102.1) methods described,
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ZrO2/ SBA-15 (wherein solid super-strong acid SO4 2-With carrier
(ZrO2And molecular sieve carrier SBA-15) total mass ratio be 20:80, wherein ZrO2Mass ratio with SBA-15 is 50:50), 100
Ml methanol and 100 grams of paraformaldehydes, react 4 hours under 130 DEG C and 0.8MPa self-generated pressures, extract after sample centrifugation
By gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, its group of composition are included in product
Cloth is following (being represented with weight %)：Dimethoxym ethane is 22.2%, and methanol is 5.1%, and paraformaldehyde is that 2.1%, n=2 is 25.1%,
N=3 is that 18.4%, n=4 is that 17.5%, n=5-10 is 9.6%, n>10, surplus, the selection selective to product n=2~10
Property is 70.6%.
Methanol, dimethoxym ethane and paraformaldehyde is used to be raw material in comparative example, molecular sieve carried solid super-strong acid is used as catalysis
Under equal conditions selectivity of product is relatively low for agent.The embodiment of the present invention 1 in contrast, the conversion ratio of reaction and product n=2~10
Selectivity is higher, is that paraformaldehyde content is relatively low in 75.1%, and product.It can obtain with zeolite molecular sieve as catalyst
When more preferable reaction result.
Table 1
N is the degree of polymerization, and product is CH3O(CH2O)nCH3
Table 2
N is the degree of polymerization, and product is CH3O(CH2O)nCH3 。
Claims (9)
1. a kind of method by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, using methanol, dimethoxym ethane and paraformaldehyde as raw material, its
Middle methanol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the consumption of methanol and dimethoxym ethane can not be simultaneously
It it is 70~200 DEG C in reaction temperature for 0, under the conditions of reaction pressure is 0.2~6MPa, raw material is contacted with catalyst, and reaction is generated
Polyoxymethylene dimethyl ether, catalyst amount be raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction by
Following components is constituted：A) 30~80 parts of carrier, carrier selected from intrinsic microporous polymer PIMs series in PIM-1, PIM-2,
At least one of intrinsic microporous polymers of PIM-6；Be loaded in b thereon) 20~70 parts be selected from SO4 2-、Cl-、S2O8 2-In extremely
A kind of few solid super-strong acid.
2. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that catalyst
Consumption is the 0.1~5% of raw material weight
3. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that reactant
The consumption sum of middle methanol and dimethoxym ethane and the mass ratio of paraformaldehyde are (0.4~5): 1；Methanol: dimethoxym ethane: paraformaldehyde
Mass ratio is (0.2~10): (0.5~10): 1.
4. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that reaction temperature
Spend for 90~130 DEG C.
5. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that reaction pressure
Power is 0.4~4.0MPa.
6. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that described many
The degree of polymerization of polyformaldehyde is 2~8.
7. the method according to claim 6 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that described many
The degree of polymerization of polyformaldehyde is 4~6.
8. the method according to claim 1 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that during reaction
Between be 1 to 20 hour.
9. the method according to claim 8 by paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that during reaction
Between be 4 to 12 hours.
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