CN105439830B - In the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers - Google Patents
In the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers Download PDFInfo
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Abstract
The present invention relates to a kind of method with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, mainly solves the problems, such as that conventional catalyst reaction efficiency is low, metaformaldehyde is higher for cost of material.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 dosage of methanol and dimethoxym ethane can not be 0 simultaneously, it it is 70~200 DEG C in reaction temperature, under the conditions of reaction pressure is 0.2~6MPa, raw material contacts 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 covalent organic aggregate carrier (COFs)；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 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, especially with regard to one kind with poly
Formaldehyde is the method for Material synthesis polyoxymethylene dimethyl ether.
Background technology
In recent years, as the industrial revolution influences to go deep into increasingly and the resource grid of China distinctive " more coals, less oil, having gas "
Office, China's oil resource growing tension, oil supply pressure unprecedentedly increase.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 is become as researcher urgent need solution
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 produces vapour lock make it that dimethyl ether is significantly raised as the cost of vehicle alternative fuel.Polyoxymethylene dimethyl ether,
That is Polyoxymethylene dimethyl ethers (PODE), are the common names of a kind of material, and its skeleton symbol can be expressed as
CH3O(CH2O)nCH3, have higher octane number (>And oxygen content (42~51%) 30).When n value is 2~10, its thing
Rationality matter, combustibility and diesel oil are very close, preferably resolve dimethyl ether and are lacked as existing for derv fuel blend component
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 thermal efficiency is improved, reduces particulate matter and CO in tail gasxAnd NOxRow
Put.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be reducedxDischarging 7~10%, PM reduces by 5~35%.By coal Ji Jia
Alcohol synthesis PODE can not only substitute part diesel oil, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce danger of the diesel combustion to environment
Evil, has important strategic importance and good economic value.
COFs skeleton is all made up of light element (H, B, O, C, Si etc.), and crystalline density is much lower compared with MOFs.Light member
Element is connected by very strong covalence key (C-C, C-O, B-O, Si-C etc.) can form one-dimensional or three-dimensional loose structure, have
There is very high specific surface area, as a kind of new hydrogen storage material, COFs has the advantages of a lot, porous, surface area is big, related
Most COFs reported in the literature surface area more reaches more than 1000m2/g, COF-102 and COF-103 specific surface area
3472m2/ g and 4210m2/g.Density is low, and metallic element is free of in COFs structures, therefore its crystalline density is much lower compared with MOFs,
COF-108 density is 0.17g/cm3, is that crystalline density is minimum in current report.The Modulatory character of structure, with MOFs and more
Number porous material is the same, can control its crystal structure by converting parent.Very high heat endurance, most COFs are to warm
Stability has exceeded 500 DEG C.COFs synthesis is based on the dehydration condensation between intramolecular hydroxyl.Identical intermolecular dehydration can shape
Into B3O3 six-membered ring structure, and different intermolecular dehydrations can form BO2C2 five-membered ring structure.According to structure
COFs can be summarised as two major classes by dimension：Two-dimentional COFs (2D-COFs) and three-dimensional COFs (3D-COFs).2D-COFs such as COF-
1st, COF-10, COF-18 etc., there is the skeleton structure and one-dimensional channels of two dimension.3D-COFs refer to three dimensional skeletal structure and
The covalent organic compound of 3 D pore canal, studies the more COF-102 that includes, and -103, -105, -108 etc..Due to its structure
Particularity, 3D-COFs have higher surface area and lower crystalline density compared with 2D-COFs.
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
It is prepared by right paraformaldehyde or paraformaldehyde and the method for methanol reaction.In recent years, polyoxymethylene dimethyl ether synthetic technology achieves
Progress.
CN 102040491A are described using β zeolites, ZSM-5 molecular sieve, MCM-22, MCM-56 or UZM-8 molecular sieve etc.
As catalyst, pass through the method that methanol, dimethoxym ethane and paraformaldehyde are reactant synthesizing polyoxymethylene dimethyl ether.CN
102040490A is described using 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 not as good as using the carrier loaded solid super-strong acid of covalent organic framework being used as catalyst.
Although it is reported above it is middle use methanol, dimethoxym ethane and paraformaldehyde as reaction raw materials, molecular sieve and solid super-strong acid
As these synthesis techniques of catalyst, but used zeolite catalyst and solid super acid catalyst separate difficult, raw material
Conversion ratio is low, selectivity of product is poor.Particularly, covalent organic framework carrier (COFs) has high heat endurance, compares surface
Product and voidage, it is considered to be crystalline-state mesoporous material.Most COFs have exceeded 500 DEG C to the stability of heat, in the process of reaction
In can be used repeatedly.
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 the problem of cost of material is higher into polyoxymethylene dimethyl ether technique, there is provided one
It is kind new with the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers and the new catalyst suitable for the technique.This method has
The advantages of 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：It is a kind of that poly- first is synthesized with 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 dosage of methanol and dimethoxym ethane can not be 0 simultaneously, be 70~200 DEG C in reaction temperature, instead
Pressure is answered as under the conditions of 0.2~6MPa, raw material contacts 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, carrier is in COF-102, COF-105, COF-108 covalent organic framework in COFs
At least one；Be loaded in b thereon) 20~70 parts be selected from SO4 2-、Cl-、S2O8 2-At least one of solid super-strong acid, preferably
Include SO simultaneously4 2-And S2O8 2-In two kinds of solid super-strong acids.
In above-mentioned technical proposal, catalyst amount preferred scope is the 0.1~5% of raw material weight.In reactant methanol with
The dosage 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 by way of filtering or centrifuging separating catalyst and liquid phase reactor thing.
In above-mentioned technical proposal, from invention technical problems 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 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-/COF-102、SO4 2-/COF-105、SO4 2-/COF-108、Cl-/COF-102、Cl-/
COF-105、Cl-/COF-108、S2O8 2-/COF-102、S2O8 2-/COF-105、S2O8 2-/ COF-108 is known substance, can
For the present invention and solves present invention problem.Covalent ion and part wherein in covalent organic framework material C OFs series
Mol ratio preferably between 1: 10 to 10: 1.
In above-mentioned technical proposal, as the most preferable scheme,
The degree of polymerization of paraformaldehyde uses Arbiso process or iodometric determination, and method comes from：Chen Yongjie, Zhao Hui, Shao Yong
Wait so long industry paraformaldehydes polymerization degree measurement and low polymerization degree paraformaldehyde preparation, Shenyang Institute of Chemical Technology journal, 15 (2)：
2001。
Due to the use of covalent organic framework material C OFs supported solid superacids acid being catalyst in the present invention, first can be realized
Alcohol, dimethoxym ethane and paraformaldehyde catalytic reaction synthesizing polyoxymethylene dimethyl ether, substitute the metaformaldehyde in traditional raw material.Due to the party
Method can be inexpensive to make production cost relatively low using paraformaldehyde as raw material, and distribution of reaction products is uniform.With covalent organic framework material
COFs supported solid superacids acid is catalyst, and covalent organic framework material C OFs carriers can make catalyst have very big specific surface area
And, so as to improve the yield of polyoxymethylene dimethyl ether, prolong with higher heat endurance and chemical stability while porosity
The service life of catalyst is grown.Used catalyst contains extremely strong acidity, by the method for distillation from methanol and paraformaldehyde
Reaction product in obtain dimethoxym ethane, make accessory substance dimethoxym ethane be recycled into acid catalytic systems again with polyformaldehyde reaction, because
This can keep higher reaction conversion ratio and product yield.It it is 70~200 DEG C in reaction temperature, instead using the inventive method
Answer pressure be 0.2~6MPa under the conditions of, it is as follows using methanol, dimethoxym ethane and polyformaldehyde reaction, its result：First, it is produced into
This is relatively low；Second, catalyst separates simply with reaction product, makes accessory substance circular response, therefore product n using the method for distillation
=2~10 yield is good, and selectivity of product is up to 73.9%, achieves preferable technique effect.In addition, the catalyst uses 10
Secondary, 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 calculates.
Embodiment
【Embodiment 1】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-102 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 20:80,100 grams of methanol and 100 grams of poly first
Aldehyde, 4h is reacted under 130 DEG C and 0.8MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 2】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-105 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-105 carriers is 20:80,100 grams of methanol and 100 grams of poly first
Aldehyde, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 3】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-108 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-108 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of polies
Formaldehyde, 4h is reacted under 130 DEG C and 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.In product
Comprising polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 4】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-/ COF-102 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 20:80,100 grams of distillation sample (87wt% first
Acetal, remaining is methanol) and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C, 0.7MPa self-generated pressures, extracts sample centrifugation point
By through gas chromatographic analysis from after.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in product,
It forms distribution such as table 1.
【Embodiment 5】
2 grams of catalyst Cl are added in 300 milliliters of tank reactors-/ COF-105 (the mol ratios of covalent groups and part
For 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-105 carriers is 20:80,100 grams of methanol and 50 grams of poly first
Aldehyde, 4h is reacted under 130 DEG C, 0.7MPa self-generated pressures, extracted after sample centrifuges by through gas chromatographic analysis.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 6】
2 grams of catalyst S are added in 300 milliliters of tank reactors2O8 2-/ COF-108 (moles of covalent groups and part
Than for 0.1), the mass fraction ratio of wherein solid super-strong acid and COF-108 carriers is 20:80,100 grams of dimethoxym ethanes and more than 100 grams
Polyformaldehyde, 4h is reacted under 130 DEG C, 0.6MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.In product
Comprising polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 7】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-102 (the mol ratios of covalent groups and part
For 10), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 20:80,100 grams of methanol and 100 grams of poly first
Aldehyde, 12h is reacted under 130 DEG C and 2MPa self-generated pressures, extracted after sample centrifuges by gas chromatographic analysis.Included in product
Polyoxymethylene dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 8】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-102 (the mol ratios of covalent groups and part
For 10), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 70:30,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, 4h is reacted under 120 DEG C and 4MPa nitrogen pressures, extracted after sample centrifuges by gas chromatographic analysis.Included in product
Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 9】
0.5 gram of catalyst SO is added in 300 milliliters of tank reactors4 2-/ COF-102 (moles of covalent groups and part
Than for 10), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of polies
Formaldehyde, 4h is reacted under 120 DEG C and 4MPa nitrogen pressures, extracted after sample centrifuges by gas chromatographic analysis.Wrapped in product
Containing polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 10】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-102 (the mol ratios of covalent groups and part
For 10), the mass fraction ratio of wherein solid super-strong acid and COF-102 carriers is 20:80,100 grams of dimethoxym ethanes and 100 grams of poly first
Aldehyde, 4h is reacted under 90 DEG C and 4MPa nitrogen pressures, extracted after sample centrifuges by gas chromatographic analysis.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 11】
By the catalyst SO in embodiment 14 2-/ COF-102 takes out after the completion of reaction, according to implementation after drying process
Reaction condition in example 1 carries out 9 reuses, extracts after sample centrifuges by gas chromatographic analysis.Comprising poly- in product
Formaldehyde dimethyl ether and unreacted material benzenemethanol and paraformaldehyde, to investigate the heat endurance of the catalyst and chemically stable
Property, it forms distribution such as table 2.
【Embodiment 12】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/ COF-102/SBA-15 (metal ion and part
Mol ratio for 0.1), wherein the mass fraction ratio of solid super-strong acid and carrier is 20:80, COF-102 and molecular sieve carrier
SBA-15 weight ratio is 50:50.100 grams of dimethoxym ethanes and 100 grams of paraformaldehydes, reacted under 130 DEG C and 4MPa nitrogen pressures
4h, extract after sample centrifuges by gas chromatographic analysis.Polyoxymethylene dimethyl ether and unreacted raw material first are included in product
Acetal and paraformaldehyde, it forms distribution such as table 1.
【Embodiment 13】
2 grams of catalyst SO are added in 300 milliliters of tank reactors4 2-/S2O8 2-/ COF-108 be (covalent groups and part
Mol ratio is 0.1, SO4 2-And S2O8 2-Mutual load is in COF-108 carriers, SO4 2-Solid super-strong acid and S2O8 2-Solid super-strong acid
Mass ratio is 50:50), the mass fraction ratio of wherein solid super-strong acid gross mass and COF-108 carriers is 20:80,100 grams of first
Acetal and 100 grams of paraformaldehydes, 4h is reacted under 130 DEG C, 0.6MPa self-generated pressures, extracted after sample centrifuges by gas phase color
Spectrum analysis.Polyoxymethylene dimethyl ether and unreacted raw material dimethoxym ethane and paraformaldehyde are included in product, it forms 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, reacted 4 hours under 130 DEG C and 0.8MPa self-generated pressures, after extracting 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%, methanol 5.1%, paraformaldehyde 2.1%, n=2 25.1%,
N=3 is 18.4%, n=4 17.5%, n=5-10 9.6%, n>10, surplus, the selection selective to product n=2~10
Property is 70.6%.
The use of methanol, dimethoxym ethane and paraformaldehyde is raw material in comparative example, molecular sieve carried solid super-strong acid is 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 73.9%, and paraformaldehyde content is relatively low in product.It can obtain with zeolite molecular sieve as catalyst
When more preferable reaction result.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Table 2
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (9)
1. in the method for paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, using methanol, dimethoxym ethane and paraformaldehyde as raw material, wherein first
Alcohol: dimethoxym ethane: the mass ratio of paraformaldehyde is (0~10): (0~10): 1, the dosage of methanol and dimethoxym ethane can not be 0 simultaneously,
It it is 70~200 DEG C in reaction temperature, under the conditions of reaction pressure is 0.2~6MPa, raw material contacts with catalyst, and reaction generates poly- first
Aldehyde dimethyl ether, catalyst amount be raw material weight 0.05~10%, wherein catalyst used in terms of weight fraction by following
Component forms：A) 30~80 parts of carrier, carrier in covalent organic framework material C OFs series COF-102, COF-105,
At least one of COF-108 covalent organic frameworks；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 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that catalyst
Dosage is the 0.1~5% of raw material weight.
3. the method according to claim 1 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that reactant
The dosage 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 with 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 with 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 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that described more
The degree of polymerization of polyformaldehyde is 2~8.
7. the method according to claim 6 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that described more
The degree of polymerization of polyformaldehyde is 4~6.
8. the method according to claim 1 with 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 with paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, it is characterised in that during reaction
Between be 4 to 12 hours.
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| CN102040490A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Synthesis method of polyformaldehyde dimethyl ether |
| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
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| CN101869850A (en) * | 2010-05-14 | 2010-10-27 | 东北师范大学 | Crystalline catalysis material for reaction of preparing dimethyl ether from methanol by dehydration and preparation method thereof |
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| CN103664549A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Polyformaldehyde dimethyl ether synthesis method |
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