CN105348053A - Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst - Google Patents
Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst Download PDFInfo
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- CN105348053A CN105348053A CN201510793662.3A CN201510793662A CN105348053A CN 105348053 A CN105348053 A CN 105348053A CN 201510793662 A CN201510793662 A CN 201510793662A CN 105348053 A CN105348053 A CN 105348053A
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- CN
- China
- Prior art keywords
- dimethyl ether
- methylal
- polyoxymethylene dimethyl
- catalyst
- metal salt
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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
- C07C41/50—Preparation of compounds having groups by reactions producing groups
- C07C41/56—Preparation of compounds having groups by reactions producing groups by condensation of aldehydes, paraformaldehyde, or ketones
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to the field of preparation of diesel additives, and particularly to a method for catalysis preparation of polyformaldehyde dimethyl ether on the basis of a metal salt catalyst. The synthesis method is as follows, paraformaldehyde and methylal are added into a high pressure reactor, one metal salt or a complex of a plurality of metal salts is used as a catalyst, nitrogen is introduced for protection, heating is performed with stirring for reaction, after completion of the reaction, a reaction product is centrifuged and separated to remove the catalyst to obtain the polyformaldehyde dimethyl ether. Compared with a strong acid (sulfuric acid and p-toluenesulfonic acid) as a catalyst, the metal salt catalyst has the advantages that the metal salt catalyst is environmentally-friendly, a container is not easy to corrode, the metal salt catalyst can be used repeatedly, conversion rate and selectivity can be maintained better, and the like.
Description
Technical field
The invention belongs to diesel-dope preparation field, particularly relate to a kind of method catalyzing and synthesizing polyoxymethylene dimethyl ether based on metal salt catalyst.
Background technology
Polyoxymethylene dimethyl ether, chemical formula is CH
3(CH
2o)
noCH
3(be called for short DMM
n, n be more than or equal to 1 integer), be the general designation of a class polyether homologue.DMM
3-8there is higher cetane value (CN>76) and oxygen level (45% ~ 51%), good with the mutual solubility of diesel oil, directly can add in diesel oil and not need to transform engine interior, be considered to a kind of excellent diesel oil and mix burning component.Add 10% ~ 30% in diesel oil after, can significantly reduce NO in tail gas
x, the discharge of CO and solid particulate matter, and the oilness that significantly can increase diesel oil, be considered to a kind of novel environment friendly diesel oil interpolation group having application prospect.
The beginning of this century, DMM
nsynthesis the most deep with the research and development of BASF (BASF) and British Petroleum Company p.l.c. (BP).The route of BASF AG is mainly with capping species (-CH
3o, methyl alcohol, dme, methylal etc.) and the material (-CH of formaldehyde chain is provided
2o, formaldehyde, paraformaldehyde, trioxymethylene etc.) synthesize in the presence of acidic.The patent of BP company then biases toward oxydehydrogenation, and by methyl alcohol, the conversion of methylal etc. and polymerization, obtain DMM
nproduct.Recent years, abroad the research of polyoxymethylene dimethyl ether is being deepened continuously, the people such as HansHasse are mainly through methylal, paraformaldehyde and trioxymethylene system synthesizing polyoxymethylene dme, obtain the mass data of molecular balance and reaction kinetics, and whole process engineering is simulated and optimizes.In addition they are investigated DMM
nas physicochemical property during diesel oil customization component.
In prior art, the technique catalyzing and synthesizing polyoxymethylene dimethyl ether is high to catalyst requirement, and making step is more loaded down with trivial details, and majority is an acidic catalyst, and some is large to reaction vessel corrodibility, not easily reclaims.
Summary of the invention
The present invention is directed to existing catalyst preparing complicated, the selectivity catalyzing and synthesizing polyoxymethylene dimethyl ether is lower, and after having reacted, the defect such as not easily separated, provides the method for the catalyst synthesizing polyoxymethylene dme of a kind of metal-salt or various metals salt compound.
Concrete technical scheme is:
Paraformaldehyde (as trioxymethylene) and methylal is added in autoclave; and using a kind of metal-salt or various metals salt composite as catalyzer; pass into nitrogen protection; under agitation heating is reacted; after having reacted, catalyzer is removed to reaction product centrifugation, obtain polyoxymethylene dimethyl ether (DMM
n),
The concrete equation of reaction is as follows:
(wherein, n be greater than 1 integer)
Wherein, the mass ratio of reactant paraformaldehyde and methylal between 5:1 ~ 1.5:1,
Add that quality is methylal and paraformaldehyde total mass 1% ~ 5% of catalyzer,
The pressure passing into nitrogen is 1MPa ~ 2MPa,
Heating the temperature of carrying out reacting is 110 DEG C ~ 130 DEG C,
It is 3h ~ 7h that stirring heats the time of carrying out reacting down,
Metal-salt is Al
2(SO
4)
3, Cd
3(PO
4)
2, CuCl
2, Fe
2(SO
4)
3, MnSO
4, Ce
2(SO
4)
3, FeSO
4, CaSO
4, Zn (NO
3)
2, NiCl
2, CoSO
4, Cr
2(PO
4)
3.
The present invention compared with prior art has the following advantages: relative to some strong acid as catalyzer (sulfuric acid, tosic acid), a kind of metal-salt or various metals salt compound better as the reactivity worth of catalyst methylal and paraformaldehyde synthesizing polyoxymethylene dme, show higher catalytic activity, higher than general an acidic catalyst catalytic activity, selectivity good.The catalyst preparation process of a kind of metal-salt or various metals salt compound is simple, and cost is low, easily reclaims, pollution-free, can repeatedly use, transformation efficiency and selectivity are all than directly using strong acid, and molecular sieve or ionic liquid are made catalyst synthesizing polyoxymethylene dme and wanted high.
Embodiment
Comparative example 1
HY type molecular sieve is taken 0.5g as catalyzer, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, the whole reaction heated and stirred 3h of control temperature 110 DEG C, leave standstill and be cooled to normal temperature (25 DEG C, lower same), catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 13.8%, and methylal transformation efficiency is 27.6%.
Comparative example 2
Take macropore strong acid cation exchange resin (CT175) catalyzer 0.7g, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 19.8%, and methylal transformation efficiency is 29.4%.
Comparative example 3
Take the sulfuric acid catalyst 0.15g of 98%, add 10g methylal and 40g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 90 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 16.8%, and methylal transformation efficiency is 44.3%.
Embodiment 1
Take 1 gram of Al
2(SO
4)
3salt, it is dried 3h at 100 DEG C, add 10g methylal and 40g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, whole reaction heated and stirred 3h under control temperature 110 DEG C of conditions, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 35.1%, and methylal transformation efficiency is 55.8%.
Embodiment 2
Take Cd
3(PO
4)
22 grams, it is dried 4h at 110 DEG C, add 10g methylal and 30g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 113 DEG C, whole reaction heated and stirred 4h, leave standstill and be cooled to normal temperature, catalyzer is removed in centrifugation, carries out gas chromatographic analysis, detected result DMM to product
3-8content is 25.5%, and methylal transformation efficiency is 42.3%.
Embodiment 3
Take CuCl
23 grams, add 10g methylal and 25g paraformaldehyde puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, at control temperature 110 DEG C, whole reaction heated and stirred 6h, leaves standstill and is cooled to normal temperature, catalyzer is removed in centrifugation, carries out gas chromatographic analysis, detected result DMM to product
3-8content is 30.1%, and methylal transformation efficiency is 49.6%.
Embodiment 4
Take Fe
2(SO
4)
3, MnSO
4each 2 grams of salt, take 4g altogether, it is dried 5h at 130 DEG C, put into 100mL autoclave, add 10g methylal and 20g trioxymethylene, passing into nitrogen pressure is 2MPa, under control temperature 120 DEG C of conditions, and whole reaction heated and stirred 3h, leave standstill and be cooled to normal temperature, catalyzer is removed in centrifugation, carries out gas chromatographic analysis, detected result DMM to product
3-8content is 32.7%, and methylal transformation efficiency is 48.1%.
Embodiment 5
Take Ce
2(SO
4)
32 grams, FeSO
40.5 gram, CaSO
40.5 gram, take 3g altogether, it is dried 6h at 160 DEG C, adds 10g methylal and 20g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 2.0MPa, control temperature 130 DEG C, whole reaction heated and stirred 4h, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 29.6%, and methylal transformation efficiency is 57.2%.
Embodiment 6
Take Zn (NO
3)
2, NiCl
2, CoSO
4, Cr
2(PO
4)
3each 1 gram of catalyzer, take 4g altogether, it is dried 8h at 180 DEG C, adds 10g methylal and 25g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 1.5MPa, control temperature 127 DEG C, whole reaction heated and stirred 5h, leaves standstill and is cooled to normal temperature, and catalyzer is removed in centrifugation, gas chromatographic analysis is carried out to product, detected result DMM
3-8content is 28.1%, and methylal transformation efficiency is 55.9%.
Embodiment 7 (revision test)
By in embodiment 1 from the isolated Al of reaction product
2(SO
4)
3catalyzer deionized water rinsing suction filtration, rinses 3 times, dries, cooling.The Al reclaimed
2(SO
4)
3catalyzer 3.8g, adds fresh Al
2(SO
4)
3catalyzer 0.2g (5% of raw catalyst weight) adds up to 4g, it is dried 3h at 100 DEG C, and add 10g methylal and 40g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 1MPa, control temperature 110 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature, catalyzer is removed in centrifugation, carries out gas chromatographic analysis to product.After having reacted, above step repeats 5 times again, carries out 6 repeated experiments altogether.
Embodiment 8 (revision test)
By in embodiment 4 from the isolated Fe of reaction product
2(SO
4)
3and MnSO
4catalyzer deionized water rinsing suction filtration, rinses 3 times, dries, cooling.The Fe reclaimed
2(SO
4)
3and MnSO
4catalyzer 3.8g, adds fresh Fe
2(SO
4)
3and MnSO
4the each 0.1g of catalyzer (5% of raw catalyst weight) adds up to 4g, it is dried 5h at 130 DEG C, add 10g methylal and 20g trioxymethylene puts into 100mL autoclave, passing into nitrogen pressure is 2MPa, control temperature 120 DEG C, whole reaction heated and stirred 3h, leaves standstill and is cooled to normal temperature, catalyzer is removed in centrifugation, carries out gas chromatographic analysis to product.Repeat above step 5 time again after having reacted, carry out 6 repeated experiments altogether.
Claims (8)
1. one kind catalyzes and synthesizes the method for polyoxymethylene dimethyl ether based on metal salt catalyst; it is characterized in that: described synthetic method is; paraformaldehyde and methylal is added in autoclave; and using a kind of metal-salt or various metals salt composite as catalyzer; pass into nitrogen protection; under agitation heating is reacted, and removes catalyzer, obtain polyoxymethylene dimethyl ether after having reacted to reaction product centrifugation.
2. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: the mass ratio of methylal and paraformaldehyde is between 3:1 ~ 2:1.
3. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: add that quality is methylal and paraformaldehyde total mass 1% ~ 5% of described catalyzer.
4. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: the pressure passing into nitrogen is 1MPa ~ 2MPa.
5. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: heating the temperature of carrying out reacting is 110 DEG C ~ 130 DEG C.
6. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: it is 3h ~ 7h that stirring heats the time of carrying out reacting down.
7. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: described metal-salt is Al
2(SO
4)
3, Cd
3(PO
4)
2, CuCl
2, Fe
2(SO
4)
3, MnSO
4, Ce
2(SO
4)
3, FeSO
4, CaSO
4, Zn (NO
3)
2, NiCl
2, CoSO
4or Cr
2(PO
4)
3.
8. catalyze and synthesize the method for polyoxymethylene dimethyl ether as claimed in claim 1, it is characterized in that: described paraformaldehyde is trioxymethylene.
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|---|---|---|---|
| CN201510793662.3A CN105348053A (en) | 2015-11-18 | 2015-11-18 | Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst |
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|---|---|---|---|
| CN201510793662.3A CN105348053A (en) | 2015-11-18 | 2015-11-18 | Method for catalysis preparation of polyformaldehyde dimethyl ether on basis of metal salt catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495996A (en) * | 2016-10-21 | 2017-03-15 | 中国石油大学(北京) | A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070260094A1 (en) * | 2004-10-25 | 2007-11-08 | Basf Aktiengesellschaft | Method for Producing Polyoxymethylene Dimethyl Ethers |
| CN102757323A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院兰州化学物理研究所 | Method for preparing alkoxy ether compounds |
| CN104151148A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether from paraformaldehyde |
-
2015
- 2015-11-18 CN CN201510793662.3A patent/CN105348053A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070260094A1 (en) * | 2004-10-25 | 2007-11-08 | Basf Aktiengesellschaft | Method for Producing Polyoxymethylene Dimethyl Ethers |
| CN102757323A (en) * | 2011-04-26 | 2012-10-31 | 中国科学院兰州化学物理研究所 | Method for preparing alkoxy ether compounds |
| CN104151148A (en) * | 2013-05-16 | 2014-11-19 | 中国石油化工股份有限公司 | Method for preparing polyformaldehyde dimethyl ether from paraformaldehyde |
Non-Patent Citations (1)
| Title |
|---|
| 赵光 等: "MoO3/γ-Al2O3催化合成聚甲醛二甲醚", 《上海市化学化工学会2011年度学术会议论文集》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106495996A (en) * | 2016-10-21 | 2017-03-15 | 中国石油大学(北京) | A kind of method with lewis acid as catalyst preparation polymethoxy dimethyl ether |
| CN106495996B (en) * | 2016-10-21 | 2019-07-19 | 中国石油大学(北京) | A method of using lewis acid as catalyst preparation polymethoxy dimethyl ether |
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Application publication date: 20160224 |
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