CN106588587A - Method for producing formaldehyde dimethyl ether with paraformaldehyde - Google Patents
Method for producing formaldehyde dimethyl ether with paraformaldehyde Download PDFInfo
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- CN106588587A CN106588587A CN201510662093.9A CN201510662093A CN106588587A CN 106588587 A CN106588587 A CN 106588587A CN 201510662093 A CN201510662093 A CN 201510662093A CN 106588587 A CN106588587 A CN 106588587A
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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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Abstract
The invention relates to a method for producing formaldehyde dimethyl ether with paraformaldehyde, which mainly resolves problems in the prior art of a long reaction time, a low percent conversion rate of paraformaldehyde and low component content in a reaction product PODE 3-5 when producing formaldehyde dimethyl ether with paraformaldehyde, methyla, methanol or dimethyl ether being the raw material. The method comprises the step A of selecting one of the methyla, methanol and dimethyl ether and paraformaldehyde as reacting materials, putting the materials into a stirred tank reactor I which the bottom part of the stirred tank is provided with a filter and performing the reaction of the materials under the influence of a catalyst A; and step B of filtrating reaction fluid of step A with the filter, putting into a reactor II fulfilled with catalyst B to perform a reaction, obtaining reaction fluid containing formaldehyde dimethyl ether. The catalyst A is chosen from at least one of the molecular sieve and solid superacid which are provided with catalytic activity while the catalyst B belongs to the technical scheme of a cation exchange resin; and therefore the problem is relative perfectly settled.
Description
Technical field
The present invention relates to the method that paraformaldehyde produces polyoxymethylene dimethyl ethers.
Background technology
Polyoxymethylene dimethyl ethers (PODE) are the common names of a class material, and its skeleton symbol can be expressed as CH3O(CH2O)nCH3,
When the value of n is 2-5, can be used as diesel fuel additives, the content in diesel oil is up to 30% (v/v).Polyformaldehyde diformazan
Base ether has higher oxygen content (42-51%) and Cetane number (more than 30), can improve diesel oil within the engine
Combustion position, improve the thermal efficiency, while reduce solid pollutant, the discharge of COx and NOx.Polyoxymethylene dimethyl ethers
Addition in diesel oil can very high (up to 30%), addition polyoxymethylene dimethyl ethers not only can replace part diesel oil,
The efficiency of combustion and discharge performance of diesel oil can also be improved, it was reported that the CH of addition 5-30%3OCH2OCH3NOx can be reduced
Discharge 7-10%, PM reduce 5-35%.Thus polyoxymethylene dimethyl ethers are considered as a kind of can be used for for great application prospect
The novel carbinol derivant that diesel oil reconciles.
At present the technology path of synthesizing polyoxymethylene dimethyl ethers mainly includes two classes, i.e., with metaformaldehyde and paraformaldehyde as raw material
Synthesizing polyoxymethylene dimethyl ethers.Wherein metaformaldehyde route makees catalyst with ionic liquid, and raw material and catalyst cost are higher,
And catalyst is difficult to be separated with product, reclaims, polyoxymethylene dimethyl ethers product stability is affected.Paraformaldehyde route, raw material
And the solid acid catalyst cost that adopts is relatively low, concise in technology and product yield is higher.
Patent ZL201210150398.8 discloses the preparation method of polyoxymethylene dimethyl ethers, with methanol or dimethyl ether and formaldehyde or
Metaformaldehyde is raw material, and the reaction under molecular sieve catalyst effect prepares polyoxymethylene dimethyl ethers；ZL201310237047.5 with
Methanol, dimethoxym ethane and paraformaldehyde be raw material, the synthesizing polyoxymethylene dimethyl ethers under the conditions of solid acid catalyst；Patent
ZL201010191075.4 gives a kind of method of synthesizing polyoxymethylene dimethyl ethers, in two steps using methanol and excessive first
Aldehyde or paraformaldehyde synthesizing polyoxymethylene dimethyl ethers, in order to improve feed stock conversion and selectivity of product.Above patent
Relate generally to the preparation method of catalyst.When paraformaldehyde is adopted for raw material, because paraformaldehyde depolymerization time length causes original
Material conversion ratio and selectivity of product are low, and to this problem the solution of reaction process and reactor is not given.
The content of the invention
The technical problem to be solved be paraformaldehyde and dimethoxym ethane/or methanol/or dimethyl ether are adopted in conventional art for
During raw material production polyoxymethylene dimethyl ethers, response time length, paraformaldehyde conversion ratio are low, DMM in product3-5Component
The low problem of content.A kind of new paraformaldehyde production polyoxymethylene dimethyl ethers method is provided.The method have the response time it is short,
Feed stock conversion is high, PODE in product3-5The characteristics of constituent content is high.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows：Paraformaldehyde produces polyoxymethylene dimethyl ethers
Method, comprise the following steps：
A) with least one and paraformaldehyde in dimethoxym ethane, methanol or dimethyl ether as reaction raw materials, input stirring
Kettle reactor, stirred tank reactor bottom sets filter, and raw material is reacted under catalyst A effects；
B) after the filter filtration described in of the reactant liquor of step a, reactor of the feeding equipped with catalyst B carries out reaction and obtains
Reactant liquor containing polyoxymethylene dimethyl ether；
Described catalyst A is the molecular sieve with surface acidity, at least one of solid acid super acids；Described catalysis
Agent B is cation exchange resin.
In above-mentioned technical proposal, the catalyst A is selected from ZSM-5 molecular sieve, MCM-22 molecular sieves, MCM-41 molecular sieves
And SO4 2-At least one in/MxOy type solid super-strong acids, wherein M be but be not limited only to Ti, Fe, Zr, Sn, Hf,
The metallic elements such as Mo.
In above-mentioned technical proposal, preferred catalyst A is preferably 5%～20% with the part by weight of raw material total amount.
In above-mentioned technical proposal, the catalyst B preferably is selected from sulfonic group cation exchange resin, carboxylic acid group's cation exchange tree
At least one of fat, phosphate cation exchange resin.
In above-mentioned technical proposal, described catalyst B is preferably macropore polystyrene strong acid ion exchange resin.
In above-mentioned technical proposal, catalyst B is preferably 5%～15% with the part by weight of raw material total amount.
In above-mentioned technical proposal, the few a kind of and paraformaldehyde weight ratio in dimethoxym ethane, methanol or dimethyl ether is preferably
1～10.
In above-mentioned technical proposal, the reaction temperature of step a is preferably 120～250 DEG C, more preferably 150～200 DEG C.
In above-mentioned technical proposal, reaction pressure is preferably 0.1～3.0MPaG, more preferably 0.2～1.5MPaG.
In above-mentioned technical proposal, the reaction temperature of step b is preferably 60～120 DEG C, more preferably 80～115 DEG C.
In above-mentioned technical proposal, the reaction pressure of step b is preferably 0.1～1.0MPaG more preferably 0.2～0.8MPaG.
In above-mentioned technical proposal, filter screen mesh number is preferably greater than 100 mesh, such as but not limited to 100～300 mesh.
In above-mentioned technical proposal, stirred tank reactor I preferably with heating and removes heat structure, and more preferably the structure adds for chuck
At least one of heat-transfer surface is set in heat, coil pipe heating or kettle.
In above-mentioned technical proposal, the time of staying of the step a raw material in stirred tank reactor is preferably 0.1～1 hour.
In above-mentioned technical proposal, the time of staying of the step b raw material in reactor II is preferably 0.5～4 hour.
In above-mentioned technical proposal, the reactant liquor of raw material and step a, the oral fluid that reflects of step b are both preferably continuous feeding and discharging
Mode.
Using technical scheme, paraformaldehyde and dimethoxym ethane/or methanol/or dimethyl ether are for polyoxymethylene dimethyl ethers
Response time can shorten more than 20%, and the conversion ratio of raw material paraformaldehyde improves more than 10%, PODE in product3-5Component contains
Amount improves more than 5%, achieves good technique effect.
Description of the drawings
Fig. 1 is the technological process that polyoxymethylene dimethyl ethers are produced using the paraformaldehyde of technical solution of the present invention.
In Fig. 1, I is stirred tank reactor, and II is the reactor equipped with catalyst B, and III is catalyst A, and IV is catalysis
Agent B, V is filter, and VI is reactor feed pump.1 is paraformaldehyde charging, and 2 is dimethoxym ethane/or methanol/or dimethyl ether
Charging, 3 are the discharging of stirred tank reactant liquor, and 4 discharge for reactor II, and 5 are the charging of stirred tank heat transferring medium, and 6 is stirred tank
Heat transferring medium discharges.
In Fig. 1, paraformaldehyde 1 and dimethoxym ethane/or methanol/or dimethyl ether 2 are reaction raw materials, continuous input stirred tank reaction
Device I, the bottom of stirred tank reactor I sets filter V, and raw material is reacted under III catalyst A effects, reaction temperature by
Flow into the heat transferring medium 5 of stirred tank reactor chuck and flow out medium 6 and control, stirred tank reactant liquor 3 agitated kettles of discharging are anti-
After answering device bottom filters V to filter, the reaction of reactor II equipped with IV catalyst B, reactor are continuously squeezed into by pump VI
Later separation is gone in II discharging 4.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
【Embodiment 1】
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction member adopts the technique of Fig. 1, and reaction raw materials are paraformaldehyde
And dimethoxym ethane, paraformaldehyde continuously puts into stirred tank reactor with 6 ton hours, dimethoxym ethane with 25 ton hour flows, stirs
Kettle reactor volume is 16 cubic metres, and equipped with catalyst A1.8 tons, catalyst A is MCM-22 molecular sieve catalysts, instead
Temperature is answered for 150 DEG C, reaction pressure is 0.8MPaG, the time of staying of the raw material in stirred tank reactor is 0.4 hour,
Stirred tank reactor bottom filters sieve number is 100 mesh, and pre-reaction liquid after filtering, is continuously squeezed into by pump and is equipped with
The fixed bed reactors of catalyst B, fixed bed reactors are axial adiabatic reactor, are filled with 2.0 tons of catalyst B, urge
Agent B is 001 × 7 strongly acidic styrene type cation exchange resin, and reaction temperature is 110 DEG C, and reaction pressure is
0.5MPaG, the time of staying of the reactant liquor in fixed bed reactors is 1.0 hours.
The device raw material is 1.4 hours in response system total residence time, and paraformaldehyde conversion ratio is 91%, and reaction is produced
PODE in thing3～5Content is 32%.
【Embodiment 2】
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction member adopts the technique of Fig. 1, and reaction raw materials are paraformaldehyde
And methanol, paraformaldehyde continuously puts into stirred tank reactor with 7 ton hours, methanol with 30 ton hour flows, and stirred tank is anti-
Body product is answered to be 16 cubic metres, equipped with catalyst A2 tons, catalyst A is MCM-41 molecular sieve catalysts, and reaction is warm
Spend for 120 DEG C, reaction pressure is 0.2MPaG, the time of staying of the raw material in stirred tank reactor is 0.3 hour, stirring
Kettle reactor bottom filter screen mesh number is 150 mesh, and reactant liquor after filtering, is continuously squeezed into equipped with catalyst by pump
The fixed bed reactors of B, fixed bed reactors are axial adiabatic reactor, are filled with 1.8 tons of catalyst B, catalyst B
For 001 × 7 strongly acidic styrene type cation exchange resin, reaction temperature is 100 DEG C, and reaction pressure is 0.4MPaG, instead
The time of staying of the liquid in fixed bed reactors is answered to be 0.7 hour.
The device raw material is 1 hour in response system total residence time, and paraformaldehyde conversion ratio is 88%, product
Middle PODE3～5Content is 29%.
【Embodiment 3】
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction member adopts the technique of Fig. 1, and reaction raw materials are paraformaldehyde
And dimethyl ether, paraformaldehyde continuously puts into stirred tank reactor with 7 ton hours, dimethyl ether with 14 ton hour flows, stirs
Kettle reactor volume is 15 cubic metres, and equipped with catalyst A3 tons, catalyst A is SO4 2-/ZrO2Solid acid superacid catalysis
Agent, reaction temperature is 180 DEG C, and reaction pressure is 2.0MPaG, and the time of staying of the raw material in stirred tank reactor is 0.6
Hour, stirred tank reactor bottom filters sieve number is 150 mesh, and pre-reaction liquid after filtering, is continuously beaten by pump
Enter the paste state bed reactor equipped with catalyst B, built with 2.0 tons of catalyst B, catalyst B is D001 to paste state bed reactor
Large hole strong acid styrene system cation exchange resin, reaction temperature is 95 DEG C, and reaction pressure is 0.38MPaG, reaction
The time of staying of the liquid in paste state bed reactor is 1.0 hours.
The device raw material is 1.6 hours in response system total residence time, and paraformaldehyde conversion ratio is 90%, and reaction is produced
PODE in thing3～5Content is 30%.
【Embodiment 4】
Certain 10,000 tons/year of polyoxymethylene dimethyl ethers device, reaction member adopts the technique of Fig. 1, and reaction raw materials are paraformaldehyde
And dimethoxym ethane, paraformaldehyde continuously puts into stirred tank reactor, stirred with 14 ton hours, dimethyl ether with 40 ton hour flows
Kettle reactor volume is mixed for 20 cubic metres, equipped with catalyst A3 tons, catalyst A is SO4 2-/TiO2/Al2O3(Ti:Al is
1:2 (mol)) solid acid super acidic catalyst, reaction temperature is 200 DEG C, and reaction pressure is 3.0MPaG, and raw material is being stirred
It is 0.5 hour to mix time of staying in kettle reactor, and stirred tank reactor bottom filters sieve number is 200 mesh, reaction
Liquid after filtering, by pump the paste state bed reactor equipped with catalyst B is continuously squeezed into, and 2.8 are filled with paste state bed reactor
Ton catalyst B, catalyst B are D001 large hole strong acid styrene system cation exchange resins, and reaction temperature is 100
DEG C, reaction pressure is 0.8MPaG, and the time of staying of the reactant liquor in fixed bed reactors is 0.7 hour.
The device raw material is 1.2 hours in response system total residence time, and paraformaldehyde conversion ratio is 89%, and reaction is produced
PODE in thing3～5Content is 30%.
【Comparative example 1】
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction raw materials are paraformaldehyde and dimethoxym ethane, and reaction process is stirring
Kettle reactor intermittent reaction, every time to amount to 20 tons of paraformaldehydes, 75 tons of dimethoxym ethanes put into the stirred tank reaction of 2 parallel connections
Device, every stirred tank reactor volume is 50 cubic metres, equipped with 001 × 7 strongly acidic styrene type cation exchange resin 3
Ton, reaction temperature is 110 DEG C, and reaction pressure is 0.5MPaG, and reactant liquor squeezes into later separation by pump after reacting 4 hours
Unit.
The device raw material is 4 hours in the response system time of staying, and paraformaldehyde conversion ratio is 70%, in product
PODE3～5Content is 20%.
【Comparative example 2】
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction raw materials are paraformaldehyde and dimethyl ether, and reaction process is slurry
Bed reactor, paraformaldehyde puts into paste state bed reactor, paste state bed reactor with 9 ton hours, dimethyl ether with 26 ton hours
Volume is 56 cubic metres, equipped with 2.5 tons of D001 large hole strong acid styrene system cation exchange resins, reaction temperature
For 110 DEG C, reaction pressure is 0.6MPaG.
The device raw material is 3.0 hours in the response system time of staying, and paraformaldehyde conversion ratio is 76%, product
Middle PODE3～5Content is 24%.
【Comparative example 3】
Complete unit except replacing Fig. 1 using slurry bed system, make paraformaldehyde raw material directly contact with dimethoxym ethane reacted with
Outward, other process conditions with embodiment 1 on year-on-year basis, specially：
Certain 5000 tons/year of polyoxymethylene dimethyl ethers device, reaction raw materials are paraformaldehyde and dimethoxym ethane, and paraformaldehyde is with 6 tons
/ hour continuously puts into paste state bed reactor, and dimethoxym ethane flow is 25 ton hours, is continuously squeezed into equipped with catalyst B by pump
Paste state bed reactor, in reactor contain 2.0 tons of catalyst B, catalyst B be 001 × 7 strongly acidic styrene system sun from
Sub-exchange resin, reaction temperature is 100 DEG C, and reaction pressure is 0.4MPaG, and raw material is in response system total residence time
3 hours, paraformaldehyde conversion ratio was 75%, PODE in product3～5Content is 22%.
Claims (10)
1. the method that paraformaldehyde produces polyoxymethylene dimethyl ethers, comprises the following steps：
A), as reaction raw materials, stirred tank is put into selected from least one of dimethoxym ethane, methanol or dimethyl ether and paraformaldehyde
Reactor I, stirred tank reactor bottom sets filter, and raw material is reacted under catalyst A effects；
B) after the filter filtration described in of the reactant liquor of step a, sending into the reactor II equipped with catalyst B carries out reacting
To the reactant liquor containing polyoxymethylene dimethyl ether；
Described catalyst A is the molecular sieve with surface acidity, at least one of solid acid super acids；Described urges
Agent B is cation exchange resin.
2. method according to claim 1, it is characterised in that the catalyst A is selected from ZSM-5 molecular sieve, MCM-22
Molecular sieve, MCM-41 molecular sieves and SO4 2-At least one in/MxOy type solid super-strong acids, wherein M be but be not limited to Ti,
The metallic elements such as Fe, Zr, Sn, Hf, Mo.
3. method according to claim 1, it is characterised in that the catalyst B is selected from sulfonic group cation exchange tree
Fat, carboxylic acid group's cation exchange resin, at least one of phosphate cation exchange resin.
4. method according to claim 1, it is characterised in that at least in dimethoxym ethane, methanol or dimethyl ether
Kind and with paraformaldehyde raw material weight ratio be (1～10):1.
5. method according to claim 1, it is characterised in that the reaction temperature of step a is 120～250 DEG C.
6. method according to claim 1, it is characterised in that the reaction pressure of step a is 0.1～3.0MPaG.
7. method according to claim 1, it is characterised in that the reaction temperature of step b is 60～120 DEG C.
8. method according to claim 1, it is characterised in that the reaction pressure of step b is 0.1～1.0MPaG.
9. method according to claim 1, it is characterised in that filter screen mesh number is more than 100 mesh.
10. method according to claim 1, it is characterised in that reactor II is fixed bed reactors or slurry reactor
Device.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724000A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Production method of polymethoxy dimethyl ether |
| CN113087603A (en) * | 2020-01-09 | 2021-07-09 | 中国石油化工股份有限公司 | Production system and production method of polymethoxy dimethyl ether |
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| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
| CN102617305A (en) * | 2012-02-28 | 2012-08-01 | 中国科学院化学研究所 | Process for preparing polyoxymethylene dimethyl ether |
| CN204079853U (en) * | 2014-09-04 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | For the production of the reaction unit of polymethoxy dimethyl ether |
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2015
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Patent Citations (3)
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| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | Method for synthesizing polyoxymethylene dimethyl ethers |
| CN102617305A (en) * | 2012-02-28 | 2012-08-01 | 中国科学院化学研究所 | Process for preparing polyoxymethylene dimethyl ether |
| CN204079853U (en) * | 2014-09-04 | 2015-01-07 | 北京旭阳化工技术研究院有限公司 | For the production of the reaction unit of polymethoxy dimethyl ether |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112724000A (en) * | 2019-10-14 | 2021-04-30 | 中国石油化工股份有限公司 | Production method of polymethoxy dimethyl ether |
| CN112724000B (en) * | 2019-10-14 | 2022-12-09 | 中国石油化工股份有限公司 | Production method of polymethoxy dimethyl ether |
| CN113087603A (en) * | 2020-01-09 | 2021-07-09 | 中国石油化工股份有限公司 | Production system and production method of polymethoxy dimethyl ether |
| CN113087603B (en) * | 2020-01-09 | 2022-12-09 | 中国石油化工股份有限公司 | Production system and production method of polymethoxy dimethyl ether |
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