CN104230684B - Process by methanol-fueled CLC polyoxymethylene dimethyl ether - Google Patents
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Abstract
The present invention relates to the process of synthesizing polyoxymethylene dimethyl ether, solve the problem that polyoxymethylene dimethyl ether synthesis cost height yield is low, use by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, this technique is divided into reaction zone and Disengagement zone；Reaction zone includes methyl alcohol storage tank, preheater, fixed bed reactors and bubbling reactor；Reaction zone processing step is entrance fixed bed reactors after the preheated vaporization of methyl alcohol mixes with air, formaldehyde is generated through the catalysis oxidation of formaldehyde synthetic catalyst, entering bubbling reactor, in bubbling reactor, the mixture with methyl alcohol and circulation and stress generates polyoxymethylene dimethyl ether through solid acid catalyst catalysis；Disengagement zone includes anion exchange resin bed layer, rectifying module, product storage tank；The processing step of Disengagement zone is that bubbling reactor discharging enters the separation of rectifying module after anion exchange resin deacidifies, the three of polyoxymethylene dimethyl ether, tetramer enters product storage tank, other components are recycled to the technical scheme of reactor, in polyoxymethylene dimethyl ether produces.
Description
Technical field
The present invention relates to by the process of methanol-fueled CLC polyoxymethylene dimethyl ether.
Background technology
In recent years, low-carbon (LC) has become a great society theme, and obtains increasingly extensive concern.Such as, how to reduce day by day
The high pollution exhaust emissions that flourish auto manufacturing is brought, the service efficiency improving fuel oil has become many mechanisms
The problem of research.
Now generally believe that oxygenatedchemicals is especially suitable for making diesel oil blending compound.The most many companies and research institute just put into
Suitable oxygenatedchemicals is found and screened to strength, and screening object includes: acetal, alcohol, carbonic ester, fat, ether, glycol derivative
Deng.For diesel oil, oxygenatedchemicals then needs high Cetane number, low self-ignition point, igniting soon.In addition it also should with commonly
Miscibilty, resistance to water that diesel oil has had are low, be readily biodegradable, production cost is low, raw material is cheap and easily-available, and particularly toxicity is asked
Inscribe more concerned.Many companies the most in the industry develop several diesel oil oxygenatedchemicals being hopeful application, have carried out tune
And with automobile-used evaluation, such as: dimethyl carbonate, dimethoxymethane, polyoxymethylene dimethyl ether, two n-pentyl ethers, glycol ether
(glycol alkyl ether) etc..And polyoxymethylene dimethyl ether receives significant attention because of the premium properties of himself as diesel fuel additives.
Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE), is the logical of a class material
Claiming, its skeleton symbol can be expressed as CH3O(CH2O)nCH3, there is higher Cetane number (> 40) and oxygen content (42～51%).When
When the value of n is 1, polyoxymethylene dimethyl ether is dimethoxym ethane, although using dimethoxym ethane also can carry as vehicle fuel addO-on therapy
High-energy source utilization ratio, reduces exhaust emissions, but still easily causes vent plug.When n value is 2～6, its physical property, flammability
With diesel oil closely can preferably resolve the defect that conventional additive exists as derv fuel blend component.Therefore gather
Formaldehyde dimethyl ether can be as novel cleaning diesel component, and the addition in diesel oil, up to more than 10% (v/v), can improve
Diesel oil combustion position within the engine, improves the thermal efficiency, reduces the particulate matter in tail gas and COxAnd NOxDischarge.With bavin
The polyoxymethylene dimethyl ether a length of n=3,4 of optimum chain of oil mixing.During n=2, the flash-point of polyoxymethylene dimethyl ether is too low, and when n is excessive, poly-
Formaldehyde dimethyl ether may precipitate blocking at low temperatures.It is reported, add 5～the CH of 30%3OCH2OCH3NO can be greatly reducedxRow
Put.
Being paraformaldehyde section in the middle of PODE, two ends are by methyl blocking.Therefore typically by the compound (first providing paraformaldehyde
Aldehyde, metaformaldehyde and paraformaldehyde etc.) and provide the compound (methyl alcohol, dimethyl ether and dimethoxym ethane etc.) of end-blocking methyl to close
Become PODE.PODE can be synthesized by acid-catalyzed dehydration by methyl alcohol and formaldehyde or paraformaldehyde, metaformaldehyde.Synthesized by coal gasification system
Gas, by synthesis gas synthesizing methanol, prepared paraformaldehyde by methyl alcohol oxidative synthesis formaldehyde, formaldehyde or metaformaldehyde is all work already
The process of industry.It is possible not only to replace part diesel oil by coal-based methanol synthesis PODE, moreover it is possible to improve the efficiency of combustion of diesel oil, reduce
The diesel combustion harm to environment, has important strategic importance and good economic worth.The resource general layout of China has " rich
Coal, few oil, have gas " feature, and the development of PODE and synthesis, the coal resources of China's abundant can be converted into liquid and substitute
Fuel, reduces China's importation dependence to oil, and then is all of great importance national energy security.
In laboratory, polyoxymethylene dimethyl ether can be by oligomeric in 150～180 DEG C of heating in the presence of trace sulfuric acid or hydrochloric acid
Right paraformaldehyde or paraformaldehyde are prepared with the method that methyl alcohol reacts.Owing to polyoxymethylene dimethyl ether has in diesel fuel additives field
Having huge using value, since a very long time, numerous companies and research institute are all raw in the practicable industry of research
Product technology.
It is the process that initial feed prepares polyoxymethylene dimethyl ether by methyl alcohol that EP2228359A1 describes a kind of.The party
Method use through ammonium molybdate and Ferric nitrate modified molecular sieve be catalyst, by methyl alcohol under 200 DEG C of conditions above of temperature with sky
Gas (oxygen) oxidation step obtains polyoxymethylene dimethyl ether.The method production cost is relatively low, but catalyst preparation process is complicated,
And the selectivity of polyoxymethylene dimethyl ether is unsatisfactory.
EP1070755 describes one and prepares per molecule by dimethoxym ethane and paraformaldehyde reaction in the presence of three fluosulfonic acid
In there is the method for polyoxymethylene dimethyl ether of 2～6 formaldehyde units.WO2006/045506A1 describes BASF AG and uses sulphur
Acid, TFMS, as catalyst, have obtained the series product of n=1～10 with dimethoxym ethane, paraformaldehyde, metaformaldehyde for raw material
Thing.Above method all uses Bronsted acid as catalyst, and this catalyst is cheap and easy to get, but corrosivity is strong, it is difficult to separate, environment
Pollute big, the shortcoming high to the requirement of equipment.
US6160174 and US6265528 describes BP company and uses methyl alcohol, formaldehyde, dimethyl ether and dimethoxym ethane to be raw material,
Cationic ion-exchange resin is used to obtain polyoxymethylene dimethyl ether as catalyst, gas-solid phase reaction.But although this method has and urges
Agent can be easily separated, beneficially the advantage such as circulation, but reaction conversion ratio is low, and productivity is the highest, complex process.
CN 200910056819.9 synthesizes using solid super-strong acid as catalyst with methyl alcohol and metaformaldehyde for raw material
Polyoxymethylene dimethyl ether, although achieve preferable feed stock conversion, the acidity yet with solid super-strong acid is strong, irregular hole
Structure makes in product that the selectivity of accessory substance dimethoxym ethane is 20～50%, and a large amount of existence of dimethoxym ethane can reduce diesel fuel mixtures
Flash-point and therefore damage its quality so that product is unsuitable for as procetane.CN 101048357A describes one
Plant the synthesis technique being Material synthesis polyoxymethylene dimethyl ether with dimethoxym ethane and metaformaldehyde.We also develop employing solid ourselves
Acid catalyst (molecular sieve CN 200910056820.1, solid super-strong acid CN 200910056819.9) is with methyl alcohol and metaformaldehyde
Polyoxymethylene dimethyl ether is prepared for raw material.
CN 101182367A describe employing acidic ionic liquid as catalyst, by formaldehyde synthesizing triformol, then with
Metaformaldehyde and the process of methanol-fueled CLC polyoxymethylene dimethyl ether.Although the method once through yield is high, but the ionic liquid used
Body catalyst is expensive, is not readily separated, and operation easier is bigger.US5,959,156 describes with dimethyl ether and methyl alcohol as raw material
The synthesis technique of polyoxymethylene dimethyl ether, use novel heterogeneous promotion condensation catalyst.Although this technique cost is relatively low, but
Product yield is undesirable.
But these technique uses reaction raw materials to have methyl alcohol, dimethyl ether, dimethoxym ethane, metaformaldehyde etc..According to market survey
Understanding, wherein the market price of methyl alcohol is minimum, is 3000 yuan/ton, we it is seen that, as produced by reasonably process optimization
Process, only produces while polyoxymethylene dimethyl ether can significantly reduce production cost with methyl alcohol for raw material and obtains higher choosing
Selecting property and yield.
Summary of the invention
The technical problem to be solved is the problem that polyoxymethylene dimethyl ether synthesis technique product cost height yield is low,
Thering is provided the process of a kind of new synthesizing polyoxymethylene dimethyl ether, the method has the advantages that the low yield of product cost is high.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is as follows: by methanol-fueled CLC polyoxymethylene dimethyl ether
Process, this technique is divided into reaction zone and Disengagement zone；Reaction zone include methyl alcohol storage tank, preheater, fixed bed reactors and
Bubbling reactor；The processing step of reaction zone is entrance fixed bed reactors after the preheated vaporization of methyl alcohol mixes with air, through first
The catalysis oxidation of aldehyde synthetic catalyst generates formaldehyde, enters bubbling reactor, with methyl alcohol and looping back in bubbling reactor
The mixture received generates polyoxymethylene dimethyl ether through solid acid catalyst catalysis；Disengagement zone includes anion exchange resin bed layer, essence
Evaporate module, product storage tank；The processing step of Disengagement zone is that bubbling reactor discharging enters after anion exchange resin deacidifies
Rectifying module separate, the three of polyoxymethylene dimethyl ether, tetramer enter product storage tank, other components are recycled to reactor.
In technique scheme, the reaction temperature in fixed bed reactors is preferably 280～700 DEG C, in fixed bed reactors
Volume of air air speed be preferably 4000 ~ 8000 h-1.Reaction pressure in fixed bed reactors is preferably 0.01～30MPa.
Methyl alcohol in bubbling reactor charging: the mass ratio of formaldehyde is preferably 0.02～50: 1.Reaction temperature in bubbling reactor is preferred
It it is 80～240 DEG C.Reaction pressure in bubbling reactor is preferably 0.01～15.0 MPa, more preferably 0 ~ 10MPa.
In technique scheme, described mixture preferably includes to be evaporated containing the first of dimethoxym ethane by what rectifying module separated
Point, the of the 3rd cut containing polyoxymethylene dimethyl ether dimer and the polyoxymethylene dimethyl ether containing more high polymerization degree (n > 4)
Five cuts；Rectifying module further preferably isolate containing methyl alcohol the second cut and containing the three of polyoxymethylene dimethyl ether, the of tetramer
Four cuts.
In technique scheme, the reaction discharging of described bubbling reactor preferably first passes through anion exchange resin bed layer and removes
After acid, enter back into rectifying module.Described rectifying module is preferably made up of 4 rectifying columns.First cut is preferably by the first rectifying
Column overhead discharging, the second cut is preferably by Second distillation column tower top discharging, and the 3rd cut is preferably ejected material by the 3rd rectifying tower,
4th cut is preferably ejected material by the 4th rectifying tower, and the 5th cut is preferably by discharging at the bottom of the 4th rectifying tower.The first, the three,
And the 5th cut be preferably recycled to liquid phase tank reactor through dehydrater except water Posterior circle.Second cut preferably removes through dehydrater
Water Posterior circle is recycled to methyl alcohol storage tank.
The operation pressure of described first rectifying column is preferably 0.2 ~ 2MPa, and the operation pressure of Second distillation column is preferably 0.1 ~
1.5MPa, the operation pressure of the 3rd rectifying column is preferably 0.05-1.2MPa, and the operation pressure of the 4th rectifying column is preferably 0.001-
0.6MPa.The theoretical cam curve of the first rectifying column is preferably 15 ~ 40, and the theoretical cam curve of Second distillation column is preferably 15 ~ 30, the
The theoretical cam curve of three rectifying columns is preferably 15 ~ 35, and the theoretical cam curve of the 4th rectifying column is preferably 15 ~ 35.
In technique scheme, formaldehyde synthetic catalyst preferably comprises one or more of following components: molybdenum oxide, oxidation
Iron, silica, aluminum oxide, argent；Solid acid catalyst preferably is selected from least one component following: acid cation exchange is set
Fat, molecular sieve, dinitrobenzoic acid, ethylenediamine tetra-acetic acid, aluminum oxide, titanium dioxide；Described solid acid catalyst is more preferably
The mixture of acid styrene type cation exchange resin and dinitrobenzoic acid, or HZSM-5 molecular sieve and ethylenediamine tetrem
The mixture of acid.
The drier that in technique scheme, dry dehydrater is used preferably is selected from least one drier following: ion is handed over
Change resin, molecular sieve, Silica hydrogel.
The present invention has a following effect: first, and yield and selection rate are high, and in product, n=3 and n=4 accounts for n=2 ~ 5 up to
97.3wt%；Second, production cost is relatively low, and the 3rd, technique is simple, easy to operate.
Accompanying drawing explanation
Fig. 1 is the present invention process chart by methanol-fueled CLC polyoxymethylene dimethyl ether.
The present invention 1 further describes with reference to the accompanying drawings.
The methyl alcohol (logistics 2) of methyl alcohol storage tank 1 output enters after heater 3 heating vaporization mixes with air (logistics 29)
Fixed bed reactors 5, are catalyzed oxidation in fixed bed reactors 5 and prepare formaldehyde, output streams 6 (the predominantly first of reactor 5
Aldehyde, methyl alcohol) feed to bubbling reactor 7, also having by the logistics 8 of output after methyl alcohol storage tank 1 to bubbling reactor 7 charging simultaneously
(predominantly liquid phase alcohol), by dehydrater 15 except logistics 16 (the predominantly dimer of polyoxymethylene dimethyl ether, the Yi Jiju of output after water
The polyoxymethylene dimethyl ether of right higher (n > 4)).Bubbling reactor 7 discharging 9 obtains after anion exchange resin bed layer 10 deacidifies
Logistics 11, logistics 11 enters rectifying column 12 and separates.Unreacted dimethoxym ethane is from rectifying column 12 tower top discharging (logistics 14), warp
Cross dehydrater 15 except being again passed through bubbling reactor 7 after water.Discharging at the bottom of rectifying column 12 tower enters rectifying column 17 and carries out next step point
From.Unreacted methyl alcohol, from rectifying column 17 tower top discharging (logistics 19), is passed through methyl alcohol storage tank after dehydrater 15 is except water again
1.Discharging at the bottom of rectifying column 17 tower (logistics 18) enters rectifying column 22 and carries out next step separation.The dimer of polyoxymethylene dimethyl ether is from essence
Evaporate tower 22 tower top discharging, after dehydrater 15 is except water, is again passed through bubbling reactor 7.The trimer of polyoxymethylene dimethyl ether and four
Polymers, from rectifying column 25 tower top discharging (logistics 27), enters product storage tank 28.The polyoxymethylene dimethyl ether of the degree of polymerization higher (n > 4) from
Discharging at the bottom of rectifying column 25 tower (logistics 26), is passed through bubbling reactor 7 after dehydrater 15 is except water again.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Loading 150g in fixed bed reactors 5, silver silica-alumina catalyst (is pressed mass fraction by silver, silica with aluminum oxide
Form than 18:75:7), filling 150g HZSM-5 molecular sieve (Si/Al=15) bubbling reactor 7 in, with nitrogen purging device,
The heated vaporization of Liquid Phase Methanol and air mixed feeding are to fixed bed reactors, and volume of air air speed is 4500h-1, methyl alcohol feeds
Speed is 93.75g/h, and the operation temperature of fixed bed reactors is 600 DEG C, and pressure is 1MPa；Add in bubbling reactor 9 simultaneously
Entering the absolute methanol of circulation and stress, the mixed liquor of polyoxymethylene dimethyl ether (n=1,2,5,6), charging rate is respectively 62.5g/h,
109g/h.The operating condition of bubbling reactor 7 be reaction temperature be 150 DEG C, reaction pressure is 3.0MPa.Reaction discharging enters the moon
Ion exchange resin bed layer.
Bubbling reactor 7 discharging 9 enters rectifying column 12 after anion exchange resin bed layer 10 deacidifies and separates, behaviour
Being 0.2 ~ 2MPa as pressure, theoretical cam curve is 20.Unreacted dimethoxym ethane, from rectifying column 12 tower top discharging (logistics 14), passes through
Dehydrater 15 is except being again passed through bubbling reactor 7 after water.Discharging at the bottom of rectifying column 12 tower enters rectifying column 17 and carries out next step separation,
Operation pressure is 0.1 ~ 1.5MPa, and theoretical cam curve is 20.Unreacted methyl alcohol is from rectifying column 17 tower top discharging (logistics 19), warp
Cross dehydrater 15 except being again passed through methyl alcohol storage tank 1 after water.Under discharging at the bottom of rectifying column 17 tower (logistics 18) entrance rectifying column 22 is carried out
One step separates, and operation pressure is 0.05 ~ 1.2MPa, and theoretical cam curve is 20.The dimer of polyoxymethylene dimethyl ether is from rectifying column 22
Tower top discharging, is passed through bubbling reactor 7 after dehydrater 15 is except water again.The trimer of polyoxymethylene dimethyl ether and tetramer from
Rectifying column 25 tower top discharging (logistics 27), operation pressure is 0.001 ~ 0.6MPa, and theoretical cam curve is 20, enters product storage tank
28.The polyoxymethylene dimethyl ether of the degree of polymerization higher (n > 4) is from discharging at the bottom of rectifying column 25 tower (logistics 26), after dehydrater 15 is except water
Again bubbling reactor 7 it is passed through.Successive reaction 80h, On-line Product samples, and by gas chromatographic analysis, in product, n=3 and n=4 accounts for n
The 91.1wt% of=2 ~ 5, experimental result is shown in Table 1.
[embodiment 2]
Loading 150g in fixed bed reactors 5, molybdenum-iron catalyst is (by molybdenum oxide and iron oxide 2.00:1 group in molar ratio
Become), in bubbling reactor 7, load 300g strongly acidic styrene type cation exchange resin, by nitrogen purging device, liquid phase
The heated vaporization of methyl alcohol and air mixing rear feeding to fixed bed reactors, volume of air air speed is 4500h-1, methyl alcohol charging speed
Degree is 93.75g/h, and the operation temperature of fixed bed reactors is 380 DEG C, and pressure is 1MPa；Add in bubbling reactor 9 simultaneously
The absolute methanol of circulation and stress, the mixed liquor of polyoxymethylene dimethyl ether (n=1,2,5,6), charging rate is respectively 93.75g/h,
85.5g/h.The operating condition of bubbling reactor 7 be reaction temperature be 110 DEG C, reaction pressure is 1.0MPa.Reaction discharging enters
Anion exchange resin bed layer.
Other operation with embodiment 1, successive reaction 80h, On-line Product samples, by gas chromatographic analysis, in product n=3 and
N=4 accounts for the 91.3wt% of n=2 ~ 5, and experimental result is shown in Table 2.
[embodiment 3]
Loading 150g in fixed bed reactors 5, molybdenum-iron catalyst is (by molybdenum oxide and iron oxide 1.90:1 group in molar ratio
Become), bubbling reactor 7 in, load 300g dinitrobenzoic acid, with nitrogen purging device, the heated vaporization of Liquid Phase Methanol and
Air mixing rear feeding is to fixed bed reactors, and volume of air air speed is 4500h-1, methanol feed rate is 93.75g/h, fixing
The operation temperature of bed reactor is 380 DEG C, and pressure is 1MPa；Add in bubbling reactor 9 simultaneously circulation and stress without water beetle
Alcohol, the mixed liquor of polyoxymethylene dimethyl ether (n=1,2,5,6), charging rate is respectively 93.75g/h, 106.1g/h.Bubbling reactor
The operating condition of 7 be reaction temperature be 110 DEG C, reaction pressure is 1.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation with embodiment 1, successive reaction 80h, On-line Product samples, by gas chromatographic analysis, in product n=3 and
N=4 accounts for the 93.7wt% of n=2 ~ 5, and experimental result is shown in Table 3.
[embodiment 4]
Loading 150g in fixed bed reactors 5, molybdenum-iron catalyst is (by molybdenum oxide and iron oxide 1.90:1 group in molar ratio
Become), in bubbling reactor 7, load 300g catalyst (by strongly acidic styrene type cation exchange resin and dinitro benzene first
Acid is pressed mass fraction and is formed than 30:70), with nitrogen purging device, the heated vaporization of Liquid Phase Methanol is with air mixing rear feeding extremely
Fixed bed reactors, volume of air air speed is 4500h-1, methanol feed rate is 93.75g/h, the operation temperature of fixed bed reactors
Degree is 380 DEG C, and pressure is 1MPa；In bubbling reactor 9, add the absolute methanol of circulation and stress, polyoxymethylene dimethyl ether (n simultaneously
=1,2,5,6) mixed liquor, charging rate is respectively 93.75g/h, 95.6g/h.The operating condition of bubbling reactor 7 is reaction
Temperature is 110 DEG C, and reaction pressure is 1.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation with embodiment 1, successive reaction 80h, On-line Product samples, by gas chromatographic analysis, in product n=3 and
N=4 accounts for the 96.2wt% of n=2 ~ 5, and experimental result is shown in Table 4.
[embodiment 5]
Loading 150g in fixed bed reactors 5, molybdenum-iron catalyst is (by molybdenum oxide and iron oxide 1.90:1 group in molar ratio
Become), in bubbling reactor 7, load 300g catalyst (by HZSM-5 molecular sieve (Si/Al=30) with ethylenediamine tetra-acetic acid by matter
Amount score ratio 60:40 composition), with nitrogen purging device, the heated vaporization of Liquid Phase Methanol with air mixing rear feeding to fixed bed
Reactor, volume of air air speed is 4500h-1, methanol feed rate is 93.75g/h, and the operation temperature of fixed bed reactors is
380 DEG C, pressure is 1MPa；In bubbling reactor 9, add the absolute methanol of circulation and stress simultaneously, polyoxymethylene dimethyl ether (n=1,
2,5,6) mixed liquor, charging rate is respectively 62.5g/h, 111g/h.The operating condition of bubbling reactor 7 is that reaction temperature is
130 DEG C, reaction pressure is 5.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operation with embodiment 1, successive reaction 80h, On-line Product samples, by gas chromatographic analysis, in product n=3 and
N=4 accounts for the 97.3wt% of n=2 ~ 5, and experimental result is listed in Table 5 below.
Table 1
Table 2
Table 3
Table 4
Table 5
Claims (10)
1., by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, this technique is divided into reaction zone and Disengagement zone；Reaction zone includes first
Alcohol storage tank, preheater, fixed bed reactors and bubbling reactor；The processing step of reaction zone is the preheated vaporization of methyl alcohol and air
Enter fixed bed reactors after mixing, through the catalysis oxidation generation formaldehyde of formaldehyde synthetic catalyst, enter bubbling reactor, rousing
In bubble reactor, the mixture with methyl alcohol and circulation and stress generates polyoxymethylene dimethyl ether through solid acid catalyst catalysis；Disengagement zone
Including anion exchange resin bed layer, rectifying module, product storage tank；The processing step of Disengagement zone is that bubbling reactor discharging is passed through
Anion exchange resin deacidification after enter rectifying module separate, the three of polyoxymethylene dimethyl ether, tetramer enter product storage tank, other
Component is recycled to reactor；Described solid acid catalyst is acid styrene type cation exchange resin and dinitrobenzoic acid
Mixture, or the mixture that described solid acid catalyst is HZSM-5 molecular sieve and ethylenediamine tetra-acetic acid.
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that fixed bed reaction
Reaction temperature in device is 280～700 DEG C, and the volume of air air speed in fixed bed reactors is 4000～8000h-1。
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that fixed bed reaction
Reaction pressure in device is 0.01～30MPa.
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that being that bubbling is anti-
Answer methyl alcohol in device charging: the mass ratio of formaldehyde is 0.02～50: 1.
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that blistering reaction
Reaction temperature in device is 80～240 DEG C.
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that blistering reaction
Reaction pressure in device is 0.01～15.0MPa.
The most according to claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that described circulation
The mixture reclaimed includes the first cut containing dimethoxym ethane separated by rectifying module, containing polyoxymethylene dimethyl ether dimer
3rd cut and containing polymerization degree n > the 5th cut of the polyoxymethylene dimethyl ether of 4；Rectifying module is also isolated containing methyl alcohol
Two cuts and containing the three of polyoxymethylene dimethyl ether, the 4th cut of tetramer.
8. according to described in claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that bubbling is anti-
After the reaction discharging answering device first passes through the deacidification of anion exchange resin bed layer, enter back into rectifying module.
The most according to claim 7 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that the first cut
Being ejected material by the first rectifying tower, the second cut is ejected by the 3rd rectifying tower by Second distillation column tower top discharging, the 3rd cut
Material, the 4th cut is ejected material by the 4th rectifying tower, and the 5th cut is by discharging at the bottom of the 4th rectifying tower.
10. as claimed in claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that described formaldehyde synthesizes
Catalyst comprises one or more of following components: molybdenum oxide, iron oxide, silica, aluminum oxide, argent.
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| CN104725203B (en) * | 2015-03-24 | 2016-05-11 | 江苏凯茂石化科技有限公司 | Process unit and the method for the synthetic polymethoxy dimethyl ether of a kind of gas formaldehyde and depickling |
| CN109651099B (en) * | 2017-10-10 | 2022-04-01 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methanol and paraformaldehyde |
| CN109651100B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process for synthesizing polyformaldehyde dimethyl ether from methanol |
| CN109651096B (en) * | 2017-10-10 | 2022-04-05 | 中国石油化工股份有限公司 | Process method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde |
| CN108191615A (en) * | 2017-12-29 | 2018-06-22 | 中国人民解放军62025部队 | A kind of method with circulating fixed bed reactor synthesis polymethoxy dialkyl ether |
| CN110156576B (en) * | 2019-04-29 | 2021-11-02 | 中国科学院山西煤炭化学研究所 | Process for continuously producing polyformaldehyde dimethyl ether at low temperature |
| KR102481854B1 (en) * | 2019-12-19 | 2022-12-27 | 완후아 케미컬 그룹 코., 엘티디 | Treatment method of production wastewater according to the production of propylene oxide through the co-oxidation method |
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