CN109651100A - By the process of methanol-fueled CLC polyoxymethylene dimethyl ether - Google Patents
By the process of methanol-fueled CLC polyoxymethylene dimethyl ether Download PDFInfo
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- CN109651100A CN109651100A CN201710940874.9A CN201710940874A CN109651100A CN 109651100 A CN109651100 A CN 109651100A CN 201710940874 A CN201710940874 A CN 201710940874A CN 109651100 A CN109651100 A CN 109651100A
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- dimethyl ether
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- polyoxymethylene dimethyl
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/08—Ion-exchange resins
- B01J31/10—Ion-exchange resins sulfonated
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/40—Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
- B01J2231/42—Catalytic cross-coupling, i.e. connection of previously not connected C-atoms or C- and X-atoms without rearrangement
- B01J2231/4277—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues
- B01J2231/4288—C-X Cross-coupling, e.g. nucleophilic aromatic amination, alkoxylation or analogues using O nucleophiles, e.g. alcohols, carboxylates, esters
Abstract
The present invention relates to the process of synthesizing polyoxymethylene dimethyl ether, solve the problems, such as that polyoxymethylene dimethyl ether synthesis cost is low in high yield, using the process by methanol-fueled CLC polyoxymethylene dimethyl ether, which is divided into reaction zone and Disengagement zone；Reaction zone includes methanol storage tank, preheater, fixed bed reactors and bubbling reactor；Reaction zone processing step is to enter fixed bed reactors after the preheated vaporization of methanol mixes with air, formaldehyde is generated through formaldehyde synthetic catalyst catalysis oxidation, into bubbling reactor, it is catalyzed with the mixture of methanol and circulation and stress through solid acid catalyst in bubbling reactor and generates polyoxymethylene dimethyl ether；Disengagement zone includes anion exchange resin bed layer, rectifying module, product storage tank；The processing step of Disengagement zone is that bubbling reactor discharges after anion exchange resin deacidifies into the separation of rectifying module, polyoxymethylene dimethyl ether three, tetramer enter product storage tank, other components are recycled to the technical solution of bubbling reactor, in polyoxymethylene dimethyl ether production.
Description
Technical field
The present invention relates to the processes by methanol-fueled CLC polyoxymethylene dimethyl ether.
Background technique
In recent years, low-carbon has become a great society theme, and obtains increasingly extensive concern.For example, how to reduce increasingly
High pollution exhaust emissions brought by booming auto manufacturing, the service efficiency for improving fuel oil have become many mechanisms
The project of research.
Now generally believe that oxygenatedchemicals is very suitable to make diesel oil blending compound.Current many companies and research institute just put into
Suitable oxygenatedchemicals is found and screened to strength, and screening object includes: acetal, alcohol, carbonic ester, rouge, ether, glycol derivative
Deng.For diesel oil, oxygenatedchemicals then needs high Cetane number, low self-ignition point, igniting fastly.Furthermore it should also with it is common
Miscibilty that diesel oil has had, water resistance is low, be readily biodegradable, production cost is low, raw material is cheap and easily-available etc., and especially toxicity is asked
It inscribes more concerned.Many companies in the industry develop several diesel oil oxygenatedchemicals for being hopeful application in recent years, have carried out tune
With 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 as diesel fuel additives because the excellent performance of its own receives significant attention.
Polyoxymethylene dimethyl ether, i.e. Polyoxymethylene dimethyl ethers (PODE) are the logical of a substance
Claim, skeleton symbol can be expressed as CH3O(CH2O)nCH3, Cetane number (> 40) with higher and oxygen content (42~51%).When
When the value of n is 1, polyoxymethylene dimethyl ether is dimethoxym ethane, although using dimethoxym ethane that can also mention as vehicle fuel addO-on therapy
High-energy source utilization efficiency reduces exhaust emissions, but still easily causes vent plug.When n value is 2~6, physical property, flammability
Can be very close with diesel oil, conventional additive is preferably resolved as defect existing for derv fuel blend component.Therefore poly-
Formaldehyde dimethyl ether can be used as novel cleaning diesel component, and the additive amount in diesel oil can improve up to 10% (v/v) or more
The combustion position of diesel oil within the engine improves the thermal efficiency, reduces particulate matter and CO in tail gasxAnd NOxDischarge.With bavin
The a length of n=3,4 of polyoxymethylene dimethyl ether optimal chain of oil mixing.When n=2, the flash-point of polyoxymethylene dimethyl ether is too low, and when n is excessive,
Polyoxymethylene dimethyl ether may precipitate blocking at low temperature.It is reported that the CH of addition 5~30%3OCH2OCH3NO can be greatly reducedx
Discharge.
It is paraformaldehyde section among PODE, both ends are by methyl blocking.Therefore generally by the compound (first of offer paraformaldehyde
Aldehyde, metaformaldehyde and paraformaldehyde etc.) and provide sealing end methyl compound (methanol, dimethyl ether and dimethoxym ethane etc.) Lai Hecheng
PODE.PODE can be synthesized by methanol and formaldehyde or paraformaldehyde, metaformaldehyde by acid-catalyzed dehydration.It is synthesized by coal gasification system
Gas prepares paraformaldehyde or metaformaldehyde by synthesis gas synthesizing methanol, by methanol oxidative synthesis formaldehyde, formaldehyde and is work already
The process of industry.Part diesel oil can not only be replaced by synthesizing PODE by coal-based methanol, moreover it is possible to be improved the efficiency of combustion of diesel oil, be reduced
Harm of the diesel combustion to environment has important strategic importance and good economic value.The resource pattern in China has " rich
Coal, has gas at few oil " the characteristics of, and the development of PODE and synthesis, China's coal resources abundant can be converted to liquid substitution
Fuel reduces China to the importation dependence of petroleum, and then is of great importance to national energy security.
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
The method preparation that right paraformaldehyde or paraformaldehyde are reacted with methanol.Since polyoxymethylene dimethyl ether has in diesel fuel additives field
There is huge application value, since a very long time, practicable industry life is all being studied by numerous companies and research institute
Production technology.
EP2228359A1 describes a kind of process for preparing polyoxymethylene dimethyl ether for initial feed by methanol.The party
It is catalyst that method, which is used by ammonium molybdate and Ferric nitrate modified molecular sieve, by methanol under 200 DEG C of conditions above of temperature with sky
The oxidation of gas (oxygen) step obtains polyoxymethylene dimethyl ether.This method production cost is relatively low, but catalyst preparation process is complicated,
And the selectivity of polyoxymethylene dimethyl ether is unsatisfactory.
EP1070755 describes a kind of react in the presence of three fluosulfonic acid by dimethoxym ethane with paraformaldehyde and prepares per molecule
In with 2~6 formaldehyde units polyoxymethylene dimethyl ether method.WO2006/045506A1 describes BASF AG and uses sulphur
Acid, trifluoromethanesulfonic acid have obtained the series of n=1~10 using dimethoxym ethane, paraformaldehyde, metaformaldehyde as raw material as catalyst
Product.Above method is all made of Bronsted acid as catalyst, and this catalyst is cheap and easy to get, but corrosivity is strong, it is difficult to separate, ring
Border pollution is big, to the demanding disadvantage of equipment.
US6160174 and US6265528 describes BP company and uses methanol, formaldehyde, dimethyl ether and dimethoxym ethane for raw material,
Using cation exchange resin as catalyst, gas-solid phase reaction obtains polyoxymethylene dimethyl ether.Although but this method have urge
The advantages that agent can be easily separated, and be conducive to circulation, but reaction conversion ratio is low, and yield is not high, complex process.
CN 200910056819.9 is synthesized using methanol and metaformaldehyde as raw material using solid super-strong acid as catalyst
Polyoxymethylene dimethyl ether, although achieving preferable feed stock conversion, since the acidity of solid super-strong acid is strong, irregular hole
Structure makes the selectivity of by-product dimethoxym ethane in product 20~50%, and a large amount of presence of dimethoxym ethane can reduce diesel fuel mixtures
Flash-point and therefore damage its quality so that product it is unsuitable be used as procetane.CN 101048357A describes one
Kind is using dimethoxym ethane and metaformaldehyde as the synthesis technology of Material synthesis polyoxymethylene dimethyl ether.We also develop using solid ourselves
Acid catalyst (molecular sieve CN 200910056820.1, solid super-strong acid CN 200910056819.9) is with methanol and metaformaldehyde
Polyoxymethylene dimethyl ether is prepared for raw material.
CN 101182367A is described using acidic ionic liquid as catalyst, by formaldehyde synthesizing triformol, then with
The process of metaformaldehyde and methanol-fueled CLC polyoxymethylene dimethyl ether.Although this method one-way yield is high, the ionic liquid used
Body catalyst is expensive, is not readily separated, and operation difficulty is larger.US5,959,156 is described using dimethyl ether and methanol as raw material
Polyoxymethylene dimethyl ether synthesis technology, condensation catalyst is promoted using novel multiphase.Although cost is relatively low for the technique,
Product yield is undesirable.
However these techniques have methanol, dimethyl ether, dimethoxym ethane, metaformaldehyde etc. using reaction raw materials.According to market survey
It is found that wherein the market price of methanol is minimum, it is 3000 yuan/ton, we by reasonably process optimization it is not difficult to find that as produced
Process only produces polyoxymethylene dimethyl ether as raw material using methanol and obtains higher choosing while capable of significantly reducing production cost
Selecting property and yield.
Summary of the invention
The technical problem to be solved by the present invention is to polyoxymethylene dimethyl ether synthesis technology product cost low problem in high yield,
A kind of process of new synthesizing polyoxymethylene dimethyl ether is provided, this method has the characteristics that the low high income of product cost.
In order to solve the above-mentioned technical problem, The technical solution adopted by the invention is as follows: by methanol-fueled CLC polyoxymethylene dimethyl ether
Process, which is divided into reaction zone and Disengagement zone；Reaction zone include methanol storage tank, preheater, fixed bed reactors and
Bubbling reactor；The processing step of reaction zone is to enter fixed bed reactors after the preheated vaporization of methanol mixes with air, through first
The catalysis oxidation of aldehyde synthetic catalyst generates formaldehyde, into bubbling reactor, in bubbling reactor with methanol and be recycled back to
The mixture of receipts is catalyzed through solid acid catalyst and generates polyoxymethylene dimethyl ether；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 separation, polyoxymethylene dimethyl ether three, tetramer enter product storage tank, other components are recycled to bubbling reactor.
Reaction temperature in above-mentioned technical proposal in fixed bed reactors is preferably 280~700 DEG C, in fixed bed reactors
Volume of air air speed be preferably 4000~8000h-1.Reaction pressure in fixed bed reactors is preferably 0.01~30MPa.Drum
Steep methanol in reactor feed: the mass ratio of formaldehyde is preferably 0.02~50: 1.Reaction temperature in bubbling reactor is preferably
80~240 DEG C.Reaction pressure in bubbling reactor is preferably 0.01~15.0MPa, more preferably 0~10MPa.
In above-mentioned technical proposal, first containing dimethoxym ethane that the mixture preferably includes to be separated by rectifying module evaporates
Point, the third fraction containing polyoxymethylene dimethyl ether dimer and the polyoxymethylene dimethyl ether containing more high polymerization degree (n > 4) the
Five fractions；Rectifying module further preferably isolate containing the second fraction of methanol and containing polyoxymethylene dimethyl ether three, tetramer
Four fractions.
In above-mentioned technical proposal, the reaction discharging of the bubbling reactor preferably first passes through anion exchange resin bed layer and removes
After acid, rectifying module is entered back into.The rectifying module is preferably made of 4 rectifying columns.First fraction is preferably by the first rectifying
Column overhead discharging, the second fraction are preferably discharged by Second distillation column tower top, and third fraction is preferably discharged by third distillation column tower top,
4th fraction is preferably discharged by the 4th the top of the distillation column, and the 5th fraction is preferably discharged by the 4th rectifying tower bottom.First, third,
And the 5th fraction preferably after dehydrater removes water circulation and stress to liquid phase tank reactor.Second fraction is preferably removed through dehydrater
Circulation and stress is to methanol storage tank after water.
The operating pressure of the first rectifying column is preferably 0.2~2MPa, and the operating pressure of Second distillation column is preferably
0.1~1.5MPa, the operating pressure of third distillation column are preferably 0.05-1.2MPa, and the operating pressure of the 4th rectifying column is preferably
0.001-0.6MPa.The theoretical cam curve of first rectifying column is preferably 15~40, and the theoretical cam curve of Second distillation column is preferably
15~30, the theoretical cam curve of third distillation column is preferably 15~35, and the theoretical cam curve of the 4th rectifying column is preferably 15~35.
Formaldehyde synthetic catalyst preferably comprises the one or more of following components: molybdenum oxide, oxidation in above-mentioned technical proposal
Iron, silica, aluminium oxide, metallic silver.
In above-mentioned technical proposal, the solid acid catalyst is selected from following one or more catalyst: sulfonic acid type polyphenyl
Ethylene cation exchange resin, metal-modified sulfonic acid polystyrene cation exchange resin, molecular sieve, dinitrobenzene first
Acid, ethylenediamine tetra-acetic acid, aluminium oxide, titanium dioxide, more preferable metal-modified sulfonic acid polystyrene cation exchange resin.
In above-mentioned technical proposal, the sulfonic acid polystyrene cation exchange resin include crosslinked polystyrene skeleton and
Sulfonic acid group；The modified metal includes Cu.
In above-mentioned technical proposal, preferably, the modified metal further includes assistant metal, the assistant metal is selected from Mn
Or at least one of Tc, Cu and assistant metal have synergistic effect in terms of improving to the selectivity of the PODE of n=2~10.
Ratio between Cu and assistant metal is not particularly limited, as long as Cu and assistant metal are existed simultaneously can obtain in catalyst
Comparable synergy.
As non-restrictive, the mass ratio of Cu and assistant metal is 0.01~100, within this range further non-limit
Qualitative citing such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the modified metal includes simultaneously more preferably Cu, Mn and Tc, and Mn and Tc is being improved at this time
There is synergistic effect to the selectivity aspect of the PODE of n=2~10.At this point, the ratio between Mn and Tc is not particularly limited, only
Comparable synergy can be obtained in catalyst by wanting Mn and Tc to exist simultaneously.
As non-restrictive, the mass ratio of Mn and Tc are 0.01~100, within this range further non-limiting act
Example such as 0.1,0.5,0.8,1,1.5,2,3,4,5,6,7,8,9,10 etc..
In above-mentioned technical proposal, the content of modified metal is not particularly limited in catalyst, such as, but not limited to modified gold
The content of category is greater than 0 and to be less than or equal to 10w%.
In above-mentioned technical proposal, the full exchange capacity of the resin is 3.0~6.0mmol/g.
In above-mentioned technical proposal, the resin can be gel-type or macroporous type.
In order to solve the above-mentioned technical problem two, technical scheme is as follows:
In above-mentioned technical proposal, the preparation method of the catalyst, including in the presence of the acid of catalytic amount, by the sulphur
Acid type polystyrene cation exchange resin contacts progress with the suspension containing the modified metal-oxide and/or hydroxide
Ion exchange.
In above-mentioned technical proposal, the acid is not particularly limited, if can with containing the modified metal-oxide and/or
The salt that hydroxide reacts can be dissolved in solvent used in the suspension and be ok, under this principle such as, but not limited to
At least one of hydrochloric acid, nitric acid or carboxylic acid of C2~C10.
In above-mentioned technical proposal, the carboxylic acid can be hydroxyl substituted carboxylic acid, such as, but not limited to hydroxyacetic acid, lactic acid,
Tartaric acid, citric acid etc..
In above-mentioned technical proposal, the carboxylic acid can be the monoacid of C2~C10, such as, but not limited to acetic acid etc..
In above-mentioned technical proposal, desiccant used in drying tube, dehydrater preferably is selected from following at least one desiccant: from
Sub-exchange resin, molecular sieve, Silica hydrogel.
In above-mentioned technical proposal, the rectifying column is preferably packed tower, and filler is preferably ordered structure stainless steel or ceramics.
The present invention has the following advantages: first, yield and selection rate are high, and the sum of n=3 and n=4 product accounts for the product of n=2~5
Summation is high；Second, lower production costs；Third makes by-product circulation and stress using the method for rectifying；Achieve preferable technology
Effect.
Detailed description of the invention
The present invention 1 is further described with reference to the accompanying drawings.
Fig. 1 is the method for the present invention flow chart.
The methanol (logistics 2) that methanol storage tank 1 exports mixes by the heating of heater 3 vaporization 4 with air (logistics 29) laggard
Enter fixed bed reactors 5, catalysis oxidation prepares formaldehyde, 6 (the predominantly first of output streams of reactor 5 in fixed bed reactors 5
Aldehyde, methanol) it is fed into bubbling reactor 7, while the logistics 8 also by exporting after methanol storage tank 1 fed to bubbling reactor 7
(predominantly liquid phase alcohol), logistics 16 (the predominantly dimer of polyoxymethylene dimethyl ether, the Yi Jiju exported after being removed water by dehydrater 15
The polyoxymethylene dimethyl ether of right higher (n > 4)).The discharging of bubbling reactor 79 obtains after the deacidification of anion exchange resin bed layer 10
Logistics 11, logistics 11 are separated into rectifying column 12.Unreacted dimethoxym ethane discharges (logistics 14) from 12 tower top of rectifying column,
16 are passed through bubbling reactor 7 again after the water removal of dehydrater 15.12 tower bottom of rectifying column discharging 13 carries out down into rectifying column 17
The separation of one step.Unreacted methanol discharges (logistics 19) from 17 tower top of rectifying column, and 21 are passed through again after the water removal of dehydrater 20
Methanol storage tank 1.17 tower bottom of rectifying column discharging (logistics 18) enters rectifying column 22 and carries out next step separation.The two of polyoxymethylene dimethyl ether
Polymers is passed through bubbling reactor 7 after the water removal of dehydrater 15 from 22 tower top of rectifying column discharging 24 again.22 tower bottom of rectifying column goes out
Material 23 enters rectifying column 25.The trimer and tetramer of polyoxymethylene dimethyl ether discharge (logistics 27) from 25 tower top of rectifying column, enter
Product storage tank 28.The polyoxymethylene dimethyl ether of the degree of polymerization higher (n > 4) discharges (logistics 26) from 25 tower bottom of rectifying column, by dehydrater
It is passed through bubbling reactor 7 again after 15 water removals.
Below by embodiment, the present invention is further elaborated.
Specific embodiment
[embodiment 1]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
The Cu (OH) that acid type polystyrene cation exchange resin and 300ml are 2 grams containing Cu21 drop ice vinegar is added in aqueous suspension mixing
Acid, mixing stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtain the catalyst that Cu content is 2w%.
2, the synthesis of polyoxymethylene dimethyl ether
150g is loaded in fixed bed reactors 5, silver-colored silica-alumina catalyst (presses mass fraction by silver, silica and aluminium oxide
Formed than 18:75:7), 150g solid acid catalyst is loaded in bubbling reactor 7, with nitrogen purging device, Liquid Phase Methanol warp
Heating vaporization, which mixes with air, is fed into fixed bed reactors, and volume of air air speed is 4500h-1, methanol feed rate is
93.75g/h, the operation temperature of fixed bed reactors are 600 DEG C, pressure 1MPa；Circulation is added into bubbling reactor 9 simultaneously
The anhydrous methanol of recycling, 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 is that reaction temperature is 150 DEG C, reaction pressure 3.0MPa.Reaction discharging enters anion and hands over
Change resin bed.
The discharging of bubbling reactor 79 enters rectifying column 12 after the deacidification of anion exchange resin bed layer 10 and is separated, and grasps
Making pressure is 0.2~2MPa, theoretical cam curve 20.Unreacted dimethoxym ethane discharges (logistics 14) from 12 tower top of rectifying column, warp
It crosses after dehydrater 15 removes water and is passed through bubbling reactor 7 again.The discharging of 12 tower bottom of rectifying column enters rectifying column 17 and divide in next step
From operating pressure is 0.1~1.5MPa, theoretical cam curve 20.Unreacted methanol from 17 tower top of rectifying column discharge (logistics
19) it, is passed through methanol storage tank 1 again after the water removal of dehydrater 15.17 tower bottom of rectifying column discharging (logistics 18) enters rectifying column 22
Next step separation is carried out, operating pressure is 0.05~1.2MPa, theoretical cam curve 20.The dimer of polyoxymethylene dimethyl ether is from essence
The discharging of 22 tower top of tower is evaporated, is passed through bubbling reactor 7 again after the water removal of dehydrater 15.The trimer of polyoxymethylene dimethyl ether and four
Polymers discharges (logistics 27) from 25 tower top of rectifying column, and operating pressure is 0.001~0.6MPa, theoretical cam curve 20, into production
Product storage tank 28.The polyoxymethylene dimethyl ether of the degree of polymerization higher (n > 4) discharges (logistics 26) from 25 tower bottom of rectifying column, by dehydrater 15
Again bubbling reactor 7 is passed through after water removal.Successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 2]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
The Cu (OH) that acid type polystyrene cation exchange resin and 300ml are 2 grams containing Cu21 drop ice vinegar is added in aqueous suspension mixing
Acid, mixing stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtain the catalyst that Cu content is 2w%.
2, the synthesis of polyoxymethylene dimethyl ether
Load 150g in fixed bed reactors 5, molybdenum-iron catalyst is (by molybdenum oxide and iron oxide 2:1 group in molar ratio
At), 150g solid acid catalyst is loaded in bubbling reactor 7, with nitrogen purging device, the heated vaporization of Liquid Phase Methanol and sky
For gas mixing rear feeding to fixed bed reactors, volume of air air speed is 4500h-1, methanol feed rate 93.75g/h, fixed bed
The operation temperature of reactor is 380 DEG C, pressure 1MPa；The anhydrous methanol of circulation and stress is added into bubbling reactor 9 simultaneously,
The mixed liquor of polyoxymethylene dimethyl ether (n=1,2,5,6), charging rate are respectively 93.75g/h, 85.5g/h.Bubbling reactor 7
Operating condition is that reaction temperature is 110 DEG C, reaction pressure 1.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 3]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Mn (OH) for being 2 grams containing Mn with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Mn content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 4]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, the Tc (OH) for being 2 grams containing Tc with 300ml under nitrogen protection2Aqueous suspension mixing, adds
Enter 1 drop glacial acetic acid, mix, stand 24 hours at room temperature, dry to constant weight in vacuum oven, obtaining Tc content is 2w%'s
Catalyst.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 5]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Cu (OH) that Cu is 1 gram and Mn is 1 gram under nitrogen protection2And Mn
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Cu content is the catalyst that 1w% and Mn content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 6]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin, with 300ml containing the Cu (OH) that Cu is 1 gram and Tc is 1 gram under nitrogen protection2And Tc
(OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature, dry extremely in vacuum oven
Constant weight, obtaining Cu content is the catalyst that 1w% and Tc content is 1w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 7]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Cu is 1 gram under nitrogen protection, Tc is 0.5 gram and Mn is 0.5 gram
Cu(OH)2、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, mixing stands 24 hours at room temperature,
Dry to constant weight in vacuum oven, it be 0.5w% and Mn content is urging for 0.5w% that obtain Cu content, which be 1w%, Tc content,
Agent.
2, the synthesis of polyoxymethylene dimethyl ether
150g catalyst is loaded in bubbling reactor 9, and 10000g is continuously added in mixing channel with nitrogen purging device
Paraformaldehyde, mixing channel temperature are 250 DEG C, and the formaldehyde gas generated after heating enters bubbling reactor after drying tube removes water
9；It is added dimethoxym ethane into bubbling reactor 9 simultaneously, the mixed liquor of circulation and stress (methanol, formaldehyde and PODEn=1,2,5,
6), wherein reaction raw materials dimethoxym ethane and formaldehyde charging rate are respectively 76g/h, 90g/h.The operating condition of bubbling reactor 9 is
Reaction temperature is 110 DEG C, reaction pressure 2.0MPa.Reaction discharging enters anion exchange resin bed layer.
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
[embodiment 8]
1, the preparation of catalyst
Sulfonic acid sodium form polystyrol cation exchange resin 7320 is washed with deionized water to outflow clear water, with 4w%'s
Salt acid soak four times, every time using the 4w%'s for being equivalent to 10 times of 7320 dry weight of sulfonic acid sodium form polystyrol cation exchange resin
Hydrochloric acid, impregnates 4h every time, is washed with deionized later to eluate and is existed without chloride ion, arrives sulphur after 60 DEG C of dryings
Acid type polystyrene cation exchange resin, full exchange capacity 4.10mmol/g.It takes and is equivalent to 98 grams of butt resin of sulphur
Acid type polystyrene cation exchange resin with 300ml containing Cu is 1.5 grams under nitrogen protection, Tc is 0.25 gram and Mn is 0.25
Gram Cu (OH)2、Tc(OH)2With Mn (OH)2Aqueous suspension mixing is mixed, 1 drop glacial acetic acid is added, it is small to stand 24 at room temperature for mixing
When, dry to constant weight in vacuum oven, it is that 0.25w% and Mn content is that obtain Cu content, which be 1.5w%, Tc content,
The catalyst of 0.25w%.
2, the synthesis of polyoxymethylene dimethyl ether
Other operations are the same as embodiment 1, successive reaction 80h, On-line Product sampling, by gas chromatographic analysis, experimental result column
In table 1.
Table 1
N is the degree of polymerization, product CH3O(CH2O)nCH3。
Claims (10)
1. the technique is divided into reaction zone and Disengagement zone by the process of methanol-fueled CLC polyoxymethylene dimethyl ether；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 methanol and air
Enter fixed bed reactors after mixing, the catalysis oxidation through formaldehyde synthetic catalyst generates formaldehyde, into bubbling reactor, in drum
It steeps to be catalyzed with the mixture of methanol and circulation and stress through solid acid catalyst in reactor and generates polyoxymethylene dimethyl ether；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, polyoxymethylene dimethyl ether three, tetramer enter product storage tank, other
Component is recycled to bubbling reactor.
2. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that fixed bed reaction
Reaction temperature in device is preferably 280~700 DEG C；Volume of air air speed in fixed bed reactors is preferably 4000~8000h-1。
3. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that fixed bed reaction
Reaction pressure in device is 0.01~30MPa.
4. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that being to be bubbled anti-
Answer methanol in device charging: the mass ratio of formaldehyde is 0.02~50: 1.
5. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that blistering reaction
Reaction temperature in device is 80~240 DEG C.
6. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that blistering reaction
Reaction pressure in device is 0.01~15.0MPa.
7. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that the mixing
Object include the first fraction containing dimethoxym ethane separated by rectifying module, the third fraction containing polyoxymethylene dimethyl ether dimer with
And the 5th fraction of the polyoxymethylene dimethyl ether containing more high polymerization degree (n > 4)；Rectifying module is also isolated to be evaporated containing methanol second
Point and three containing polyoxymethylene dimethyl ether, tetramer the 4th fraction.
8. the process according to claim 1 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that be bubbled anti-
After answering the reaction discharging of device to first pass through the deacidification of anion exchange resin bed layer, rectifying module is entered back into.
9. the process according to claim 7 by methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterised in that the first fraction
It is discharged by first rectifying column tower top, the second fraction is discharged by Second distillation column tower top, and third fraction is gone out by third distillation column tower top
Material, the 4th fraction are discharged by the 4th the top of the distillation column, and the 5th fraction is discharged by the 4th rectifying tower bottom.
10. as described in claim 1 by the process of methanol-fueled CLC polyoxymethylene dimethyl ether, it is characterized in that the formaldehyde synthesizes
Catalyst includes the one or more of following components: molybdenum oxide, iron oxide, silica, aluminium oxide, metallic silver；The solid acid
Catalyst is selected from following at least one components: acid cation exchange resin, molecular sieve, dinitrobenzoic acid, ethylenediamine tetrem
Acid, aluminium oxide, titanium dioxide.
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