CN107652169A - A kind of preparation technology of polymethoxy dimethyl ether production formaldehyde alcoholic solution - Google Patents
A kind of preparation technology of polymethoxy dimethyl ether production formaldehyde alcoholic solution Download PDFInfo
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- CN107652169A CN107652169A CN201711091342.9A CN201711091342A CN107652169A CN 107652169 A CN107652169 A CN 107652169A CN 201711091342 A CN201711091342 A CN 201711091342A CN 107652169 A CN107652169 A CN 107652169A
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- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 title claims abstract description 155
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000001476 alcoholic effect Effects 0.000 title claims abstract description 13
- 238000005516 engineering process Methods 0.000 title claims description 17
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 87
- 238000006243 chemical reaction Methods 0.000 claims abstract description 35
- 239000007791 liquid phase Substances 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract description 10
- 238000007599 discharging Methods 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 230000009194 climbing Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- 239000012071 phase Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 238000011049 filling Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 238000009834 vaporization Methods 0.000 claims description 4
- 230000008016 vaporization Effects 0.000 claims description 4
- 238000002309 gasification Methods 0.000 claims description 3
- 238000005191 phase separation Methods 0.000 claims description 2
- 229910001220 stainless steel Inorganic materials 0.000 claims 1
- 239000010935 stainless steel Substances 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 11
- 238000003786 synthesis reaction Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 238000006116 polymerization reaction Methods 0.000 abstract description 10
- 238000009835 boiling Methods 0.000 abstract description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000000926 separation method Methods 0.000 abstract description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 235000019253 formic acid Nutrition 0.000 abstract description 3
- 238000009833 condensation Methods 0.000 abstract description 2
- 230000005494 condensation Effects 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 2
- 230000008719 thickening Effects 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000003245 coal Substances 0.000 description 6
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical compound [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 4
- 229930040373 Paraformaldehyde Natural products 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 description 3
- 150000002373 hemiacetals Chemical class 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 229920002866 paraformaldehyde Polymers 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 125000005704 oxymethylene group Chemical group [H]C([H])([*:2])O[*:1] 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000008098 formaldehyde solution Substances 0.000 description 1
- REHUGJYJIZPQAV-UHFFFAOYSA-N formaldehyde;methanol Chemical compound OC.O=C REHUGJYJIZPQAV-UHFFFAOYSA-N 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention decides the feasibility of DMMn synthesis for obtaining the formaldehyde of low water content, directly affect the problem of product Synthesis conversion, aldehyde can be concentrated into 85% by vacuum concentration system, moisture in formaldehyde is taken off within 0.5 3% in dehydrating tower, by lower boiling methanol and formaldehyde condensation, realize formaldehyde extent of polymerization controllability in the liquid phase, the formaldehyde alcoholic solution that the degree of polymerization is n=3 10 is obtained, so as to have found the formaldehyde alcoholic solution of most suitable reaction raw materials-low water content for polymethoxy dimethyl ether synthesis.Formaldehyde vacuum concentration system is combined with stripper principle, realize the preparation of low water content formaldehyde alcoholic solution, reduce the water content in reaction system, avoid the decomposition of product, DMMn Synthesis conversion is efficiently improved, while the introducing of methanol avoids the risk of high-concentration formaldehyde concentration process polymerization, reduces thickening temperature, so as to reduce the generation of formic acid, the separation to follow-up polymethoxy dimethyl ether product serves advantageous effect.
Description
Technical field
The present invention relates to polymethoxy dimethyl ether production technology, formaldehyde alcohol is used in specially a kind of polymethoxy dimethyl ether production
The preparation technology of solution.
Background technology
Global energy comes into the serious productive life.High-grade energy is fewer and fewer, and energy prices are growing.Special crude oil
After crisis, various countries have started the underproduction and have improved crude oil price step by step.Following oil price will gradually rise.And China's energy resource structure
Feature is：Rich coal, oil-poor, few gas, economic maintaining sustained and rapid growth is increasing to energy demand, society, expanding economy with
The contradiction of oil supply.Development of coal, which is liquefied as oil tech, undoubtedly has strategic significance.In addition, China's methanol produces
Can be serious superfluous, exploitation Downstream Products of Methanol, extension Chemical Industry chain, all with realistic meaning.Northwest producing coal industry is through state
The multiple industrial restructuring of family, the original rough industrial chain of coal is further after upgrading.The further deep processing of coal be methanol and under
The tendency of trip has become the trend of following emerging coal industry.
With the progress of social economy, automobile quantity showed increased, and motor vehicle exhaust emission thing is as city haze
One of major reason.Compared to gasoline, diesel oil has higher boiling point, and H/C mass ratioes are low, therefore are discharged in diesel combustion process
Waste gas CO, oxynitrides, particulate matter etc. it is more, caused by damage ratio gasoline it is more serious.Therefore, diesel combustion effect is improved
Rate, disposal of pollutants is reduced, it is environmentally friendly task important at present to improve urban air-quality.
Polymethoxy dimethyl ether is a kind of universally acknowledged cleaning diesel oil component, its Cetane number >=70, not sulfur-bearing, no
Containing aromatic hydrocarbons.It is added in 5%-20% ratios in diesel oil, it is possible to increase diesel cetane-number, promote burning, it will be apparent that reduce vapour
The discharge of the pernicious gas such as PM2.5, PM10, NOx, CO in tail gas.Due to the excellent properties of polymethoxy dimethyl ether, it is synthesized
Technique turns into the heat subject studied both at home and abroad.
At present, the synthesis material of polymethoxy dimethyl ether is in acidic catalyst mostly with dimethoxym ethane/methanol and formaldehyde
Generation is reacted under catalytic action.The formaldehyde of low water content may be from the Pintsch process of metaformaldehyde/paraformaldehyde and discharge at present
The technique of formaldehyde.Or formaldehyde is extracted from formalin.
Metaformaldehyde generates complex process, and cost is high.It is very low for generating dmmn economic values.Paraformaldehyde is by highly concentrated
Oxymethylene polymerization is spent into high molecular formaldehyde solid.Depolymerization release formaldehyde needs higher temperature, is produced in dmmn techniques are synthesized
Substantial amounts of formic acid.Insurmountable difficulty is caused to equipment and separation.And if using high concentration formaldehyde solution (85%), compared with
More water contents is unfavorable for the positive progress of reaction.Yield is relatively low.
The content of the invention
The technical problem to be solved in the present invention is overcome at present with paraformaldehyde/trimerization production polymethoxy dimethyl ether process
In the problem of cost brought is high, Synthesis conversion and yield are low, and use and converted in 85% formalin method production process
A kind of the problem of rate is not high, and highly concentrated oxymethylene polymerization risk is big, there is provided polymethoxy dimethyl ether production formaldehyde alcoholic solution
Preparation technology.
In order to solve the above-mentioned technical problem, the invention provides following technical scheme：
A kind of polymethoxy dimethyl ether production preparation technology of formaldehyde alcoholic solution, comprises the following steps：
1) high-concentration formaldehyde that concentration is 50-55%, is pumped into climbing film evaporator bottom, adjusts the pressure in climbing film evaporator
By force<20Kpa so that Formaldehyde Gasification；
2) gas-liquid mixture of the vaporization obtained by 1), is entered into I grade of separator, I grade of separator is completed gas-liquid and be separated, gas
Subsequent cell mutually is delivered to through vapor delivery line, obtains formaldehyde mass fraction>75%, water quality fraction<15% liquid phase is transferred to I grade and delayed
Rush tank storage；
3), the material in I grade of surge tank is pumped out by discharging pump, is entered after being mixed with the methanol of certain flow complete in reactor
The hemiacetalization reaction less than normal into the degree of polymerization, the temperature of reaction is 80~150 DEG C, reaction pressure 0.1-1.0Mpa, aldehyde alcohol
Mol ratio is 3~7.5, is reacted；Preferably, reactor is fixed bed reactors；
4), by reaction solution 3) in II grade of separator at 80-110 DEG C, be concentrated in vacuo under pressure 5-50Kpa, gas
Liquid phase separation, gas phase deliver to subsequent cell through vapor delivery line, and liquid phase is transferred to II grade of surge tank storage；
5), the liquid phase in II grade of surge tank is pumped into dehydrating tower through discharging pump, and a certain amount of methanol is filled into dehydrating tower, adjusts
Temperature is 80~120 DEG C in whole tower, and the mass ratio of the methanol amount of filling into and the liquid phase out of II grade surge tank is 10~50:500, enter
Row dehydration.In dehydrating tower, the free methanol gas of excessive low boiling adds content of the moisture in gas phase, and with hemiacetal shape
Methanol boiling point is of a relatively high existing for state, is produced by discharging pump, so as to realize that methanol replaces the moisture in formalin.
Preferably, reaction temperature is 100 DEG C in step 3), and the mol ratio of aldehyde alcohol is 7.5.
Preferably, reaction temperature is 110~120 DEG C in step 5), the methanol amount of filling into and the liquid phase out of II grade surge tank
Mass ratio be 12.5：500.
Preferably, described climbing film evaporator uses 0.4~2Mpa saturated vapors, tubulation select internal diameter for 20-25mm not
Become rusty steel pipe, pipe range 2200-3500mm.
Preferably, chuck is provided with outside I grade of separator, 80-100 DEG C of hot water is passed through in chuck, be incubated for system.
Preferably, described dehydrating tower is plate column, plate number 10-30 plates.
Preferably, the liquid phase in II grade of surge tank is pumped into from tower top or is pumped at 5-10 plates, the feed entrance point of methanol
At 5-10 plates reciprocal.
Preferably, the vacuum of the dehydrating tower is 20-25Kpa.Reboiler is provided with dehydrating tower.
Preferably, the preferred neutral catalyst of catalyst in device is answered, component is aluminum oxide, iron oxide, zirconium oxide and calcium oxide
Different proportion miscellaneous more acidulous catalysts.
For the synthetic reaction principle of polymethoxy dimethyl ether, DMMn and water with sour environment under can decompose.
Therefore the formaldehyde for obtaining low water content decides the feasibility of DMMn synthesis, directly affects product Synthesis conversion.The present invention
Formaldehyde vacuum concentration system is combined with stripper principle, realizes the preparation of low water content formaldehyde alcoholic solution, it is dense by vacuum
Aldehyde can be concentrated into 85% by compression system, take off moisture in formaldehyde to 0.5-3% in dehydrating tower, by lower boiling methanol
With formaldehyde condensation, formaldehyde extent of polymerization controllability in the liquid phase is realized, obtains the formaldehyde alcoholic solution that the degree of polymerization is n=3-10, from
And it is the formaldehyde alcoholic solution that polymethoxy dimethyl ether synthesis have found most suitable reaction raw materials-low water content.Reduce reaction
Water content in system, avoids the decomposition of product, efficiently improves DMMn Synthesis conversion.The introducing of methanol avoids simultaneously
The risk of high-concentration formaldehyde concentration process polymerization, reduces thickening temperature, so as to reduce the generation of formic acid.To follow-up poly- methoxy
The separation of base diformazan ether product serves advantageous effect.
Brief description of the drawings
Accompanying drawing is used for providing a further understanding of the present invention, and a part for constitution instruction, the reality with the present invention
Apply example to be used to explain the present invention together, be not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the structural representation of the present invention.
Embodiment
The preferred embodiments of the present invention are illustrated below in conjunction with accompanying drawing, it will be appreciated that described herein preferred real
Apply example to be merely to illustrate and explain the present invention, be not intended to limit the present invention.
Embodiment
A kind of polymethoxy dimethyl ether production preparation technology of formaldehyde alcoholic solution, comprises the following steps：
1) high-concentration formaldehyde that concentration is 50-55%, is pumped into the bottom of climbing film evaporator 11 from logistics 1, adjustment rises film and steamed
Send out the pressure in device 11<20Kpa so that Formaldehyde Gasification；
2) gas-liquid mixture of the vaporization obtained by 1), is entered into I grade of separator 12, I grade of separator 12 completes liquid phase point
From gas phase delivers to subsequent cell through logistics 2, obtains formaldehyde>75% liquid phase is transferred to I grade of surge tank 13 and stored；
3), the material in I grade of surge tank 13 is pumped out by discharging pump, is mixed (logistics 3) with the methanol (logistics 4) of certain flow
Enter afterwards in reactor 14 and complete degree of polymerization hemiacetalization reaction less than normal, the temperature of reaction is 80~150 DEG C, and reaction pressure is
0.1-1.0Mpa, the mol ratio of aldehyde alcohol is 3~7.5, is reacted；Preferably, reactor 14 is fixed bed reactors；
Material is well mixed in pipeline and is pumped into reactor 14.The quantity of steam of control reactor 14 carrys out controlling reaction temperature.
Methanol carries out hemiacetal reaction with formaldehyde in reactor.Reaction equation is as follows：
CH30H+CH2O<====>CH3OCH2OH one-levels partly contracting
CH3OCH2OH+CH2O<====>CH3O(CH2O)2H two levels partly contracting
CH3O(CH2O)2H+CH2O<====>CH3O(CH2O)3H three-levels partly contracting
CH30H+nCH2O<====>CH3O(CH2O)nHn levels partly contracting
Side reaction：
2CH30H+CH2O<====>CH3OCH2O CH3+H2O aldolisations
3CH2O<====>(CH2O)3Metaformaldehyde
Using orthogonal test scheme, temperature, aldehyde/alcohol mol ratios and four kinds of different catalysts are tested respectively, experiment knot
Fruit is as follows：
Composition table after reacted is as follows：
Through analysis of experimental data it can be seen that：There is certain decline with the reacted other components content of rise of temperature.
Mainly based on dimethoxym ethane, methylal synthesis is exothermic reaction for side reaction.Raised with temperature, side reaction carries out degree and pressed down
System.
Relatively reasonable several reaction results are selected to carry out next step process.
4) reaction solution 3), is delivered to II grade of separator 15 by logistics 5.In 80-110 in II grade of separator 15
DEG C, it is concentrated in vacuo under pressure 5-50Kpa, gas-liquid is separated, and gas phase delivers to subsequent cell through logistics 6, and liquid phase is transferred to II grade
Surge tank 16 stores；
The material for testing 2,4,5,6,12,15,16 is imported into II grade of separator 15 by logistics 5 respectively, under the same terms
Separation obtains, the liquid phase component in II grade of surge tank is as follows：
To the liquid phase interpretation of result in II grade of surge tank 16：The material that reacted device hemiacetalization reaction obtains is in II fraction
From vacuum vaporization tower reactor composition in device 15, there occurs larger change with the concentration of conventional formaldehyde.Water content reduces in component, part
Methanol substitution moisture is present in dense aldehyde liquid.The effective preparation for realizing formaldehyde alcoholic solution.
The experimental project higher with respect to formaldehyde is that experiment 12 is with experiment 16. and higher because of 16 temperature of experiment, first in operation
The amount of acid generation is more.Therefore optimal experiment item choice experiment 12.
5), the liquid phase in II grade of surge tank 16 is pumped into dehydrating tower 17 through discharging pump from logistics 7, and one is filled into dehydrating tower 17
Quantitative methanol stream 8, it is 80~120 DEG C to adjust temperature in tower, and the mass ratio of logistics 8 and logistics 7 is 10~50:500, carry out
Dehydration.In dehydrating tower, the free methanol gas of excessive low boiling adds content of the moisture in gas phase, and in the form of hemiacetal
Existing methanol boiling point is of a relatively high, is produced by discharging pump through logistics 9, so as to realize that methanol replaces the water in formalin
Point.Reboiler 18 is provided with dehydrating tower 17.
The amount (logistics 8) of methanol and the temperature of dehydrating tower filled into is adjusted, the liquid phase pumped out in II grade of surge tank is entered
Row dehydration, discharging export by logistics 10, and experimental data is as follows：
According to data analysis：The apparent moisture being stripped of in formaldehyde of stripper, the limpid no white polymer of tower reactor discharging
Produce.Optimal experimental project is selected to test d.Water content 2.9% in composition, methanol 6.69%, content of formaldehyde is up to
88.95%.It is the raw material of preferable dmmn reactions.
In summary：Optimal experiment is that 12. catalyst of experiment are B classes, and reaction temperature is 100 DEG C, and aldehyde/alcohol is 7.5.Stripping
Tower charge ratio (logistics 7./8.) is 110-120 DEG C of 40/1. temperature control.
Finally it should be noted that：The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention,
Although the present invention is described in detail with reference to the foregoing embodiments, for those skilled in the art, it still may be used
To be modified to the technical scheme described in foregoing embodiments, or equivalent substitution is carried out to which part technical characteristic.
Within the spirit and principles of the invention, any modification, equivalent substitution and improvements made etc., it should be included in the present invention's
Within protection domain.
Claims (9)
1. a kind of preparation technology of polymethoxy dimethyl ether production formaldehyde alcoholic solution, it is characterised in that comprise the following steps：
1) high-concentration formaldehyde that concentration is 50-55%, is pumped into climbing film evaporator bottom, adjusts the pressure in climbing film evaporator<
20Kpa so that Formaldehyde Gasification；
2) gas-liquid mixture of the vaporization obtained by 1), is entered into I grade of separator, I grade of separator is completed gas-liquid and be separated, gas phase warp
Vapor delivery line delivers to subsequent cell, obtains formaldehyde mass fraction>75%, water quality fraction<15% liquid phase formalin turns
Enter I grade of surge tank storage；
3), the material in I grade of surge tank is pumped out by discharging pump, enters after being mixed with the methanol of certain flow and half is completed in reactor
Acetalation, the temperature of reaction is 80~150 DEG C, reaction pressure 0.1-1.0Mpa, and the mol ratio of aldehyde alcohol is 3~7.5, is entered
Row reaction；
4), by reaction solution 3) in II grade of separator at 80-110 DEG C, be concentrated in vacuo under pressure 5-50Kpa, liquid phase
Separation, gas phase deliver to subsequent cell through vapor delivery line, and liquid phase is transferred to II grade of surge tank storage；
5), the liquid phase in II grade of surge tank is pumped into dehydrating tower through discharging pump, and a certain amount of methanol is filled into dehydrating tower, adjusts tower
Interior temperature is 80~120 DEG C, and the mass ratio of the methanol amount of filling into and the liquid phase out of II grade surge tank is 10~50:500, taken off
Water.
2. preparation technology as claimed in claim 1, it is characterised in that reaction temperature is 100 DEG C in step 3), the mol ratio of aldehyde alcohol
For 7.5.
3. preparation technology as claimed in claim 1, it is characterised in that reaction temperature is 110~120 DEG C in step 5), methanol
The mass ratio of the amount of filling into and the liquid phase out of II grade surge tank is 12.5：500.
4. preparation technology as claimed in claim 1, it is characterised in that described climbing film evaporator is steamed using 0.4~2Mpa saturations
Vapour, tubulation selection internal diameter is 20-25mm stainless steel tubes, pipe range 2200-3500mm.
5. preparation technology as claimed in claim 1, it is characterised in that be provided with chuck outside I grade of separator, be passed through in chuck
80-100 DEG C of hot water, it is incubated for system.
6. preparation technology as claimed in claim 1, it is characterised in that described dehydrating tower is plate column, plate number 10-30
Plate.
7. preparation technology as claimed in claim 6, it is characterised in that the liquid phase in II grade of surge tank is pumped into from tower top or from 5-
It is pumped at 10 plates, the feed entrance point of methanol is at 5-10 plate reciprocal.
8. preparation technology as claimed in claim 1, it is characterised in that the vacuum of the dehydrating tower is 20-25Kpa.
9. preparation technology as claimed in claim 8, it is characterised in that be provided with reboiler on the dehydrating tower.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109761770A (en) * | 2019-01-25 | 2019-05-17 | 中石化广州工程有限公司 | The technique of polymerizable raw material is reduced in a kind of preparation of polymethoxy dimethyl ether |
| CN109761771A (en) * | 2019-01-25 | 2019-05-17 | 中石化广州工程有限公司 | The method of polymerizable raw material is reduced in a kind of preparation of polymethoxy dimethyl ether |
| CN112225648A (en) * | 2019-07-15 | 2021-01-15 | 中国石油化工股份有限公司 | Formaldehyde removal method in polymethoxy dimethyl ether separation process |
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| CN101898943A (en) * | 2010-06-04 | 2010-12-01 | 洪正鹏 | A kind of method of synthesizing polyoxymethylene dimethyl ether |
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| CN105906492A (en) * | 2016-04-27 | 2016-08-31 | 四川省乐山市福华通达农药科技有限公司 | Method for preparing hemiacetal methanol solution from methanol |
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2017
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| CN112225648B (en) * | 2019-07-15 | 2023-05-02 | 中国石油化工股份有限公司 | Aldehyde removing method in polymethoxy dimethyl ether separation process |
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