CN104447239A - Method for continuously producing polymethoxy dimethyl ether by using methanol as original reaction material - Google Patents
Method for continuously producing polymethoxy dimethyl ether by using methanol as original reaction material Download PDFInfo
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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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- 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
- C07C41/58—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
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Abstract
The invention discloses a method for continuously producing polymethoxy dimethyl ether by using methanol as an original reaction material. The method comprises: 1, performing condensation reaction on methanol serving as the original reaction material and dilute formaldehyde (return material) to produce methylal of which the mass purity is more than 95%; 2, catalytically oxidizing methylal with air in the presence of an iron-molybdenum catalyst in a separator to obtain solid formaldehyde of which the mass purity is not less than 95%; 3, melting solid formaldehyde by steam heating, then performing polymerizing etherification reaction on the solid formaldehyde and the methylal under the catalytic action of self-developed modified strong acid cation exchange resin to generate polymethoxy dimethyl ether, and dehydrating and refining the polymethoxy dimethyl ether to obtain PODE3-5 of which the mass purity is more than 99.5%. By adopting the method, the single pass yield of the polymethoxy dimethyl ether can be improved from general 40-50% to 97%, wherein the PODE3-5 yield is improved from 25% to 92%; and the method is low in equipment investment, low in energy consumption, low in production cost, simple and easy to operate, and can realize large-scale continuous industrial production.
Description
Technical field
The invention discloses the method that one take methyl alcohol as primitive reaction material, continuous seepage polymethoxy dimethyl ether.
Background technology
Along with world petroleum resource day by day reduce and the demand of countries in the world to fuel oil growing, the R&D intensity of various countries to novel energy continues to increase.
China's improving constantly along with rapid development of economy and living standards of the people, constantly increase the demand of oil, became net importer from 1993 from net exporter, external dependence degree improves year by year, and 2012 years more than 55%.In recent years along with China's vehicle guaranteeding organic quantity increases fast, the consumption of oil product sharply increases, and the pollution that fuel oil causes is also day by day serious.Carbon monoxide on current big city 80%, the oxynitride of more than 40%, come from automotive emission.
China is that petroleum resources are deficient, and coal resources are quite abundant, are coal production states maximum in the world.Coal-based methanol is that China develops Chemical Industry rapidly, and by the end of the year 2013, China's methyl alcohol aggregated capacity will reach 5,592 ten thousand tons.Therefore, present China faces consumption methyl alcohol field cannot digest its production capacity increased fast, forms serious methyl alcohol problem of excess production capacity.In order to solve methyl alcohol problem of excess production capacity, develop a kind of domestic market the Downstream Products of Methanol Novel Fuel Additive polymethoxy dimethyl ether that lacks, be conducive to making up the in short supply and emission from vehicles environmental issue of China's oil, promote China's methanol industry to develop well and there is very important social strategic importance.
Polymethoxy dimethyl ether take methoxyl group as the lower molecular weight acetal polymer of main chain, and general formula is CH
3(OCH
2) nOCH
3, be high boiling point colourless liquid.The compound of n=3 ~ 6 is diesel-dopes of a kind of excellent property, its physical property is close with diesel oil, not only there is very high cetane value, its oxygen level is also very high, when adding 15% in diesel oil, does not need to transform vehicle motor oil supply system, obviously can improve the combustioncharacteristics of diesel oil, improve diesel quality, reduce discharging more than 50% tail gas pollution, significantly reduce the discharge of oxynitrides and carbon monoxide.
Polymethoxy dimethyl ether adopts methyl alcohol, formaldehyde, paraformaldehyde etc. to be raw material in early days, synthesizes with sulfuric acid catalysis.In recent years, BASF AG uses the protonic acid such as sulfuric acid, trifluoromethane sulfonic acid to be catalyzer, and methyl alcohol and paraformaldehyde (or trioxymethylene) are raw material, reacts 8 ~ 12 hours, the PODE obtained at 100 DEG C
3-8content is lower than 26%.In China in recent years, Ye Youjijia scientific research institutions and institution of higher learning have also carried out the Test And Research Work of this respect, also obtain many achievements, but expose many critical technical problems, wait to solve.The patent of invention of this respect that current country openly announces is also more, but Problems existing is still many.Some patent of invention catalyzer are corrosive, separation difficulty, and ubiquity catalytic activity is low, PODE
3-8selectivity is not high; Some patent of invention catalyzer, raw material paraformaldehyde or trioxymethylene cost are high; Some patent of invention complex technical process, production efficiency are low, are difficult to realize industrialization etc.
Summary of the invention
Technical problem to be solved by this invention is for above-mentioned the deficiencies in the prior art, and providing a kind of take methyl alcohol as the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether.
One take methyl alcohol as the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, and it comprises methylal productive unit, methylal oxidation produces solid formaldehyde unit and polymethoxy dimethyl ether productive unit,
A, methylal productive unit
Condensation reaction is carried out by sending into be filled with in the pre-reactor of catalyzer after primitive reaction material methyl alcohol and rare formaldehyde (returning charge) mixing, then the material after condensation reaction is entered in methylal reactive distillation column, in rectifying, unreacted methyl alcohol and rare formaldehyde are extracted out to enter external reactor from tower middle and lower part and are reacted further, reacted material is got back to again in tower, iterative cycles like this, be greater than the methylal of 95% at overhead extraction quality purity, at the bottom of tower, release the waste water that formaldehyde mass concentration is less than 500Pmm; Described catalyzer is highly acid Zeo-karb;
B, methylal oxidation produce solid formaldehyde unit
Most of methylal solution from methylal productive unit is obtained methylal steam through steam heating, then after methylal steam and air (waste gas returned on a small quantity) mixing are preheated to 200 DEG C ~ 240 DEG C, send into be filled with in the tubular reactor of iron-molybdic catalyst and carry out catalytic oxidation, reacted material enters separator, the solid formaldehyde that quality purity is greater than 95% is obtained from separator bottom, remain rare formaldehyde and gas enters in rare formaldehyde absorbing tower, tower top releases waste gas, waste gas goes boiler or emptying up to standard, rare formaldehyde solution is released at the bottom of tower, and remove methylal productive unit as returning charge, the spray water on absorption tower comes from the waste water of methylal productive unit and the waste water of rear workshop section depickling dehydration, described iron-molybdic catalyst is the iron-molybdic catalyst mixing a small amount of chromium and cobalt, obtains by the preparation method of routine,
C, polymethoxy dimethyl ether productive unit
By from a part of methylal solution of methylal productive unit and solid formaldehyde after 120 DEG C ~ 150 DEG C steam heating are dissolved, be (0.4-0.5) according to methylal and formaldehyde mole ratio: 1 mixes rear feeding is filled with in the polymerization methyltertiarvbutyl ether reactor of modification storng-acid cation exchange resin and carries out polymerization etherification reaction, after simultaneous reactions material extraction section enters and sloughs moisture content in external film dewatering unit, in Returning reactor, limit coronite dehydration, iterative cycles is continuous, release reacted material from reactor bottom simultaneously and enter rectifying polymerization etherificate reactive distillation column, unreacted formaldehyde and methylal etc. enter external being filled with in the reactor of modification storng-acid cation exchange resin and return in tower after further reaction, iterative cycles is continuous, PODE is released at the bottom of tower
2-10be delivered in depickling dehydration tower, adopt 3A molecular sieve to carry out depickling dehydration, bed stuffing height 8 meters, then the PODE after depickling dehydration
2-10send in rectifying tower, overhead extraction PODE
2, returned in polymerization methyltertiarvbutyl ether reactor, at the bottom of tower, released PODE
3-10send in treating tower, the PODE that treating tower overhead extraction quality purity is greater than 99.5%
3-5product, releases PODE at the bottom of tower
6-10, PODE
6-10return in polymerization methyltertiarvbutyl ether reactor.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, comprises methylal pre-reactor 1 described in methylal productive unit, methylal reactive distillation column 2, external reactor 3
(A), tower top is provided with condensation reflux unit.() in accompanying drawing slightly
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, and pre-reactor temperature of reaction described in methylal productive unit is 60 DEG C-90 DEG C, and reaction pressure is 2.0Mpa ~ 6.0Mpa; Reactive distillation column bottom temperature is 105 DEG C ~ 120 DEG C, and tower top temperature is 42 DEG C ~ 45 DEG C, and pressure is 5Kpa ~ 60Kpa, and reflux ratio is 1.0 ~ 3.0, and external reactor reaction temperature is 60 DEG C-90 DEG C, reaction pressure 2.0Mpa-6.0Mpa.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, methylal reactive distillation column described in methylal productive unit, and the sieve plate number at the bottom of tower is 8-30 block, and the number of plies of bed of packings is 5-8 layer, and the sieve plate number of tower top is 8-30 block.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, and the part of waste water described in methylal productive unit is sent in rare formaldehyde absorbing tower as absorbing formaldehyde water.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, and methylal oxidation is produced described in solid formaldehyde unit and comprised methylal oxidation device 4, solid formaldehyde separator 5, rare formaldehyde absorbing tower 6, mixing preheater.() in accompanying drawing slightly
Above-mentioned methyl alcohol is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is 250 DEG C ~ 350 DEG C that methylal oxidation produces catalytic oxidation temperature described in solid formaldehyde unit, reaction pressure is 50Kpa ~ 350Kpa, and controlling methylal in tubular reactor/oxygen mol ratio in reaction process is 2: 3; Air speed 5000h
-1~ 12000h
-1.
Above-mentioned methyl alcohol is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is send forth in separator upper end with a small amount of solid formaldehyde fine powder as crystal seed that methylal oxidation produces the separation of solid formaldehyde described in solid formaldehyde unit, lower the temperature with condensation, solid formaldehyde is formed in separator bottom, remain in rare formaldehyde and gas feeding absorption tower, tower top is released waste gas and is gone boiler or emptying up to standard, at the bottom of tower, rare formaldehyde solution returns methylal productive unit, absorption tower is packing tower, and packed height is 8 meters-12 meters.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, and it is the iron-molybdic catalyst being mixed with a small amount of chromium and cobalt that methylal oxidation produces catalyzer described in solid aldehyde unit, adopts customary preparation methods to obtain.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, comprises solid formaldehyde steam heater 7 described in polymethoxy dimethyl ether productive unit, polymerization methyltertiarvbutyl ether reactor 8, film dewatering unit 9, polymerization etherificate reactive distillation column 10, external anti-device 11
(B), depickling dehydration tower 12, rectifying tower 13, treating tower 14.
Above-mentioned formaldehyde is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, the temperature of reaction of being polymerized etherificate described in polymethoxy dimethyl ether productive unit is 50 DEG C ~ 150 DEG C, reaction pressure is 1Mpa-5Mpa, and the water deviate from external film dewatering unit goes rare formaldehyde absorbing tower to make spray water.
Above-mentioned methyl alcohol is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, the preparation method of the storng-acid cation exchange resin of modification described in polymethoxy dimethyl ether productive unit is: first prepare the methylsulphonic acid zinc solution that mass concentration is 10%, then common storng-acid cation exchange resin is placed in this solution to soak 8 ~ 12 hours, filter in the modified resin whizzer after immersion, again the resin after filtration is placed in vacuum drier, temperature is 40 DEG C ~ 60 DEG C, vacuum tightness is be dried to its water content under the condition of 1Kpa ~ 2Kpa to be not more than 0.1%, obtain modification storng-acid cation exchange resin, available copper methanesulfonate or methylsulphonic acid neodymium solution, preferable methyl sulfonic acid neodymium.
Above-mentioned methyl alcohol is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, being polymerized etherificate reactive distillation column tower top temperature described in polymethoxy dimethyl ether productive unit is 45 DEG C ~ 55 DEG C, column bottom temperature is 105 DEG C ~ 120 DEG C, sieve plate at the bottom of tower is 8-30 block, and the sieve plate number of tower top is 8-30 block, and the number of plies of bed of packings is 5-8 layer, in external reactor, temperature of reaction is 50 DEG C-150 DEG C, and reaction pressure is 1Mpa-5Mpa.
Above-mentioned methyl alcohol is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, depickling dehydration tower described in polymethoxy dimethyl ether productive unit, adopts 3A molecular sieve to carry out depickling dehydration; Rectifying tower is tray column, and stage number is 20-45, and tower top temperature is 105 DEG C-108 DEG C, and column bottom temperature is 125 DEG C-135 DEG C; Treating tower is tray column, and stage number is 20-50, and tower top temperature is 150 DEG C-180 DEG C, and column bottom temperature is 180 DEG C-250 DEG C, and tower internal pressure is-300Kpa-450Kpa.
Owing to present invention employs solid formaldehyde isolation technique, the high activated catalyst of independent research and reactive distillation, the Technologies such as limit coronite dehydration, so beneficial effect is:
1, the present invention is polymerized the modification storng-acid cation exchange resin that the catalyzer of etherification reaction is independent research, catalytic activity is high, modified more than 95% is brought up to by 35% before unmodified, selectivity brings up to modified 92% by 35% before modified, easily separated with reaction mixture, to the weak corrosion of equipment or do not corrode.
2, present invention employs the production technique of coronite rectifying limit, limit dehydration, greatly reduce the generation of the hydrolysis reaction of product, improve purity and yield, once through yield brings up to 97% by general 40% ~ 50%, product P ODE
3-5quality purity can reach more than 99.5%.
3, method of the present invention simplifies production process, reduces energy consumption, and production cost is minimum, also can save facility investment.
4, method of the present invention can realize continuous industry scale operation, solves the contradiction of China's methyl alcohol production capacity surplus, has a extensive future, economic, social, obvious environment benefit.
Below in conjunction with drawings and Examples, technical scheme of the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is technological process of production sketch of the present invention.
Description of reference numerals:
1---methylal pre-reactor; 2---methylal reactive distillation column;
3---external reactor (A); 4---methylal oxidation device;
5---solid formaldehyde separator; 6---rare formaldehyde absorbing tower;
7---solid formaldehyde steam heater; 8---polymerization methyltertiarvbutyl ether reactor;
9---external film dewatering unit; 10---polymerization etherificate reactive distillation column;
11---external reactor (B); 12---depickling dehydration tower;
13---rectifying tower; 14---treating tower.
Embodiment
Embodiment 1
As shown in Figure 1, the synthetic method of the present embodiment is:
Comprise methylal productive unit: be rare formaldehyde of 25% by primitive reaction material methyl alcohol and mass concentration, be send into after 2.0: 1 mixing to be filled with in the methylal pre-reactor 1 of storng-acid cation exchange resin and to carry out condensation reaction according to methyl alcohol and formaldehyde mole ratio, temperature of reaction is 85 DEG C, reaction pressure is 6Mpa, then the material after condensation reaction is sent in methylal reactive distillation column 2, the sieve-board type of the tower top of methylal reactive distillation column 2 is 30 pieces, sieve plate number at the bottom of tower is 30 pieces, the number of plies of bed of packings is 8 layers, control tower pressure on top surface is 60Kpa, tower top temperature is 45 DEG C, column bottom temperature is 115 DEG C, reflux ratio 3.0, the methyl alcohol of the non-complete reaction in tower middle and lower part and rare formaldehyde are extracted out and are sent into that to be filled with in the external reactor 3 (A) of storng-acid cation exchange resin in temperature of reaction be 85 DEG C, reaction pressure is return again in the middle part of tower after reacting further under 6Mpa, methylal is changed in working cycle, and be the methylal of more than 95% from overhead extraction quality purity, the waste water that formaldehyde mass concentration is less than 500Pmm is released at the bottom of tower, part waste water is sent in rare formaldehyde absorbing tower 6 as absorbing formaldehyde water,
Comprise methylal oxidation and produce solid formaldehyde unit: the most methylal solution from methylal productive unit is mixed with air (returning part waste gas and air mixed) after heating is in methylal steam and carries out continuous catalysis oxidizing reaction in the tubular type methylal oxidation reactor 4 entering after being preheated to 220 DEG C and be filled with iron-molybdic catalyst and produce formaldehyde gas mixture, the temperature of reaction of catalytic oxidation is 280 DEG C, reaction pressure is 50Kpa, oxygen mol ratio in methylal and air is 2: 3, air speed 10000h
-1, catalyzer is the iron-molybdic catalyst being mixed with a small amount of chromium and cobalt, is prepared from by ordinary method;
Above-mentioned methylal oxidation is produced the formaldehyde gas mixture that described in solid formaldehyde unit, catalytic oxidation generates and is entered in solid formaldehyde separator 5, send forth with a small amount of solid formaldehyde fine powder in the top of solid formaldehyde separator 5 as crystal seed, along with the bottom of condensation cooling solid formaldehyde separator 5 forms solid formaldehyde product, remain rare formaldehyde and gas is sent in rare formaldehyde absorbing tower 6, tower top combustion gas, waste gas goes boiler or emptying up to standard, few part waste gas returns methylal oxidation device, rare formaldehyde solution is released at the bottom of tower, rare formaldehyde solution returns in methylal productive unit as producing methylal reaction mass, spray water is from film dehydration and depickling waste water in the part waste water of methylal productive unit and rear workshop section,
Comprise polymethoxy dimethyl ether productive unit: the solid formaldehyde (solid formaldehyde after steam heater 7 is heated to 150 DEG C in melt) of solid formaldehyde unit will be produced from the part methylal solution of methylal productive unit and methylal oxidation, be enter be filled with being polymerized in methyltertiarvbutyl ether reactor 8 of modification storng-acid cation exchange resin carry out polymerization etherification reaction at 2: 5 according to methylal and formaldehyde mole ratio, extraction section material enters in external film dewatering unit 9 and dewaters simultaneously, in material Returning reactor after dehydration, continuous circulation, limit coronite dehydration, rectifying in polymerization etherificate reactive distillation column 10 sent into again by resultant of reaction material, the unreacted extraction such as formaldehyde and methylal completely enters in external reactor 11 (B), return after further reaction in reactive distillation column, iterative cycles is continuous, the temperature of reaction of polymerization etherification reaction is 95 DEG C, reaction pressure is 1.5Mpa, described catalyzer is the storng-acid cation exchange resin of modification, its preparation method is: first prepare the methylsulphonic acid zinc solution that mass concentration is 10%, but common storng-acid cation exchange resin is placed in this solution immersion 8 hours, modification storng-acid cation exchange resin after soaking is filtered in centrifugal filter, it being placed in temperature is 50 DEG C again, vacuum tightness is be dried to its water content in the vacuum drier of 1Kpa when being not more than 0.1%, obtain the storng-acid cation exchange resin of modification,
Etherificate reactive distillation column is polymerized, the polymethoxy dimethyl ether PODE of extraction at the bottom of tower described in above-mentioned polymethoxy dimethyl ether productive unit
2-10send in depickling dehydration tower 12, adopt 3A molecular sieve to carry out depickling dehydration, packed height 8 meters, the material PODE after depickling is dewatered
2-10send in rectifying tower 13, overhead extraction PODE
2, returned in polymerization methyltertiarvbutyl ether reactor 8, releasing quality purity at the bottom of tower is the PODE of 98%
3-10; Described polymerization etherificate reactive distillation column, tower top temperature is 45 DEG C, and column bottom temperature is 120 DEG C; The sieve plate number of tower top is 30 pieces, and the sieve plate number at the bottom of tower is 30 pieces, and the number of plies of bed of packings is 8 layers;
Described in above-mentioned polymethoxy dimethyl ether productive unit, rectifying tower 13 is tray columns, and plate number is 35 pieces, and tower top temperature is 105 DEG C, and column bottom temperature is 125 DEG C, and the quality purity of releasing at the bottom of tower is the PODE of 98%
3-10send in treating tower 14, treating tower 14 is tray columns, and plate number is 45 pieces, and controlling tower top temperature is 155 DEG C, and column bottom temperature is 200 DEG C, and pressure tower is-250Kpa ~ 150Kpa.The PODE that overhead extraction quality purity is greater than 99.5%
3-5product, releases PODE at the bottom of tower
6-10, PODE
6-10return in polymerization methyltertiarvbutyl ether reactor 8.
The synthetic method of the present embodiment 1 can make the once through yield of polymethoxy dimethyl ether bring up to 90% by 40% ~ 50% of general technology, and wherein the product yield of n=3-5 brings up to 85% by 25%, and its quality purity can reach more than 99.5%.
Experimental example 2
As shown in Figure 1, the synthesis condition of the synthetic method of the present embodiment 2 is identical with embodiment 1, and difference replaces zine methqne-sulfonate by copper methanesulfonate.
The synthetic method of the present embodiment 2, can make the once through yield of polymethoxy dimethyl ether bring up to 93% by 40% ~ 50% of general technology, wherein PODE
3-5product yield brings up to 90% by 25%, and its quality purity is greater than 99.5%.
Embodiment 3
As shown in Figure 1, the synthesis condition of the synthetic method of the present embodiment 3 is identical with embodiment 1, and difference replaces zine methqne-sulfonate with methylsulphonic acid neodymium.
The synthetic method of the present embodiment 3, can make the once through yield of polymethoxy dimethyl ether bring up to 97% by 40% ~ 50% of general technology, wherein PODE
3-5product yield brings up to 92% by 25%.
Embodiment 4
As shown in Figure 1, the synthesis condition of the synthetic method of the present embodiment 4 is identical with embodiment 1, and difference is zine methqne-sulfonate, copper methanesulfonate, methylsulphonic acid neodymium mixing solutions replacement methylsulphonic acid zinc solution by equivalent.
The synthetic method of the present embodiment 4, can make the once through yield of polymethoxy dimethyl ether bring up to 96% by 40% ~ 50% of general technology, wherein PODE
3-5product yield brings up to 92% by 25%.
The above; it is only most preferred embodiment of the present invention; not any restriction is done to the present invention, every above embodiment is done according to invention technical spirit any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. be the method for a primitive reaction material, continuous seepage polymethoxy dimethyl ether with methyl alcohol, it is characterized in that, the method comprises methylal productive unit, methylal oxidation produces solid formaldehyde unit and polymethoxy dimethyl ether productive unit,
A, methylal productive unit
Condensation reaction is carried out by sending into be filled with in the pre-reactor of catalyzer after primitive reaction material methyl alcohol and rare formaldehyde (returning charge) mixing, then the material after condensation reaction is entered in methylal reactive distillation column, in rectifying, unreacted methyl alcohol and formaldehyde are extracted out to enter external reactor from position, tower middle and lower part and are reacted further, reacted material is got back to again in tower, iterative cycles like this, be greater than the methylal of 95% at overhead extraction quality purity, at the bottom of tower, release the waste water that formaldehyde mass concentration is less than 500Pmm; Described catalyzer is storng-acid cation exchange resin;
B, methylal oxidation produce solid formaldehyde unit
Most methylal solution from methylal productive unit is obtained methylal steam through steam heating, then after methylal steam and air (returning waste gas on a small quantity) mixing are preheated to 200 DEG C ~ 240 DEG C, send into be filled with in the tubular reactor of iron-molybdic catalyst and carry out catalytic oxidation, reacted material enters separator, the solid formaldehyde that quality purity is greater than 95% is obtained from separator bottom, remain rare formaldehyde and gas enters in rare formaldehyde absorbing tower, tower top releases waste gas, waste gas removes boiler or up to standard emptying, rare formaldehyde solution is released at the bottom of tower, and remove methylal productive unit as returning charge, the spray water on absorption tower comes from waste water and the depickling of rear workshop section of methylal productive unit, the waste water of dehydration, described iron-molybdic catalyst is the iron-molybdic catalyst mixing a small amount of chromium and cobalt, obtains by the preparation method of routine,
C, polymethoxy dimethyl ether productive unit
By from a part of methylal solution of methylal productive unit and solid formaldehyde after 120 DEG C ~ 150 DEG C steam heating are dissolved, according to methylal and formaldehyde (0.4 ~ 0.5): the mixed in molar ratio of 1 is evenly sent into be filled with in the polymerization methyltertiarvbutyl ether reactor of modification storng-acid cation exchange resin afterwards and carried out polymerization etherification reaction, after simultaneous reactions material extraction part enters and sloughs moisture content in external film dewatering unit, in Returning reactor, limit coronite dehydration, iterative cycles is continuous, release reacted material from reactor bottom simultaneously and send into rectifying polymerization etherificate reactive distillation column, unreacted formaldehyde and methylal enter external being filled with in the reactor of modification storng-acid cation exchange resin and return in tower after further reaction, iterative cycles is continuous, PODE is released at the bottom of tower
2-10, be delivered in depickling dehydration tower, adopt 3A molecular sieve to carry out depickling dehydration, filler floor height 8 meters, then the PODE after depickling dehydration
2-10send in rectifying tower, overhead extraction PODE
2, returned in polymerization methyltertiarvbutyl ether reactor, at the bottom of tower, released PODE
3-10send in treating tower, the PODE that treating tower overhead extraction quality purity is greater than 99.5%
3-5product, releases PODE at the bottom of tower
6-10, PODE
6-10return in polymerization methyltertiarvbutyl ether reactor.
2. methyl alcohol according to claim 1 is the method for primitive reaction material, continuous seepage polymethoxy dimethyl ether, it is characterized in that, setting-up point described in methylal productive unit is 60 DEG C ~ 90 DEG C, and reaction pressure is 2.0Mpa-6.0Mpa; The tower top pressure of methylal reactive distillation column described in methylal productive unit is 5Kpa-60Kpa, and tower top temperature is 42 DEG C-45 DEG C, and column bottom temperature is 105 DEG C-120 DEG C, and reflux ratio is 1.0 ~ 3.0.
3. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, the sieve plate number of the tower top of methylal reactive distillation column described in methylal productive unit is 8-30 block, sieve plate number at the bottom of tower is 8 ~ 30 pieces, and the number of plies of bed of packings is 5-8 layer.
4. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, the temperature of reaction that methylal oxidation produces catalytic oxidation described in solid formaldehyde unit is 250 DEG C-350 DEG C, reaction pressure is 50Kpa-350Kpa, controlling oxygen mol ratio in methylal in tubular reactor and air in reaction process is 2: 3, air speed 5000h
-1~ 12000h
-1.
5. methyl alcohol according to claim 1 is primitive reaction material, continuous seepage polymethoxy dimethyl ether, it is characterized in that, it is be crystal seed with a small amount of solid formaldehyde fine powder that methylal oxidation produces that solid formaldehyde described in solid formaldehyde unit is separated, send forth in separation vessel top in condensation temperature-fall period, form the solid formaldehyde that quality purity is greater than 95% in separator bottom.
6. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, it is packing tower that methylal oxidation produces rare formaldehyde absorbing tower described in solid formaldehyde unit, packed height 8 meters-12 meters, spray water comes from the waste water of methylal productive unit and rear workshop section dewaters, the waste water of depickling.
7. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, the temperature of reaction of being polymerized etherification reaction described in polymethoxy dimethyl ether productive unit is 50 DEG C ~ 150 DEG C, and reaction pressure is 1Mpa ~ 5Mpa; In the reactor arranged outside polymerization etherificate reactive distillation column side, temperature of reaction is 50 DEG C ~ 150 DEG C, and reaction pressure is 1Mpa ~ 5Mpa.
8. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, the preparation method of the storng-acid cation exchange resin of modification described in polymethoxy dimethyl ether productive unit is: first prepare the methylsulphonic acid zinc solution that mass concentration is 10%, then common storng-acid cation exchange resin is placed in this solution to soak 8 hours ~ 12 hours, filter in the modification storng-acid cation exchange resin centrifugal filter after immersion, again the resin after filtration is placed in vacuum drier, temperature is 40 DEG C-60 DEG C, vacuum tightness is be dried to its water content under the condition of 1Kpa-2Kpa to be not more than 0.1%, obtain modification strong acid cation exchange resin catalyst, available methylsulphonic acid copper solutions or methylsulphonic acid neodymium solution, preferable methyl sulfonic acid neodymium.
9. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, etherificate reactive distillation column is polymerized described in polymethoxy dimethyl ether productive unit, the sieve plate number of tower top is 8-30 block, sieve plate number at the bottom of tower is 8-30 block, and the number of plies of bed of packings is 5-8 layer; Tower top temperature is 45 DEG C ~ 55 DEG C, and column bottom temperature is 105 DEG C ~ 120 DEG C.
10. methyl alcohol according to claim 1 is primitive reaction material, the method of continuous seepage polymethoxy dimethyl ether, it is characterized in that, described in polymethoxy dimethyl ether productive unit, rectifying tower is tray column, stage number is 20-45, tower top temperature is 105 DEG C ~ 108 DEG C, and column bottom temperature is 125 DEG C ~ 135 DEG C; Treating tower is tray column, and stage number is 20-50, and tower top temperature is 150 DEG C ~ 180 DEG C, and column bottom temperature is 180 DEG C ~ 250 DEG C, and tower internal pressure is-300Kpa-450Kpa.
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