CN108129445A - The method that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying - Google Patents
The method that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying Download PDFInfo
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- CN108129445A CN108129445A CN201611104609.9A CN201611104609A CN108129445A CN 108129445 A CN108129445 A CN 108129445A CN 201611104609 A CN201611104609 A CN 201611104609A CN 108129445 A CN108129445 A CN 108129445A
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Abstract
The present invention relates to the methods that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying, and the present apparatus is using 60%~75% formalin as reaction raw materials；After formaldehyde enters metaformaldehyde synthesis pre-reactor pre-reaction, into reactive distillation column, reactive distillation column materials at bottom of tower is polycondensed into metaformaldehyde being transported to main reactor, mixed liquor after reaction is being transported to reactive distillation column rectifying, formaldehyde synthesizing triformol in the presence of rare-earth element modified strongly acidic styrene type cation exchange resin, first pass through rectifying concentrate, extraction, using rectifying, obtain the metaformaldehyde of content 99.99%；The present invention solves the problems, such as that synthesizing triformol production process conversion ratio, selectivity and yield are low, low with catalyst reaction efficiency and corrosive problem, and complex process with high energy consumption the problem of, also solve polymethoxy dimethyl ether raw materials for production, after polymethoxy dimethyl ether realizes industrialization, solves domestic methanol problem of excess production capacity.
Description
Technical field
The present invention relates to the methods that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying.More particularly to one
Kind is catalyst using rare-earth element modified strongly acidic styrene type cation exchange resin.Belong to chemical synthesising technology neck
Domain.
Background technology
Metaformaldehyde（TOX）And numerous related industries are extremely important links in one chemical industrial chain of carbon.First, trimerization
Formaldehyde is to prepare polyformaldehyde（POM）The raw material of engineering plastics, polyformaldehyde are one of three large-engineering plastics of the world, domestic demand amount day
Benefit is incremented by.Meanwhile the alternative formaldehyde of metaformaldehyde is widely used in and prepares bulk chemical and fine chemicals, including disinfectant,
Antimicrobial, fumigant, insecticide, bonding agent are the primary raw materials of daily cosmetics cold wave lotion and depilatory agent, are also used to synthesize
The basic material isooctyl thioglycolate of the heat stabilizers such as transparent plastic and antimony organic, organotin, reagent manufacture be examine iron,
The sensitive reagents of the metal ions such as molybdenum, silver, tin.
Metaformaldehyde is to prepare polymethoxy dimethyl ether（PODE3-8 main raw material(s)), and PODE3-8 is public in the world
The novel environment-friendly fuel oil oxygen-containing component for reducing oil consumption and reducing flue gas emission recognized.More than 76 Cetane number of PODE3-8, contains
Oxygen is 47%~50%, and boiling range is 156 DEG C -320 DEG C, low condensation point, and no sulphur is without aromatic hydrocarbons, due to PODE3-8 Cetane number height, object
Property is close with diesel oil, 5%~30% is blended into diesel oil in proportion under the premise of diesel engine is not changed, can increase oil product and contain
Oxygen amount improves diesel quality, PODE3-8 good environmental protections, and the tail gas pollution of more than 50% emission reduction is greatly reduced NOx, CO and
The discharge of hydrocarbon particulate matter and PM2.5.After metaformaldehyde synthesis PODE3-8 technological achievements realize industrialization, a large amount of first can be digested
Alcohol solves the problems, such as domestic methanol excess capacity, provides direction for Modern Coal-based Chemical enterprise transformation upgrading, opens China's hair
Exhibition advantage coal resource substitutes the new way of the clean energy technology of petroleum resources, and social benefit is notable.
Generally use H2SO4 technique productions metaformaldehydes in the world at present：It will be less than 55% first（Mass percent）First
Aldehyde aqueous solution is through being overpressurized decompression concentrate to 60%~75%, and then using sulfuric acid as catalyst, reaction temperature is at 100 DEG C -115 DEG C
Under the conditions of synthesizing triformol, in view of the problems of sulfur process, the new catalyst in the prior art substituting H2SO4 is ground
Study carefully it is very active always, including hydrochloric acid, phosphoric acid, sulfonic acid or heteropoly acid, solid acid, activated carbon supported silico-tungstic acid, solid acid catalysis
Agent loads and modification, ion exchange colloid, super acidic catalyst etc..Since these catalyst existing defects (refer to
CN102020630A), Chen Jing et al. (US7244854, CN1978438A, CN101211154A, CN101211154B,
CN102020630A refined et al. (CN102643265A), Bai Zhenmin et al. (CN102643264A) and Yi Zujian et al.), are grasped
It is catalyst synthesis that (CN102633769A, CN102633769B), which is proposed respectively by raw material, ionic liquid of formalin,
The method of metaformaldehyde.But no matter using above what type of catalyst, these are based on formalin synthesizing triformol
Method greatest problem be need to by more than 65% formalin concentrate to, and react metaformaldehyde yield in phase it is very low (on
The equilibrium concentration that metaformaldehyde in kettle liquid is reacted when under the conditions of stating using sulfuric acid and ionic liquid as catalyst only respectively may be about 1.8%
With 2.5%, mass percent), while have the generations such as formic acid, methyl formate, so reactive distillation process must be used to produce
Metaformaldehyde.The taking back and process problem of the dilute formaldehyde of such technique also generally existing, dilute formaldehyde recycling use distillation scheme substantially,
Yield is big, high energy consumption, and big to equipment material requirement height, investment.
Invention content
The technical problems to be solved by the invention are in view of the above shortcomings of the prior art, to provide a kind of formaldehyde through fixation
The method that bed reaction, boundling extraction, rectifying prepare metaformaldehyde.This method is changed using high concentration formaldehyde solution in rare earth element
Property strongly acidic styrene type cation exchange resin be synthesizing triformol under the action of catalyst, using reactive distillation work
Skill, side border ring rectifying can improve the equilibrium concentration of metaformaldehyde in reactor liquid phase, and the mixed liquor after reaction is extracted using boundling
Extraction efficiency can be improved by taking, and the liquid after extraction obtains 99.99% metaformaldehyde after rectifying.Three are prepared using this method
Polyformaldehyde makes the equilibrium concentration of the metaformaldehyde in reactor be increased to 6%~9% from the 1.8%~2.5% of common process, more can
The dosage of extractant is reduced, the consumption of power of rectifying is reduced, metaformaldehyde concentration is increased to 99.99% from 98.5%, so as to
Production cost can be reduced.
In order to solve the above technical problems, the technical solution adopted by the present invention is：Formaldehyde through fixed bed reaction, boundling extraction,
The method that rectifying prepares metaformaldehyde.It is characterized in that, this method includes the following steps：
Step 1: formaldehyde condensation polymer metaformaldehyde：That the formalin of raw material 60% ~ 75%% is transported to that dress carries catalyst
Pre-reaction is carried out in one fixed bed reactors, then the material after pre-reaction is sent into reactive distillation column, from reactive distillation column
The material that bottom of towe comes out is delivered in reboiler by pumping a part after gasification in return reactive distillation column, and remainder is delivered to
Dress carries in the second fixed bed main reactor A and B of catalyst and carries out polycondensation reaction, and the reaction mass after polycondensation reaction returns to
In reactive distillation column, by steam and the inert gas rectifying after heating and air lift, so recycle, produced not from reactive distillation column
15% ~ 35% formalin of reaction, material of the overhead extraction containing metaformaldehyde.The catalyst changes for rare earth element
The strongly acidic styrene type cation exchange resin of property；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
Autoclave Phase separation device is transported to after condensation, pre-extracted split-phase is carried out using extractant, obtains lower floor's water phase and upper oil phase,
It lower floor's water phase is transported to bundle pipe type extractor carries out quintessence with extractant and take split-phase, obtain lower floor's water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of bundle pipe type extractor described in step 2 is returned into reaction essence
Evaporate in tower, upper oil phase is transported in the first treating column, from the mass concentration of the first treating column overhead extraction be 5% ~ 10% it is dilute
Formaldehyde is sent into stripper removal microextraction agent, and the extractant produced from the first treating column tower, which is transported to storage tank, which carries out cycle, makes
With the material produced from the first treating column bottom of towe is transported in the second treating column, from the second refined overhead extraction PODE2, from
The material of two treating column bottom of towe extraction is transported in third treating column, and the quality purity that overhead extraction is refined from third is not less than
99.9% metaformaldehyde produces PODE from third treating column bottom3, and from the second refined overhead extraction PODE2, it is defeated together after merging
It is sent in byproduct recycling hydrolyzer, PODE2With PODE3Formaldehyde and methanol are hydrolyzed under the action of catalyst water, after hydrolysis
Material is transported to autoclave Phase separation device in step 2 and recycles；It is 52 DEG C ~ 72 DEG C to be confused the first refined column overhead temperatures, the first essence
Tower column bottom temperature processed is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107 DEG C ~ 120 DEG C, the second treating column column bottom temperature
It it is 128 DEG C ~ 138 DEG C, it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, and third treating column column bottom temperature is 132 DEG C ~ 145
DEG C, the tower top pressure of the first treating column, the second treating column and third treating column is 5kpa ~ 30kpa, and tower bottom pressure is
40kpa~100kpa；
The method that above-mentioned formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying, reacts essence described in step 1
It is 5 pieces ~ 30 pieces to evaporate column overhead sieve plate number, and bottom of towe sieve plate number is 5 pieces ~ 30 pieces, and the number of plies of packed bed is 2 layers ~ 8 layers in tower.；Step
The reaction temperature of pre-reaction described in rapid one is 90 DEG C~130 DEG C, and reaction pressure is 90kPa~130kPa；In step 1
The reaction temperature of the polycondensation reaction is 90 DEG C~130 DEG C, and reaction pressure is 10kPa~90kPa；Described in step 3
The sieve plate number of one treating column, the second treating column and third treating column is 30~75 pieces.
Compared with the prior art, the present invention has the following advantages：
1st, the catalyst used in polycondensation reaction of the present invention for the rare-earth element modified strongly acidic styrene of independent research be sun from
Sub-exchange resin, the catalysis effective active of catalyst is generally higher by 60% using H2SO4 or ionic liquid in the world than at present, with sulphur
The equilibrium concentration of metaformaldehyde only respectively may be about 1.8% and 2.5% in reactor liquid phase when acid and ionic liquid are catalyst,
Mass percent, and reactor liquid during the catalyst of the rare-earth element modified strongly acidic styrene type cation exchange resin of use
For the equilibrium concentration of metaformaldehyde up to 9%, catalyst makes reaction mixture easily separated for solid acid in phase, reduces separating energy consumption, pair sets
Standby weak corrosion reduces equipment investment.
2nd, the present invention is by the way that the material after being reacted in fixed bed reactors is sent into reactive distillation column, side border ring essence
It evaporates, greatly reduces the residence time of metaformaldehyde in the reactor, pressure makes to reach the three of equilibrium concentration in reactor liquid phase
Polyformaldehyde removes reactor, improves metaformaldehyde conversion per pass.
3rd, method using the present invention prepares metaformaldehyde, can make the conversion per pass of metaformaldehyde by conventional method 30%
70% is increased to, product purity is increased to 99.99% by 98.5%.
4th, the present invention in extraction process using Xi'an Shanghua Technology Development Co., Ltd. and Jiangsu bigization forever
The boundling extraction tower of construction equipment Co., Ltd joint invention, the extraction can increase phase border contact area and mass tranfer coefficient.Than tradition
Autoclave extractor, packed extraction tower, perforated-plate extraction tower, turntable extracting tower extraction effect is high, and extractant usage amount is small, produces energy
Power is big, to the adaptable of object system.
5th, method of the invention easily realizes industrialization, can accelerate to promote polymethoxy PODE3-8 industrialization after industrialization, and
Polyformaldehyde production cost can be reduced, improves polyformaldehyde performance, moreover it is possible to consume a large amount of methanol, solve China's methanol excess capacity
Contradiction, meanwhile, the clean energy resource strategy that petroleum resources are substituted for China's advantages for development coal resource opens a Tiao Xin roads.The present invention
It has a extensive future, economic, society, obvious environment benefit.
Technical scheme of the present invention is described in further detail with reference to the accompanying drawings and examples.
Description of the drawings
Fig. 1 is the process flow diagram of the present invention.
Reference sign：
1-pre-reactor；2-reactive distillation column；3-reboiler；
4-column bottoms pump；5-main reactor A；6-main reactor B；
7-condenser；8-autoclave Phase separation device；9-bundle pipe type extractor；
10-the first water phase pumps；11-the second water phase pumps；12-oil phase pumps；
13-the first treating column；14-the second treating column；15-third treating column；
16-stripper；17-byproduct recover；
Specific embodiment
Embodiment 1
As shown in Fig. 1, the synthetic method of the present embodiment is：
Step 1: formaldehyde condensation polymer metaformaldehyde：That the formalin of raw material 60% ~ 75%% is transported to that dress carries catalyst
Pre-reaction is carried out in one fixed bed reactors 1, then the material after pre-reaction is sent into reactive distillation column 2, from reactive distillation
The material that 2 bottom of towe of tower comes out is delivered in reboiler 3 by pumping 4 parts after gasification in return reactive distillation column 2, remainder
It is delivered to and fills the second fixed bed main reactor A 5 for carrying catalyst and carry out polycondensation reaction in B 6, the reaction after polycondensation reaction
Material is returned in reactive distillation column 2, by steam and the nitrogen rectifying after heating and air lift, is so recycled, from reactive distillation column 2
The formalin of middle extraction unreacted 15% ~ 25%, material of the overhead extraction containing metaformaldehyde.The catalyst is dilute
The strongly acidic styrene type cation exchange resin that earth elements are modified；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
It is transported in autoclave Phase separation device 8 after 7 condensations, pre-extracted split-phase is carried out using extractant, obtain lower floor's water phase and upper strata oil
Phase carries out quintessence with extractant and takes split-phase, obtains lower floor lower water is mutually transported to by pump 10 in bundle pipe type extractor 9
Water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of bundle pipe type extractor described in step 29 is returned into reaction essence
It evaporates in tower 2, upper oil phase is transported in the first treating column 13, is 5% ~ 10% from the mass concentration of 13 overhead extraction of the first treating column
Dilute formaldehyde be sent into stripper 16 remove microextraction agent, the extractant produced from 13 tower of the first treating column be transported to storage tank into
Row recycles, and the material produced from 13 bottom of the first treating column tower is transported in the second treating column 14, is pushed up from the second treating column 14
Produce PODE2, it is transported in third treating column from the material of 14 bottom of towe of the second treating column extraction, overhead extraction is refined from third
Quality purity is not less than 99.9% metaformaldehyde, and PODE is produced from 15 bottom of third treating column3, with being adopted from the second treating column 14 top
Go out PODE2, it is transported to together after merging in byproduct recycling hydrolyzer 17, PODE2With PODE3Under the action of catalyst water water
Formaldehyde and methanol are hydrolyzed into, the material after hydrolysis is transported in step 2 and is recycled in autoclave Phase separation device 8；Described first is refined
Column overhead temperatures are 52 DEG C ~ 72 DEG C, and the first treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107
DEG C ~ 120 DEG C, the second treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, third
Treating column column bottom temperature is 132 DEG C ~ 145 DEG C, and the tower top pressure of the first treating column, the second treating column and third treating column is
5kpa ~ 30kpa, tower bottom pressure are 40kpa ~ 100kpa.
Embodiment 2
As shown in Fig. 1, the synthetic method of the present embodiment is：
Step 1: formaldehyde condensation polymer metaformaldehyde：That the formalin of raw material 60% ~ 75%% is transported to that dress carries catalyst
Pre-reaction is carried out in one fixed bed reactors 1, then the material after pre-reaction is sent into reactive distillation column 2, from reactive distillation
The material that 2 bottom of towe of tower comes out is delivered in reboiler 3 by pumping 4 parts after gasification in return reactive distillation column 2, remainder
It is delivered to and fills the second fixed bed main reactor A 5 for carrying catalyst and carry out polycondensation reaction in B 6, the reaction after polycondensation reaction
Material return to reactive distillation column 2 in, so recycle, produced from reactive distillation column 2 unreacted 20% ~ 25% formaldehyde it is water-soluble
Liquid, material of the overhead extraction containing metaformaldehyde.The catalyst is rare-earth element modified strongly acidic styrene's cation
Exchanger resin；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
It is transported in autoclave Phase separation device 8 after 7 condensations, pre-extracted split-phase is carried out using extractant, obtain lower floor's water phase and upper strata oil
Phase carries out quintessence with extractant and takes split-phase, obtains lower floor lower water is mutually transported to by pump 10 in bundle pipe type extractor 9
Water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of bundle pipe type extractor described in step 29 is returned into reaction essence
It evaporates in tower 2, upper oil phase is transported in the first treating column 13, is 5% ~ 10% from the mass concentration of 13 overhead extraction of the first treating column
Dilute formaldehyde be sent into stripper 16 remove microextraction agent, the extractant produced from 13 tower of the first treating column be transported to storage tank into
Row recycles, and the material produced from 13 bottom of the first treating column tower is transported in the second treating column 14, is pushed up from the second treating column 14
Produce PODE2, it is transported in third treating column from the material of 14 bottom of towe of the second treating column extraction, overhead extraction is refined from third
Quality purity is not less than 99.9% metaformaldehyde, and PODE is produced from 15 bottom of third treating column3, with being adopted from the second treating column 14 top
Go out PODE2, it is transported to together after merging in byproduct recycling hydrolyzer 17, PODE2With PODE3Under the action of catalyst water water
Formaldehyde and methanol are hydrolyzed into, the material after hydrolysis is transported in step 2 and is recycled in autoclave Phase separation device 8；Described first is refined
Column overhead temperatures are 52 DEG C ~ 72 DEG C, and the first treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107
DEG C ~ 120 DEG C, the second treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, third
Treating column column bottom temperature is 132 DEG C ~ 145 DEG C, and the tower top pressure of the first treating column, the second treating column and third treating column is
5kpa ~ 30kpa, tower bottom pressure are 40kpa ~ 100kpa.
Embodiment 3
As shown in Fig. 1, the synthetic method of the present embodiment is：
Step 1: formaldehyde condensation polymer metaformaldehyde：That the formalin of raw material 60% ~ 75%% is transported to that dress carries catalyst
Pre-reaction is carried out in one fixed bed reactors 1, then the material after pre-reaction is sent into reactive distillation column 2, from reactive distillation
The material that 2 bottom of towe of tower comes out is delivered in reboiler 3 by pumping 4 parts after gasification in return reactive distillation column 2, remainder
It is delivered to fill in the second fixed bed main reactor A 5 or B 6 for carrying catalyst and carries out polycondensation reaction, the reaction after polycondensation reaction
Material return to reactive distillation column 2 in, so recycle, produced from reactive distillation column 2 unreacted 20% ~ 30% formaldehyde it is water-soluble
Liquid, material of the overhead extraction containing metaformaldehyde.The catalyst is rare-earth element modified strongly acidic styrene's cation
Exchanger resin；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
It is transported in autoclave Phase separation device 8 after 7 condensations, pre-extracted split-phase is carried out using extractant, obtain lower floor's water phase and upper strata oil
Phase carries out quintessence with extractant and takes split-phase, obtains lower floor lower water is mutually transported to by pump 10 in bundle pipe type extractor 9
Water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of bundle pipe type extractor described in step 29 is returned into reaction essence
It evaporates in tower 2, upper oil phase is transported in the first treating column 13, is 5% ~ 10% from the mass concentration of 13 overhead extraction of the first treating column
Dilute formaldehyde be sent into stripper 16 remove microextraction agent, the extractant produced from 13 tower of the first treating column be transported to storage tank into
Row recycles, and the material produced from 13 bottom of the first treating column tower is transported in the second treating column 14, is pushed up from the second treating column 14
Produce PODE2, it is transported in third treating column from the material of 14 bottom of towe of the second treating column extraction, overhead extraction is refined from third
Quality purity is not less than 99.9% metaformaldehyde, and PODE is produced from 15 bottom of third treating column3, with being adopted from the second treating column 14 top
Go out PODE2, it is transported to together after merging in byproduct recycling hydrolyzer 17, PODE2With PODE3Under the action of catalyst water water
Formaldehyde and methanol are hydrolyzed into, the material after hydrolysis is transported in step 2 and is recycled in autoclave Phase separation device 8；Described first is refined
Column overhead temperatures are 52 DEG C ~ 72 DEG C, and the first treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107
DEG C ~ 120 DEG C, the second treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, third
Treating column column bottom temperature is 132 DEG C ~ 145 DEG C, and the tower top pressure of the first treating column, the second treating column and third treating column is
5kpa ~ 30kpa, tower bottom pressure are 40kpa ~ 100kpa.
As shown in Fig. 1, the synthetic method of the present embodiment is：
Step 1: formaldehyde condensation polymer metaformaldehyde：That the formalin of raw material 60% ~ 75%% is transported to that dress carries catalyst
Pre-reaction is carried out in one fixed bed reactors 1, then the material after pre-reaction is sent into reactive distillation column 2, from reactive distillation
The material that 2 bottom of towe of tower comes out is delivered in reboiler 3 by pumping 4 parts after gasification in return reactive distillation column 2, remainder
It is delivered to fill in the second fixed bed main reactor A 5 or B 6 for carrying catalyst and carries out polycondensation reaction, the reaction after polycondensation reaction
Material return to reactive distillation column 2 in, so recycle, produced from reactive distillation column 2 unreacted 25% ~ 30% formaldehyde it is water-soluble
Liquid, material of the overhead extraction containing metaformaldehyde.The catalyst is rare-earth element modified strongly acidic styrene's cation
Exchanger resin；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
It is transported in autoclave Phase separation device 8 after 7 condensations, extraction split-phase is carried out using extractant, obtains lower floor's water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of the device of autoclave Phase separation described in step 28 is returned into reaction essence
It evaporates in tower 2, upper oil phase is transported in the first treating column 13, is 5% ~ 10% from the mass concentration of 13 overhead extraction of the first treating column
Dilute formaldehyde be sent into stripper 16 remove microextraction agent, the extractant produced from 13 tower of the first treating column be transported to storage tank into
Row recycles, and the material produced from 13 bottom of the first treating column tower is transported in the second treating column 14, is pushed up from the second treating column 14
Produce PODE2, it is transported in third treating column from the material of 14 bottom of towe of the second treating column extraction, overhead extraction is refined from third
Quality purity is not less than 99.9% metaformaldehyde, and PODE is produced from 15 bottom of third treating column3, with being adopted from the second treating column 14 top
Go out PODE2, it is transported to together after merging in byproduct recycling hydrolyzer 17, PODE2With PODE3Under the action of catalyst water water
Formaldehyde and methanol are hydrolyzed into, the material after hydrolysis is transported in step 2 and is recycled in autoclave Phase separation device 8；Described first is refined
Column overhead temperatures are 52 DEG C ~ 72 DEG C, and the first treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107
DEG C ~ 120 DEG C, the second treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, third
Treating column column bottom temperature is 132 DEG C ~ 145 DEG C, and the tower top pressure of the first treating column, the second treating column and third treating column is
5kpa ~ 30kpa, tower bottom pressure are 40kpa ~ 100kpa.
Embodiment 5
As shown in Fig. 1, the synthetic method of the present embodiment is：
Step 1: formaldehyde condensation polymer metaformaldehyde：The formalin of raw material 60% ~ 75%% is transported in reactive distillation column 2, from
The material that 2 bottom of towe of reactive distillation column comes out is delivered in reboiler 3 by pumping 4 parts after gasification in return reactive distillation column 2,
Remainder, which is delivered to fill in the second fixed bed main reactor A 5 for carrying catalyst, carries out polycondensation reaction, after polycondensation reaction
Reaction mass is returned in reactive distillation column 2, is so recycled, and unreacted 25% ~ 35% formaldehyde is produced from reactive distillation column 2
Aqueous solution, material of the overhead extraction containing metaformaldehyde.The catalyst is sun for rare-earth element modified strongly acidic styrene
Ion exchange resin；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
It is transported in autoclave Phase separation device 8 after 7 condensations, extraction split-phase is carried out using extractant, obtains lower floor's water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of the device of autoclave Phase separation described in step 28 is returned into reaction essence
It evaporates in tower 2, upper oil phase is transported in the first treating column 13, is 5% ~ 10% from the mass concentration of 13 overhead extraction of the first treating column
Dilute formaldehyde be sent into stripper 16 remove microextraction agent, the extractant produced from 13 tower of the first treating column be transported to storage tank into
Row recycles, and the material produced from 13 bottom of the first treating column tower is transported in the second treating column 14, is pushed up from the second treating column 14
Produce PODE2, it is transported in third treating column from the material of 14 bottom of towe of the second treating column extraction, overhead extraction is refined from third
Quality purity is not less than 99.9% metaformaldehyde, and PODE is produced from 15 bottom of third treating column3, with being adopted from the second treating column 14 top
Go out PODE2, it is transported to together after merging in byproduct recycling hydrolyzer 17, PODE2With PODE3Under the action of catalyst water water
Formaldehyde and methanol are hydrolyzed into, the material after hydrolysis is transported in step 2 and is recycled in autoclave Phase separation device 8；Described first is refined
Column overhead temperatures are 52 DEG C ~ 72 DEG C, and the first treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and the second refined column overhead temperatures are 107
DEG C ~ 120 DEG C, the second treating column column bottom temperature is 128 DEG C ~ 138 DEG C, and it is 120 DEG C ~ 125 DEG C that third, which refines column overhead temperatures, third
Treating column column bottom temperature is 132 DEG C ~ 145 DEG C, and the tower top pressure of the first treating column, the second treating column and third treating column is
5kpa ~ 30kpa, tower bottom pressure are 40kpa ~ 100kpa.
Following table is the metaformaldehyde conversion ratio and steam consumption of embodiment 1 ~ 5
| Project | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Metaformaldehyde conversion ratio | ≥ 80% | ≥75% | ≥70% | ≥65% | ≥60% |
| Consume quantity of steam | ≤ 3.5 t/t | ≤ 4.0 t/t | ≤ 4.5 t/t | ≤ 5.0 t/t | ≤ 5.5 t/t |
The above is only presently preferred embodiments of the present invention, and any restrictions are not done to the present invention, every according to invention skill
Any simple modification, change and the equivalent structure that art essence makees above example change, and still fall within the technology of the present invention
In the protection domain of scheme.
Claims (9)
1. the method that formaldehyde prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying, which is characterized in that this method includes
Following steps：
Step 1: formaldehyde condensation polymer metaformaldehyde：The formalin of raw material 60%~75%% is transported to dress and has carried catalyst
The first fixed bed reactors in carry out pre-reaction, then by after pre-reaction material be sent into reactive distillation column in, from reaction essence
It evaporates the material that tower bottom of towe comes out to be delivered in reboiler after gasification in return reactive distillation column by pumping a part, remainder is defeated
It send in the second fixed bed main reactor A and B for carrying catalyst to dress and carries out polycondensation reaction, the reaction mass after polycondensation reaction returns
It returns in reactive distillation column, by steam and the nitrogen rectifying after heating and air lift, so recycles, produced not from reactive distillation column
15%~35% formalin of reaction, material of the overhead extraction containing metaformaldehyde.The catalyst is rare earth element
Modified strongly acidic styrene type cation exchange resin；
Step 2: metaformaldehyde extraction and separation：By material of the overhead extraction described in step 1 containing metaformaldehyde, condensed device
Autoclave Phase separation device is transported to after condensation, pre-extracted split-phase is carried out using extractant, obtains lower floor's water phase and upper oil phase,
It lower floor's water phase is transported to bundle pipe type extractor carries out quintessence with extractant and take split-phase, obtain lower floor's water phase and upper oil phase；
Step 3: metaformaldehyde rectifying detaches：Lower floor's water phase of bundle pipe type extractor described in step 2 is returned into reaction essence
Evaporate in tower, the inert gas after adding in 1~3 burst of heating at reactive distillation column lower curtate or middle part, improve rectifying and steam stripping efficiency and
The generation of side reaction, upper oil phase are transported in the first treating column, from the mass concentration of the first treating column overhead extraction for 5%~
10% dilute formaldehyde is sent into stripper removal microextraction agent, the extractant produced from the first treating column tower be transported to storage tank into
Row recycles, and the material produced from the first treating column bottom of towe is transported in the second treating column, from the second refined overhead extraction
PODE2, it is transported in third treating column from the material of the second treating column bottom of towe extraction, the quality that overhead extraction is refined from third is pure
Metaformaldehyde of the degree not less than 99.9% produces PODE from third treating column bottom3, and from the second refined overhead extraction PODE2, close
It is transported to together after and in byproduct recycling hydrolyzer, PODE2With PODE3Be hydrolyzed under the action of catalyst and water formaldehyde with
Methanol, the material after hydrolysis are transported to autoclave Phase separation device in step 2 and recycle；It is 52 to be confused the first refined column overhead temperatures
DEG C~72 DEG C, the first treating column column bottom temperature is 128 DEG C~138 DEG C, and the second refined column overhead temperatures are 107 DEG C~120 DEG C, the
Two treating column column bottom temperatures are 128 DEG C~138 DEG C, and it is 120 DEG C~125 DEG C that third, which refines column overhead temperatures, third treating column tower
Bottom temperature is 132 DEG C~145 DEG C, the tower top pressure of the first treating column, the second treating column and third treating column be 5kpa~
30kpa, tower bottom pressure are 40kpa~100kpa.
2. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, the first fixed bed pre-reactor setting-up point described in step 1 is 90 DEG C~130 DEG C, and reaction pressure is
2.0Mpa~8.0Mpa；Second fixed bed main reactor A described in step 1 is 90 DEG C~130 DEG C with B polycondensation reactions temperature, instead
It is 80kpa~200kpa to answer pressure；Reactive distillation pressure tower described in step 1 is 5kpa~50kpa, and tower top temperature is 90 DEG C
~110 DEG C, column bottom temperature is 100 DEG C~120 DEG C, and reflux ratio is 1.0~3.0.
3. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, the sieve plate of reactive distillation column overhead described in step 1 number is 5 pieces~30 pieces, and bottom of towe sieve plate number is 5 pieces~30 pieces, tower
The number of plies of middle packed bed is 2 layers~8 layers.
4. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
Be characterized in that, the device of autoclave Phase separation described in step 2 extraction temperature be 60 DEG C~80 DEG C, extracting pressure for 10kpa~
90kpa, density are 0.890~0.995ppm, and interface is 30 ± 5%；The extraction temperature of bundle pipe type extractor described in step 2
It it is 70 DEG C~95 DEG C, extracting pressure is 10kpa~90kpa, and density is 0.890~0.995ppm, and interface is 30 ± 5%.
5. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, extractant described in step 2 is selected from:In benzene, dichloromethane, a fluorine dichloroethanes, dimethoxym ethane extractant at least
It is a kind of.
6. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, the inert gas after heating described in step 3, inert gas is nitrogen or argon gas, and inert gas heating temperature is 70
DEG C~120 DEG C, flow is according to 0.1~20 times of adjustment of production capacity.
7. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, the sieve plate number of first rectifying column, Second distillation column and third distillation column described in step 3 is 30 pieces~75 pieces.
8. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, passes through air lift from dilute formaldehyde that the mass concentration of the first treating column overhead extraction is 5%~10% described in step 3
The extractant of in component 3%~6% methyl formate and 100~500ppm are proposed to convey by tower using inert gas from tower overhead gas
Generation Steam Recovery is burned to incinerator to apply mechanically.
9. the method that formaldehyde according to claim 1 prepares metaformaldehyde through fixed bed reaction, boundling extraction, rectifying,
It is characterized in that, the preparation method of rare-earth element modified strongly acidic styrene type cation exchange resin described in step 1 is：
By the alkali formula cerous nitrate aqueous solution that lanthanum nitrate aqueous solution and mass concentration that mass concentration is 1%~5% are 1%~5% according to
The mass ratio of lanthanum nitrate and alkali formula cerous nitrate is (1~2):1 ratio is uniformly mixed, then by strongly acidic styrene's cation
Exchanger resin is placed in immersion 7h~9h in mixed solution, and soaking temperature is controlled at 80 DEG C~110 DEG C, by the strong acid after immersion
Property styrene type cation exchange resin, which is placed in filter centrifugal, to be filtered, then by strongly acidic styrene's cation after filtering
Exchanger resin is placed in vacuum desiccator, is 80 DEG C~90 DEG C in temperature, vacuum degree is dried extremely under conditions of being 1kPa~2kPa
Water content is not more than 0.1%, obtains rare-earth element modified strongly acidic styrene type cation exchange resin.
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| CN109277056A (en) * | 2018-11-15 | 2019-01-29 | 凯瑞环保科技股份有限公司 | Azeotropic catalytic tower |
| CN110467595A (en) * | 2019-08-26 | 2019-11-19 | 江苏道尔顿石化科技有限公司 | A kind of no sulfuric acid process metaformaldehyde synthesizer and its synthesis route |
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| CN109277056B (en) * | 2018-11-15 | 2024-04-16 | 凯瑞环保科技股份有限公司 | Azeotropic catalytic reaction tower |
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| CN112237749A (en) * | 2020-06-11 | 2021-01-19 | 鄂尔多斯应用技术学院 | Device and method for synthesizing trioxymethylene by rectifying through salt effect reaction |
| CN113582967A (en) * | 2021-08-18 | 2021-11-02 | 苏州双湖化工技术有限公司 | Device and method for preparing trioxymethylene |
| CN114591287A (en) * | 2022-03-09 | 2022-06-07 | 赛鼎工程有限公司 | Process for synthesizing and concentrating trioxymethylene |
| CN114591287B (en) * | 2022-03-09 | 2024-03-22 | 赛鼎工程有限公司 | Process for synthesizing and concentrating trioxymethylene |
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