CN107417662A - A kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower - Google Patents
A kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower Download PDFInfo
- Publication number
- CN107417662A CN107417662A CN201710532957.4A CN201710532957A CN107417662A CN 107417662 A CN107417662 A CN 107417662A CN 201710532957 A CN201710532957 A CN 201710532957A CN 107417662 A CN107417662 A CN 107417662A
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- CN
- China
- Prior art keywords
- extractive reaction
- tower
- metaformaldehyde
- extractive
- benzene
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 74
- 239000007788 liquid Substances 0.000 title claims abstract description 25
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000000034 method Methods 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 239000002253 acid Substances 0.000 title claims abstract description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims abstract description 69
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 66
- 238000000605 extraction Methods 0.000 claims abstract description 24
- 239000012074 organic phase Substances 0.000 claims abstract description 12
- 239000003377 acid catalyst Substances 0.000 claims abstract description 11
- 239000008346 aqueous phase Substances 0.000 claims abstract description 11
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 4
- 230000008676 import Effects 0.000 claims description 10
- 239000000945 filler Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 238000012856 packing Methods 0.000 claims description 4
- 238000006116 polymerization reaction Methods 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 229920006324 polyoxymethylene Polymers 0.000 claims 1
- 238000009835 boiling Methods 0.000 abstract description 3
- 238000005265 energy consumption Methods 0.000 abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 238000005829 trimerization reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D323/00—Heterocyclic compounds containing more than two oxygen atoms as the only ring hetero atoms
- C07D323/04—Six-membered rings
- C07D323/06—Trioxane
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0426—Counter-current multistage extraction towers in a vertical or sloping position
- B01D11/043—Counter-current multistage extraction towers in a vertical or sloping position with stationary contacting elements, sieve plates or loose contacting elements
Abstract
The invention discloses a kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower, using liquid acid catalyst, it is polymerize to obtain metaformaldehyde in extractive reaction unit by top-down formalin, and extracted with benzene extractant from bottom to top simultaneously, finally produced because the organic phase that full liquid is operated after causing unit extractions at different levels rises to upper strata extractive reaction unit from column plate hole, and unreacted formaldehyde aqueous phase continues to polymerize and extracted into lower unit.Boiling is carried out to reaction product without extra steam in the present invention, reduces steam energy consumption；The multilevel hierarchy that the present invention is moved by counter current flow simultaneously reacts, and substantially increases the conversion ratio of formaldehyde.
Description
Technical field
The invention belongs to the industrial manufacture process method and apparatus of field of energy and chemical technology, more particularly to metaformaldehyde.
Background technology
The production method of metaformaldehyde is all by the way that 37% formalin is entered at a temperature of 56 DEG C or so at present
Row concentrate obtains 60wt% concentrated formaldehyde as raw material, then using sulfuric acid as catalyst, polymerize at 101~106 DEG C, and lead to
Cross continuous boiling and obtain metaformaldehyde product.
Need to expend substantial amounts of steam under the technique and reacted and separated, and the conversion ratio of formaldehyde is not more than
30%, also need big by multi-stage reacting kettle back flow reaction, the input of equipment.
The content of the invention
Goal of the invention：For above-mentioned existing problem and shortage, it is an object of the invention to provide a kind of liquid acid type
Metaformaldehyde manufacturing technique method and extractive reaction tower, there is the formaldehyde conversion more than 45%, and there is course of reaction steam
The features such as consumption is small, and equipment investment is small.
Technical scheme：In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：A kind of life of metaformaldehyde
Production. art method, comprises the following steps：
(1) entered using benzene or benzene derivate as extractant from extractive reaction tower bottom；
(2) by formalin and liquid acid catalyst that mass concentration ratio is 50~85% respectively from extractive reaction tower
The extractive reaction unit that top is sent into extractive reaction tower, formalin are answering the extractive reaction in tower with liquid acid catalyst
Unit contact carries out polymerisation, and enter benzene extractant from bottom occurs extractive reaction with polymeric reaction product simultaneously, obtains
Organic phase containing metaformaldehyde, and the aqueous phase containing formaldehyde and liquid acid catalyst, the extractive reaction tower of this reaction is that full liquid is grasped
Make；
(3) step (2) obtains organic phase is separated from the water to be gradually enriched with to upper strata, and from the pedal of extractive reaction unit
On through hole rise in the extractive reaction unit of upper strata, finally from the overhead extraction of extractive reaction tower；The aqueous phase is then from extraction
The downspout of reaction tower passes through multi-step polymerization and extractive reaction by the extractive reaction unit of lower floor step by step, and is produced from bottom of towe；
(4) separated again by rectifying from the organic phase product of extractive reaction column overhead extraction, obtain extractant benzene and trimerization
Formaldehyde products.
Preferably, the reaction temperature of the extractive reaction tower is 110 ± 5 DEG C, the flow of extractant benzene for 0.3~
1.5m/s。
Preferably, the extraction pressure of the extractive reaction column overhead is 0~0.5MPa.
Present invention also offers a kind of extractive reaction tower for being used to produce metaformaldehyde, including tower body, tower body lower end is located at
Extractant import, be located at tower body top formalin import and liquid acid import, be located at the top of tower body reactant extraction
Mouth, the aqueous phase extraction mouth for being located at tower body bottom and the multitple extraction reaction member set gradually from bottom to up, the extractant enter
Mouth is provided with a distributor, dividing plate with holes is provided between adjacent extractive reaction unit, the dividing plate is provided with downspout, described
Filler is provided with extractive reaction unit；The top of the tower body, which is provided with, stands area.
Preferably, the stage casing of the tower body is provided with benzene quadratic distribution device.
Preferably, the filler is wire packing or perforated plate corrugated filler.
Beneficial effect：Compared with prior art, two steps of the polymerization of metaformaldehyde and extract and separate are closed two by the present invention
For one, production efficiency is improved, and reduces subsequently refined difficulty；The present invention uses liquid acid catalyst, by from top to bottom
Formalin polymerize to obtain metaformaldehyde in extractive reaction unit, and carried out with benzene extractant from bottom to top simultaneously
Extraction, because full liquid operates the organic phase after causing units at different levels extraction, from column plate hole to rise to upper strata extractive reaction unit final
Extraction, and unreacted formaldehyde aqueous phase continues to polymerize and extracted into lower unit.Without extra steam to reaction in the present invention
Product carries out boiling, reduces steam energy consumption；The multilevel hierarchy that the present invention is moved by counter current flow simultaneously reacts, and substantially increases first
The conversion ratio of aldehyde.
Brief description of the drawings
Fig. 1 is the structural representation of extractive reaction tower of the present invention.
Wherein, tower body 1, column plate 2, filler 3, primary distributor 4, two level distributor 5, standing area 6.
Embodiment
Below in conjunction with the accompanying drawings and specific embodiment, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate
The present invention rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are each to the present invention's
The modification of the kind equivalent form of value falls within the application appended claims limited range.
As shown in figure 1, the extractive reaction tower for being used to produce metaformaldehyde of the present invention, tower body lower end sets extractant import
Mouth is produced with the aqueous phase containing dilute formaldehyde, the top of tower body is provided with formalin import and liquid acid import, and the top of tower body is set
Reaction product produces mouth.Tower body is internally provided with multitple extraction reaction member, and wire packing is provided with extractive reaction unit
Carrier, every grade of extractive reaction unit is both provided with column plate, and the column plate sets the multiple through holes passed through for organic phase, while column plate
On be additionally provided with downspout the aqueous phase of upper strata extractive reaction unit can be enable to pass through the extractive reaction list for entering lower floor from downspout
Continue to react in member；And set at the top of tower body and stand area, the extractant entrance connection fraction of liquid one of the bottom of tower body
Cloth device.
The extractive reaction tower of the present invention is that full liquid operates, and extractant benzene enters in tower to upstream from the primary distributor of bottom of towe
It is dynamic, while the formalin and liquid acid catalyst being sent into from tower top flow the filler in extractive reaction unit downwardly together
Polymerisation occurs in section, when formaldehyde and liquid acid catalyst have higher contact area and stop during the effect of packing section
Between, so as to improve the conversion ratio of formaldehyde.The metaformaldehyde TOX products that polymerisation obtains are not soluble in water and density is less than water,
Remaining benzene extractant risen is obtained by extraction the organic phase containing benzene and TOX and is in the water containing formaldehyde and liquid acid catalyst
The upper strata of phase, the organic phase on upper strata are upward through constantly to tower top end under the flowing for the material sent constantly into from the through hole of column plate
The flowing of standing area, and produce the organic phase on upper strata after being stood by standing area and be sent to follow-up treating column from extraction mouth and carry out
The isolated metaformaldehyde product of rectifying and benzene extractant, the circulation of benzene extractant can continue with extractive reaction tower.And lower floor
The aqueous phase containing formaldehyde and liquid catalyst by downspout enter lower floor's extractive reaction unit further polymerization and extraction,
Last dilute formalin produces from bottom of towe.Present invention control extractant benzene desired flow is in 0.8~1.0m/s, the formaldehyde of entrance
Solution concentration is 65~85wt%, and reaction temperature is controlled at 110 ± 5 DEG C, and the extraction pressure of tower top is 0.3MPa.
Preferably, the two level distributor of extractant benzene is set in the stage casing of tower body, and carrying out quadratic distribution to benzene carries
The utilization rate of high extraction efficiency and benzene, and then follow-up separating energy consumption and difficulty can be reduced, so as to improve trimerization first of the present invention
The market competitiveness of aldehyde.
Claims (6)
1. a kind of manufacturing technique method of metaformaldehyde, comprises the following steps：
(1) entered using benzene or benzene derivate as extractant from extractive reaction tower bottom；
(2) by formalin and liquid acid catalyst that mass concentration ratio is 50~85% respectively from the middle and upper part of extractive reaction tower
The extractive reaction unit being sent into extractive reaction tower, formalin are answering the extractive reaction unit in tower with liquid acid catalyst
Contact carries out polymerisation, and enter benzene extractant from bottom occurs extractive reaction with polymeric reaction product simultaneously, obtains containing three
The organic phase of polyformaldehyde, and the aqueous phase containing formaldehyde and liquid acid catalyst, the extractive reaction tower of this reaction is that full liquid operates；
(3) organic phase that step (2) obtains is separated from the water gradually to upper strata enrichment, and from the pedal of extractive reaction unit
Through hole is risen in the extractive reaction unit of upper strata, finally from the overhead extraction of extractive reaction tower；The aqueous phase is then from extractive reaction
The downspout of tower passes through multi-step polymerization and extractive reaction by the extractive reaction unit of lower floor step by step, and is produced from bottom of towe；
(4) separated again by rectifying from the organic phase product of extractive reaction column overhead extraction, obtain extractant benzene and metaformaldehyde
Product.
2. the manufacturing technique method of metaformaldehyde according to claim 1, it is characterised in that：The reaction of the extractive reaction tower
Temperature is 110 ± 5 DEG C, and the flow of extractant benzene is 0.3~1.5m/s.
3. the manufacturing technique method of metaformaldehyde according to claim 1, it is characterised in that：The extractive reaction column overhead
Extraction pressure is 0~0.5MPa.
A kind of 4. extractive reaction tower for being used to produce metaformaldehyde, it is characterised in that：Including tower body, the extraction of tower body lower end is located at
Agent import, the formalin import for being located at tower body top and liquid acid import, the reactant being located at the top of tower body extraction mouth, it is located at
The aqueous phase extraction mouth of tower body bottom and the multitple extraction reaction member set gradually from bottom to up, the extractant import are provided with one
Secondary distributor, dividing plate with holes is provided between adjacent extractive reaction unit, the dividing plate is provided with downspout, the extractive reaction
Filler is provided with unit；The top of the tower body, which is provided with, stands area.
5. the extractive reaction tower of metaformaldehyde is produced according to claim 4, it is characterised in that：The stage casing of the tower body is provided with
Benzene quadratic distribution device.
6. the extractive reaction tower of metaformaldehyde is produced according to claim 4, it is characterised in that：The filler is wire packing
Or perforated plate corrugated filler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532957.4A CN107417662A (en) | 2017-07-03 | 2017-07-03 | A kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532957.4A CN107417662A (en) | 2017-07-03 | 2017-07-03 | A kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107417662A true CN107417662A (en) | 2017-12-01 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710532957.4A Pending CN107417662A (en) | 2017-07-03 | 2017-07-03 | A kind of liquid acid type metaformaldehyde manufacturing technique method and extractive reaction tower |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109011694A (en) * | 2018-09-21 | 2018-12-18 | 山东泓达生物科技有限公司 | A kind of novel energy-conserving composite stirring extraction tower |
| CN110540177A (en) * | 2019-10-12 | 2019-12-06 | 山东省化工研究院 | method for preparing hydroxylamine salt through continuous multistage reaction |
| CN111111601A (en) * | 2019-12-30 | 2020-05-08 | 西安建筑科技大学 | Two-stage reactor and method for preparing furfural |
| CN113862117A (en) * | 2021-10-26 | 2021-12-31 | 华南理工大学 | Device and method for splitting chiral substance by multi-liquid-phase system continuous enzymatic method |
Citations (4)
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| DE3571617D1 (en) * | 1984-06-08 | 1989-08-24 | Hoechst Ag | Process for the recovery of trioxan from aqueous solutions by high-pressure extraction |
| CN1136812A (en) * | 1993-12-06 | 1996-11-27 | 赫希斯特人造丝公司 | Process for production of trioxane from formaldehyde |
| CN101918388A (en) * | 2007-12-19 | 2010-12-15 | 巴斯夫欧洲公司 | Method for the production of crude trioxane |
| CN203947051U (en) * | 2014-07-09 | 2014-11-19 | 山东辰信新能源有限公司 | A kind of device of preparing trioxymethylene |
-
2017
- 2017-07-03 CN CN201710532957.4A patent/CN107417662A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3571617D1 (en) * | 1984-06-08 | 1989-08-24 | Hoechst Ag | Process for the recovery of trioxan from aqueous solutions by high-pressure extraction |
| CN1136812A (en) * | 1993-12-06 | 1996-11-27 | 赫希斯特人造丝公司 | Process for production of trioxane from formaldehyde |
| CN101918388A (en) * | 2007-12-19 | 2010-12-15 | 巴斯夫欧洲公司 | Method for the production of crude trioxane |
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Non-Patent Citations (1)
| Title |
|---|
| 申奕主编: "《化工单元操作技术》", 化学工业出版社, pages: 228 - 292 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109011694A (en) * | 2018-09-21 | 2018-12-18 | 山东泓达生物科技有限公司 | A kind of novel energy-conserving composite stirring extraction tower |
| CN110540177A (en) * | 2019-10-12 | 2019-12-06 | 山东省化工研究院 | method for preparing hydroxylamine salt through continuous multistage reaction |
| CN111111601A (en) * | 2019-12-30 | 2020-05-08 | 西安建筑科技大学 | Two-stage reactor and method for preparing furfural |
| CN113862117A (en) * | 2021-10-26 | 2021-12-31 | 华南理工大学 | Device and method for splitting chiral substance by multi-liquid-phase system continuous enzymatic method |
| CN113862117B (en) * | 2021-10-26 | 2024-03-12 | 华南理工大学 | Device and method for separating chiral substances by multi-liquid-phase system continuous enzyme method |
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