CN107474036A - A kind of metaformaldehyde manufacturing technique method and extractive reaction tower - Google Patents
A kind of metaformaldehyde manufacturing technique method and extractive reaction tower Download PDFInfo
- Publication number
- CN107474036A CN107474036A CN201710532950.2A CN201710532950A CN107474036A CN 107474036 A CN107474036 A CN 107474036A CN 201710532950 A CN201710532950 A CN 201710532950A CN 107474036 A CN107474036 A CN 107474036A
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- China
- Prior art keywords
- extractive reaction
- metaformaldehyde
- extractive
- reaction
- tower
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Links
- 238000006243 chemical reaction Methods 0.000 title claims abstract description 90
- BGJSXRVXTHVRSN-UHFFFAOYSA-N 1,3,5-trioxane Chemical compound C1OCOCO1 BGJSXRVXTHVRSN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000000605 extraction Methods 0.000 claims abstract description 29
- 239000011973 solid acid Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 13
- 239000000376 reactant Substances 0.000 claims abstract description 4
- 230000008676 import Effects 0.000 claims abstract description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 60
- 239000012074 organic phase Substances 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 239000008346 aqueous phase Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000945 filler Substances 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000007171 acid catalysis Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000000926 separation method Methods 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
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000126 substance Substances 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
-
- 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
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/04—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds
- B01J8/0403—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal
- B01J8/0407—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds
- B01J8/0411—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds the fluid passing successively through two or more beds the fluid flow within the beds being predominantly horizontal through two or more cylindrical annular shaped beds the beds being concentric
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Fluid Mechanics (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of metaformaldehyde manufacturing technique method and extractive reaction tower, wherein extractive reaction tower includes being located at the extractant import of bottom, the reactant extraction mouth for being located at top and the multitple extraction reaction member set gradually from bottom to up, adjacent extractive reaction unit is separated by band hole column plate, and downspout is additionally provided between adjacent extractive reaction unit, it is additionally provided with solid acid catalyst in the extractive reaction unit.The present invention has formaldehyde conversion more than 45%, and small with course of reaction steam consumption, the features such as under equipment investment.
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 metaformaldehyde
Manufacturing technique method and extractive reaction tower, there is the formaldehyde conversion more than 45%, and it is small with course of reaction steam consumption,
The features such as under equipment investment.
Technical scheme：In order to solve the above-mentioned technical problem, the present invention uses following technical scheme：One kind production metaformaldehyde
Extractive reaction tower, including be located at the extractant import of bottom, the reactant extraction that is located at top and is set mouth successively from bottom to up
The multitple extraction reaction member put, adjacent extractive reaction unit are separated by band hole column plate, and between adjacent extractive reaction unit
Downspout is additionally provided with, solid acid catalyst is additionally provided with the extractive reaction unit.
Preferably, the solid acid catalyst is located at the space between two neighboring column plate.
Preferably, the solid acid filler is located in downspout.
Preferably, the extractive reaction unit includes the extraction section being located in extractive reaction tower and the reaction being located at outside tower
Plug-in, plug-in circulated by circulating pump and pipeline with corresponding extraction section of the reaction is connected, and the solid acid filler is located at instead
Answer in plug-in.
Present invention also offers a kind of manufacturing technique method of metaformaldehyde, comprise the following steps：
(1) entered using benzene or benzene derivate as extractant from extractive reaction tower bottom；
(2) formalin that mass concentration ratio is 50~85% is entered from the middle and upper part of extractive reaction tower, extractive reaction
There is multitple extraction reaction member, formaldehyde polymerisation under solid acid catalysis obtains trimerization in every grade of extractive reaction unit in tower
Formaldehyde reaction product, at the same time the organic phase containing benzene and metaformaldehyde is obtained by extraction in metaformaldehyde reaction product and benzene
And the aqueous phase containing the complete formaldehyde of unreacted, the extractive reaction tower of this reaction is that full liquid operates；
(3) organic phase is separated from the water is gradually enriched with to upper strata, and from the aperture on the column plate of extractive reaction unit
Rise in the extractive reaction unit of upper level, finally from the overhead extraction of extractive reaction tower；The aqueous phase is then from extractive reaction
The downspout of tower flows to bottom of towe step by step；
(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.
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 solid acid catalyst, by from top to bottom
Formalin polymerize to obtain metaformaldehyde in extractive reaction unit, and carried out with benzene catalyst 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；
Fig. 2 is the structural representation of extractive reaction unit in extractive reaction tower in embodiment 1；
Fig. 3 is the structural representation of extractive reaction unit in extractive reaction tower in embodiment 2.
Wherein extractive reaction tower 1, column plate 2, downspout 3, solid acid catalyst 4, distributor 5.
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.
Embodiment 1
As shown in Fig. 1~2, extractive reaction tower of the invention includes tower body, sets multitple extraction to react from bottom to up in tower
Unit, separated between adjacent by column plate, column plate is provided with multiple through holes, and downspout is provided with every layer of column plate.Adjacent towers
Solid acid packing layer is fixedly mounted in extractive reaction section of the space as extractive reaction unit between plate, the top in this section.
And bottom of towe is provided with distributor and is connected with the delivery pipe of extractant benzene, tower top is provided with reactant extraction mouth and is connected with extraction pipe,
Tower top sets the formaldehyde delivery port entered for formalin.Benzene enters tower after bottom of towe entrance by liquid distribution trough distribution
It is interior, 20~35% dilute formaldehyde can be finally produced from bottom of towe.
The extractive reaction tower of the present invention is that full liquid operates, and extractant benzene enters in tower from tower distributor to be flowed up, together
When the formalin be sent into from tower top flow downward and contacted in extractive reaction unit with solid acid filler at 110 DEG C or so
Lower generation polymerisation obtains metaformaldehyde product, and metaformaldehyde product product occurs extraction with extractant benzene and forms organic phase.
Float on the upper strata of the aqueous phase containing formaldehyde because organic phase density is light, by control the suitable flow of benzene extractant (generally 0.3~
1.5m/s) so as to controlling the organic phase on upper strata to be ascended into from the through hole of column plate in the extractive reaction unit on upper strata；And not
The formalin reacted is given birth to polymerisation into the extractive reaction unit relaying supervention of lower floor from downspout and extracted, from
And multistage continuous polymerization and extractive reaction are formed, so as to make the conversion ratio of formalin up to 46.2%.From overhead extraction
Metaformaldehyde and the organic phase of benzene obtaining the target product of metaformaldehyde by rectifying separation and purification.Because the present invention only needs
Required reaction temperature in maintenance reaction tower, boiling separation is carried out without extra steam consumption.In the present embodiment, solid acid
Catalyst is located between column plate.In order that thing liquid flow equilibrium, the feed rate of bottom of towe catalyst benzene is controlled in 0.8~1.0m/s
Flow velocity, and the extraction pressure of tower top is preferably 0.3MPa.
Embodiment 2
In Fig. 3 the present embodiment, solid acid catalyst is directly arranged in downspout, formalin is from upper strata extractive reaction
When unit flows through downspout, contacted with solid acid catalyst and polymerisation occurs.
Embodiment 3
In the present embodiment, by setting plug-in form outside tower, solid acid catalyst is located in plug-in reactor, on
The formalin that layer declines is sent into outward appearance reactor by circulating pump and pipeline and carries out polymerisation, the product of polymerisation
After sending back to, into lower floor's extractive reaction unit, organic phase rises, and aqueous phase declines.It can ensure that formalin is being urged in the embodiment
Residence time in agent, improve reaction conversion ratio.
Claims (7)
- A kind of 1. extractive reaction tower for producing metaformaldehyde, it is characterised in that：Including being located at the extractant import of bottom, being located at top The reactant extraction mouth in portion and the multitple extraction reaction member set gradually from bottom to up, adjacent extractive reaction unit passes through with holes Column plate is separated, and downspout is additionally provided between adjacent extractive reaction unit, and being additionally provided with solid acid in the extractive reaction unit urges Agent.
- 2. extractive reaction tower according to claim 4, it is characterised in that：The solid acid catalyst is located at two neighboring column plate Between space.
- 3. extractive reaction tower according to claim 4, it is characterised in that：The solid acid filler is located in downspout.
- 4. extractive reaction tower according to claim 4, it is characterised in that：The extractive reaction unit includes being located at extractive reaction Extraction section in tower and the reaction being located at outside tower are plug-in, and the reaction is plug-in to be followed by circulating pump and pipeline with corresponding extraction section Ring connects, and it is plug-in interior that the solid acid filler is located at reaction.
- 5. 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) formalin that mass concentration ratio is 50~85% is entered from the middle and upper part of extractive reaction tower, in extractive reaction tower With multitple extraction reaction member, formaldehyde polymerisation under solid acid catalysis obtains metaformaldehyde in every grade of extractive reaction unit Reaction product, at the same time metaformaldehyde reaction product and benzene be obtained by extraction the organic phase containing benzene and metaformaldehyde and Aqueous phase containing the complete formaldehyde of unreacted, the extractive reaction tower of this reaction is that full liquid operates；(3) organic phase is separated from the water is gradually enriched with to upper strata, and rises from the aperture on the column plate of extractive reaction unit Into the extractive reaction unit of upper level, finally from the overhead extraction of extractive reaction tower；The aqueous phase is then from extractive reaction tower Downspout flows to bottom of towe step by step；(4) separated again by rectifying from the organic phase product of extractive reaction column overhead extraction, obtain extractant benzene and metaformaldehyde Product.
- 6. 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.
- 7. 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532950.2A CN107474036A (en) | 2017-07-03 | 2017-07-03 | A kind of metaformaldehyde manufacturing technique method and extractive reaction tower |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710532950.2A CN107474036A (en) | 2017-07-03 | 2017-07-03 | A kind of metaformaldehyde manufacturing technique method and extractive reaction tower |
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| CN107474036A true CN107474036A (en) | 2017-12-15 |
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| CN201710532950.2A Pending CN107474036A (en) | 2017-07-03 | 2017-07-03 | A kind of metaformaldehyde manufacturing technique method and extractive reaction tower |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383082A (en) * | 2018-02-01 | 2018-08-10 | 北京凯瑞英科技有限公司 | Nitromethane hydrolysis prepares the by-product separator and method of hydroxylamine hydrochloride |
| CN110156747A (en) * | 2019-04-16 | 2019-08-23 | 天津大学 | A kind of partition wall reactive distillation manufacturing technique method and device for metaformaldehyde |
| CN112451993A (en) * | 2020-11-25 | 2021-03-09 | 中国石油化工股份有限公司 | Spray extraction equipment and solvent extraction method |
| CN114105937A (en) * | 2022-01-29 | 2022-03-01 | 中化学科学技术研究有限公司 | Trioxymethylene reaction method and production method thereof |
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| CN1087908A (en) * | 1992-08-04 | 1994-06-15 | 泛塑料株式会社 | The preparation method of trioxane |
| CN1136812A (en) * | 1993-12-06 | 1996-11-27 | 赫希斯特人造丝公司 | Process for production of trioxane from formaldehyde |
| CN106256822A (en) * | 2016-09-19 | 2016-12-28 | 江苏永大化工设备有限公司 | Methanol is through condensation, oxidation, polycondensation, the method for process synthesizing triformol |
-
2017
- 2017-07-03 CN CN201710532950.2A patent/CN107474036A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1087908A (en) * | 1992-08-04 | 1994-06-15 | 泛塑料株式会社 | The preparation method of trioxane |
| CN1136812A (en) * | 1993-12-06 | 1996-11-27 | 赫希斯特人造丝公司 | Process for production of trioxane from formaldehyde |
| CN106256822A (en) * | 2016-09-19 | 2016-12-28 | 江苏永大化工设备有限公司 | Methanol is through condensation, oxidation, polycondensation, the method for process synthesizing triformol |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108383082A (en) * | 2018-02-01 | 2018-08-10 | 北京凯瑞英科技有限公司 | Nitromethane hydrolysis prepares the by-product separator and method of hydroxylamine hydrochloride |
| CN108383082B (en) * | 2018-02-01 | 2020-10-16 | 北京凯瑞英科技有限公司 | Device and method for separating by-products generated in preparation of hydroxylamine hydrochloride by hydrolysis of nitromethane |
| CN110156747A (en) * | 2019-04-16 | 2019-08-23 | 天津大学 | A kind of partition wall reactive distillation manufacturing technique method and device for metaformaldehyde |
| CN110156747B (en) * | 2019-04-16 | 2023-05-23 | 天津大学 | Separation wall reaction rectification production process method and device for trioxymethylene |
| CN112451993A (en) * | 2020-11-25 | 2021-03-09 | 中国石油化工股份有限公司 | Spray extraction equipment and solvent extraction method |
| CN114105937A (en) * | 2022-01-29 | 2022-03-01 | 中化学科学技术研究有限公司 | Trioxymethylene reaction method and production method thereof |
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Application publication date: 20171215 |