CN219972045U - Aldehyde-containing wastewater treatment process device for methyl acrylate and methyl methacrylate production process - Google Patents
Aldehyde-containing wastewater treatment process device for methyl acrylate and methyl methacrylate production process Download PDFInfo
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- CN219972045U CN219972045U CN202320165855.4U CN202320165855U CN219972045U CN 219972045 U CN219972045 U CN 219972045U CN 202320165855 U CN202320165855 U CN 202320165855U CN 219972045 U CN219972045 U CN 219972045U
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- tower
- reaction
- methyl methacrylate
- methyl acrylate
- rectifying tower
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- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 24
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 title claims 7
- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 44
- 239000002351 wastewater Substances 0.000 claims abstract description 34
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000000605 extraction Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003054 catalyst Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 239000011973 solid acid Substances 0.000 claims description 6
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 3
- 125000002091 cationic group Chemical group 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 150000001299 aldehydes Chemical class 0.000 abstract description 7
- 238000005882 aldol condensation reaction Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 51
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 12
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 8
- 150000007524 organic acids Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 6
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 6
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 5
- 229940017219 methyl propionate Drugs 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 235000019260 propionic acid Nutrition 0.000 description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012856 packing Methods 0.000 description 3
- 238000000066 reactive distillation Methods 0.000 description 3
- JBEZRANSXKWFIF-UHFFFAOYSA-N CC=C(C(=O)O)C.COC(C=C)=O Chemical compound CC=C(C(=O)O)C.COC(C=C)=O JBEZRANSXKWFIF-UHFFFAOYSA-N 0.000 description 2
- 238000005575 aldol reaction Methods 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 2
- 235000005985 organic acids Nutrition 0.000 description 2
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- -1 methyl acrylate (methyl methacrylate) aldehyde Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The utility model discloses an aldehyde-containing wastewater treatment process device for methyl acrylate and methyl methacrylate production process, which comprises a layering device, a pre-reactor, a reaction rectifying tower and a rectifying tower, wherein the layering device is provided with an overflow plate and divides a space in a tank into a water phase area and an oil phase area, the oil phase area is connected with an inlet of the pre-reactor through a pipeline, the inlet of the pre-reactor is also provided with a methanol feeding pipe, an outlet of the pre-reactor is communicated with the middle part of the reaction rectifying tower, the top outlet of the reaction rectifying tower is connected with the rectifying tower, the bottom of the reaction rectifying tower is provided with a wastewater outlet, and the top and the bottom of the rectifying tower are respectively provided with a methylal extraction outlet and a product extraction outlet. The utility model can effectively separate the wastewater from the preparation of methyl acrylate or methyl methacrylate by aldol condensation, and meets the wastewater discharge standard.
Description
Technical Field
The utility model belongs to the technical field of energy and chemical industry, and particularly relates to an industrial wastewater treatment technology of a methyl acrylate (methyl methacrylate) aldol condensation method.
Background
With the development of the coal chemical industry, the production of high added value products such as methyl acrylate and methyl methacrylate by taking coal chemical products such as methyl acetate and formaldehyde as raw materials becomes a new research direction in recent years. Methyl acetate and formaldehyde are used as raw materials, and methyl acrylate can be generated through aldol reaction. Methyl propionate and formaldehyde are used as raw materials, and methyl methacrylate can be generated through aldol reaction. The existing patent reports the preparation of a reaction catalyst in the methyl acrylate (methyl methacrylate) aldehyde condensation process route, the existing catalyst is deeply researched, and the conversion rate, yield and other relevant properties of the catalyst meet the requirements of industrial production.
The aldol condensation reaction is affected by reaction balance, the conversion rate is lower, formaldehyde does not completely participate in the reaction, part of formaldehyde is returned to the reaction system after being recovered, and part of formaldehyde is finally in the wastewater and is difficult to treat due to higher formaldehyde concentration. Meanwhile, in the reaction process, due to the occurrence of hydrolysis side reaction, organic acids such as acetic acid, acrylic acid, propionic acid and the like are generated in the reaction products, and finally the organic acids also enter the wastewater, so that the wastewater treatment difficulty is increased, and meanwhile, the raw materials are lost. The conventional organic acid wastewater adopts a neutralization method and an oxidation method, so that materials are lost and cannot be recovered, and the treatment cost is increased.
The wastewater treatment is the difficulty of industrialization of methyl acrylate (methyl methacrylate) aldol condensation method, and no report is presented at present.
Disclosure of Invention
The utility model aims to: aiming at the problems and the defects existing in the prior art, the utility model aims to provide an aldehyde-containing wastewater treatment process device for a production process of methyl acrylate and methyl methacrylate, which can efficiently separate wastewater from the preparation of methyl acrylate or methyl methacrylate by aldol condensation and meet the wastewater discharge standard.
The technical scheme is as follows: in order to solve the technical problems, the utility model adopts the following technical scheme: the utility model provides a methyl acrylate and methyl methacrylate production technology contain aldehyde effluent treatment plant, includes layering ware, prereactor, reaction rectifying column and rectifying column, the layering ware is equipped with the overflow board and divide into water phase district and oil phase district with jar interior space, the oil phase district passes through the entry linkage of pipeline with prereactor, prereactor's entry still is equipped with the methyl alcohol and throws the material pipe, prereactor's export and reaction rectifying column's middle part intercommunication, reaction rectifying column's top of the tower exit linkage rectifying column, reaction rectifying column's tower bottom is equipped with the waste water export, and rectifying column's top of the tower and tower bottom are equipped with methylal outlet and product outlet respectively.
Preferably, the outlet of the oil phase zone of the delaminator is connected with a plurality of prereactors which are connected in series and/or in parallel.
Preferably, the middle part of the reaction rectifying tower is provided with a middle extraction port, the middle extraction port is connected with a plurality of side reactors connected in series and/or in parallel, and the outlet of the side reactor is circularly communicated with the middle part of the reaction rectifying tower.
Preferably, a catalyst bed layer is arranged in the reaction rectifying tower.
Preferably, the reactive rectifying tower adopts a plate tower or a packed tower and comprises a reaction section, a rectifying section and a stripping section, and the catalyst bed layer is arranged in the reaction section.
Preferably, the catalyst bed layer adopts a solid acid catalyst, and the solid acid catalyst is an acidic cationic resin, a zeolite molecular sieve catalyst, an alumina or silica supported acidic catalyst.
The beneficial effects are that: compared with the prior art, the method realizes the treatment of the wastewater containing aldehyde and acid through reactive distillation, converts formaldehyde into methylal, and removes formaldehyde from the wastewater. The organic acid in the wastewater is converted into methyl acetate (methyl acrylate and methyl propionate), so that the effective recovery of materials is realized. Formaldehyde in the wastewater is removed, methylal is generated, the raw material loss of the process is reduced, and the economy is improved. Meanwhile, the treated wastewater almost contains no formaldehyde and organic acid, so that the treatment cost of a subsequent sewage treatment device is reduced.
Drawings
FIG. 1 is a schematic diagram of the device for treating aldehyde-containing wastewater in the process of producing methyl acrylate and methyl methacrylate.
Wherein, the device comprises a layering device 1, a pre-reactor 2, a reaction rectifying tower 3, a lateral reactor 4, a rectifying tower 5, a reaction section 6, a rectifying section 7 and a stripping section 8.
Detailed Description
The present utility model is further illustrated in the accompanying drawings and detailed description which are to be understood as being merely illustrative of the utility model and not limiting of its scope, and various modifications of the utility model, which are equivalent to those skilled in the art upon reading the utility model, will fall within the scope of the utility model as defined in the appended claims.
In the process of producing methyl acrylate, methyl propionate and methyl methacrylate by the aldol condensation reaction of methyl acetate and formaldehyde, formaldehyde cannot completely react, part of formaldehyde is finally added into wastewater, and meanwhile, the wastewater also contains a series of impurities such as methanol, acetic acid and propionic acid, so that waste of materials and difficulty in wastewater treatment are caused.
The utility model can be used for treating aldehyde-containing wastewater in methyl acrylate and methyl methacrylate production processes, and particularly comprises a layering device, a pre-reactor, a reaction rectifying tower and a rectifying tower, wherein the layering device is provided with an overflow plate and divides a space in a tank into a water phase area and an oil phase area, the oil phase area is connected with an inlet of the pre-reactor through a pipeline, the inlet of the pre-reactor is also provided with a methanol feeding pipe, an outlet of the pre-reactor is communicated with the middle part of the reaction rectifying tower, the top outlet of the reaction rectifying tower is connected with the rectifying tower, the bottom of the reaction rectifying tower is provided with a wastewater outlet, and the top and the bottom of the rectifying tower are respectively provided with a methylal collecting outlet and a product collecting outlet.
Preferably, the outlet of the oil phase zone of the separator is connected to two prereactors in series. The reaction rectifying tower comprises a stripping section, a reaction section and a rectifying section from bottom to top, wherein the reaction section is a catalyst bed filled with a solid acid catalyst, and the solid acid catalyst is an acidic cationic resin, a zeolite molecular sieve catalyst, and an acidic catalyst of alumina or silica carrier.
When the wastewater is treated, the device sends the wastewater into a layering device, a small amount of hydrocarbon and aromatic hydrocarbon oily substances in the wastewater are separated, the wastewater after the oil phase is separated is sent into a pre-reactor, formaldehyde and methanol in the wastewater undergo a condensation reaction to generate methylal, acetic acid and methanol undergo an esterification reaction to generate methyl acetate, and propionic acid and methanol react to produce methyl propionate. The pre-reaction can only react partially, but can not completely react key components such as formaldehyde, methanol, acetic acid, propionic acid and the like. The reaction pressure is 0.1-1.0MPa, and the reaction temperature is 80-120 ℃; the residence time of the materials in the pre-reactor is controlled to be 30-90 min.
According to the content of methanol, formaldehyde and organic acid in the wastewater, supplementing methanol through a methanol feeding pipe, and controlling the molar ratio of the methanol to the formaldehyde in the pre-reactor to be 2-2.2:1, wherein the molar ratio of the organic acid to the methanol to be 1-1.2:1. And (3) feeding the pre-reacted materials into a reaction rectifying tower for further reaction, and simultaneously realizing separation of reaction products.
The reactive rectifying tower adopts a composite structure of a plate tower and a packing tower, 2 sections of packing are sequentially arranged from top to bottom, 30 trays filled with catalyst are arranged, 5 side reactors are arranged in the tray reaction section, and a section of packing is arranged at the lowest part. The pressure at the top of the reactive rectifying tower is controlled to be 0-0.1MPa, the reflux ratio is set to be 4-5, and the residence time of the pre-reactor and the side reactor material flows is 60min. The mixture of methylal, methyl acetate and methyl propionate is obtained at the top of the reactive distillation tower, and the wastewater which almost contains no methanol and organic acid is obtained at the bottom of the tower. Finally, the COD of the wastewater after the reactive distillation treatment is less than 5000mg/L, the formaldehyde content is 1-100ppm, and the emission standard is met.
Claims (6)
1. A process device for treating aldehyde-containing wastewater in a methyl acrylate and methyl methacrylate production process is characterized in that: including layering ware, prereactor, reaction rectifying column and rectifying column, the layering ware is equipped with the overflow plate and divide into water phase district and oil phase district with jar interior space, the oil phase district passes through the entry linkage of pipeline and prereactor, prereactor's entry still is equipped with the methyl alcohol feeding pipe, prereactor's export and the middle of the tower intercommunication of reaction rectifying column, the top of the tower exit linkage rectifying column of reaction rectifying column, the bottom of the tower of reaction rectifying column is equipped with waste water export, and the top of the tower and the bottom of the tower of rectifying column are equipped with methylal outlet and product outlet respectively.
2. The process device for treating aldehyde-containing wastewater in a process for producing methyl acrylate and methyl methacrylate according to claim 1, which is characterized in that: the outlets of the oil phase areas of the delaminators are connected with a plurality of pre-reactors which are connected in series and/or in parallel.
3. The process device for treating aldehyde-containing wastewater in a process for producing methyl acrylate and methyl methacrylate according to claim 1, which is characterized in that: the middle part of the reaction rectifying tower is provided with a middle extraction port, the middle extraction port is connected with a plurality of side reactors which are connected in series and/or in parallel, and the outlet of the side reactor is circularly communicated with the middle part of the reaction rectifying tower.
4. The process device for treating aldehyde-containing wastewater in a process for producing methyl acrylate and methyl methacrylate according to claim 1, which is characterized in that: a catalyst bed layer is arranged in the reaction rectifying tower.
5. The process device for treating aldehyde-containing wastewater in a process for producing methyl acrylate and methyl methacrylate according to claim 4, which is characterized in that: the reaction rectifying tower adopts a plate tower or a packed tower and comprises a reaction section, a rectifying section and a stripping section, and the catalyst bed layer is arranged in the reaction section.
6. The process device for treating aldehyde-containing wastewater in a process for producing methyl acrylate and methyl methacrylate according to claim 4, which is characterized in that: the catalyst bed layer adopts a solid acid catalyst, and the solid acid catalyst is an acidic cationic resin, a zeolite molecular sieve catalyst, and an acidic catalyst with alumina or silica carrier.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211577059 | 2022-12-09 | ||
| CN2022115770598 | 2022-12-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN219972045U true CN219972045U (en) | 2023-11-07 |
Family
ID=88579414
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202320165855.4U Active CN219972045U (en) | 2022-12-09 | 2023-02-09 | Aldehyde-containing wastewater treatment process device for methyl acrylate and methyl methacrylate production process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN219972045U (en) |
-
2023
- 2023-02-09 CN CN202320165855.4U patent/CN219972045U/en active Active
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