CN117486418A - Treatment device and method for caprolactam concentrated waste liquid - Google Patents
Treatment device and method for caprolactam concentrated waste liquid Download PDFInfo
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- CN117486418A CN117486418A CN202311615524.7A CN202311615524A CN117486418A CN 117486418 A CN117486418 A CN 117486418A CN 202311615524 A CN202311615524 A CN 202311615524A CN 117486418 A CN117486418 A CN 117486418A
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- waste liquid
- caprolactam
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- concentrated waste
- fixed bed
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- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000007788 liquid Substances 0.000 title claims abstract description 89
- 239000002699 waste material Substances 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 30
- 238000002425 crystallisation Methods 0.000 claims abstract description 42
- 230000008025 crystallization Effects 0.000 claims abstract description 42
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 claims abstract description 34
- 230000003647 oxidation Effects 0.000 claims abstract description 34
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 34
- 238000001704 evaporation Methods 0.000 claims abstract description 26
- 230000008020 evaporation Effects 0.000 claims abstract description 26
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 18
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002861 polymer material Substances 0.000 claims abstract description 10
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims description 24
- 238000001179 sorption measurement Methods 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 7
- 239000012141 concentrate Substances 0.000 claims description 4
- 239000005416 organic matter Substances 0.000 claims description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 3
- 241000219793 Trifolium Species 0.000 claims description 3
- BJLLEZDLIAARQJ-UHFFFAOYSA-N cobalt copper manganese Chemical compound [Mn][Cu][Co] BJLLEZDLIAARQJ-UHFFFAOYSA-N 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 230000001788 irregular Effects 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 description 14
- 239000002351 wastewater Substances 0.000 description 10
- 238000011084 recovery Methods 0.000 description 7
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 6
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 6
- 235000011130 ammonium sulphate Nutrition 0.000 description 6
- NZNMSOFKMUBTKW-UHFFFAOYSA-N cyclohexanecarboxylic acid Chemical compound OC(=O)C1CCCCC1 NZNMSOFKMUBTKW-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- VEZUQRBDRNJBJY-UHFFFAOYSA-N cyclohexanone oxime Chemical compound ON=C1CCCCC1 VEZUQRBDRNJBJY-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 238000006237 Beckmann rearrangement reaction Methods 0.000 description 1
- 239000005711 Benzoic acid Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 235000010233 benzoic acid Nutrition 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- VZFUCHSFHOYXIS-UHFFFAOYSA-N cycloheptane carboxylic acid Natural products OC(=O)C1CCCCCC1 VZFUCHSFHOYXIS-UHFFFAOYSA-N 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000013021 overheating Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/043—Details
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/048—Purification of waste water by evaporation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/03—Pressure
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/38—Gas flow rate
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/40—Liquid flow rate
Abstract
The invention provides a device and a method for treating caprolactam concentrated waste liquid, wherein the device comprises an absorption tower, an evaporation crystallization device and a fixed bed wet catalytic oxidation reactor; the feed inlet of the absorption tower is used for receiving caprolactam concentrated waste liquid, the discharge outlet of the absorption tower is communicated with the feed inlet of the evaporation crystallization device, and the discharge outlet of the evaporation crystallization device is communicated with the feed inlet of the fixed bed wet catalytic oxidation reactor; the absorption tower is filled with super-crosslinked microporous polymer material. According to the invention, organic matters in the caprolactam concentrated waste liquid are effectively adsorbed by the super-crosslinked microporous polymer material in the absorption tower, so that COD of the caprolactam concentrated waste liquid is reduced, inorganic salts are effectively recovered by the evaporation crystallization device, and then the caprolactam concentrated waste liquid enters the fixed bed wet catalytic oxidation reactor for wet oxidation reaction, so that not only is the effective treatment of the caprolactam concentrated waste liquid ensured, but also other pollution is avoided, and the problem that the catalyst bed is blocked by inorganic salt crystals is avoided by removing the inorganic salts.
Description
Technical Field
The invention relates to the technical field of chemical preparation, in particular to a device and a method for treating caprolactam concentrated waste liquid.
Background
In the caprolactam production process, the final step is liquid-phase Beckmann rearrangement reaction, rearrangement, neutralization and crystallization of cyclohexanone oxime to obtain amide oil, and extraction, alkali washing, refining and other steps of the amide oil to obtain caprolactam product. The process can produce a large amount of wastewater containing ammonium sulfate, and the wastewater mainly contains caprolactam, ammonium sulfate, acetic acid, toluene, benzoic acid, cyclohexane carboxylic acid sulfonic acid, hexahydrobenzoic acid, cyclohexane and other components, has various organic species, high COD (Chemical Oxygen Demand ) value and high salt content. The main process for treating the waste water at present is to subject the evaporated condensate to biochemical treatment by stripping, deamination and evaporation procedures, then discharge the condensate up to standard, and subject the concentrated waste liquid to incineration treatment by an incinerator.
For example, patent publication No. CN112174423 discloses a method for treating caprolactam wastewater, recovering organic and inorganic matters in the wastewater by distillation, and concentrating the obtainedAnd (5) burning the waste liquid. However, the incineration treatment method consumes a large amount of energy and generates CO 2 And the emission is not in accordance with the requirements of energy conservation and carbon reduction. Meanwhile, the problem of blockage of corresponding equipment and a flue is found in the wastewater treatment process, so that the use of tail equipment is affected, and the equipment cannot continuously and stably run.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a device and a method for treating caprolactam concentrated waste liquid, which ensure the effective treatment of the caprolactam concentrated waste liquid.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a treatment device for caprolactam concentrated waste liquid, which comprises an absorption tower, an evaporation crystallization device and a fixed bed wet catalytic oxidation reactor;
the feed inlet of the absorption tower is used for receiving caprolactam concentrated waste liquid, the discharge outlet of the absorption tower is communicated with the feed inlet of the evaporative crystallization device, and the discharge outlet of the evaporative crystallization device is communicated with the feed inlet of the fixed bed wet catalytic oxidation reactor;
the absorption tower is filled with super-crosslinked microporous polymer materials.
The invention has the beneficial effects that: the organic matter in the caprolactam concentrated waste liquid is effectively adsorbed by the super-crosslinked microporous polymer material in the absorption tower, so that the COD of the caprolactam concentrated waste liquid is reduced, inorganic salt is effectively recovered by the evaporation crystallization device, and then the caprolactam concentrated waste liquid enters the fixed bed wet catalytic oxidation reactor for wet oxidation reaction, so that the effective treatment of the caprolactam concentrated waste liquid is ensured, other pollution is avoided, and the problem that the catalyst bed is blocked by inorganic salt crystals is avoided by removing the inorganic salt.
Optionally, the catalyst in the fixed bed wet catalytic oxidation reactor is a ruthenium-based catalyst supported by a copper cobalt manganese composite oxide.
Optionally, the shape of the catalyst is bar, ingot, single column, ring, sphere, clover or irregular.
Optionally, an air inlet pipe is arranged on the fixed bed wet catalytic oxidation reactor and is used for introducing air required by the reaction.
Optionally, the device further comprises a waste heat recovery pipe, wherein the waste heat recovery pipe is arranged between the fixed bed wet catalytic oxidation reactor and the evaporative crystallization device.
According to the description, the inorganic salt is firstly removed, so that the problem that inorganic salt crystals block the catalyst bed layer due to heat release of the reaction bed layer is avoided, the reaction speed is more favorably controlled, and the reaction heat of the wet oxidation process is recovered for the multi-effect evaporation crystallization working section.
Optionally, the device further comprises a heat exchanger, wherein the heat exchanger is arranged between a discharge hole of the absorption tower and a feed hole of the evaporative crystallization device.
In a second aspect, the present invention provides a method for treating a caprolactam concentrate waste liquid, using the treatment device for a caprolactam concentrate waste liquid of the first aspect, comprising the steps of:
s1, enabling caprolactam concentrated waste liquid to enter an absorption tower, and carrying out organic adsorption by a super-crosslinked microporous polymer material in the absorption tower to obtain first waste liquid with low organic content;
s2, the first waste liquid enters an evaporation crystallization device, inorganic salt obtained by evaporation crystallization is recovered, and mother liquid obtained by evaporation crystallization and steam condensate are mixed to obtain second waste liquid with low organic matter content and low inorganic salt content;
s3, the second waste liquid enters a fixed bed wet catalytic oxidation reactor to carry out wet oxidation reaction, and final waste liquid is obtained.
Optionally, the adsorption temperature of the absorption tower is 10-35 ℃.
Optionally, the reaction pressure of the fixed bed wet catalytic oxidation reactor is 2.5-4.5 MPa, the reaction temperature is 130-240 ℃ and the liquid hourly space velocity is 0.1-10 h -1 The air inlet pipe is filled with air with the stoichiometric ratio of 200-450%.
The technical effects corresponding to the treatment method of caprolactam concentrated waste liquid provided in the second aspect are described with reference to the related description of the treatment device of caprolactam concentrated waste liquid provided in the first aspect.
Drawings
FIG. 1 is a schematic structural diagram of a device for treating caprolactam concentrated waste liquid according to an embodiment of the present invention;
FIG. 2 is a schematic flow chart of a method for treating caprolactam concentrated waste liquid according to an embodiment of the present invention.
[ reference numerals description ]
1. An absorption tower; 2. an evaporative crystallization device; 3. a fixed bed wet catalytic oxidation reactor; 4. a waste heat recovery pipe; 5. an air inlet pipe;
100. and (5) a biochemical pool.
Detailed Description
In order that the above-described aspects may be better understood, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. While exemplary embodiments of the present invention are shown in the drawings, it should be understood that the present invention may be embodied in various forms and should not be limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.
Example 1
Since a large amount of wastewater containing ammonium sulfate is generated in the caprolactam production process, the existing caprolactam wastewater treatment method is to perform incineration treatment, and has the problems of environmental pollution, high energy consumption, unstable treatment process and the like. Thus, the improvement of the conventional caprolactam concentrated waste liquid treatment device in this embodiment is as follows:
referring to fig. 1, a treatment device for caprolactam concentrated waste liquid comprises an absorption tower 1, an evaporation crystallization device 2, a fixed bed wet catalytic oxidation reactor 3 and a waste heat recovery tube 4; the feed inlet of the absorption tower 1 is used for receiving caprolactam concentrated waste liquid, the discharge outlet of the absorption tower 1 is communicated with the feed inlet of the evaporation crystallization device 2, and the discharge outlet of the evaporation crystallization device 2 is communicated with the feed inlet of the fixed bed wet catalytic oxidation reactor 3; the waste heat recovery pipe 4 is arranged between the fixed bed wet catalytic oxidation reactor 3 and the evaporative crystallization device 2.
In this embodiment, the absorption tower 1 is filled with a super-crosslinked microporous polymer material, such as a MOF (Metal Organic Frameworks, metal organic framework) material, so that the nitrogen-containing organic matters can be adsorbed in a directional and efficient manner, and the adsorption rate is 50-60%. Unlike the physical adsorption of traditional active carbon, the adsorption belongs to chemical adsorption, and has high specific surface area and better adsorption effect.
In this embodiment, the catalyst in the fixed bed wet catalytic oxidation reactor 3 is a ruthenium-based catalyst supported by a copper-cobalt-manganese composite oxide, and its shape is a bar, an ingot, a single column, a ring, a sphere, a clover or an irregular shape.
In this embodiment, an air inlet pipe 5 is provided on the fixed bed wet catalytic oxidation reactor 3, and the air inlet pipe 5 is used for introducing air required for the reaction.
Not shown in the drawings, the present embodiment further includes a heat exchanger disposed between the discharge port of the absorption tower 1 and the feed port of the evaporative crystallization apparatus 2.
Thus, as can be seen from fig. 1, the process flow of this embodiment is as follows:
(1) In the concentrated waste liquid of caprolactam, COD content is 100000 ~ 200000mg/L, salt content is 20-40%, and the waste liquid is fed into absorption tower 1, and the super-crosslinked microporous polymer material in absorption tower 1 is used for adsorbing organic matter at normal pressure of 10-35 deg.C, and the adsorption process can be implemented by means of low-pressure N 2 The method realizes the purging analysis and the recycling, and the COD of the waste water after the absorption is about 60000-80000 mg/L;
(2) Waste liquid from the absorption tower 1 enters an evaporation crystallization device 2 after heat exchange, and is subjected to multi-effect evaporation through LS (low-pressure steam), so that inorganic salt is crystallized, the inorganic salt obtained by crystallization enters a thermal power plant for ammonium sulfate recovery, and steam condensate is added into mother liquor after evaporation crystallization to adjust COD to 60000-80000 mg/L;
(3) The waste liquid from which part of organic matters and inorganic salts are removed enters a fixed bed wet catalytic oxidation reactor 3, the reaction pressure is 2.5-4.5 MPa, the reaction temperature is 130-240 ℃, and the liquid hourly space velocity is0.1~10h -1 The air with the stoichiometric ratio of 200-450% is blown into the reactor through the air compressor and the air inlet pipe 5, and the waste water after wet oxidation reaction has COD of about 2000-3500 mg/L and can directly enter the biochemical tank 100 of public engineering for conventional treatment.
(4) The wet catalytic oxidation process generates a large amount of heat sources, and HS (high pressure steam, high-pressure steam) is used as waste heat to be recovered to the front end of the multi-effect evaporation crystallization section for heat supply.
Therefore, the embodiment realizes heterogeneous wet oxidation reaction through the adsorption of the early-stage organic matters and the desalination pretreatment, and ensures the effective treatment of the caprolactam concentrated waste liquid.
Example two
Referring to fig. 1 and 2, a method for treating caprolactam concentrated waste liquid, using a caprolactam concentrated waste liquid treatment device in embodiment one, comprises the following steps:
s1, enabling caprolactam concentrated waste liquid to enter an absorption tower 1, and carrying out organic adsorption by a super-crosslinked microporous polymer material in the absorption tower 1 to obtain first waste liquid with low organic content;
wherein the adsorption temperature of the absorption tower 1 is 10-35 ℃, the discharged COD of the first waste liquid is 70000mg/L, and the salt content is 20-40%.
S2, the first waste liquid enters an evaporation crystallization device 2, inorganic salt obtained by evaporation crystallization is recovered, and a second waste liquid with low organic matters and low inorganic salt content is obtained after the mother liquid obtained by evaporation crystallization and the steam condensate are mixed;
in this example, the reaction temperature of the evaporative crystallization device 2 was 100 ℃, wherein the salt removal rate of the second waste liquid relative to the first waste liquid was 60%.
S3, the second waste liquid enters a fixed bed wet catalytic oxidation reactor 3 to carry out wet oxidation reaction, and final waste liquid is obtained.
Wherein the reaction pressure of the fixed bed wet catalytic oxidation reactor 3 is 2.5-4.5 MPa, the reaction temperature is 130-240 ℃, and the liquid hourly space velocity is 0.1-10 h -1 The air inlet pipe 5 is filled with air with the stoichiometric ratio of 200-450%.
In this example, the reaction pressure of the fixed bed wet catalytic oxidation reactor 3 was 2.5MPa, the reaction temperature was 130℃and the liquid hourly space velocity was 0.1h -1 The intake pipe 5 thereof is filled with air of 200% of the stoichiometric ratio.
For other descriptions in this embodiment two, reference is made to embodiment one.
Through the above process parameters, the COD in the final waste liquid of this example was 3200mg/L.
Example III
Referring to fig. 1 and 2, on the basis of the second embodiment, parameters of the evaporative crystallization device 2 and the fixed bed wet catalytic oxidation reactor 3 are adjusted as follows:
in this example, the reaction temperature of the evaporative crystallization device 2 was 110 ℃, wherein the salt removal rate of the second waste liquid relative to the first waste liquid was 65%.
In this example, the reaction pressure of the fixed bed wet catalytic oxidation reactor 3 was 3MPa, the reaction temperature was 200℃and the liquid hourly space velocity was 0.5h -1 The intake pipe 5 thereof is introduced with air of 320% of the stoichiometric ratio.
Through the above process parameters, the COD in the final waste liquid of this example was 2500mg/L.
Example IV
Referring to fig. 1 and 2, on the basis of the second embodiment, parameters of the evaporative crystallization device 2 and the fixed bed wet catalytic oxidation reactor 3 are adjusted as follows:
in this example, the reaction temperature of the evaporative crystallization device 2 was 115 ℃, wherein the salt removal rate of the second waste liquid relative to the first waste liquid was 66%.
In this example, the reaction pressure of the fixed bed wet catalytic oxidation reactor 3 was 4MPa, the reaction temperature was 240℃and the liquid hourly space velocity was 0.8h -1 The intake pipe 5 thereof is filled with air of 430% of stoichiometric ratio.
Through the above process parameters, the COD in the final waste liquid of this example was 2300mg/L.
In summary, the first to fourth embodiments have the following advantages:
1. avoiding fuel consumption caused by burning waste liquid and reducing carbon emission;
2. organic matters in the concentrated waste liquid are effectively recovered, and the recovered organic matters can be used as X-oil for recycling through analysis and detection;
3. inorganic salt in the concentrated waste liquid is effectively recovered, and the recovered inorganic salt is analyzed and detected to be ammonium sulfate as a main component, so that the ammonium sulfate can enter a desulfurization device of a thermal power plant for recovery;
4. the evaporation mother liquor is treated by adopting a fixed bed wet catalytic oxidation process, so that the material consumption of oxidizing agents such as hydrogen peroxide, ozone and the like is avoided, the effective treatment of caprolactam concentrated waste liquid is ensured, other toxic and harmful gas pollution is avoided, the inorganic salt is removed, the catalyst bed is prevented from being blocked by inorganic salt crystallization caused by overheating of the reaction bed, the reaction speed is controlled, and the reaction heat of the wet oxidation process is recovered;
5. the steam condensate generated in the process of concentrating the waste liquid and the waste water after wet oxidation reaction treatment can directly enter public engineering for conventional treatment, and then the waste water can reach the discharge standard.
In the description of the present invention, it should be understood that the terms "first," "second," and the like are used for descriptive purposes only and are not to be construed as indicating or implying a relative importance or number of technical features indicated. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include one or more such feature. In the description of the present invention, the meaning of "a plurality" is two or more, unless explicitly defined otherwise.
In the present invention, unless explicitly specified and limited otherwise, the terms "mounted," "connected," "secured," and the like are to be construed broadly, and may be, for example, fixedly connected, detachably connected, or integrally formed; can be mechanically or electrically connected; can be directly connected or indirectly connected through an intermediate medium; may be a communication between two elements or an interaction between two elements. The specific meaning of the above terms in the present invention can be understood by those of ordinary skill in the art according to the specific circumstances.
In the present invention, unless expressly stated or limited otherwise, a first feature is "on" or "under" a second feature, which may be in direct contact with the first and second features, or in indirect contact with the first and second features via an intervening medium. Moreover, a first feature "above," "over" and "on" a second feature may be a first feature directly above or obliquely above the second feature, or simply indicate that the first feature is higher in level than the second feature. The first feature being "under", "below" and "beneath" the second feature may be the first feature being directly under or obliquely below the second feature, or simply indicating that the first feature is level lower than the second feature.
In the description of the present specification, the terms "one embodiment," "some embodiments," "examples," "particular examples," or "some examples," etc., refer to particular features, structures, materials, or characteristics described in connection with the embodiment or example as being included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that alterations, modifications, substitutions and variations may be made in the above embodiments by those skilled in the art within the scope of the invention.
Claims (9)
1. The treatment device for the caprolactam concentrated waste liquid is characterized by comprising an absorption tower, an evaporation crystallization device and a fixed bed wet catalytic oxidation reactor;
the feed inlet of the absorption tower is used for receiving caprolactam concentrated waste liquid, the discharge outlet of the absorption tower is communicated with the feed inlet of the evaporative crystallization device, and the discharge outlet of the evaporative crystallization device is communicated with the feed inlet of the fixed bed wet catalytic oxidation reactor;
the absorption tower is filled with super-crosslinked microporous polymer materials.
2. The device for treating concentrated waste caprolactam liquid according to claim 1, wherein the catalyst in the fixed bed wet catalytic oxidation reactor is a ruthenium-based catalyst supported by a copper-cobalt-manganese composite oxide.
3. The apparatus for treating concentrated waste caprolactam liquid according to claim 2, wherein the catalyst is in the form of a bar, an ingot, a single column, a ring, a ball, a clover or an irregular shape.
4. The caprolactam concentrated waste liquid treatment device according to claim 1, wherein an air inlet pipe is arranged on the fixed bed wet catalytic oxidation reactor and is used for introducing air required by the reaction.
5. The apparatus for treating concentrated waste caprolactam liquid according to claim 1, further comprising a waste heat recovering pipe disposed between the fixed bed wet catalytic oxidation reactor and the evaporative crystallization apparatus.
6. The apparatus for treating concentrated waste caprolactam liquid according to any one of claims 1 to 5, further comprising a heat exchanger disposed between the outlet of the absorption tower and the inlet of the evaporative crystallization apparatus.
7. A method for treating a caprolactam concentrate waste liquid, using a caprolactam concentrate waste liquid treating apparatus according to any one of claims 1 to 6, characterized by comprising the steps of:
s1, enabling caprolactam concentrated waste liquid to enter an absorption tower, and carrying out organic adsorption by a super-crosslinked microporous polymer material in the absorption tower to obtain first waste liquid with low organic content;
s2, the first waste liquid enters an evaporation crystallization device, inorganic salt obtained by evaporation crystallization is recovered, and mother liquid obtained by evaporation crystallization and steam condensate are mixed to obtain second waste liquid with low organic matter content and low inorganic salt content;
s3, the second waste liquid enters a fixed bed wet catalytic oxidation reactor to carry out wet oxidation reaction, and final waste liquid is obtained.
8. The method for treating a caprolactam concentrated waste liquid according to claim 7, wherein the adsorption temperature of the absorption tower is 10-35 ℃.
9. The method for treating concentrated waste caprolactam liquid according to claim 7, wherein the reaction pressure of the fixed bed wet catalytic oxidation reactor is 2.5-4.5 MPa, the reaction temperature is 130-240 ℃ and the liquid hourly space velocity is 0.1-10 h -1 The air inlet pipe is filled with air with the stoichiometric ratio of 200-450%.
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