CN114409171A - Process for deeply treating and recycling BT (BT) from rubber accelerator DCBS (dichlorodifluoromethane) mother liquor wastewater - Google Patents
Process for deeply treating and recycling BT (BT) from rubber accelerator DCBS (dichlorodifluoromethane) mother liquor wastewater Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000012452 mother liquor Substances 0.000 title claims abstract description 30
- 229920001971 elastomer Polymers 0.000 title claims abstract description 21
- CMAUJSNXENPPOF-UHFFFAOYSA-N n-(1,3-benzothiazol-2-ylsulfanyl)-n-cyclohexylcyclohexanamine Chemical compound C1CCCCC1N(C1CCCCC1)SC1=NC2=CC=CC=C2S1 CMAUJSNXENPPOF-UHFFFAOYSA-N 0.000 title claims abstract description 21
- 239000005060 rubber Substances 0.000 title claims abstract description 21
- 238000004064 recycling Methods 0.000 title claims abstract description 19
- 239000004338 Dichlorodifluoromethane Substances 0.000 title description 2
- PXBRQCKWGAHEHS-UHFFFAOYSA-N dichlorodifluoromethane Chemical compound FC(F)(Cl)Cl PXBRQCKWGAHEHS-UHFFFAOYSA-N 0.000 title description 2
- 235000019404 dichlorodifluoromethane Nutrition 0.000 title description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 63
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000011001 backwashing Methods 0.000 claims abstract description 22
- 230000003647 oxidation Effects 0.000 claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 230000003197 catalytic effect Effects 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000000706 filtrate Substances 0.000 claims abstract description 6
- 238000011268 retreatment Methods 0.000 claims abstract description 3
- 238000001704 evaporation Methods 0.000 claims description 20
- 230000008020 evaporation Effects 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims description 2
- 230000000996 additive effect Effects 0.000 claims description 2
- KGRVJHAUYBGFFP-UHFFFAOYSA-N 2,2'-Methylenebis(4-methyl-6-tert-butylphenol) Chemical compound CC(C)(C)C1=CC(C)=CC(CC=2C(=C(C=C(C)C=2)C(C)(C)C)O)=C1O KGRVJHAUYBGFFP-UHFFFAOYSA-N 0.000 claims 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims 1
- 239000005977 Ethylene Substances 0.000 claims 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- KZTYYGOKRVBIMI-UHFFFAOYSA-N S-phenyl benzenesulfonothioate Natural products C=1C=CC=CC=1S(=O)(=O)C1=CC=CC=C1 KZTYYGOKRVBIMI-UHFFFAOYSA-N 0.000 abstract description 2
- -1 methylene diphenyl Chemical group 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 19
- 238000001179 sorption measurement Methods 0.000 description 14
- 230000008929 regeneration Effects 0.000 description 13
- 238000011069 regeneration method Methods 0.000 description 13
- 239000000126 substance Substances 0.000 description 7
- 239000005416 organic matter Substances 0.000 description 6
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 238000005189 flocculation Methods 0.000 description 2
- 230000016615 flocculation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- 238000012795 verification 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
- C02F1/041—Treatment of water, waste water, or sewage by heating by distillation or evaporation by means of vapour compression
-
- 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
- C02F1/22—Treatment of water, waste water, or sewage by freezing
-
- 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
- C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
-
- 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
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Water Treatment By Sorption (AREA)
Abstract
The invention belongs to the field of wastewater treatment, and particularly relates to a process for deeply treating and recycling BT (methylene diphenyl sulfone) from rubber accelerator DCBS mother liquor wastewater. The method comprises the following steps: 1) the rubber auxiliary DCBS mother liquor wastewater is subjected to cooling at the temperature of-10 ℃ to remove a part of salt and organic matters; 2) then catalytic oxidation is carried out, COD is reduced to below 5000mg/L after most organic matters are separated out; 3) filtrate is evaporated and concentrated by MVR, and mother liquor returns to a raw water system for retreatment; the condensed water is absorbed by active carbon and returns to the production system for recycling; 4) the saturated activated carbon can be recycled after steam backwashing. The invention effectively combines the four process schemes, solves the problem of the prior water treatment, has economic and feasible treatment process and reduces the environmental protection risk of the prior treatment means.
Description
Technical Field
The invention belongs to the field of wastewater treatment, and particularly relates to a process for deeply treating and recycling BT (methylene diphenyl sulfone) from rubber accelerator DCBS mother liquor wastewater.
Background
The rubber accelerator DCBS can generate byproducts in the synthetic process, the byproducts are heterocyclic compounds with stable chemical compositions and structures and difficult degradation, the byproducts are dissolved in water, so that the wastewater has complex components, difficult degradation and high biological toxicity, the degradation of microorganisms to biochemical organic matters is seriously inhibited, the mother liquor of the wastewater is more difficult to treat after evaporation concentration, the salt content of the wastewater is up to more than 20 percent, the organic matter content COD is up to more than 50000mg/L, the wastewater is difficult to biochemically treat after organic matters are removed, the strain requirement is higher, the wastewater treatment difficulty is high, the COD is high, the salt content is high, and the complete degradation is difficult to realize by adopting a process method.
The current treatment scheme aiming at the wastewater comprises the following 3 types:
one) flocculation sedimentation, activated carbon adsorption and multiple-effect evaporation: and (3) firstly settling under the condition of a flocculating agent, removing a part of resin by settling, adsorbing by using activated carbon, then performing evaporation and concentration, and returning condensed water to a workshop production system for recycling.
II) MVR evaporation + Fenton oxidation method: the MVR is adopted to directly evaporate the wastewater, condensed water is subjected to Fenton oxidation and then returned to a production system for recycling, and mother liquor is returned to raw water for treatment again.
Three) extraction method + MVR evaporation: the wastewater is pretreated firstly, part of organic matters are recycled by adopting an extracting agent, the extracting agent is reused, MVR evaporation concentration is carried out, condensed water is directly returned to a production system for recycling, and mother liquor is returned to raw water for secondary treatment.
Aiming at the scheme I), the wastewater has high salt content and high COD organic matter content, the organic matter is difficult to completely degrade only through sedimentation, flocculation and adsorption, and after circulation for a certain period, the COD of the condensate water can rise, so that the product quality of a workshop is influenced through verification.
Aiming at the scheme II), raw water is not subjected to pretreatment and is directly subjected to MVR evaporation concentration, the COD (chemical oxygen demand) of the waste water is high, the number of organic matters is large, the boiling point is increased, the operation load of an MVR system is large, the loss of equipment is large, the content of low-volatile organic matters in condensed water is high, the number of organic matters is large, Fenton oxidation is performed, and the cost is high.
Aiming at the third scheme), because the COD (chemical oxygen demand) of the wastewater is high, the salt content is high, the organic matter components are complex, the requirement on the extracting agent is high, and new chemical components are introduced, once the extraction process is not completely separated, the extracting agent is brought into an MVR (mechanical vapor recompression) evaporation system and easily enters condensate which is then returned to a workshop for use, the product quality is influenced, meanwhile, the loss of the extracting agent is higher, and the cost is high.
In summary, because the rubber accelerator wastewater has complex components and high salt content, a single scheme is difficult to completely treat, and multiple manufacturers adopt comprehensive treatment schemes, which have been reported to include 'evaporation + adsorption', 'oxidation + evaporation', 'advanced oxidation + coagulating sedimentation + filtration + activated carbon adsorption', and the like. However, despite the fact that various treatment schemes can solve the current short-term discharge problem, the problems of large equipment investment, high operation cost, difficult long-term stable operation of the treatment process and the like still exist.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a process for deeply treating and recycling BT from rubber accelerator DCBS mother liquor wastewater.
In order to achieve the purpose, the invention adopts the technical scheme that:
a process for deeply treating and recycling BT from rubber accelerator DCBS mother liquor wastewater comprises the following steps:
1) the rubber additive DCBS mother liquor wastewater, COD is more than 50000mg/L, and a part of salt and organic matters are removed through cooling at-10 ℃ to ensure that the COD is stabilized at 50000 mg/L;
2) then catalytic oxidation is carried out, COD is reduced to below 5000mg/L after most organic matters are separated out, then filtration is carried out, and filtrate is taken out and sent to an MVR evaporation system;
3) filtrate is evaporated and concentrated by MVR, and mother liquor returns to a raw water system for retreatment; the condensed water is adsorbed by active carbon, and then COD is less than 500mg/L, and the condensed water returns to a production system for recycling;
4) the saturated activated carbon can be recycled after steam backwashing.
Specifically, the catalyst for catalytic oxidation in the step 2) is copper sulfate, and the content of the catalyst is 5wt per thousand; the reaction temperature is 150 ℃ and 280 ℃, and the reaction pressure is 2-5 Mpa.
Specifically, the MVR evaporation concentration ratio in the step 3) is controlled at 80%.
Specifically, the backwashing temperature of the activated carbon in the step 4) is 100-.
Preferably, the reaction in step 2) is carried out at a temperature of 250 ℃ and a reaction pressure of 5 MPa.
Preferably, the volume mass ratio of the added amount of the activated carbon to the condensed water in the step 3) is 1: 100.
preferably, the temperature of the activated carbon backwashing in the step 4) is 120-.
Compared with the prior art, the invention has the beneficial effects that:
the invention develops a rubber accelerator DCBS mother liquor wastewater treatment process method, because DCBS has a large amount of byproducts in the synthesis process, mainly a mixture of some benzene ring complex organic matters, the byproducts are difficult to completely degrade, the organic matters have high biological toxicity and are difficult to biochemically generate, and simultaneously sulfonate is easy to generate in the DCBS oxidation synthesis process, so that a large amount of sulfonate exists in the recovered sodium chloride, the salt purity is not enough, and the following process is adopted aiming at the wastewater with high salt and high COD:
the process adopts the steps of firstly cooling and settling, then removing the sulfonate in the wastewater, and independently collecting the sulfonate from the wastewater, thereby reducing the difficulty of subsequent catalytic oxidation and simultaneously improving the purity of the recovered industrial salt.
And (3) catalyzing and oxidizing the macromolecular organic matters into carbon dioxide and water under the conditions of the existence of a catalyst, the pressure of 5MPa and the temperature of 250 ℃, so that the organic matters are thoroughly degraded, and most of COD can be removed.
And the MVR evaporation is adopted for evaporation concentration, so that steam can be saved, meanwhile, through the previous pretreatment, the purity of the recycled sodium chloride salt is high, the requirement of industrial salt can be met, the MVR mother liquor is returned to the raw water system again, and the condensed water is treated in the next step.
The condensed water is absorbed by the activated carbon and then returns to the production system for recycling, the activated carbon has strong adsorption capacity, the residual organic matters can be effectively removed, and the discharged water meets the discharge requirement. Meanwhile, the activated carbon can meet the requirement of recycling through steam regeneration, the steam regeneration condition is simple and easy to operate, meanwhile, steam condensate can be separated from the oil phase through static layering, the separated oil phase is recovered BT, the purity of the recovered BT is high, the recovered BT is used as a raw material of the synthetic rubber accelerator MBT, and the steam condensate is returned to a raw water system for treatment again.
This technology adopts the cooling to subside and retrieves sulfonate in the mother liquor, the salt concentration of waste water has been reduced, most organic matters are got rid of in catalytic oxidation again, the quality of water of MVR system has been improved, the load of MVR evaporation has been reduced, the quality of production reuse water has been improved after the active carbon adsorption again to the condensate water, BT in the waste water can also be retrieved simultaneously, raw materials use as MBT, the effective combination of above technology, thoroughly solved the difficult problem of this high salt high COD waste water of mother liquor, can degrade the organic matter macromolecule completely, the reuse water quality has been promoted, the quality of salt has been promoted simultaneously, and can also effectively retrieve organic matter in the waste water, the treatment cost is low, the environmental protection problem has still been solved simultaneously.
Detailed Description
In order to make those skilled in the art better understand the technical solution of the present invention, the following provides a detailed description of the present invention with reference to the embodiments.
Example 1: the embodiment provides a method for treating rubber accelerator wastewater, which comprises the following steps: (1) under the condition of low-temperature sedimentation of rubber accelerator DCBS mother liquor wastewater (COD is more than 50000 mg/L), COD can be effectively removed, and the salt content is reduced; table 1 shows the effect of the reduced temperature sedimentation treatment. The sodium sulfonate can be effectively removed from the wastewater through cooling, and the COD is also reduced, so that the difficulty of catalytic oxidation can be effectively reduced;
TABLE 1
(2) Firstly adding copper sulfate as catalyst of about 5 wt% copper into waste water (COD is approximately equal to 50000 mg/L), and catalyzing, oxidizing and degrading organic matters (COD is less than 5000 mg/L) at 250 ℃;
respectively investigating the oxidation effect under the conditions of 2MPa/3MPa/4MPa/5 MPa; table 2 shows the oxidation effect under different pressure conditions;
TABLE 2
The oxidation effect is different under different pressure conditions, and the COD removal rate under the condition of 5MPa can reach 96 percent at most, and the effect is optimal.
(3) Firstly adding about 5 per thousand copper catalysts into wastewater (COD is approximately equal to 50000 mg/L), catalyzing, oxidizing and degrading organic matters (COD is less than 5000 mg/L), and respectively observing the oxidation effect under the conditions of 150 ℃/180 ℃/200 ℃/250 ℃/280 ℃ under the condition of 5 MPa; table 3 shows the effect of oxidation at different temperatures.
TABLE 3
The data show that the oxidation process can achieve the effect under the conditions of the temperature of 180-280 ℃ and the pressure of 2-5MPa, and the optimal conditions are the temperature of 250 ℃ and the pressure of 5 MPa.
(4) Evaporating and concentrating the oxidized filtrate by MVR, wherein the concentration proportion is 80%, the COD of the inlet water is different, and the COD of the condensate water is different from that of the mother liquor; table 4 shows the COD of the evaporation condensate of the different waste waters.
TABLE 4
In the MVR evaporation process, concentration ratio control is at 80%, has certain influence to congealing water and mother liquor COD, and concentration ratio control is when 80%, and different COD water processes after the oxidation, congeals water COD homoenergetic and controls at 1000mg/L, and mother liquor COD is less than the raw water, returns to former water system, does not influence the treatment effect.
(5) COD of condensed water evaporated by MVR is less than 1000mg/L, COD of discharged water is less than 500mg/L after the condensed water is adsorbed by active carbon, and the active carbon adsorption tank is about 10m3The active carbon has different water adsorption amounts and different COD of the effluent. Table 5 shows the effect of different amounts of attached water on the effluent.
TABLE 5
The same batch of activated carbon absorbs more than 1000m of water when the water absorption amount is more than 1000m3At the same time, the COD of the effluent begins to rise, lm3The optimal water treatment amount of the activated carbon is less than 100 times of the activated carbon.
(6) After the activated carbon is saturated, the activated carbon is regenerated by adopting steam backwashing, so that the activated carbon has the re-adsorption capacity, the adsorption capacity is investigated through COD (chemical oxygen demand) of inlet and outlet water after backwashing, BT is recovered from steam condensate, the steam pressure is 0.2MPa, and the activated carbon is regenerated for 1 h; respectively inspecting the backwashing effect under the conditions of 100 ℃/110 ℃/120 ℃/130 ℃/; table 6 shows the backwash effect at different temperature conditions.
TABLE 6
The data show that the active carbon backwashing regeneration process can achieve the effect at the temperature of 100-130 ℃ under the pressure of 0.2MPa, the optimal condition is that the temperature is 120-130 ℃, the BT recovered by each backwashing regeneration can reach 55L, and the purity can reach more than 98%.
(7) After the activated carbon is saturated, backwashing the regenerated activated carbon by using steam to enable the activated carbon to have the re-adsorption capacity, observing the adsorption capacity through COD (chemical oxygen demand) of inlet and outlet water after backwashing, and recovering BT from steam condensate, wherein the backwashing effect under the conditions of 0.1MPa/0.2MPa/0.3MPa/0.4 MPa/0.1 MPa is respectively observed under the conditions of steam temperature of 120 ℃ and regeneration for 1.5 h; table 7 shows the backwash effect at different pressure conditions.
TABLE 7
According to the data, the active carbon backwashing regeneration process can achieve the effect under the condition that the temperature is 120 ℃ and the pressure is 0.1-0.4MPa, the optimal condition is that the temperature is 0.2MPa, the temperature rise time is longer when the steam pressure is lower than 0.2MPa, the temperature rise is fast when the steam pressure is higher than 0.2MPa, the regeneration is carried out for 1.5 hours, the energy is wasted, the optimal pressure is 0.2MPa, the BT recovered by each backwashing regeneration can reach 55L, and the purity can reach more than 98%.
(8) After the activated carbon is saturated, the activated carbon is regenerated by adopting steam backwashing, so that the activated carbon has the re-adsorption capacity, the adsorption capacity is investigated through COD (chemical oxygen demand) of inlet and outlet water after backwashing, BT is recovered from steam condensate, and the backwashing effect under the conditions of steam temperature of 120 ℃ and steam pressure of 2MPa is respectively investigated under the conditions of 0.5h/1h/1.5h/2 h; table 7 shows the backwash effect for different regeneration times.
TABLE 8
According to the data, the active carbon backwashing regeneration process can achieve the effect at 120 ℃ and regeneration for more than 1.5h under the pressure of 2MPa, the optimal regeneration time is 1.5h for saving energy, the BT recovered by each backwashing regeneration can reach 55L, and the purity can reach more than 98%.
The invention effectively combines the four process schemes, solves the problem of the prior water treatment, has economic and feasible treatment process and reduces the environmental protection risk of the prior treatment means.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A process for deeply treating and recycling BT from rubber accelerator DCBS mother liquor wastewater is characterized by comprising the following steps:
1) the rubber additive DCBS mother liquor wastewater, COD is more than 50000mg/L, and a part of salt and organic matters are removed through cooling at-10 ℃ to ensure that the COD is stabilized at 50000 mg/L;
2) then catalytic oxidation is carried out, COD is reduced to below 5000mg/L after most organic matters are separated out, then filtration is carried out, and filtrate is taken out and sent to an MVR evaporation system;
3) filtrate is evaporated and concentrated by MVR, and mother liquor returns to a raw water system for retreatment; the condensed water is adsorbed by active carbon, and then COD is less than 500mg/L, and the condensed water returns to a production system for recycling;
4) the saturated activated carbon can be recycled after steam backwashing.
2. The process for deeply treating and recycling BT (methylene bis) sulfide) mother liquor wastewater of a rubber accelerator DCBS as claimed in claim 1, wherein a catalyst for catalytic oxidation in the step 2) is copper sulfate, and the content of the catalyst is 5wt per thousand; the reaction temperature is 150 ℃ and 280 ℃, and the reaction pressure is 2-5 Mpa.
3. The process for deeply treating and recycling BT (rubber accelerator DCBS) mother liquor wastewater as claimed in claim 1, wherein the MVR evaporation concentration ratio in step 3) is controlled at 80%.
4. The process for deeply treating and recovering BT from mother liquor wastewater of rubber accelerator DCBS as claimed in claim 1, wherein the backwashing temperature of the activated carbon in the step 4) is 100-.
5. The process for deeply treating and recycling BT (methylene bis (ethylene bis) borate) mother liquor wastewater of a rubber accelerator DCBS according to claim 1, wherein the reaction in the step 2) is carried out at a temperature of 250 ℃ and a reaction pressure of 5 MPa.
6. The process for deeply treating and recycling BT (BT) rubber accelerator DCBS mother liquor wastewater as claimed in claim 1, wherein the volume-to-mass ratio of the added amount of activated carbon to condensed water in step 3) is 1: 100.
7. the process for deeply treating and recovering BT from rubber accelerator DCBS mother liquor wastewater as claimed in claim 1, wherein the backwashing temperature of the activated carbon in the step 4) is 120-130 ℃, the steam pressure is 0.24MPa, and the time is 1 h.
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