CN114212931B - Wet oxidation alkaline waste water aqueous crystallization treatment method for ethylene alkali slag - Google Patents
Wet oxidation alkaline waste water aqueous crystallization treatment method for ethylene alkali slag Download PDFInfo
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- 239000002351 wastewater Substances 0.000 title claims abstract description 93
- 238000002425 crystallisation Methods 0.000 title claims abstract description 60
- 230000008025 crystallization Effects 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 31
- 238000009279 wet oxidation reaction Methods 0.000 title claims abstract description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 239000005977 Ethylene Substances 0.000 title claims abstract description 27
- 239000003513 alkali Substances 0.000 title claims abstract description 22
- 239000002893 slag Substances 0.000 title description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims abstract description 46
- 238000001816 cooling Methods 0.000 claims abstract description 42
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 40
- 239000012452 mother liquor Substances 0.000 claims abstract description 31
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000001704 evaporation Methods 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims abstract description 25
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 25
- 230000008020 evaporation Effects 0.000 claims abstract description 24
- 230000003197 catalytic effect Effects 0.000 claims abstract description 23
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims abstract description 23
- 235000017557 sodium bicarbonate Nutrition 0.000 claims abstract description 23
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 22
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 22
- 238000005516 engineering process Methods 0.000 claims abstract description 21
- 150000003839 salts Chemical class 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 239000003518 caustics Substances 0.000 claims abstract description 15
- 239000010802 sludge Substances 0.000 claims abstract description 15
- 239000010446 mirabilite Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 5
- 239000002699 waste material Substances 0.000 claims abstract description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 38
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- 239000000047 product Substances 0.000 claims description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 24
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 14
- 239000003054 catalyst Substances 0.000 claims description 14
- 239000012528 membrane Substances 0.000 claims description 14
- 239000011780 sodium chloride Substances 0.000 claims description 14
- 239000001569 carbon dioxide Substances 0.000 claims description 12
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 8
- 238000001640 fractional crystallisation Methods 0.000 claims description 8
- 229910000510 noble metal Inorganic materials 0.000 claims description 6
- 239000006227 byproduct Substances 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 229920006395 saturated elastomer Polymers 0.000 claims 1
- 238000004064 recycling Methods 0.000 abstract description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 239000002957 persistent organic pollutant Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 238000000909 electrodialysis Methods 0.000 description 4
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000013505 freshwater Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 159000000011 group IA salts Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- 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
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2101/101—Sulfur compounds
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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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/02—Temperature
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- 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
- C02F2209/06—Controlling or monitoring parameters in water treatment pH
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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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
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- 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
- C02F2209/10—Solids, e.g. total solids [TS], total suspended solids [TSS] or volatile solids [VS]
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- 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
- C02F2209/44—Time
Abstract
The invention belongs to the technical field of resource recycling science and engineering, and relates to a method for crystallizing treatment of alkaline waste water obtained by wet oxidation of ethylene caustic sludge. Carrying out ozone catalytic advanced oxidation treatment on the ethylene alkali residue wet oxidation alkaline wastewater, and separating sodium sulfate from the wastewater by a primary concentration and cooling crystallization technology; and cooling and crystallizing the product mirabilite to dissolve, and then evaporating and recrystallizing to obtain the anhydrous sodium sulfate product. Cooling crystallization mother liquor, performing secondary concentration and secondary ozone catalytic oxidation treatment, and separating out sodium bicarbonate crystals in a carbonization system to obtain sodium bicarbonate products; part of carbonized mother liquor is discharged to a tail salt evaporation crystallization treatment system, the generated tail salt is transported back to the backfill, and the rest mother liquor and sodium bicarbonate product washing waste liquor are circulated and returned to the cooling crystallization unit. The invention recovers sodium sulfate and realizes the comprehensive utilization of resources of wastewater carbonate, forms two inorganic salt products of sodium bicarbonate and sodium sulfate, reduces the wastewater and mixed salt by more than 90%, and realizes the green recycling treatment of petrochemical alkaline high-salt organic wastewater.
Description
Technical Field
The invention belongs to the technical field of resource recycling science and engineering, and particularly relates to a quality-dividing crystallization treatment technology of ethylene alkali residue wet-type oxidation alkaline wastewater, which is suitable for green recycling treatment of petrochemical alkaline salt-containing wastewater.
Background
The petrochemical industry can generate strong alkaline high-concentration organic wastewater, namely alkaline residue wastewater, in the oil alkaline washing refining process, contains a large amount of organic pollutants such as sulfides, phenols, oils, naphthenic acid and the like, and is typical high-concentration organic wastewater difficult to degrade. Along with the improvement of environmental protection requirements and the progress of treatment technologies, the petrochemical ethylene caustic sludge wastewater currently adopts a wet oxidation treatment technology to carry out oxidative degradation treatment on toxic and harmful organic pollutants. However, the COD of the alkaline wastewater after wet oxidation treatment is still up to 1000-3000mg/L, and a large amount of sulfate and partial carbonate are generated in the oxidation process, so that the high-alkalinity wastewater mainly comprising sodium sulfate and sodium carbonate is formed, and meanwhile, the alkaline wastewater contains partial sodium hydroxide, a small amount of sodium chloride and sodium bicarbonate, the sodium sulfate content of typical wastewater is about 6%, the alkalinity (calculated by sodium carbonate) is about 2%, and the water quality fluctuation is large. Because the waste water carbonate and sulfate cannot be effectively separated due to the limitation of the phase balance rule of a water-salt system, the waste water carbonate and sulfate are usually directly treated by a neutralization method, so that a large amount of acid is consumed, the waste water carbonate is converted into sulfate, the amount of impurity salt generated by subsequent treatment is large, and the treatment cost is high. Therefore, the research on the resource treatment of the petrochemical ethylene alkali slag wet oxidation alkaline wastewater is urgent.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides a method for separating and crystallizing alkaline waste water from ethylene alkali residue wet oxidation, solves the problem of recycling the alkaline residue wet oxidation waste water, and realizes near zero emission of the waste water and separate recycling of inorganic salt of the waste water.
The main components of the wastewater subjected to wet oxidation treatment of ethylene caustic sludge are sodium sulfate 2.5% -9%, sodium carbonate 0.1% -7%, sodium hydroxide 0.05% -1.5%, and small amounts of sodium chloride and sodium bicarbonate are contained, the total content of the two is generally not more than 1%, the wastewater contains various organic pollutants, and the COD of the wastewater is generally 1000-3000mg/L, so that the wastewater has typical characteristics of high COD, high sulfate and low alkalinity.
The aim of the invention is realized by the following technical scheme:
the wet oxidation alkaline waste water crystallization treatment method of ethylene alkali slag mainly comprises the following steps:
(1) Ozone catalytic advanced oxidation treatment is carried out on the ethylene alkali residue wet oxidation wastewater, the filling volume of the catalyst accounts for 60% -80% of the total volume of the reactor, the adding amount of the enhanced oxidant hydrogen peroxide is 0.1% -1% of the mass of the wastewater, and the operation pH is not lower than 10, so that key organic pollution factors of alkaline wastewater are removed, the chromaticity of the wastewater is reduced, and the quality of subsequent salt separation products is ensured.
(2) The wastewater after ozone catalytic oxidation treatment is concentrated for one time through an alkali-resistant film or an evaporation technology, so that the technical difficulty of converting the wastewater from a high-sulfate and low-alkalinity system to a low-sulfate and high-alkalinity system in the subsequent cooling crystallization process is reduced, and the hydroxide concentration of the system in the film concentration process is not higher than 1%.
(3) The waste water after primary concentration is subjected to forced external circulation cooling crystallization treatment, the cooling crystallization temperature is controlled to be 2-15 ℃, the cooling crystallization residence time is controlled to be 2-10 hours, and mirabilite is obtained through separation, so that the ratio of the alkalinity of cooling crystallization mother liquor (calculated by sodium carbonate) to sodium sulfate is improved, the subsequent recycling of sodium bicarbonate is possible, and meanwhile, the byproduct mirabilite is dissolved and then is subjected to evaporation crystallization to further prepare a glauber salt product;
(4) The cooling crystallization mother liquor is subjected to secondary concentration through an alkali-resistant film or an evaporation technology, the alkalinity and inorganic salt content of waste water are improved to be close to the saturation state, so that the recovery rate of sodium bicarbonate in the subsequent carbonization process is improved, and meanwhile, the chromaticity of the waste water can be further removed through an ozone catalytic oxidation technology according to the actual chromaticity of the cooling crystallization mother liquor, so that the quality of the subsequent sodium bicarbonate product is ensured; the method comprises the steps of carrying out a first treatment on the surface of the
(5) Directly feeding the secondary concentrated solution subjected to ozone catalytic oxidation treatment into a carbonization system, reacting with carbon dioxide under specific temperature and pressure conditions to crystallize and separate out sodium bicarbonate, controlling the mass ratio of the carbon dioxide fed in per unit time to the alkalinity of the feed wastewater (calculated by sodium carbonate) to be 0.4-3.6, filtering, washing and drying to obtain sodium bicarbonate products, returning the washing waste liquid of the products to a cooling crystallization unit, and controlling the drying temperature of the products to be 25-50 ℃;
(6) And (3) part of carbonized mother liquor enters a tail salt evaporation crystallization treatment system according to the sodium chloride content, the evaporated and crystallized tail salt is directly transported and backfilled, the rest carbonized mother liquor returns to a cooling crystallization unit, and sodium bicarbonate returns to react with sodium hydroxide in the original wastewater to be converted into sodium carbonate, so that the content of system hydroxide in the membrane concentration process is controlled to be not higher than 1%.
Further, the residence time of the ozone catalytic oxidation technology in the above steps is controlled to be 0.5-2 hours, the ozone adding amount is controlled to be 0.5-2 times of the total COD, the filling catalyst is one of noble metal supported alumina type catalyst, noble metal supported ceramsite filter material catalyst or particle activated carbon, or can be a combination of the catalysts, the filling volume of the catalyst accounts for 60% -80% of the total volume of the reactor, hydrogen peroxide is taken as a strong oxidant to realize the strengthening of the ozone catalytic oxidation process, the adding amount is 0.1% -1% of the wastewater mass, and the operation pH is not lower than 10, so that the organic matter degradation effect is ensured, and the organic pollutant entrainment of the fractional crystallization product is reduced.
Further, the primary concentration of the wastewater can adopt electrodialysis, reverse osmosis and other alkali-resistant membrane concentration or evaporation concentration technologies, and also can adopt related membrane concentration and evaporation concentration combination technologies, and the total dissolved solid content (TDS) of the primary concentrated solution is not less than 16%, so that the treatment capacity of a subsequent cooling crystallization unit can be effectively reduced, the cooling crystallization operation temperature is improved, the technical difficulty of a cooling crystallization process is reduced, and meanwhile, the concentration of hydroxide radical in a membrane concentration process system is not more than 1%, so that the long-period stable operation of a membrane material is ensured.
Further, the ratio of the alkalinity of wastewater (calculated by sodium carbonate) after primary concentrated solution cooling crystallization to sodium sulfate is controlled to be 1.4-2.5 so as to meet the production requirement of subsequent sodium bicarbonate carbonization crystallization, the corresponding cooling crystallization temperature is controlled to be 2-15 ℃, the cooling crystallization residence time is controlled to be 2-10 hours, the cooling crystallization operation temperature and residence time can effectively ensure large-particle crystallization products, the entrainment influence of organic pollutants is reduced, and the sodium sulfate byproduct is evaporated and crystallized again after being dissolved, so that the anhydrous sodium sulfate products are obtained after treatment.
Further, the secondary concentration of the wastewater can adopt electrodialysis, reverse osmosis and other alkali-resistant membrane concentration or evaporation concentration technologies, and can also adopt related membrane concentration and evaporation concentration combination technologies, and the total dissolved solid content (TDS) of the secondary concentrated solution is not lower than 21%, so that the treatment scale of the subsequent carbonization process can be effectively reduced, and the recovery rate of sodium bicarbonate in the carbonization process can be greatly improved.
Further, the concentration of gaseous carbon dioxide in the carbonization system is not lower than 25%, the partial pressure control range of carbon dioxide is 0.70-0.15 MPa, the mass ratio of carbon dioxide introduced in unit time to the alkalinity of the feed wastewater (calculated by sodium carbonate) is controlled to be 0.4-3.6, the control range of carbonization reaction temperature is 30-60 ℃, so as to promote the growth of sodium bicarbonate crystal particles, reduce the entrainment of residual organic pollutants, obtain sodium bicarbonate products after slurry is filtered, washed and dried after carbonization reaction, the washing waste liquid of the products is returned to a cooling crystallization unit, and the control range of drying temperature of the products is 25-50 ℃.
Further, the discharged carbonized mother liquor enters a tail salt evaporation crystallization treatment system, the sodium chloride content control range is 5% -10%, the rest carbonized mother liquor returns to a cooling crystallization unit, and sodium bicarbonate in the returning liquor reacts with sodium hydroxide in the raw wastewater to be converted into sodium carbonate, so that the system hydroxyl content in the membrane concentration process is controlled to be not higher than 1%.
Compared with the prior art, the invention has the following positive effects:
the invention effectively realizes recycling of waste water alkali resources while recycling sodium sulfate of alkaline waste water of ethylene alkali residue wet oxidation, has simple process operation, remarkable reduction effect of waste water and mixed salt, small environmental pollution risk and high safety, particularly, two qualified inorganic salt products of sodium bicarbonate and sodium sulfate are recycled under the conditions of high COD, high sulfate and low alkalinity of a waste water system, the purity is more than 99%, the added value of the products is high, the alkalinity of the waste water (calculated by sodium carbonate) and the recovery rate of sodium sulfate are both over 90%, the produced membrane concentrated fresh water and evaporated condensate water can realize reclaimed water recycling, thereby effectively realizing reduction, harmless, recycling and high-value utilization of the waste water of ethylene alkali residue wet oxidation treatment, and simultaneously supporting national strategy of carbon neutralization and carbon peak development with remarkable social and economic benefits.
Drawings
FIG. 1 is a schematic flow chart of a method for crystallizing alkaline waste water from wet oxidation of ethylene caustic sludge.
Detailed Description
The following provides a specific embodiment of a method for wet-oxidizing alkaline waste water to crystallize ethylene caustic sludge.
Example 1
Taking 18.74L of wastewater after wet oxidation treatment of ethylene caustic sludge, wherein the specific composition of the wastewater after wet oxidation treatment is 5.82 percent of sodium sulfate, 1.15 percent of sodium carbonate, 0.01 percent of sodium bicarbonate, 0.68 percent of sodium hydroxide and 0.15 percent of sodium chloride, wherein the COD content is 2530mg/L.
The ethylene caustic sludge wet oxidation wastewater is subjected to ozone catalytic oxidation, the ozone catalytic oxidation time is 2 hours, the ozone adding amount is 2000mg/L, the noble metal supported alumina type catalyst loading amount is 70%, the hydrogen peroxide adding amount is 0.6%, and the COD is reduced from 2530mg/L to 1132mg/L.
The ozone catalytic oxidation wastewater is concentrated for one time by adopting an evaporation concentration technology, and the total dissolved solid content (TDS) of the concentrated wastewater is 26.85 percent, and the specific compositions of the wastewater comprise 20.00 percent of sodium sulfate, 3.93 percent of sodium carbonate, 2.35 percent of sodium hydroxide and 0.52 percent of sodium chloride.
The wastewater after primary concentration is subjected to cooling crystallization treatment, the cooling crystallization temperature is controlled to be 12 ℃, mirabilite is precipitated at 2.21kg, the ratio of the alkalinity (calculated as sodium carbonate) of cooling crystallization mother liquor to sodium sulfate is 1.43, and the total dissolved solid content (TDS) is 17.92%. Adding water 1.54kg into mirabilite as byproduct, stirring thoroughly, evaporating again for crystallization after the mirabilite is completely dissolved, filtering, washing and drying to obtain 0.87kg of sodium sulfate product with purity of more than 99%.
The evaporation concentration technology is adopted to carry out secondary concentration on the cooled crystallization mother liquor, the total solid content (TDS) of the wastewater is improved to 26.70 percent, the concentrated solution is subjected to ozone catalytic oxidation treatment, the retention time is 2 hours, the ozone adding amount is 1000mg/L, the loading amount of the noble metal supported alumina type catalyst is 70 percent, the hydrogen peroxide adding amount is 0.2 percent, and the chromaticity of the wastewater is further reduced.
Directly introducing 0.1MPa high-purity carbon dioxide gas into the secondary concentrated wastewater subjected to ozone catalytic oxidation treatment at 60 ℃, crystallizing and separating out 0.44kg of sodium bicarbonate, 2.40kg of residual carbonized mother liquor, and completely recycling the sodium chloride content in the carbonized mother liquor to a cooling crystallization unit.
After fifteen times of circulation stabilization, 1.12kg of anhydrous sodium sulfate product can be obtained, meanwhile, the sodium chloride content in the carbonized mother liquor is enriched to 5.79%, 10% of the carbonized mother liquor is directly discharged to a tail salt evaporation crystallization treatment system, the discharged mother liquor amount is 0.50kg, and 0.12kg of tail salt is produced after evaporation crystallization. And adding 1.14kg of evaporating condensate water into 0.77kg of sodium bicarbonate produced by the carbonization unit, fully washing, centrifuging and drying to obtain 0.61kg of sodium bicarbonate product, wherein the COD entrainment of the product is less than 50mg/kg, the purity is more than 99%, and the sodium bicarbonate washing wastewater and the residual carbonization mother liquor are recycled to the cooling crystallization unit.
Example 2
37.04L of wastewater after wet oxidation treatment of ethylene caustic sludge is taken, and the specific composition of the wastewater after wet oxidation treatment is 3.77 percent of sodium sulfate, 0.33 percent of sodium carbonate, 0.01 percent of sodium bicarbonate, 0.27 percent of sodium hydroxide and 0.14 percent of sodium chloride, wherein the COD content is 1870mg/L.
The ethylene caustic sludge wet oxidation wastewater is subjected to ozone catalytic oxidation, the ozone catalytic oxidation time is 2 hours, the ozone adding amount is 2000mg/L, the activated carbon catalyst loading amount is 80%, the hydrogen peroxide adding amount is 1.0%, and the COD is reduced from 1870mg/L to 853mg/L.
The alkali-resistant electrodialysis membrane is adopted to concentrate the ozone catalytic oxidation wastewater once, the total solid content (TDS) of the concentrated wastewater is 17.99%, and the main components of the wastewater comprise 15.01% of sodium sulfate, 1.30% of sodium carbonate, 1.08% of sodium hydroxide and 0.55% of sodium chloride.
And (3) carrying out cooling crystallization treatment on the wastewater after primary concentration, wherein the cooling crystallization temperature is controlled to be 3 ℃, 3.18kg of mirabilite is precipitated, and the total solid content (TDS) of the cooling crystallization mother solution is 6.98%. Adding water 4.00kg into the byproduct mirabilite, fully stirring, re-evaporating and crystallizing after the mirabilite is completely dissolved, filtering, washing and drying to obtain 1.30kg of anhydrous sodium sulfate product, wherein the purity of sodium sulfate is more than 99%.
The cooling crystallization mother liquor is subjected to secondary concentration by adopting an alkali-resistant electrodialysis membrane and evaporation concentration combined technology, the total solid content (TDS) of the wastewater solubility is increased to 28.45%, the concentrated solution is subjected to ozone catalytic oxidation treatment, the retention time is 2 hours, the ozone adding amount is 1000mg/L, the activated carbon catalyst filling amount is 80%, and the hydrogen peroxide adding amount is 0.4%, so that the chromaticity of the wastewater is further reduced.
Directly introducing purified flue gas (carbon dioxide partial pressure is 0.12 MPa) with the mass fraction of carbon dioxide of 0.4MPa of 30% into the secondary concentrated wastewater subjected to ozone catalytic oxidation treatment at 50 ℃, crystallizing and separating out 0.29kg of sodium bicarbonate, and recycling the rest 1.60kg of carbonized mother liquor to a cooling crystallization unit, wherein the sodium chloride content in the carbonized mother liquor is 3.42%.
After twelve times of circulation stabilization, the ratio of the alkalinity (calculated by sodium carbonate) in the cooled crystallization mother liquor to sodium sulfate reaches 2.4, and glauber salt is evaporated and recrystallized to obtain 1.45kg of anhydrous sodium sulfate. The sodium chloride content in the carbonized mother liquor is enriched to 9.09%, 15% of the carbonized mother liquor is directly discharged to a tail salt evaporation crystallization treatment system, the discharged mother liquor amount is 0.47kg, and 0.13kg of tail salt is generated after evaporation crystallization. Meanwhile, the carbonization unit produces 0.64kg of sodium bicarbonate, 1.69kg of evaporation condensate water is added for full washing, 0.40kg of sodium bicarbonate product is obtained after centrifugal drying, the COD entrainment of the product is less than 50mg/kg, the purity is greater than 99%, and the sodium bicarbonate washing liquid and the residual carbonization mother liquid are circulated to the cooling crystallization unit.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the concept of the present invention, and are intended to be within the scope of the present invention.
Claims (7)
1. The wet oxidation alkaline waste water fractional crystallization treatment method for the ethylene alkaline residue is characterized by mainly comprising the following steps of:
(1) Carrying out ozone catalytic advanced oxidation treatment on the alkaline wastewater of ethylene alkali residue wet oxidation, wherein the catalyst filling volume is 60% -80% of the total volume of the reactor, the adding amount of the reinforced oxidant hydrogen peroxide is 0.1% -1% of the wastewater mass, and the operation pH is not lower than 10;
(2) Concentrating the wastewater subjected to ozone catalytic oxidation for one time through an alkali-resistant film or an evaporation technology to reduce the technical difficulty of converting the wastewater from a high-sulfate and low-alkalinity system to a low-sulfate and high-alkalinity system in the subsequent cooling crystallization process, wherein the concentration of hydroxide in the film concentration process system is not higher than 1%;
(3) Carrying out forced external circulation cooling crystallization treatment on the wastewater after primary concentration, controlling the cooling crystallization temperature to be 2-15 ℃, controlling the cooling crystallization residence time to be 2-10 hours, and separating to obtain mirabilite, wherein the control range of the ratio of the alkalinity of the cooling crystallization mother liquor calculated by sodium carbonate to sodium sulfate is 1.4-2.5; meanwhile, the byproduct mirabilite is dissolved and then is evaporated and crystallized to further prepare a sodium sulfate product;
(4) Performing secondary concentration on the cooling crystallization mother liquor through an alkali-resistant film or an evaporation technology, improving the alkalinity and inorganic salt content of the wastewater to be close to a saturated state, and simultaneously, further removing the chromaticity of the wastewater through an ozone catalytic oxidation technology according to the actual chromaticity situation of the cooling crystallization mother liquor;
(5) Directly feeding the secondary concentrated solution subjected to ozone catalytic oxidation treatment into a carbonization system, reacting with carbon dioxide under specific temperature and pressure conditions to crystallize and separate out sodium bicarbonate, controlling the mass ratio of the carbon dioxide fed in per unit time to the alkalinity of the feed wastewater calculated by sodium carbonate to be 0.4-3.6, filtering, washing and drying to obtain a sodium bicarbonate product, returning the product washing waste liquid to a cooling crystallization unit, and controlling the product drying temperature to be 25-50 ℃;
(6) And (3) part of carbonized mother liquor enters a tail salt evaporation crystallization treatment system according to the sodium chloride content, the evaporated and crystallized tail salt is directly transported and backfilled, the rest carbonized mother liquor returns to a cooling crystallization unit, and sodium bicarbonate returns to react with sodium hydroxide in the original wastewater to be converted into sodium carbonate, so that the content of system hydroxide in the membrane concentration process is controlled to be not higher than 1%.
2. The method for the fractional crystallization treatment of alkaline waste water from the wet oxidation of ethylene caustic sludge according to claim 1, wherein the residence time of the ozone catalytic advanced oxidation technology in the step (1) is controlled to be 0.5-2 hours, and the ozone adding amount is 0.5-2 times of the total amount of COD.
3. The method for the fractional crystallization treatment of alkaline waste water from the wet oxidation of ethylene caustic sludge according to claim 1, wherein the catalyst loaded in the step (1) is one or a combination of a noble metal-loaded alumina catalyst, a noble metal-loaded ceramsite filter material catalyst or granular activated carbon.
4. The method for the fractional crystallization treatment of alkaline waste water from wet oxidation of ethylene caustic sludge according to claim 1, wherein the primary concentration is performed by alkali-resistant membrane concentration or evaporation concentration technology, and the Total Dissolved Solids (TDS) of the primary concentrate is not less than 16%.
5. The method for the fractional crystallization treatment of alkaline waste water from wet oxidation of ethylene caustic sludge according to claim 1, wherein the secondary concentration is performed by alkali-resistant membrane concentration or evaporation concentration technology, and the Total Dissolved Solids (TDS) of the secondary concentrate is not less than 21%.
6. The method for the fractional crystallization treatment of alkaline waste water from wet oxidation of ethylene caustic sludge according to claim 1, wherein the mass concentration of gaseous carbon dioxide in the carbonization system is not lower than 25%, the partial pressure control range of carbon dioxide is 0.70-0.15 MPa, and the reaction temperature control range is 30-60 ℃.
7. The method for the fractional crystallization treatment of the alkaline waste water from the wet oxidation of the ethylene caustic sludge according to claim 1, wherein the content of sodium chloride in the carbonized mother liquor entering the tail salt evaporation crystallization treatment system is controlled to be 5% -10%.
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