CN114715855A - Method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater - Google Patents

Method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater Download PDF

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Publication number
CN114715855A
CN114715855A CN202210051377.4A CN202210051377A CN114715855A CN 114715855 A CN114715855 A CN 114715855A CN 202210051377 A CN202210051377 A CN 202210051377A CN 114715855 A CN114715855 A CN 114715855A
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CN
China
Prior art keywords
wastewater
caustic sludge
sodium thiosulfate
thiosulfate pentahydrate
sludge wastewater
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Pending
Application number
CN202210051377.4A
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Chinese (zh)
Inventor
邓文海
刘笑天
曹实
皮新燕
马永学
陈素宁
赵玉安
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South Venture Tianjin Technology Development Co ltd
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South Venture Tianjin Technology Development Co ltd
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Priority to CN202210051377.4A priority Critical patent/CN114715855A/en
Publication of CN114715855A publication Critical patent/CN114715855A/en
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00Sulfur; Compounds thereof
    • C01B17/64Thiosulfates; Dithionites; Polythionates
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/02Treatment of water, waste water, or sewage by heating
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/38Treatment of water, waste water, or sewage by centrifugal separation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Inorganic Chemistry (AREA)
  • Removal Of Specific Substances (AREA)
  • Treatment Of Water By Ion Exchange (AREA)

Abstract

The invention provides a method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater, which comprises the following operation steps: and (3) filtering: filtering the caustic sludge wastewater to remove impurities in the caustic sludge wastewater; heat exchange: the filtered wastewater is subjected to heat exchange and then cooled and crystallized; separation: and (3) cleaning the crystallized feed liquid, and separating out solids. The invention adopts the cold separation technology to treat the caustic sludge wastewater, and finally extracts the sodium thiosulfate pentahydrate, the sulfur removal efficiency of the caustic sludge wastewater can reach 90 percent, the resource recycling is realized while the wastewater is treated, the investment is low, the operation cost is low, and the invention is worthy of being widely applied to the pretreatment of the caustic sludge wastewater of petrochemical enterprises.

Description

Method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater
Technical Field
The invention relates to the technical field of wastewater treatment, in particular to a method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater.
Background
The alkaline residue wastewater belongs to high-concentration organic wastewater in a refinery, contains a large amount of salt, sulfide and the like, has high concentration, greatly influences the normal operation of wastewater treatment facilities of the petrochemical plant and the qualification rate of wastewater treatment, has high toxicity, and has the toxic substances, so that some pollutants are extremely toxic substances, enter organisms and human bodies, are combined with protein, and can cause permanent damage. In the prior art, a low-pressure wet oxidation method, a neutralization method and an advanced oxidation method are generally adopted for treatment. For example, chinese patent application No. 201210521764.6 discloses a method for treating sodium sulfide wastewater, comprising the steps of: mixing the sodium sulfide waste water, the industrial waste sulfur and the catalyst, and then introducing air to carry out oxidation reaction; and filtering after the oxidation reaction is finished, concentrating the filtrate, cooling and crystallizing, filtering to obtain sodium thiosulfate crystals and crystallization mother liquor, and drying the sodium thiosulfate crystals to obtain sodium thiosulfate pentahydrate. Through the technical scheme, a single product can be obtained, certain economic benefits are achieved, substances such as sulfur and a catalyst need to be added, the operation is complicated, and the defects of high investment and high operation cost exist. How to design a method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater, which is simple and convenient to operate, so as to obtain the sodium thiosulfate pentahydrate with less investment and lower operation cost is the technical problem to be solved by the application.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater.
The invention is realized by the following technical scheme:
a method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater comprises the following operation steps:
(1) and (3) filtering: filtering the alkaline residue wastewater to remove impurities in the alkaline residue wastewater;
(2) heat exchange: the filtered wastewater is subjected to heat exchange and then cooled and crystallized;
(3) separation: and (3) cleaning the crystallized feed liquid, and separating out solids.
Preferably, in the step (1), the filtration precision is 100 μm, and the hydraulic retention time during filtration is 0.5-1 h.
Further preferably, in the step (2), a heat exchanger is adopted for heat exchange, the working temperature of the heat exchanger is 0-5 ℃, and the heat exchange time is 2 min; the cooling crystallization time is 1-2 h.
Further preferably, the heat exchanger is cooled by a refrigerant at-20 ℃ to-10 ℃.
More preferably, in the step (2), a cold precipitation circulation system for exchanging heat again for the crystalline substance to be cooled is further provided during cooling crystallization, and the circulation ratio is 1: 5.
most preferably, in the step (3), the feed liquid is firstly cleaned by using a cleaning agent, and then the cleaned feed liquid is separated by using a centrifugal separator; the cleaning agent is 5 deg.C clear water, cleaning time is 10min, and centrifuging time is 10 min.
In consideration of the extraction effect and the economic benefit of extraction, the caustic sludge wastewater related to the method is specifically caustic sludge wastewater with the salt content of not more than 200000mg/L and the sulfide content of not more than 200000 mg/L.
Compared with the prior art, the method adopts a cold separation technology to treat the caustic sludge wastewater to extract the sodium thiosulfate pentahydrate, the sulfur removal efficiency of the caustic sludge wastewater can reach 90 percent, the resource reutilization is realized while the wastewater is treated, the investment is low, the occupied area is small, the operation cost is low, and the method is worthy of being widely applied to the pretreatment of the caustic sludge wastewater of petrochemical enterprises.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
The sulfide content of the catalytic gasoline alkaline residue in a refinery is 1.09 multiplied by 105mgA salt content of 1.46X 105mg/L. The method of the invention is used for processing: firstly, filtering the alkaline residue wastewater by adopting a tubular filter with the filtering precision of 100 mu m, wherein the hydraulic retention time is 1h during filtering; the filtered wastewater is subjected to heat exchange through a heat exchanger, the working temperature of the heat exchanger is 5 ℃, and the heat exchange time is 2 min; after heat exchange, standing the wastewater, cooling and crystallizing for 2 hours; and cleaning the crystal with 5 deg.C clear water for 10min, and separating the cleaned material liquid with a centrifuge for 10 min.
The sulfide content of the alkaline residue after the treatment is 1.05 multiplied by 104mg/L, the removal rate of sulfide reaches more than 90 percent; the salt content is 1.15 × 105mg/L, and the removal rate can reach more than 20 percent.
Example 2
The sulfide content in the water coming from alkali dregs of a certain refinery is 4.4X 104mg/L, salt content 7.38X 104mg/L. The method of the invention is used for processing: firstly, filtering the alkaline residue wastewater by adopting a tubular filter with the filtering precision of 100 mu m, wherein the hydraulic retention time is 30min during filtering; the filtered wastewater is subjected to heat exchange through a heat exchanger, the working temperature of the heat exchanger is 0 ℃, and the heat exchange time is 2 min; standing the waste water after heat exchange, cooling and crystallizing for 1 h; and cleaning the crystal with 5 deg.C clear water for 10min, and separating the cleaned material liquid with a centrifuge for 10 min.
The sulfide content of the alkaline residue wastewater after the treatment is 3696mg/L, and the sulfide removal rate reaches 91.6%; the salt content is 5.73 × 104mg/L, the removal rate can reach 22.4 percent.
Example 3
1.4X 10 times sulfide content in water from alkaline residue of a certain refinery5mg/L, salt content 4.2X 104mg/L. The method of the invention is used for processing: firstly, filtering the alkaline residue wastewater by using a tubular filter with the filtering precision of 100 mu m, wherein the hydraulic retention time is 45min during filtering; the filtered wastewater is subjected to heat exchange through a heat exchanger, the working temperature of the heat exchanger is 2 ℃, and the heat exchange time is 2 min; after heat exchange, the wastewater is stood for cooling crystallization, and the cooling crystallization time is 1.5 h; mining Washing the crystal with 5 deg.C clear water for 10min, and separating the washed liquid with centrifuge for 10 min.
The sulfide content of the alkali residue wastewater after the treatment is 11200mg/L, and the sulfide removal rate reaches 92%; the salt content is 3.17 × 104mg/L, the removal rate can reach 24.5 percent.
Example 4
Compared with the embodiment 1, the cooling crystallization is also provided with a cold precipitation circulating system for carrying out heat exchange on the crystalline substance to be cooled again, and the circulating ratio is 1: 5. the rest is the same as in example 1.
The sulfide content of the treated alkaline residue is 5450mg/L, and the sulfide removal rate reaches 95%; the salt content is 1.0 × 105mg/L, the removal rate can reach 31.5 percent. Therefore, after the cold separation circulating system is additionally arranged, the cold separation effect is better, and the sulfide and salt content are also obviously reduced.
The above description is only exemplary of the present invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. The construction or connection of parts not described in detail in the present invention is prior art.

Claims (7)

1. A method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater is characterized by comprising the following steps: the method comprises the following operation steps:
(1) And (3) filtering: filtering the caustic sludge wastewater to remove impurities in the caustic sludge wastewater;
(2) heat exchange: the filtered wastewater is subjected to heat exchange and then cooled and crystallized;
(3) separation: and (3) cleaning the crystallized feed liquid, and separating out solids.
2. The method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater as claimed in claim 1, which is characterized in that: in the step (1), the filtration precision is 100 μm, and the hydraulic retention time during filtration is 0.5-1 h.
3. The method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater as claimed in claim 1, which is characterized in that: in the step (2), heat exchange is carried out by adopting a heat exchanger, the working temperature of the heat exchanger is 0-5 ℃, and the heat exchange time is 2 min; the cooling crystallization time is 1-2 h.
4. The method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater as claimed in claim 3, which is characterized in that: the heat exchanger provides cold energy by the refrigerant with the temperature of minus 20 ℃ to minus 10 ℃.
5. The method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater as claimed in claim 1, which is characterized in that: in the step (2), a cold separation circulating system for carrying out heat exchange on the substances to be cooled and crystallized again is further arranged during cooling and crystallization, and the circulation ratio is 1: 5.
6. The method for extracting sodium thiosulfate pentahydrate by using the caustic sludge wastewater as claimed in claim 1, which is characterized in that: in the step (3), firstly, cleaning the feed liquid by using a cleaning agent, and then separating the cleaned feed liquid by using a centrifugal separator; the cleaning agent is clear water with the temperature of 5 ℃, the cleaning time is 10min, and the centrifugation time is 10 min.
7. The method for extracting sodium thiosulfate pentahydrate by using caustic sludge wastewater as claimed in any one of claims 1 to 6, which is characterized in that: the salt content of the alkaline residue wastewater is less than or equal to 200000mg/L, and the sulfide content of the alkaline residue wastewater is less than or equal to 200000 mg/L.
CN202210051377.4A 2022-01-17 2022-01-17 Method for extracting sodium thiosulfate pentahydrate by using alkaline residue wastewater Pending CN114715855A (en)

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CN101161596A (en) * 2007-05-14 2008-04-16 中国科学院过程工程研究所 A method for resource processing non-ferro metals processing wastewater containing ammonia and sulfate radical
CN101200336A (en) * 2007-12-18 2008-06-18 赵志军 Process for zero-discharge treatment of o-phenylenediamine sodium sulfide reduction wastewater
CN105174582A (en) * 2015-09-15 2015-12-23 山东农业大学 Resource treatment process of 1-amino anthraquinone sulfurization reduction wastewater
CN105819406A (en) * 2016-03-09 2016-08-03 北京富海天环保科技有限公司 Apparatus and method for preparing sodium hyposulfite through purifying coking desulphurization waste liquid salt extraction filter residues used as raw material
CN109179453A (en) * 2018-08-16 2019-01-11 天津大学 A kind of Crystallization Separation method for coking desulfurization waste water salt extraction extraction filter residue
CN109422409A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of ammonium salt-containing waste water
CN109422407A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of catalyst production waste water
CN109422402A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of catalyst production waste water
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CN101200336A (en) * 2007-12-18 2008-06-18 赵志军 Process for zero-discharge treatment of o-phenylenediamine sodium sulfide reduction wastewater
CN105174582A (en) * 2015-09-15 2015-12-23 山东农业大学 Resource treatment process of 1-amino anthraquinone sulfurization reduction wastewater
CN105819406A (en) * 2016-03-09 2016-08-03 北京富海天环保科技有限公司 Apparatus and method for preparing sodium hyposulfite through purifying coking desulphurization waste liquid salt extraction filter residues used as raw material
CN109422409A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of ammonium salt-containing waste water
CN109422407A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of catalyst production waste water
CN109422402A (en) * 2017-08-28 2019-03-05 中国石油化工股份有限公司 The processing method of catalyst production waste water
CN109179453A (en) * 2018-08-16 2019-01-11 天津大学 A kind of Crystallization Separation method for coking desulfurization waste water salt extraction extraction filter residue
CN112357966A (en) * 2020-11-04 2021-02-12 成都千砺金科技创新有限公司 Crystallization method of ferrous sulfate heptahydrate in production process of titanium dioxide by sulfuric acid method

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