CN106315930A - Method for regeneration and recycling of ethylene waste alkali liquor - Google Patents

Method for regeneration and recycling of ethylene waste alkali liquor Download PDF

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Publication number
CN106315930A
CN106315930A CN201510346558.XA CN201510346558A CN106315930A CN 106315930 A CN106315930 A CN 106315930A CN 201510346558 A CN201510346558 A CN 201510346558A CN 106315930 A CN106315930 A CN 106315930A
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bipolar membrane
membrane electrodialysis
type bipolar
room
lye
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马克存
褚洪岭
王斯晗
徐显明
杜龙弟
贺德福
曹婷婷
王立艳
李霞
尹燕磊
郭立明
郭英姿
刘丽军
周传勇
姚奕
赵铁凯
王亚丽
孟锐
左艳梅
曹媛媛
雪晶
姜伟
朱丽娜
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China Petroleum and Natural Gas Co Ltd
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China Petroleum and Natural Gas Co Ltd
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Abstract

The present invention relates to a method for regeneration and recycling of an ethylene waste alkali liquor, and the process is as follows: degreasing treatment, oxidation treatment, filtration treatment and bipolar membrane electrodialysis treatment. A two-room bipolar membrane and a three-room bipolar membrane are sequentially used for electrodialysis treatment of the ethylene waste alkali liquor, remaining sodium hydroxide is recovered, meanwhile sodium carbonate can be converted into carbon dioxide and sodium hydroxide, sodium sulfate can be converted into sulfuric acid and sodium hydroxide, an obtained 8%-15% sodium hydroxide solution can be directly returned to an ethylene cracking gas alkaline cleaning device for recycling, material consumption of the ethylene cracking gas alkaline cleaning device is reduced, the production cost is reduced, and the shortcomings of low recovery alkali concentration and difficulty in direct recycling in prior art can be overcome.

Description

A kind of method of ethylene waste lye regeneration
Technical field
The invention belongs to oil-refining chemical field, relate to the Regeneration Treatment of ethylene waste lye, be also suitable for liquid simultaneously The process of the sulfur-containing waste lyes such as state hydrocarbon alkali cleaning spent lye.
Background technology
In oil-refining chemical production process, the strong base solution such as sodium hydroxide of the most commonly used about 8% is washed CO in method removing natural gas, liquid hydrocarbon or the ethylene cracking gas washed2、H2The sour gas such as S, Thus produce substantial amounts of alkali-washing waste liquid (sour gas alkali-washing waste liquid).Except containing residue in sour gas alkali-washing waste liquid NaOH outside, possibly together with in alkaline cleaning procedure generate Na2S、Na2CO3Deng inorganic salt.Simultaneously because The processes such as the heavy constituent condensation occurred in alkali cleaning and unsaturated hydro carbons condensation, make substantial amounts of Organic substance enter useless In alkali liquor, it is contained therein with forms such as oil slick, dispersed oil and emulsus oil.Therefore, sour gas alkali-washing waste liquid Improvement relate to removing oily substance, go the asking of the several respects such as comprehensive utilization of sulphide removal and residue alkali Topic.
Process for sour gas alkali-washing waste liquid both at home and abroad develops substantial amounts of method, and these methods can be classified as Innoxious and the big class of resource two.
What innoxious process for treating application was wider has acidifying-vaporizing extract process and all kinds of oxidizing process.
Acidifying-vaporizing extract process is once commonly used to process in China's the eighties from the external ethylene unit introduced and splits Vent one's spleen alkali-washing waste liquid.First cracking gas alkali-washing waste liquid is acidified by the method with concentrated sulphuric acid, and being re-fed into stripper will H2S、CO2Etc. being stripped off sending torch to burn.Although this method technique is simple, high treating effect, but It is the seriously corroded to equipment, produces secondary pollution simultaneously.The method is abandoned the most both at home and abroad at present With.
Oxidizing process is that the sulfide in sour gas alkali-washing waste liquid is converted by the Oxidation by various oxidants For harmless thiosulfate or sulfate etc..Difference according to the oxidant used and process technique again may be used To be divided into air oxidation process, wet air oxidation, chlorine oxidation process, advanced oxidation processes and catalysis oxidation Method etc..The advantage of these methods is that processing speed is fast and thorough, will not produce secondary pollution, but it lacks Point is complex process, long flow path, equipment investment is big, operating cost is high.Wet type in current this kind of method is empty Gas oxidizing process technology is more ripe, and Application comparison is extensive.But the waste liquid after Chu Liing also needs to through neutralizing, life Change processes could qualified discharge.
The recycling treatment of sour gas alkali-washing waste liquid be initially pass it through simple oil removal treatment after for making Slurry papermaking.Due to NaOH and Na in sour gas alkali-washing waste liquid2S is having in soda pulping process cooking liquor Effect composition, therefore can be used for pulping and paper-making by the sour gas alkali-washing waste liquid after oil removing.The shortcoming of this method It is that the oily substance in spent lye is generally difficult to Ex-all, with abnormal flavour, finally affects paper quality.
It addition, certain enterprise domestic once used H2S neutralisation reclaims in ethylene cracking gas alkali-washing waste liquid Sodium sulfide.This technique can utilize ethylene cracking gas alkali-washing waste liquid to produce Na2S.But cannot be to it In Na2CO3Reclaiming, the waste liquid of discharge need nonetheless remain for acid adding and neutralizes, and Na2The matter of S product Measure the highest.
United States Patent (USP) US 4981556 describes one and " utilizes copper oxide preparation without the technique of sulfur alkali liquor ". Sodium carbonate is first changed into sodium hydroxide with causticizing process by this patent, then with in the solution after copper oxide and causticization Sodium sulfide reaction generates sodium hydroxide and copper sulfide.Copper sulfide regenerates oxygen with rotary furnace calcining after filtering Change copper to recycle.But this patent copper sulfide regenerative process produces SO2, cause secondary pollution.
Chinese patent CN1789162A proposes the Regeneration Treatment of a kind of ethylene cracking gas alkali-washing waste liquid Technique.This technique uses transition metal oxide and alkaline earth oxide to be split by ethylene unit after oil removing respectively Vent one's spleen the Na in alkali-washing waste liquid2S and Na2CO3It is converted into NaOH, makes ethylene waste lye be regenerated.Should The advantage of patent is to have carried out regenerating completely by ethylene cracking gas alkali-washing waste liquid, enables to return ethylene Cracking alkaline cleaner recycles.But, this patent the most specifically proposes the copper sulfide of sweetening process generation and sinks The processing method formed sediment.
Chinese patent CN102815815A is respectively adopted the metal-oxides such as CuO and CaO as desulfurizing agent With caustic, spent lye being carried out desulfurization and causticization regeneration, desulfurization precipitation processes through wet oxidation process and is converted into Sulfate, then generates metal oxide desulfurizer recycling utilization with alkaline reaction, and caustic precipitation passes through Calcination and regeneration is that caustic recycles.The method treatment effect is preferable, it is achieved that desulfurizing agent pollution-free again Give birth to and recycle.
Chinese patent CN102452673A discloses a kind of method reclaiming sodium sulfate from ethylene waste lye, Ethylene waste lye after first wet oxidation process is processed by the method is neutralized, and then uses evaporative crystallization method Reclaim anhydrous sodium sulfate product.
Wei Yanxin (" bipolar membrane electrodialysis method processes typical case's wastewater from chemical industry research ", China Science & Technology University Ph.D. Dissertation, 2012) propose to use the hydrogen in bipolar membrane electrodialysis technology recovery ethylene waste lye Sodium oxide, when electrolyte concentration is 0.20~0.30mol/L, and the initial concentration of alkali is 0.10~0.25mol/L Low energy consumption and high current efficiency can be obtained.Additionally, want to obtain high current efficiency and relatively low energy consumption, Electric current density selects 30~60mA/cm2Scope.Under optimal experiment condition, laboratory scale After running 2h on equipment, the naoh concentration regenerating recovery from spent lye reaches 0.11mol/L, process Cost about reclaims every kilogram sodium hydroxide and needs 0.97 dollar, and a small amount of oil in spent lye is to NaOH Regeneration is almost no impact, and result shows, utilizes bipolar membrane electrodialysis technology to regenerate back from spent lye It is feasible for receiving sodium hydroxide.Its shortcoming is that the alkali concn reclaimed is relatively low, only 0.44%, it is difficult to meet and follow The requirement that ring utilizes, this research simultaneously is not mentioned and the sodium carbonate in ethylene waste lye and sodium sulfate being converted For carbon dioxide, sulphuric acid and sodium hydroxide.
Zhang Ni (" research of bipolar membrane electrodialysis cleaning production organic acid ", HeFei University of Technology's master's degree Paper, 2008) formic acid in BP-A two chamber-type bipolar membrane electrodialysis recovery oxalic acid abstraction waste liquor is proposed, This research paper result of study shows 20~80mA/cm2Current density range in, the electrodialysis of carbonic acid Energy consumption difference 20.1~96.3kwh/kg, it is clear that use BP-C-A tri-Room type bipolar membrane electrodialysis to process second The energy consumption of alkene spent lye will be the highest.
Gold can bravely wait (the industrial applications research of BPM2 type bipolar membrane device sodium sulfate alkaline, water process skill Art volume 39 the 7th phase, Vol.39No.7, in July, 2013,81-83) use BP-C-A tri-compartment type double Pole EDBM sodium sulfate preparing hydrogen sodium oxide, uses BPM2-2500 type equipped with 60 groups, effective face Long-pending total 15m2Equipment, preset 600A/m2(total current 150A) carries out under constant current operation, and electric current is imitated Rate is 70%, produce alkali energy consumption be 1800kWh/t, produce alkali integrated cost be 2135 yuan/ton, less than 2300~ The cost of the conventional ion embrane method of 2500 yuan/ton.
Summary of the invention
For the defect of prior art, it is an object of the invention to provide a kind of economical and effective, without additional component The New Method for Processing of ethylene waste lye, the method utilizes ethylene waste lye preparing hydrogen sodium oxide, sulphuric acid and dioxy Changing carbon, sodium hydroxide solution returns ethene cracking gas alkaline cleaner and recycles, and sulphuric acid, carbon dioxide are comprehensive Utilize or sell as side-product, thoroughly realizing the recycling treatment of this strand of spent lye, reduce efflux wastewater Discharge capacity, and the salt rejection rate of waste water is greatly improved.
A kind of method for reclaiming of ethylene waste lye, including following technical process:
(1) oil removal treatment: use the oily substance in gravitational separation process and/or extraction removing spent lye, Described oily substance includes oil slick, dispersed oil and oil emulsion;
(2) oxidation processes: use oxidizing process that the ethylene waste lye after oil removing is carried out desulfurization process, should Sulfide in spent lye is converted into sulfate;
(3) filtration treatment: use the float in Filtration removing ethylene waste lye and solid precipitation;
(4) bipolar membrane electrodialysis processes: use two chamber-type bipolar membrane electrodialysis-filtration-three room type Bipolar Membrane Spent lye after filtering is processed by electrodialysis, first, uses two chamber-type bipolar membrane electrodialysis device to reclaim Remaining sodium hydroxide in spent lye, is converted into sodium hydroxide and dioxy by the sodium carbonate in this spent lye simultaneously Changing carbon, obtain metabisulfite solution, carbon dioxide uses sodium bicarbonate solution and desalted water to wash and be dried successively Refined recovery;Then, use three Room type bipolar membrane electrodialysis devices that metabisulfite solution is converted into sulphuric acid and hydrogen Sodium oxide, processes, by two chamber-type and three Room type bipolar membrane electrodialysis, the sodium hydroxide solution merging obtained and directly returns Return ethylene alkali-washing device to recycle;
The water part, salt room of described three Room type bipolar membrane electrodialysis devices is as two chamber-type bipolar membrane electrodialysis The alkali room water inlet of device, remainder is discharged into sewage farm.
In step (4), described two chamber-type bipolar membrane electrodialysis device is BP-C configuration, described three Room types Bipolar membrane electrodialysis device is BP-A-C configuration.
In step (4), during described two chamber-type bipolar membrane electrodialysis, electric current density be preferably 600~ 1200A/m2
In step (4), during described two chamber-type bipolar membrane electrodialysis, the pH of salt room discharging be 2.0~ 4.4。
In step (4), during described three Room type bipolar membrane electrodialysis, electric current density be 800~ 1500A/m2
In step (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and sulphuric acid quality is dense Degree is 7.8%~8.5%.
In step (4), described CO 2 refining reclaim time sodium bicarbonate solution mass concentration be 1%~ 15%.
In step (2), described oxidation processes is wet oxidation process, and oxidizing temperature is 200~260 DEG C, Partial pressure of oxygen is 0.5~2MPa, and oxidant is oxygen, and the time of staying is 1~3h.
The present invention, with ethylene waste lye preparing hydrogen sodium oxide, sulphuric acid and carbon dioxide, achieves ethylene comprehensively and gives up The minimizing of alkali liquor, resource, compared with prior art, this technology mainly has the advantage that
1. in bipolar membrane electrodialysis processing procedure, initially with two chamber-type bipolar membrane electrodialysis device to useless Alkali liquor processes, it is possible to electricity acidifying spent lye, while reclaiming residual hydrogen sodium oxide therein, by it In sodium carbonate be converted into sodium hydroxide and carbon dioxide, CO 2 refining reclaims subsequently, and as by-product Product comprehensively utilize;The raw material of three follow-up Room type bipolar membrane electrodialysis devices can be made to be mainly sodium sulfate simultaneously Solution, it is to avoid electrodialysis energy consumption required in the presence of sodium carbonate, thus reduce the purpose of energy consumption.So After, use three Room type bipolar membrane electrodialysis devices that filtrate is further processed, reclaim sulphuric acid and hydroxide Sodium.Finally, hydrogen-oxygen two chamber-type bipolar membrane electrodialysis device and three Room type bipolar membrane electrodialysis devices prepared Change sodium solution merging return ethylene alkali-washing device to recycle.
2. in bipolar membrane electrodialysis processing procedure, the salt room outlet part of three Room type bipolar membrane electrodialysis devices It is allocated as the alkali room for two chamber-type and three Room type bipolar membrane electrodialysis devices to intake, has no effect on produced hydrogen-oxygen Changing recycling of sodium, remainder is discharged into sewage farm.
3. using the part salt room discharging of three Room bipolar membrane electrodialysis devices as two Room bipolar membrane electrodialysis and three The alkali room charging of room bipolar membrane electrodialysis so that the discharge capacity of efflux wastewater can reduce by more than 85%, with Time spent lye in sodium carbonate and sodium sulfate owing to being converted into carbon dioxide, sodium hydroxide and sulphuric acid, hydrogen-oxygen The form changing sodium reclaims and is removed so that salt content therein is down to less than 0.5%, and salt rejection rate reaches More than 90%, solve a discharge difficult problem for the ethylene waste lye of high saliferous in ethylene production, favorably In the stable operation of follow-up biological sewage treatment device, it is more beneficial for carrying out of follow-up reusing sewage further.
In sum, the present invention uses two chamber-type bipolar membrane electrodialysis device and three Room type Bipolar Membrane electric osmoses successively Analysis apparatus processes ethylene waste lye, while reclaiming remaining sodium hydroxide, it is possible to be converted into by sodium carbonate Carbon dioxide and sodium hydroxide, sodium sulfate is converted into sulphuric acid and sodium hydroxide, obtains the hydrogen-oxygen of 8%~15% Change sodium solution can directly return ethene cracking gas alkaline cleaner and recycle, and reduces ethene cracking gas alkali cleaning The supplies consumption of device, thus reduce production cost, alkali concn is low, be difficult to straight to overcome prior art recovery Connect the shortcoming recycled;The present invention uses 1%~20% sodium bicarbonate solution and desalted water to wash also successively It is dried to refine and has reclaimed the GHG carbon dioxide discharged in two Room bipolar membrane electrodialysis processing procedures, pure Degree is more than 99.5%, it is achieved that the reduction of discharging of carbon dioxide, overcomes prior art and can not reclaim carbon dioxide Shortcoming.
It addition, after the present invention uses oxidation technology to be sodium sulfate by oxidizing sodium sulphide, then use Bipolar Membrane electric osmose Analysis PROCESS FOR TREATMENT prepares 2%~15% sulphuric acid, it is achieved that in ethylene waste lye, the resource of institute's sulfur compound is returned Receive, comprehensively utilized or sell as side-product, it is possible to improving product is worth, obtain certain economic effect Benefit.
Detailed description of the invention
Embodiments of the invention are as follows:
Embodiment 1:
(1) oil removal treatment: use the oily substance in gravitational separation process removing spent lye, oily substance bag Include oil slick, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3: 0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 260 DEG C, partial pressure of oxygen is 2MPa, reaction time is 1h.After reaction terminates, S in spent lye2-Concentration is 0mg/L, desulfurization degree It is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration Spent lye after filtration carries out electrodialysis process, and electric current density is 600A/m2, salt room middle outlet feed liquid PH is 4.4, reclaims the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this 1% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure Degree is 99.5%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 800A/m2, by sulphuric acid Sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed And, mensuration volume is 7.20L, and naoh concentration is 8.0%, meets and returns ethene cracking gas alkaline cleaner The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously Sulphuric acid volume in dialyser acid room is 1.47L, and sulfuric acid concentration is 8.5%.
Finally, the most final volume processing water outlet in three type electrodialyzer salt rooms, Room is 1.19L, and salt content is down to 0.43%, wastewater discharge reduces 88.1%, and salt rejection rate is 94.5%.
Embodiment 2
(1) oil removal treatment: using the oily substance in extraction removing spent lye, oily substance includes floating Oil, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3: 0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 220 DEG C, partial pressure of oxygen is 1MPa, reaction time be 2h.After reaction terminates, the S of spent lye2-Concentration 0mg/L, desulfurization Rate is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration Spent lye after filtration carries out electrodialysis process, and electric current density is 1200A/m2, salt room middle outlet feed liquid PH is 4.0, reclaims the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this 15% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure Degree is 99.6%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 1500A/m2, by sulfur Acid sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed And, mensuration volume is 6.95L, and naoh concentration is 8.3%, meets and returns ethene cracking gas alkaline cleaner The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously Sulphuric acid volume in dialyser acid room is 1.61L, and sulfuric acid concentration is 7.8%.
Finally, the most final volume processing water outlet of three Room type electrodialyzer salt room water outlets is 1.28L, salt content Being down to 0.03%, wastewater discharge reduces 87.2%, and salt rejection rate is 99.8%.
Embodiment 3
(1) oil removal treatment: use the oily substance in gravitational separation process and extraction removing spent lye, oil Class material includes oil slick, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3: 0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 200 DEG C, partial pressure of oxygen is 2MPa, reaction time is 3h.After reaction terminates, the S of spent lye2-Concentration 0mg/L, desulfurization degree It is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration Spent lye after filtration carries out electrodialysis process, and electric current density is 800A/m2, salt room middle outlet feed liquid PH is 4.0.Reclaim the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this 10% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure Degree is 99.5%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 1000A/m2, by sulfur Acid sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed And, mensuration volume is 7.22L, and naoh concentration is 8.0%, meets and returns ethene cracking gas alkaline cleaner The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously Sulphuric acid volume in dialyser acid room is 1.57L, and sulfuric acid concentration is 8.0%.
Finally, the volume of three Room type electrodialyzer salt room water outlets is 1.22L, and salt content is down to 0.03%, useless Water discharge capacity reduces by 89.2%, and salt rejection rate is 99.8%.

Claims (10)

1. the method for reclaiming of an ethylene waste lye, it is characterised in that include following technical process:
(1) oil removal treatment: use the oily substance in gravitational separation process and/or extraction removing spent lye, Described oily substance includes oil slick, dispersed oil and oil emulsion;
(2) oxidation processes: use oxidizing process that the ethylene waste lye after oil removing is carried out desulfurization process, should Sulfide in spent lye is converted into sulfate;
(3) filtration treatment: use the float in Filtration removing ethylene waste lye and solid precipitation;
(4) bipolar membrane electrodialysis processes: use two chamber-type bipolar membrane electrodialysis-filtration-three room type Bipolar Membrane Spent lye after filtering is processed by electrodialysis, first, uses two chamber-type bipolar membrane electrodialysis device to reclaim Remaining sodium hydroxide in spent lye, is converted into sodium hydroxide and dioxy by the sodium carbonate in this spent lye simultaneously Changing carbon, obtain metabisulfite solution, carbon dioxide uses sodium bicarbonate solution and desalted water to wash and be dried successively Refined recovery;Then, use three Room type bipolar membrane electrodialysis devices that metabisulfite solution is converted into sulphuric acid and hydrogen Sodium oxide, processes, by two chamber-type and three Room type bipolar membrane electrodialysis, the sodium hydroxide solution merging obtained and directly returns Return ethylene alkali-washing device to recycle;
The water part, salt room of described three Room type bipolar membrane electrodialysis devices is as two chamber-type bipolar membrane electrodialysis The alkali room water inlet of device, remainder is discharged into sewage farm.
The method for reclaiming of ethylene waste lye the most according to claim 1, it is characterised in that step Suddenly in (4), described two chamber-type bipolar membrane electrodialysis device is BP-C configuration, described three Room type Bipolar Membrane Electrodialysis plant is BP-A-C configuration.
The method for reclaiming of ethylene waste lye the most according to claim 2, it is characterised in that step Suddenly, in (4), during described two chamber-type bipolar membrane electrodialysis, electric current density is respectively 600~1200A/m2
4. according to the method for reclaiming of the ethylene waste lye described in any one of claim 1-3, its feature Be, in step (4), during described two chamber-type bipolar membrane electrodialysis, the pH of salt room discharging be 2.0~ 4.4。
5. according to the method for reclaiming of the ethylene waste lye described in Claims 2 or 3, it is characterised in that In step (4), during described three Room type bipolar membrane electrodialysis, electric current density is 800~1500A/m2
The method for reclaiming of ethylene waste lye the most according to claim 4, it is characterised in that step Suddenly, in (4), during described three Room type bipolar membrane electrodialysis, electric current density is 800~1500A/m2
The method for reclaiming of ethylene waste lye the most according to claim 5, it is characterised in that step Suddenly in (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and h 2 so 4 concentration is 7.8%~8.5%.
The method for reclaiming of ethylene waste lye the most according to claim 6, it is characterised in that step Suddenly in (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and h 2 so 4 concentration is 7.8%~8.5%.
9., according to the method for reclaiming of the ethylene waste lye described in any one of claim 1-3, its feature exists In, in step (4), described CO 2 refining reclaim time sodium bicarbonate solution mass concentration be 1%~ 15%.
The method for reclaiming of ethylene waste lye the most according to claim 1, it is characterised in that step Suddenly in (2), described oxidation processes is wet oxidation process, and oxidizing temperature is 200~260 DEG C, and oxygen divides Pressure is 0.5~2MPa, and oxidant is oxygen, and the time of staying is 1~3h.
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CN111135603A (en) * 2019-12-31 2020-05-12 大连汉诺工程技术有限公司 Waste alkali treatment method
CN111778061A (en) * 2020-08-05 2020-10-16 伯尔菲特沧州科技中心 Method and system for regenerating light hydrocarbon desulfurization alcohol alkali liquor
CN112358079A (en) * 2020-10-23 2021-02-12 锦州泰丰精细化工有限公司 Regeneration process of sulfur-containing waste alkali liquor
CN113716809A (en) * 2021-09-09 2021-11-30 南方创业(天津)科技发展有限公司 Alkali residue wastewater treatment and alkali recovery method
CN114212931A (en) * 2021-11-18 2022-03-22 华东理工大学 Ethylene alkaline residue wet oxidation alkaline wastewater quality-divided crystallization treatment method

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Cited By (9)

* Cited by examiner, † Cited by third party
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CN109289823A (en) * 2018-11-06 2019-02-01 湖南鸿捷新材料有限公司 A kind of regeneration method of the waste active carbon of hydrometallurgy extraction process
CN109289823B (en) * 2018-11-06 2021-07-27 湖南鸿捷新材料有限公司 Regeneration method of waste activated carbon in wet smelting extraction process
CN111135603A (en) * 2019-12-31 2020-05-12 大连汉诺工程技术有限公司 Waste alkali treatment method
CN111778061A (en) * 2020-08-05 2020-10-16 伯尔菲特沧州科技中心 Method and system for regenerating light hydrocarbon desulfurization alcohol alkali liquor
CN112358079A (en) * 2020-10-23 2021-02-12 锦州泰丰精细化工有限公司 Regeneration process of sulfur-containing waste alkali liquor
CN113716809A (en) * 2021-09-09 2021-11-30 南方创业(天津)科技发展有限公司 Alkali residue wastewater treatment and alkali recovery method
CN113716809B (en) * 2021-09-09 2022-12-27 南方创业(天津)科技发展有限公司 Alkali residue wastewater treatment and alkali recovery method
CN114212931A (en) * 2021-11-18 2022-03-22 华东理工大学 Ethylene alkaline residue wet oxidation alkaline wastewater quality-divided crystallization treatment method
CN114212931B (en) * 2021-11-18 2023-12-29 华东理工大学 Wet oxidation alkaline waste water aqueous crystallization treatment method for ethylene alkali slag

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