CN102452672B - Method for recycling sodium sulfate from waste alkali liquor of ethylene unit - Google Patents
Method for recycling sodium sulfate from waste alkali liquor of ethylene unit Download PDFInfo
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Abstract
The invention relates to a method for recycling sodium sulfate from a waste alkali liquor of an ethylene unit, specifically to a technology of wet oxidation treatment of the waste alkali liquor of ethylene and separation of sodium sulfate from a waste liquid. The method comprises the steps of: (1) under wet oxidizing condition, performing wet oxidation to the waste alkali liquor of ethylene by air or oxygen to obtain an oxidized liquid; (2) neutralizing the oxidized liquid to obtain a neutralization liquid; (3) crystallizing water-entrained anhydrous sodium sulfate from the neutralization liquid; (4) returning a part of evaporative mother liquor to a neutralizing unit and performing de-biochemical treatment for frozen mother liquor after freezing the other part of evaporative mother liquor to recycle sodium sulfate decahydrate, wherein the recycled sodium sulfate decahydrate returns to the neutralizing unit; and (5) drying the water-entrained sodium sulfate decahydrate to obtain anhydrous sodium sulfate product. The method solves the technical problem that high content of salt still impacts the biochemical system after deodorization of waste alkali liquor of ethylene through wet oxidation and biochemical treatment after dilution and can be used in the fields of petrochemical and chemical industries, environment protection, comprehensive utilization of resources and light industry and the like.
Description
Technical field
The present invention relates to the technology of reclaim(ed) sulfuric acid sodium from the ethylene unit waste lye, the technology of sodium sulfate, the i.e. oxidation of ethylene unit waste lye, neutralization, crystallization reclaim(ed) sulfuric acid sodium are handled and are isolated in the wet oxidation that more particularly relates to waste lye from waste liquid.
Background technology
Sour gas in the ethene cracking gas mainly comprises hydrogen sulfide, carbonic acid gas, organosulfur etc., for removing sour gas, takes the washing of alkaline solution and splitting gas counter current contact, and the waste liquid of generation is called ethylene waste lye.Remove in the waste lye and contain Na
2S, Na
2CO
3, NaOH and minor N a
2SO
3, Na
2S
2O
3Also contain organic sulfides such as mercaptan, thereby have unpleasant stink outward.
Methods such as biochemical treatment, comprehensive use were advanced in dilution after the method for improvement ethylene waste lye comprised direct facture, pre-treatment.In the ethylene industry early stage of development, the direct facture of the many employings of the processing of waste lye comprises deep-well injection, landfill, dilution discharge and burning, the use because environmental protection requirement has been under an embargo of preceding several method; The burning method energy consumption is big, the running cost height.
The deodorization technique that wet air oxidation is handled ethylene waste lye is proven technique.Adopt the wet type air oxidation to carry out carrying out the important means that biochemical treatment has progressively become the ethylene waste lye processing after back other wastewater dilution of recycling is handled in deodorization.Contain a large amount of inorganic salt through the ethylene waste lye after the wet oxidation processing, biodegradability is poor.Directly enter composite wastewater treatment plant, will impact to biochemical treatment system, influence the sewage discharge compliance rate, dilution back biochemical treatment is still difficult.For making ethylene waste lye not enter biochemical treatment system, the comprehensive utilization of ethylene waste lye looks like up-and-coming method.
The method of comprehensive utilization ethylene waste lye comprises crystallization recovery sulfide method, precipitation sulfide regeneration NaOH method etc.Can obtain Na behind the secondary crystal
2The industrial goods of S content 28%～31% contain NaOH and Na
2CO
3If mother liquor circulation be used for absorbing the sour gas of splitting gas, can cause Na
2CO
3Alkali lye in accumulation and influence device and operate.Cupric oxide, magnesium oxide precipitation method are regenerated as sodium hydroxide with sodium sulphite, yellow soda ash, make ethylene waste lye obtain holomorphosis, but this precipitation agent is expensive, and the precipitation poor quality who obtains is not high as the commodity selling price.
CN1789162 has proposed a kind of technique for reclaiming ethylene alkali-washing waste liquid, uses the transition metal oxide desulfurization behind the employing alkaline earth metal oxide causticization waste lye, and the sulfide that obtains is expected to become high value-added product, but does not have product to detect.
It is the method for feedstock production S-WAT that CN1305954 has proposed with liquid hydrocarbon or waste alkali solution of gasoline, and it mainly is that the sulfurous gas gas mixture that sulfur burning produces is delivered to absorption tower I bottom, and waste lye neutralizes under the cat head spray.The tail gas of absorption tower I is delivered to absorption tower II bottom through the sulfur dioxide gas that contains that burning produces.3～10% sodium hydroxide solutions from the cat head spray down.To deliver to the stirred pot from the liquid that absorption tower I comes out in addition, and add ferrous sulfate or zinc sulfate and stir.The S-WAT of this method preparation still exists in solution, and contains more sodium sulfate impurity.
CN101143293 has proposed a kind of method of deodorant waste lye absorbing treating smoke, adopts the deodorant waste lye after the wet type air oxide treatment that sulfur in smoke, flue dust and oxynitride are absorbed.Adopt two sections absorption patterns, leading portion adopts the absorption liquid of back segment discharging directly to contact with flue gas, to reduce flue-gas temperature, removes wherein part pollutent simultaneously; Back segment is that absorption liquid contacts with the flue gas that passes through after leading portion is lowered the temperature with the deodorant waste lye, absorbs the pollutent that comprises oxysulfide or oxynitride, the flue gas after being purified discharging.This method has produced the waste liquid that more contains high salt, and this method is worth not as reclaim(ed) sulfuric acid sodium for the comprehensive utilization of the ethylene waste lye after the wet oxidation.
Ethylene waste lye carries out carrying out biochemical treatment again after deodorization is handled, diluted through wet oxidation, and contained high salt still can produce biochemical treatment system and impact; And existing comprehensive utilization technique: or the alkali lye utilization is limited, or waste lye direct crystallization mother liquor still gets nowhere, or precipitation agent is expensive, the precipitation poor quality that obtains.
In view of sodium sulfate concentration in the waste lye of in the extensive utilization of ethylene waste lye wet air oxidation deodorization, the deodorization and back higher, the present invention is the sodium sulfate in the ethylene waste lye after the reclaim(ed) sulfuric acid neutralizing treatment on the basis that the wet oxidation deodorization is handled, reduced the saltiness of waste lye, can reduce or avoid the impact of the water outlet of wet type air oxide treatment and the follow-up biochemical treatment of contained high salt pair thereof, also be conducive to ethylene production enterprise and carry out waste water recycling work.
Term
The wet type air oxidation (Wet Air Oxidation, WAO): be under high temperature, high top pressure operation condition, in liquid phase, use air as oxygenant, a kind for the treatment of process that is the organism of solubilised state or suspended state in the oxidizing water or goes back the ortho states inorganics.
The wet type dioxygen oxidation: in the wet type air oxidation operation, it also is feasible replacing air with oxygen, can call the wet type dioxygen oxidation to this method.
Wet oxidation: comprise wet type air oxidation and wet type dioxygen oxidation.
Ethylene waste lye: the sour gas in the ethene cracking gas mainly is hydrogen sulfide, carbonic acid gas, organosulfur etc., ethylene waste lye results from the counter current contact of alkaline solution and splitting gas, sour gas and sodium hydroxide reaction generate sodium salt, and the multiple hydrocarbon component in the cleaved gas of waste lye while is saturated.Can contain Na in the waste lye
2S, Na
2CO
3, NaOH and minor N a
2SO
3, Na
2S
2O
3, also may contain NaHCO
3, and contain organic sulfides such as mercaptan, have unpleasant stink.
Oxidation liquid: ethylene waste lye is carried out the wet oxidation operation, and the liquid that obtains is referred to herein as oxidation liquid.
Intermediate oxidation liquid: when ethylene waste lye is carried out 2 grades of wet oxidations operation, go out the oxidized liquid that the 1st grade of wet oxidation advance the 2nd grade of wet oxidation and be called intermediate oxidation liquid.
Regulate the pH value: for the high ethylene waste lye of Sodium sulfhydrate content, complete oxidation can make its pH value be reduced to acidity, be subjected to the restriction of wet oxidation reaction equipment matter, possibly rooting according to Sodium sulfhydrate content regulate earlier waste lye pH value or/and divide two-stage oxidizing and control the pH value of intermediate oxidation liquid according to Sodium sulfhydrate content.The present invention requires to regulate with sodium hydroxide the pH value of intermediate oxidation liquid between waste lye pH value and two-stage oxidizing reaction member.
Neutralizer: oxidation liquid is carried out neutralization operation, and the liquid that obtains is referred to herein as neutralizer.Neutralize with the vitriol oil or sodium hydroxide at this paper.
Single stage method, two step method: enterprise is during according to sodium sulfate-aqueous systems phase diagram theory processing saltcake, can be directly from solution crystallization go out thenardite, be called single stage method; Can adopt also that crystallization goes out saltcake from the aqueous solution, saltcake is dehydration method again, is called two step method.Single stage method generally adopts vacuum vapor deposition method; The saltcake dehydration method is divided into seasoning evaporation, widely different commentaries on classics desiccating method, scorification, vacuum-evaporation evaporation etc. again.
Sodium sulfate anhydrous.min(99): the trade(brand)name of industrial anhydrous sodium sulfate/be commonly called as.
Summary of the invention
The present invention is in order to overcome the above-mentioned defective that existing ethylene waste lye treatment process exists separately, and neutralizing treatment ethylene waste lye and the method for reclaim(ed) sulfuric acid sodium therefrom are provided after a kind of wet oxidation.This invention can reduce the saltiness of waste lye, and the impact that can reduce or avoid wet oxidation to handle the follow-up biochemical treatment of high salt pair in the water outlet reaches the disadvantageous effect to reusing sewage, simultaneously the sodium sulfate in the ethylene waste lye after the reclaim(ed) sulfuric acid neutralizing treatment.
The invention provides after a kind of wet oxidation neutralizing treatment ethylene waste lye and the method for reclaim(ed) sulfuric acid sodium therefrom.Particularly, this method comprises: (1) carries out wet oxidation with air or oxygen to it under the wet oxidation condition, obtain oxidation liquid; (2) oxidation liquid is neutralized, obtain neutralizer; (3) adopt the crystallization from neutralizer of evaporative crystallization method to go out to contain the anhydrous sodium sulphate of water entrainment; (4) the part mother liquid evaporation returns neutralisation unit, and the part mother liquid evaporation goes freezing mother liquor to biochemical treatment behind freezing recovery sal glauberi, and the sal glauberi that reclaims returns neutralisation unit; (5) anhydrous sodium sulphate that contains water entrainment is carried out drying, obtain the anhydrous sodium sulphate product.
In step (1), the ethylene waste lye oxidizing temperature is greater than (pressure is on hold-up vapour pressure at each temperature) in 150～250 ℃ the scope.
In step (3), adopt the method for vacuum evaporating crystalization directly from neutralizer, to obtain moisture anhydrous sodium sulphate crystallization, obtain the anhydrous sodium sulphate product after the drying, i.e. Sodium sulfate anhydrous.min(99).When the crystalline product quality can not meet the demands, with the mother liquid evaporation freezing and crystallizing, freezing and crystallizing returned neutralization operation, and freezing mother liquor carries out biochemical treatment.
Gained Sodium sulfate anhydrous.min(99) quality can reach or be higher than the requirement of II class salable product in the industrial anhydrous sodium sulfate quality standard (GB/T 6009-2003), and the rate of recovery of whole process sodium is greater than 90%, and namely the quantity discharged of salt reduces approximately greater than 90%.
Preferred implementation of the present invention:
The condition of step (1) wet oxidation: the wet oxidation temperature requirement of ethylene waste lye is greater than 150 ℃～250 ℃, reaction pressure is more than 20%, guarantee enough residence time and oxygen partial pressure so that sodium sulphite fully is converted into sodium sulfate greater than at each temperature saturated vapor pressure.Different wet type oxidizing temperatures require the minimum residence time:
For the high ethylene waste lye of Sodium sulfhydrate content, complete oxidation can make its pH value be reduced to acidity, be subjected to the restriction of wet oxidation reaction equipment matter, rooting is according to the first pH value of regulating pH value or the branch two-stage oxidizing of waste lye and controlling intermediate oxidation liquid according to Sodium sulfhydrate content of Sodium sulfhydrate content possibly.The present invention requires to regulate with sodium hydroxide the pH value of intermediate oxidation liquid between waste lye pH value and two-stage oxidizing reaction member.
Control with pH in the step (2): neutralization reaction stirs or feeds under the pressurized air stirring in brute force carries out, with the CO that guarantees that solution mixes, generates
2Fully discharge.Go out the neutralizer pH control of reactor 3.5～5.5, for reaching higher anhydrous sodium sulphate product hierarchy, more excellent scope is 4.5～5.1.Neutralizer is handled through sedimentation and is removed impurity.
For the high ethylene waste lye of Sodium sulfhydrate content, complete oxidation can make its pH value be reduced to acidity.For the acidic oxidation liquid of acidity surplus, the present invention requires to use in the sodium hydroxide and unnecessary acidity, because the price of yellow soda ash is higher than sodium hydroxide, and uses yellow soda ash can increase yellow soda ash foreign matter content in the sodium sulfate.Sodium sulfhydrate
Step (3) crystallization mode: the wet oxidation temperature also can adopt evaporative crystallization directly to reclaim anhydrous sodium sulphate product in the neutralizer greater than 150 ℃～250 ℃ the time.
The processing of step (4) evaporative crystallization mother liquor: part is got back to neutralisation unit, and part reclaims the sal glauberi crystal through freezing and crystallizing, and the sal glauberi crystal is got back to neutralisation unit, and freezing mother liquor removes biochemistry.
The pH value control of evaporative crystallization mother liquor is below 9, and the pH of evaporative crystallization mother liquor reaches at 8.5～9 o'clock, returns neutralisation unit.When the color of evaporative crystallization mother liquor, COD surpassed certain value, the freezing mother liquor after freezing and crystallizing reclaims the sal glauberi crystal removed biochemistry, and the TOC content of this color, COD value and ethylene waste lye, reactor material, temperature of reaction etc. are relevant.Those skilled in the art are through after the limited experiment, this value of having the ability fully to determine.The basic reason of control step (4) is: when evaporative crystallization gained Sodium sulfate anhydrous.min(99) does not satisfy the quality product requirement, no longer return neutralisation unit, but the freezing mother liquor of mother liquid evaporation after freezing and crystallizing reclaims the sal glauberi crystal gone biochemical treatment.
The essential distinction of the present invention and prior art is,
For the treatment process of ethylene waste lye, reclaim sodium sulfate on existing wet oxidation basis, have new meaning.For reclaim(ed) sulfuric acid sodium, the report of the existing reclaim(ed) sulfuric acid sodium of other several industries, but then do not appear in the newspapers for reclaim(ed) sulfuric acid sodium from ethylene waste lye.
For reclaim(ed) sulfuric acid sodium, the wet oxidation that the present invention relates to the processing ethylene waste lye, neutralization, crystallization, crystalline mother solution are handled and have all been carried out preferably:
For wet oxidation operation, carried out preferably for the residence time under differing temps and the pressure.The operational condition that the wet oxidation of existing different enterprises is handled is as follows:
The operational condition difference that the wet oxidation of the different enterprises of table 3 is handled
Ethylene waste lye after the deodorization goes biochemical will the neutralization before, but neutralization gets final product to pH 7～9.Because Na in the ethylene waste lye
2CO
3Content be higher than Na in saltcake ore deposit, the bittern
2CO
3Content, in it and the pH of the pH of terminal point saltcake solution when also various conventional sodium sulfate is produced.Remove the carbonate in the waste lye, will be reduced to pH lower.The present invention will be preferably 3.5～5.5 with terminal point pH in the oxidation liquid, and more excellent is 4.5-5.1.
Crystallization mode to neutralization back gained neutralizer after the wet oxidation in the ethylene waste lye differing temps scope has carried out preferably.The present invention does not carry out preferably acid and the concentration of neutralization because at present sewage work substantially all use in the vitriol oil with deodorization after ethylene waste lye.
For the evaporative crystallization mother liquor, be behind freezing and crystallizing, again gained crystal nitre to be got back to the evaporative crystallization operation in the general sodium sulfate production, the present invention gets back to oxidation liquid neutralisation unit with its part and carries out neutralization operation, and part is got back to the gained crystal oxidation liquid neutralisation unit again and carried out neutralization operation behind freezing and crystallizing.
The invention has the beneficial effects as follows:
Ethylene waste lye after the deodorization is further processed, reclaim(ed) sulfuric acid sodium, can reduce the quantity discharged of waste lye, reduce or avoid the impact of the follow-up biochemical treatment of high salt pair in the wet oxidation processing water outlet, also be conducive to ethylene production enterprise and carry out other waste water recycling work.The mother liquor amount of ethylene waste lye after reclaim(ed) sulfuric acid sodium is handled reduces, and the saltiness of freezing and crystallizing mother liquor reduces greatly, and the biochemical treatment difficulty is reduced greatly.By implementing optimal conditions of the present invention, can make the sodium sulfate good product quality of recovery, method such as need not burn and can reach " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product and above index.
Description of drawings
Fig. 1 reclaims anhydrous sodium sulphate and reduces the schematic flow sheet of mother liquor amount through evaporative crystallization through the ethene alkali lye after handling greater than 150 ℃～250 ℃ wet oxidations.
Embodiment
Use the ethylene waste lye after certain enterprise's oil removing removes the gred to consist of (mass percent): NaOH17.9%, Na among the embodiment
2S 3.8%, Na
2CO
31.7%, COD 25000mg/L, TOC1300mg/L; Impurity metallic elements content is extremely low, Fe 0.6mg/L, Cr 1.2mg/L, Ni1.8mg/L, Cu 0.8mg/L, Ca, Mg (in Mg) 0.6mg/L, Cl 73.8mg/L.
Below in conjunction with accompanying drawing, the present invention is specifically described.
Embodiment 1
This ethylene waste lye is under the situation of not diluting with pH regulator, through 160 ℃ of (6MPa) wet type air oxidation 5h, gained oxidation liquid is with the vitriol oil pH4.64 that neutralizes, neutralizer adopts vacuum evaporating crystalization, evaporative crystallization is dried to Sodium sulfate anhydrous.min(99), the part mother liquid evaporation removes freezing and crystallizing, and freezing and crystallizing returns neutralisation unit, and freezing mother liquor removes biochemistry.The part mother liquid evaporation returns neutralisation unit, to reduce carbonate content, improves the salable product yield.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 97.05%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/20, COD 2800mg/L, total dissolved solidss 7%.
About step (4): along with the carrying out of evaporative crystallization, the color of mother liquid evaporation can deepen, and as by colourless, light green, pale yellow darker green or the tawny of becoming, COD can increase simultaneously, carbonate content can increase.Darken is that metal ion mainly comes from the oxidation corrosion of wet oxidation reaction device and neutralization reactor, the metal ion that ethylene waste lye brings because concentration of metal ions increases.The index of color is also relevant with reactor material, temperature of reaction etc.It is because increases such as sulphite, thiosulphate, organic impuritys that COD increases.The value of COD is relevant with TOC content, the oxidizing temperature of ethylene waste lye.These two factors all can make the quality of Sodium sulfate anhydrous.min(99) descend.Quality product that yellow soda ash causes descends and can return neutralisation unit and sulfuric acid reaction is controlled by the evaporative crystallization mother liquor.The color of mother liquid evaporation, COD can return neutralisation unit before surpassing certain value, after freezing and crystallizing reclaims sal glauberi freezing mother liquor are gone biochemical treatment afterwards.
Embodiment 2
This ethylene waste lye is under the situation of not diluting with pH regulator, through 180 ℃ of (6MPa) wet type air oxidation 5h, gained oxidation liquid is with the vitriol oil pH4.01 that neutralizes, neutralizer adopts vacuum evaporating crystalization, evaporative crystallization is dried to Sodium sulfate anhydrous.min(99), the part mother liquid evaporation removes freezing and crystallizing, and freezing and crystallizing returns neutralisation unit, and freezing mother liquor removes biochemistry.The part mother liquid evaporation returns neutralisation unit, to reduce carbonate content, improves the salable product yield.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 97.12%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/18, COD 2000mg/L, total dissolved solidss 6%.
Embodiment 3
This ethylene waste lye is under the situation of not diluting with pH regulator, through 210 ℃ of (6MPa) wet type dioxygen oxidation 2h, gained oxidation liquid is with the vitriol oil pH4.70 that neutralizes, neutralizer adopts vacuum evaporating crystalization, evaporative crystallization is dried to Sodium sulfate anhydrous.min(99), the part mother liquid evaporation removes freezing and crystallizing, and freezing and crystallizing returns neutralisation unit, and freezing mother liquor removes biochemistry.The part mother liquid evaporation returns neutralisation unit, to reduce carbonate content, improves the salable product yield.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 97.13%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/18, COD 1200mg/L, total dissolved solidss 6%.
Claims (7)
1. handle ethylene waste lye and the method for reclaim(ed) sulfuric acid sodium therefrom for one kind, this method comprises:
(1) under the wet oxidation condition, with air or oxygen it is carried out wet oxidation, obtain oxidation liquid;
Wherein, the condition of wet oxidation: the wet oxidation temperature requirement of ethylene waste lye is greater than 150 ℃～250 ℃, and reaction pressure is greater than at each temperature saturated vapor pressure more than 20%, and different wet type oxidizing temperatures require the minimum residence time:
(2) oxidation liquid is neutralized, obtain neutralizer;
Wherein, neutralization reaction stirs or feeds under the pressurized air stirring in brute force carries out, and goes out the neutralizer pH control of reactor 3.5～5.5;
(3) adopt the crystallization from neutralizer of evaporative crystallization method to go out to contain the anhydrous sodium sulphate of water entrainment;
(4) the part mother liquid evaporation returns neutralisation unit, and the freezing mother liquor of part mother liquid evaporation behind freezing recovery sal glauberi goes biochemical treatment, and the sal glauberi that reclaims returns neutralisation unit;
(5) anhydrous sodium sulphate that contains water entrainment is carried out drying, obtain the anhydrous sodium sulphate product.
2. method according to claim 1 in step (3), adopts the method for vacuum evaporating crystalization directly to obtain moisture anhydrous sodium sulphate crystallization from neutralizer.
3. method according to claim 1 goes out the neutralizer pH control of reactor 4.5～5.1 in the step (2).
4. method according to claim 1 adopts the vitriol oil to neutralize in step (2).
5. method according to claim 1 for the high ethylene waste lye of Sodium sulfhydrate content, neutralizes with sodium hydroxide in step (2).
6. method according to claim 1 for the high ethylene waste lye of Sodium sulfhydrate content, is regulated ethylene waste lye pH value with sodium hydroxide earlier and is carried out oxidation again in step (1), adopts sodium hydroxide or the vitriol oil to neutralize in step (2).
7. according to claim 1 or 6 described methods, for the high ethylene waste lye of Sodium sulfhydrate content, oxidation divides two sections in the step (1), regulates the pH value of intermediate oxidation liquid between the two-stage oxidizing reaction member with sodium hydroxide, adopts sodium hydroxide or the vitriol oil to neutralize in step (2).
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| CN103771457B (en) * | 2012-10-23 | 2016-03-30 | 中国石油化工股份有限公司 | The treatment process of waste lye in a kind of production of propylene |
| CN103771612B (en) * | 2012-10-23 | 2015-08-12 | 中国石油化工股份有限公司 | The treatment process of waste lye in production of propylene |
| CN104609625B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司 | A kind of processing method of ethylene waste lye |
| CN104609626B (en) * | 2013-11-05 | 2016-08-17 | 中国石油化工股份有限公司大连石油化工研究院 | A kind of processing method of liquid hydrocarbon spent lye |
| CN104609622B (en) * | 2013-11-05 | 2016-11-16 | 中国石油化工股份有限公司 | The processing method of spent lye in a kind of ethylene production |
| CN104609623B (en) * | 2013-11-05 | 2017-02-01 | 中国石油化工股份有限公司 | Ethylene alkaline cleaning waste liquid processing method |
| CN105000732B (en) * | 2014-04-22 | 2017-07-28 | 中国石油化工股份有限公司 | A kind of processing method of the Utilization Techniqueof Water Alkali of Oil Refining containing organic nitrogen |
| CN105016552B (en) * | 2014-04-22 | 2017-08-22 | 中国石油化工股份有限公司 | A kind of processing method of oil refinery spent lye |
| CN105016551B (en) * | 2014-04-22 | 2017-08-22 | 中国石油化工股份有限公司 | The processing method of the spent lye containing organic nitrogen during refining liquid hydrocarbon |
| CN106746347B (en) * | 2017-01-11 | 2019-02-26 | 江苏南大华兴环保科技股份公司 | A kind of imidazole aldehyde waste water treatment process and its operation method |
| CN107758964B (en) * | 2017-11-16 | 2024-04-26 | 凯姆德（北京）能源环境科技有限公司 | System for treating waste alkali liquid and treatment method thereof |
| CN110152340A (en) * | 2018-03-27 | 2019-08-23 | 新疆环境工程技术有限责任公司 | One kind dividing salt evaporative crystallization and purification process |
| CN111408157B (en) * | 2020-04-14 | 2021-09-14 | 中石化南京工程有限公司 | Ammonium sulfate crystallization method and device thereof |
| CN113526647A (en) * | 2021-09-14 | 2021-10-22 | 北京惠宇乐邦环保科技有限公司 | Treatment method of sulfur-containing wastewater |
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| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
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| WO2009035642A1 (en) * | 2007-09-11 | 2009-03-19 | Siemens Water Technologies Corp. | Treatment of spent caustic waste |
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| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
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