CN102815811B - Short flow method for recycling sodium sulfate from ethylene waste alkali liquid - Google Patents

Short flow method for recycling sodium sulfate from ethylene waste alkali liquid Download PDF

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Publication number
CN102815811B
CN102815811B CN 201110155497 CN201110155497A CN102815811B CN 102815811 B CN102815811 B CN 102815811B CN 201110155497 CN201110155497 CN 201110155497 CN 201110155497 A CN201110155497 A CN 201110155497A CN 102815811 B CN102815811 B CN 102815811B
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oxidation
waste lye
ethylene waste
liquid
neutralizer
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CN102815811A (en
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程学文
高凤霞
张宾
莫馗
纪然
李海龙
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Sinopec Beijing Research Institute of Chemical Industry
China Petroleum and Chemical Corp
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Abstract

A short flow method for recycling sodium sulfate from ethylene waste alkali liquid includes the following process steps: (1) conducting wet oxidizing through air or oxygen under the wet oxidizing condition to obtain oxidizing liquid; (2) conducting neutralization operation on the oxidizing liquid to obtain neutralization liquid; (3) separating the neutralization liquid to obtain clear liquid or filtering liquid and (4) drying the clear liquid or the filtering liquid to obtain anhydrous sodium sulfate. The short flow method resolves the technical problem that ethylene waste alkali liquid is subjected to the wet oxidizing processing to be diluted and then subjected to biochemical treatment, and high salinity contained in the short flow method still impacts a biochemical treatment system. The short flow method simultaneously shortens the process flow, reduces equipment investment for recycling sodium sulfate, and can be applied to the fields of petrifaction, chemical engineering, environment protection, resource comprehensive utilization, light industry and the like.

Description

A kind of from ethylene waste lye the short flow and method of reclaim(ed) sulfuric acid sodium
Technical field
The present invention is specifically related to a kind of method of comprehensive utilization of ethylene waste lye, particularly from wet oxidation process, the method for separating anhydrous sodium sulfate ethylene waste lye after neutralization, belong to the recycling field of industrial effluent.
Background technology
Sour gas in 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 waste lye and contain Na 2S, Na 2CO 3, NaOH and a small amount of Na 2SO 3, Na 2S 2O 3Also contain the organic sulfides such as mercaptan, thereby have unpleasant stink outward.
After the method for improvement ethylene waste lye comprises direct facture, pre-treatment, the methods such as biochemical treatment, comprehensive use are carried out in dilution.Directly facture, comprise deep-well injection, landfill, dilution discharge and burning, due to the requirement of the environmental protection use that has been under an embargo.The pre-treatment that ethylene waste lye is carried out comprises oxidation style or neutralisation, but pretreated ethylene waste lye contains a large amount of inorganic salt, directly enters composite wastewater treatment plant, will impact biochemical treatment system, and cause the waste of inorganic salt.
The method forefathers of comprehensive utilization ethylene waste lye also have research.CN1789162 has proposed a kind of technique for reclaiming ethylene alkali-washing waste liquid, uses the transition metal oxide desulfurization after 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; CN1305954 has proposed to prepare the method for S-WAT as raw material take liquid hydrocarbon or waste alkali solution of gasoline, and 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, and this method has produced the waste liquid that more contains high salt, and the method is worth not as reclaim(ed) sulfuric acid sodium for the comprehensive utilization of the ethylene waste lye after wet oxidation.
If in ethylene waste lye, the recovery of anhydrous sodium sulphate adopts oxidation-neutralization-crystallization-drying process to carry out, this process is used for such the recovery on a small scale of ethylene waste lye and has complex process on anhydrous sodium sulphate, the problem that cost of investment is too high.
Summary of the invention
The technical problem to be solved in the present invention:
After the invention provides a kind of wet oxidation, the neutralizing treatment ethylene waste lye, and the short flow path processing method of reclaim(ed) sulfuric acid sodium therefrom, reduced the salt amount to Waste Water Treatment and environmental emission, can reduce or avoid wet oxidation to process the impact of water outlet 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, shorten the technological process that reclaims anhydrous sodium sulphate, can have been met the anhydrous sodium sulphate of the specification of quality of " GB/T 6009-2003 industrial anhydrous sodium sulfate " without crystallization.
Technical scheme provided by the invention:
The short flow and method of reclaim(ed) sulfuric acid sodium in a kind of ethylene waste lye specifically comprises following processing step:
(1) ethylene waste lye is carried out wet oxidation and process, wherein sulfide mainly is oxidized to vitriol;
(2) in and oxidation after ethylene waste lye, obtain neutralizer;
(3) neutralizer is separated obtain clear liquid or filtrate;
(4) clear liquid or filtrate drying are obtained anhydrous sodium sulphate.
Described ethylene waste lye is through the ethylene waste lye of water or water vapour dilution, without any one in the ethylene waste lye of water or water vapour dilution; For the ethylene waste lye without the dilution of water or water vapour, the neutralizer after oxidation, neutralization can be selected through water or water vapour dilution or in without water or water vapour dilution.
In step (1), sulfide mainly is oxidized to the judgement of vitriol mainly according to following method: S 2-, S 2O 3 2-, SO 3 2-, SO 4 2-Can be by chemical analysis and ion-chromatographic determination, its measuring method is all with reference to GB; Can judge whether that by concentration ratio primary product is vitriol.
Described molar content ratio for Sodium sulfhydrate and sodium carbonate directly carries out wet oxidation less than 1 ethylene waste lye.
Described molar content ratio for Sodium sulfhydrate and sodium carbonate is greater than 1 ethylene waste lye, complete oxidation can make its pH value be reduced to acidity, be subjected to the restriction of wet oxidation reaction equipment matter, rooting is first regulated pH value or minute two-stage oxidizing of waste lye according to Sodium sulfhydrate content and is controlled the pH value of intermediate oxidation liquid according to Sodium sulfhydrate content possibly.
Described pH value of first regulating waste lye according to Sodium sulfhydrate content, be first that 30~45% sodium hydroxide solution is regulated molar content ratio that ethylene waste lye makes Sodium sulfhydrate and sodium carbonate in 0.95 to 1 scope with massfraction in step (1), then carry out wet oxidation.
Described minute two-stage oxidizing also controlled the pH value of intermediate oxidation liquid according to Sodium sulfhydrate content, in step (1), oxidation divides two sections, be the pH value that 30~45% sodium hydroxide solution is regulated intermediate oxidation liquid with massfraction between the two-stage oxidizing reaction member, the pH that first paragraph is oxidizing to ethylene waste lye stopped wet oxidation at 4.3~7.5 o'clock, and the pH value of regulating intermediate oxidation liquid with sodium hydroxide is 8.8~10.5; And then carry out the second segment wet oxidation.
Described wet oxidation is treated to any one in wet type air oxide treatment or the processing of wet type dioxygen oxidation.
The temperature that described wet oxidation is processed is 160 ℃~250 ℃; Pressure is higher than the saturated vapor pressure 20% of waste lye at each temperature; The residence time of wet oxidation reaction is different and change according to treatment temp, when being specially 160 ℃ for the treatment of temps, and the residence time 〉=5h; When treatment temp was 180 ℃, the residence time was 〉=3h; When treatment temp is 210 ℃, the residence time 〉=2h; When treatment temp is 250 ℃, the residence time 〉=1h.The residence time can infinitely extend, but the sulphate content of oxidation solution only can increase slightly, only limits from economic considerations the minimum time that stops
In step (2), described to adopt the sulphuric acid soln of mass percent concentration 70~98% or massfraction for the ethylene waste lye after oxidation be that 30~45% sodium hydroxide solution carries out neutralization reaction.
The churned mechanically neutralization reactor of the optional airtight normal pressure of described neutralization reactor (if any the mechanical stirring neutralization reactor of venting port) or blast any one in the neutralization reactor of pneumatic blending; For the churned mechanically neutralization reactor of airtight normal pressure (if any the mechanical stirring neutralization reactor of venting port), the neutralizer pH value that goes out reactor is controlled at 4.36~5.36; For the neutralization reactor that blasts pneumatic blending, the neutralizer pH value that goes out reactor is controlled at 5.36~6.36.
In step (3), can select any one in sedimentation, filtration or air supporting described neutralizer is separated; Sedimentation can be selected any one in gravity settling or centrifugal settling; All can select not add flocculation agent or add flocculation agent to the separation of neutralizer;
Described neutralizer is during without the dilution of water or water vapour, adopts when not adding the gravity settling of flocculation agent, and the required settling time is 16h to 48h.
Described neutralizer is when the dilution of water or water vapour, adopts the centrifugal settling that does not add flocculation agent, and the required settling time can adopt the gravity settling time that does not add flocculation agent for without water or water vapour dilution the time lower than neutralizer.
Described neutralizer is after water or water vapour dilution, employing adds gravity settling or the centrifugal settling of flocculation agent, the required settling time can adopt the gravity settling time that does not add flocculation agent for without the dilution of water or water vapour the time lower than neutralizer, dimly releases degree, the flocculation agent kind is determined by experiment again.
Described neutralizer comprises through the dilution of water or water vapour the neutralizer that ethylene waste lye first obtains after water or water vapour dilution and then oxidation, neutralization, perhaps without the neutralizer that obtains after the ethylene waste lye oxidation of water or water vapour dilution, neutralization any one in water or water vapour dilution again.
Any one in the optional polyacrylamide of described flocculation agent, cationic-type polyacrylamide or multiple.
Described neutralizer does not add flocculation agent, process to obtain meeting the product that quality product requires (specific targets " GB/T 6009-2003 industrial anhydrous sodium sulfate ") through air supporting, suitably use flocculation agent can make product quality grade improve (such as bringing up to the II class from the III class).
In step (4), described drying means can select that atmospheric evaporation is dry, vacuum-evaporation is dry, any one in spraying drying; Also can select to allow flame contact the submerged combustion evaporation of saltcake liquid, obtain the anhydrous sodium sulphate product.
The invention has the beneficial effects as follows:
Ethylene waste lye after deodorization is further processed, reclaim(ed) sulfuric acid sodium, can reduce the salt amount to Sewage treatment systems and environmental emission, reduce or avoid wet oxidation to process the impact of the follow-up biochemical treatment of high salt pair in water outlet, also being conducive to ethylene production enterprise and carrying out other waste water recycling work.By implementing optimal conditions of the present invention, reduce approximately more than 90% to the salt amount of wastewater biochemical treatment facility and environmental emission, wastewater discharge reduces approximately more than 90%; The anhydrous sodium sulphate that the reclaims method such as need not burn can reach the specification of quality of " GB/T 6009-2003 industrial anhydrous sodium sulfate ".
Description of drawings
Fig. 1 is through the schematic flow sheet of the ethene alkali lye after 160 ℃~250 ℃ wet oxidations processing through neutralization, dried recovered anhydrous sodium sulphate.
Embodiment
Use the ethylene waste lye after certain enterprise's oil removing removes the gred to consist of (mass percent): NaOH 17.9%, Na in embodiment 1-4 2S 3.8%, Na 2CO 31.7%, COD 25000mg/L, TOC 1300mg/L; Impurity metallic elements content is extremely low, Fe 0.6mg/L, Cr 1.2mg/L, Ni 1.8mg/L, Cu 0.8mg/L, Ca, Mg (in Mg) 0.6mg/L, Cl 73.8mg/L.
Below in conjunction with accompanying drawing, be specifically described by embodiment.
Embodiment 1
This ethylene waste lye is not in the situation that dilute and pH regulator, through 160 ℃ of (6MPa) wet type air oxidation 5h; The gained oxidation solution is that 98% the vitriol oil pH value that neutralizes is 5.64 with mass concentration in the neutralization reactor of drum pneumatic blending; The gained neutralizer add polyacrylamide (PAM) flocculation agent to 1ppm by filter removing impurity; The dry products therefrom sodium sulphate content of filtrate is 98.65%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.
Embodiment 2
This ethylene waste lye is not in the situation that dilute and pH regulator, through 180 ℃ of (6MPa) wet type air oxidation 3h; The gained oxidation solution is that 98% the vitriol oil pH value that neutralizes is 6.23 with mass concentration in the neutralization reactor of drum pneumatic blending; The gained neutralizer is removed impurity through gravity settling 36h; The stillness of night, dry products therefrom sodium sulphate content was 98.08%, met " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.
Embodiment 3
This ethylene waste lye is not in the situation that dilute and pH regulator, through 210 ℃ of (6MPa) wet type dioxygen oxidation 2h; The gained oxidation solution is that 98% the vitriol oil pH value that neutralizes is 4.70 in mechanical stirring, during the neutralization reactor of venting port is arranged with mass concentration; The gained neutralizer add cationic polyacrylamide (CPAM) to the 0.3ppm gas through the floating impurity of removing; The dry products therefrom sodium sulphate content of clear liquid is 99.13%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " I class standard.
Embodiment 4
This ethylene waste lye is not in the situation that dilute and pH regulator, through 240 ℃ of (6MPa) wet type dioxygen oxidation 1h; The gained oxidation solution is that 70% the vitriol oil pH value that neutralizes is 5.26 in mechanical stirring, during the neutralization reactor of venting port is arranged with mass concentration; The gained neutralizer adds cationic polyacrylamide (CPAM) and removes impurity through gravity settling 3h to 0.1ppm; The stillness of night, dry products therefrom sodium sulphate content was 98.51%, met " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.
Use the ethylene waste lye after certain enterprise's oil removing removes the gred to consist of (mass percent): NaOH 0% in embodiment 5-8, NaHS 8.8%, Na 2CO 38.3%, COD 75000mg/L, TOC 2300mg/L; Impurity metallic elements content is extremely low, Fe 0.8mg/L, Cr 1.3mg/L, Ni 1.8mg/L, Cu 0.8mg/L, Ca, Mg (in Mg) 0.7mg/L, Cl 75.8mg/L.
Below in conjunction with accompanying drawing, be specifically described by embodiment.
Embodiment 5
This ethylene waste lye is not in the situation that dilute and pH regulator, through 160 ℃ of (6MPa) wet type air oxidation 2.5h, gained intermediate oxidation liquid pH is 7.3, is that the pH value that 30% sodium hydroxide is regulated intermediate oxidation liquid is 9.5 with mass concentration, and continuation oxidation 2.5h gets oxidation solution; The gained oxidation solution is that 98% the vitriol oil pH value that neutralizes is 5.65 with mass concentration in the neutralization reactor of drum pneumatic blending; The gained neutralizer add polyacrylamide (PAM) flocculation agent to 1ppm by filter removing impurity; The dry products therefrom sodium sulphate content of filtrate is 98.63%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.
Embodiment 6
This ethylene waste lye is not in the situation that dilute and pH regulator, through 180 ℃ of (6MPa) wet type air oxidation 1.5h, gained intermediate oxidation liquid pH is 6.3, is that the pH value that 30% sodium hydroxide is regulated intermediate oxidation liquid is 10.5 with mass concentration, and continuation oxidation 1.5h gets oxidation solution; Oxidation solution is that 98% the vitriol oil pH value that neutralizes is 6.25 with mass concentration in the neutralization reactor of drum pneumatic blending; The gained neutralizer is removed impurity through gravity settling 36h; The stillness of night, dry products therefrom sodium sulphate content was 98.05%, met " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.
Embodiment 7
This ethylene waste lye is 0.95: 1 with the molar content ratio that sodium hydroxide solution (massfraction is 30%) is adjusted to Sodium sulfhydrate and sodium carbonate, the mass concentration of using is that 30% sodium hydroxide solution quality is for 11.0% of this ethylene waste lye quality, then through 210 ℃ of (6MPa) wet type dioxygen oxidation 2h; The gained oxidation solution is that 30% the sodium hydroxide pH value that neutralizes is 4.72 in mechanical stirring, during the neutralization reactor of venting port is arranged with mass concentration; The gained neutralizer add cationic polyacrylamide (CPAM) to the 0.3ppm gas through the floating impurity of removing; The dry products therefrom sodium sulphate content of clear liquid is 99.15%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " I class standard.
Embodiment 8
This ethylene waste lye is 0.97: 1 with the molar content ratio that sodium hydroxide solution (massfraction is 30%) is adjusted to Sodium sulfhydrate and sodium carbonate, the mass concentration of using is that 30% sodium hydroxide solution quality is for 10.8% of this ethylene waste lye quality, then through 240 ℃ of (6MPa) wet type dioxygen oxidation 1h; The gained oxidation solution is that 98% the vitriol oil pH value that neutralizes is 5.26 in mechanical stirring, during the neutralization reactor of venting port is arranged with mass concentration; The gained neutralizer adds cationic polyacrylamide (CPAM) and removes impurity through gravity settling 3h to 0.1ppm; The stillness of night, dry products therefrom sodium sulphate content was 98.50%, met " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class standard.

Claims (10)

1. the short flow and method of reclaim(ed) sulfuric acid sodium in an ethylene waste lye is characterized in that comprising following processing step:
(1) ethylene waste lye is carried out wet oxidation and process, wherein sulfide mainly is oxidized to vitriol; Wherein: less than 1 ethylene waste lye, directly carry out wet oxidation for the molar content ratio of Sodium sulfhydrate and sodium carbonate; For the molar content ratio of Sodium sulfhydrate and sodium carbonate greater than 1 ethylene waste lye, oxidation divides two sections, be the pH value that 30~45% sodium hydroxide solution is regulated intermediate oxidation liquid with massfraction between the two-stage oxidizing reaction member, the pH that first paragraph is oxidizing to ethylene waste lye stopped wet oxidation at 4.3~7.5 o'clock, the pH value of regulating intermediate oxidation liquid with sodium hydroxide is 8.8~10.5, and then carries out the second segment wet oxidation;
(2) in and oxidation after ethylene waste lye, obtain neutralizer;
(3) neutralizer is separated obtain clear liquid or filtrate;
(4) clear liquid or filtrate drying are obtained anhydrous sodium sulphate.
2. method according to claim 1 is characterized in that step (1) ethylene waste lye is for through the ethylene waste lye of water or water vapour dilution, without any one in the ethylene waste lye of water or water vapour dilution.
3. method according to claim 2, is characterized in that for the ethylene waste lye without water or water vapour dilution, and the neutralizer after oxidation, neutralization can be selected through water or water vapour dilution or dilute without water or water vapour.
4. method according to claim 1, it is characterized in that for the molar content ratio of Sodium sulfhydrate and sodium carbonate greater than 1 ethylene waste lye, be first that 30~45% sodium hydroxide solution is regulated molar content ratio that ethylene waste lye makes Sodium sulfhydrate and sodium carbonate in 0.95 to 1 scope with massfraction in step (1), then carry out wet oxidation.
5. according to claim 1,4 described either method, it is characterized in that wet oxidation is treated to any one in processing of wet type air oxide treatment or wet type dioxygen oxidation.
6. according to claim 1,4 described either method, it is characterized in that the temperature that wet oxidation is processed is 160 ℃~250 ℃; Pressure is higher than the saturated vapor pressure 20% of waste lye at each temperature; The residence time of wet oxidation reaction is different and change according to treatment temp, when being specially 160 ℃ for the treatment of temps, and the residence time 〉=5h; When treatment temp was 180 ℃, the residence time was 〉=3h; When treatment temp is 210 ℃, the residence time 〉=2h; When treatment temp is 250 ℃, the residence time 〉=1h; The residence time can infinitely extend, but the sulphate content of oxidation solution only can increase slightly, only limits from economic considerations the minimum time that stops.
7. according to claim 1,4 described either method, it is characterized in that adopting the sulphuric acid soln of mass percent concentration 70~98% or massfraction for the ethylene waste lye after oxidation is that 30~45% sodium hydroxide solution carries out neutralization reaction.
8. method according to claim 1, it is characterized in that neutralization reactor is optional has the mechanical stirring neutralization reactor of venting port or blasts any one in the neutralization reactor of pneumatic blending; For the mechanical stirring neutralization reactor that venting port is arranged, the neutralizer pH value that goes out reactor is controlled at 4.36~5.36; For the neutralization reactor that blasts pneumatic blending, the neutralizer pH value that goes out reactor is controlled at 5.36~6.36.
9. method according to claim 1 is characterized in that step (3) is separated neutralizer can select any one in sedimentation, filtration or air supporting; Sedimentation can be selected any one in gravity settling or centrifugal settling; All can select not add flocculation agent or add flocculation agent to the separation of neutralizer;
10. method according to claim 1 is characterized in that drying means in step (4) can select that atmospheric evaporation is dry, vacuum-evaporation is dry, any one in spraying drying; Also can select to allow flame contact the submerged combustion evaporation of saltcake liquid, obtain the anhydrous sodium sulphate product.
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