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
- Publication number
- CN102452672B CN102452672B CN 201010526697 CN201010526697A CN102452672B CN 102452672 B CN102452672 B CN 102452672B CN 201010526697 CN201010526697 CN 201010526697 CN 201010526697 A CN201010526697 A CN 201010526697A CN 102452672 B CN102452672 B CN 102452672B
- Authority
- CN
- China
- Prior art keywords
- sodium sulfate
- oxidation
- waste lye
- liquid
- ethylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000002699 waste material Substances 0.000 title claims abstract description 82
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000005977 Ethylene Substances 0.000 title claims abstract description 60
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 51
- 229910052938 sodium sulfate Inorganic materials 0.000 title claims abstract description 29
- 235000011152 sodium sulphate Nutrition 0.000 title claims abstract description 29
- 239000003513 alkali Substances 0.000 title abstract description 9
- 238000004064 recycling Methods 0.000 title abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 54
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 36
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 33
- 230000008014 freezing Effects 0.000 claims abstract description 31
- 238000007710 freezing Methods 0.000 claims abstract description 31
- 239000012452 mother liquor Substances 0.000 claims abstract description 27
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 199
- 230000003647 oxidation Effects 0.000 claims description 41
- 238000007254 oxidation reaction Methods 0.000 claims description 41
- 238000002425 crystallisation Methods 0.000 claims description 28
- 230000008025 crystallization Effects 0.000 claims description 26
- 238000001704 evaporation Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 16
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 13
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000011084 recovery Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 238000004332 deodorization Methods 0.000 abstract description 10
- 230000003472 neutralizing effect Effects 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 7
- 238000010790 dilution Methods 0.000 abstract description 5
- 239000012895 dilution Substances 0.000 abstract description 5
- 238000005516 engineering process Methods 0.000 abstract description 4
- RSIJVJUOQBWMIM-UHFFFAOYSA-L sodium sulfate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]S([O-])(=O)=O RSIJVJUOQBWMIM-UHFFFAOYSA-L 0.000 abstract 3
- 238000000926 separation method Methods 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 15
- 229960003010 sodium sulfate Drugs 0.000 description 11
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 11
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000001556 precipitation Methods 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 235000017550 sodium carbonate Nutrition 0.000 description 5
- 229910000029 sodium carbonate Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 238000007865 diluting Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- -1 mercaptan Chemical class 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 235000019600 saltiness Nutrition 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 235000011089 carbon dioxide Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003500 flue dust Substances 0.000 description 1
- 235000011194 food seasoning agent Nutrition 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000010587 phase diagram Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- WBHQBSYUUJJSRZ-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [H+].[H+].[Na+].[O-]S([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
Images
Landscapes
- Treating Waste Gases (AREA)
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).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010526697 CN102452672B (en) | 2010-11-01 | 2010-11-01 | Method for recycling sodium sulfate from waste alkali liquor of ethylene unit |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010526697 CN102452672B (en) | 2010-11-01 | 2010-11-01 | Method for recycling sodium sulfate from waste alkali liquor of ethylene unit |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102452672A CN102452672A (en) | 2012-05-16 |
| CN102452672B true CN102452672B (en) | 2013-08-14 |
Family
ID=46036416
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010526697 Active CN102452672B (en) | 2010-11-01 | 2010-11-01 | Method for recycling sodium sulfate from waste alkali liquor of ethylene unit |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102452672B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8734648B2 (en) * | 2007-09-11 | 2014-05-27 | Siemens Energy, Inc. | Treatment of spent caustic waste |
-
2010
- 2010-11-01 CN CN 201010526697 patent/CN102452672B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1789162A (en) * | 2005-12-06 | 2006-06-21 | 河北工业大学 | Technique for reclaiming ethylene alkali-washing waste liquid |
Non-Patent Citations (2)
| Title |
|---|
| 乙烯废碱液处理技术研究进展;马克存等;《石油化工》;20081231;第37卷;第678-680页 * |
| 马克存等.乙烯废碱液处理技术研究进展.《石油化工》.2008,第37卷第678-680页. |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102452672A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102452672B (en) | Method for recycling sodium sulfate from waste alkali liquor of ethylene unit | |
| CN102424498B (en) | Circular and comprehensive utilization method for ethylene alkali waste liquid | |
| RU2126863C1 (en) | Method of separating out of sulfur compounds (versions) | |
| CN103045288B (en) | Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid | |
| CN103769407B (en) | A kind of renovation process of sulfur-bearing alkaline residue | |
| CN103045289B (en) | Comprehensive treatment method of liquid hydrocarbon alkali residue waste liquid | |
| CN102452674B (en) | Processing method for recycling sodium sulfate from waste alkali liquor in ethylene unit | |
| CN102452673B (en) | Recovery processing method of waste alkaline liquor in ethylene plant | |
| CN104609623A (en) | Ethylene alkaline cleaning waste liquid processing method | |
| CN104609622B (en) | The processing method of spent lye in a kind of ethylene production | |
| CN103771608A (en) | Treatment method of alkaline residue waste liquid from oil refining | |
| CN101104132A (en) | Biological desulfurizing technology for transferring sulfur-containing compound into elemental sulfur | |
| CN103771607B (en) | The treatment process of refinery alkaline residue | |
| CN103721546B (en) | Process for recycling sulfur-containing mixed waste gas in viscose fiber production | |
| CN102452769B (en) | Processing method for waste alkali liquor in ethylene unit | |
| CN103771609B (en) | A kind for the treatment of process of naphthenic acid alkali residue waste liquid | |
| CN102815812B (en) | Optimization process method for recovering sodium sulfate form ethylene waste alkali | |
| KR20210033016A (en) | Biological treatment of industrial alkaline streams | |
| CN103771610B (en) | The integrated conduct method of naphthenic acid alkali residue waste liquid | |
| CN104609625A (en) | Ethylene waste alkali liquor processing method | |
| CN114956432A (en) | Waste alkali liquor recycling method and system | |
| CN103771612A (en) | Treatment method of spent lye in propylene production | |
| CN102815811B (en) | Short flow method for recycling sodium sulfate from ethylene waste alkali liquid | |
| CN103773426B (en) | The treatment process of liquid hydrocarbon alkali residue waste liquid | |
| CN107051155B (en) | Method for preparing nitrate by using low-grade alkali-containing brine for flue gas desulfurization-oxidation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |