CN102452673B - Recovery processing method of waste alkaline liquor in ethylene plant - Google Patents
Recovery processing method of waste alkaline liquor in ethylene plant Download PDFInfo
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- CN102452673B CN102452673B CN201010526708.2A CN201010526708A CN102452673B CN 102452673 B CN102452673 B CN 102452673B CN 201010526708 A CN201010526708 A CN 201010526708A CN 102452673 B CN102452673 B CN 102452673B
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- oxidation
- waste lye
- sodium
- wet oxidation
- ethylene waste
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- 239000002699 waste material Substances 0.000 title claims abstract description 80
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000005977 Ethylene Substances 0.000 title claims abstract description 58
- 238000011084 recovery Methods 0.000 title abstract description 4
- 238000003672 processing method Methods 0.000 title abstract 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 56
- 238000000034 method Methods 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 43
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 36
- 238000002425 crystallisation Methods 0.000 claims abstract description 31
- 238000001704 evaporation Methods 0.000 claims abstract description 25
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 23
- 230000008020 evaporation Effects 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 195
- 230000003647 oxidation Effects 0.000 claims description 40
- 238000007254 oxidation reaction Methods 0.000 claims description 40
- 230000008025 crystallization Effects 0.000 claims description 28
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 26
- 235000011152 sodium sulphate Nutrition 0.000 claims description 26
- 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
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 5
- 229920006395 saturated elastomer Polymers 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 abstract description 7
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 18
- 239000011734 sodium Substances 0.000 description 18
- 239000000243 solution Substances 0.000 description 16
- 239000012452 mother liquor Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 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
- 238000004332 deodorization Methods 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 230000008014 freezing Effects 0.000 description 5
- 238000007710 freezing Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 229910052708 sodium Inorganic materials 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
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- -1 mercaptan Chemical class 0.000 description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 4
- 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 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002781 deodorant agent Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000004064 recycling Methods 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
- 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
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 2
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-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
- 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
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 150000004763 sulfides Chemical class 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001131796 Botaurus stellaris Species 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000005864 Sulphur Substances 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
- 238000001816 cooling Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 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
- 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
- 239000003517 fume Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 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
- 239000010446 mirabilite Substances 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
- 238000002203 pretreatment Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 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
- 239000000779 smoke Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 235000010265 sodium sulphite Nutrition 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
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 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
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention provides a recovery processing method of waste alkaline liquor in an ethylene plant. The method comprises the following steps: (1) under the condition of wet oxidation, carrying out wet oxidation on waste alkaline liquor with air or oxygen so as to obtain oxidized liquid; (2) neutralizing the oxidized liquid so as to obtain a neutralized liquid; (3) crystallizing the neutralized liquid by adopting an evaporation and crystallization method so as to obtain anhydrous sodium sulfate containing entrained water; (4) returning a part of evaporation mother liquid back to a neutralization unit, and carrying out non-biochemical treatment on another part of evaporation mother liquid; and (5) drying the anhydrous sodium sulfate containing entrained water so as to obtain the anhydrous sodium sulfate product. By using the method, the technical problem that high-content salt still generates impact on a biochemical treatment system after the ethylene waste alkaline liquor is deodorized and diluted through wet oxidation and then is subjected to biochemical treatment can be solved; and the method provided by the invention can be used for the fields of petrifaction, chemical industry, environmental conservation, comprehensive resource utilization, light industry and the like.
Description
Technical field
The present invention relates to the technology of reclaim(ed) sulfuric acid sodium from waste alkali liquor of ethylene unit, the technology of sodium sulfate, the i.e. oxidation of waste alkali liquor of ethylene unit, neutralization, crystallization reclaim(ed) sulfuric acid sodium are processed and are isolated from waste liquid in the wet oxidation that more particularly relates to waste lye.
Background technology
Sour gas in ethene cracking gas mainly comprises hydrogen sulfide, carbonic acid gas, organosulfur etc., for removing sour gas, takes alkaline solution and the washing of splitting gas counter current contact, and the waste liquid of generation is called ethylene waste lye.Remove and contain Na in waste lye
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 there is unpleasant stink outward.
After comprising direct facture, pre-treatment, the method for improvement ethylene waste lye dilutes into methods such as biochemical treatment, comprehensive uses.At the Ethylene Development initial stage, the direct facture of the many employings of the processing of waste lye, comprise deep-well injection, landfill, dilution discharge and burning, and front several method is because the requirement of environmental protection is prohibited from using; The burning method energy consumption is large, and running cost is high.
The deodorization technique that wet air oxidation is processed ethylene waste lye is proven technique.Carry out the important means that biochemical treatment has progressively become the ethylene waste lye processing after adopting the wet type air oxidation to carry out after deodorization is processed recycling other wastewater dilution.Ethylene waste lye after wet oxidation is processed contains a large amount of inorganic salt, and biodegradability is poor.Directly enter composite wastewater treatment plant, will impact biochemical treatment system, affect the sewage discharge compliance rate, after dilution, biochemical treatment is still more 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, precipitated sulfur compound regeneration NaOH method etc.Can obtain Na after secondary crystal
2the industrial goods of S content 28%～31%, containing NaOH and Na
2cO
3if mother liquor be cycled to used in the sour gas that absorbs splitting gas, can cause Na
2cO
3alkali lye in accumulation and affect device and operate.Cupric oxide, magnesium oxide precipitation method are regenerated as sodium hydroxide by sulphur hydrogen sodium, sodium carbonate, make ethylene waste lye obtain holomorphosis, but this precipitation agent are 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, after employing alkaline earth metal oxide causticization waste lye, uses the transition metal oxide desulfurization, and the sulfide obtained is expected to become high value-added product, but does not have product to detect.
CN1305954 has proposed to take liquid hydrocarbon or waste alkali solution of gasoline and has prepared the method for S-WAT as raw material, and it is mainly that the sulfurous gas gas mixture that sulfur burning is produced is delivered to absorption tower I bottom, and waste lye is neutralized from the tower top spray.What the tail gas of absorption tower I produced through burning delivers to absorption tower II bottom containing sulfur dioxide gas.3～10% sodium hydroxide solutions are from the tower top spray.Separately will be from absorption tower I liquid out deliver to stirred pot, add ferrous sulfate or zinc sulfate to stir.S-WAT prepared by this method still exists in solution, and containing 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 to be absorbed the sulfurous gas in flue gas, flue dust and oxynitride.Adopt two sections absorption patterns, leading portion adopts the absorption liquid of back segment discharge directly to contact with flue gas, to reduce flue-gas temperature, removes wherein part pollutent simultaneously; Back segment be take deodorant waste lye as absorption liquid contacts with the flue gas after the leading portion cooling, absorbs the pollutent that comprises oxysulfide or oxynitride, the fume emission after purification.This method has produced the more waste liquid containing 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.
Ethylene waste lye carries out biochemical treatment after deodorization processing, dilution are carried out in wet oxidation again, and contained high salt still can produce and impact biochemical treatment system; 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 extensive utilization of ethylene waste lye wet air oxidation deodorization, deodorization and in rear waste lye higher, sodium sulfate in ethylene waste lye on the basis that the present invention processes in the wet oxidation deodorization after the reclaim(ed) sulfuric acid neutralizing treatment, 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:
Wet type air oxidation (Wet Air Oxidation, WAO): be under high temperature, high top pressure operation condition, use air as oxygenant in liquid phase, be a kind for the treatment of process of organism or the reduction-state inorganics of solubilised state or suspended state in oxidizing water.
The wet type dioxygen oxidation: in the wet type air oxidation operation, it is also 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 ethene cracking gas is mainly hydrogen sulfide, carbonic acid gas, organosulfur etc., ethylene waste lye results from the counter current contact of alkaline solution and splitting gas, sour gas reacts with sodium hydroxide and generates sodium salt, and the hydrocarbons component in cleaved gas of waste lye while is saturated.Can contain Na in waste lye
2s, Na
2cO
3, NaOH and a small amount of Na
2sO
3, Na
2s
2o
3, also may contain NaHCO
3, and contain the organic sulfides such as mercaptan, there is unpleasant stink.
Oxidation solution: ethylene waste lye is carried out to the wet oxidation operation, and the liquid obtained is referred to herein as oxidation solution.
Intermediate oxidation liquid: when ethylene waste lye is carried out to 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: the high ethylene waste lye for Sodium sulfhydrate content, complete oxidation can make its pH value be reduced to acidity, be subject to the restriction of wet oxidation reaction equipment matter, rooting is first regulated the pH value of waste lye or/and minute two-stage oxidizing according to Sodium sulfhydrate content and is controlled the pH value of intermediate oxidation liquid according to 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.
Neutralizer: oxidation solution is carried out to neutralization operation, and the liquid obtained is referred to herein as neutralizer.At this paper, with the vitriol oil or sodium hydroxide, neutralized.
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; Also can adopt crystallization from the aqueous solution to go out saltcake, the method that saltcake dewaters again, be called two step method.Single stage method generally adopts vacuum vapor deposition method; The method of saltcake dehydration is divided into again seasoning evaporation, widely different desiccating method, scorification, the vacuum-evaporation evaporation etc. of turning.
Sodium sulfate anhydrous.min(99): the trade(brand)name of industrial anhydrous sodium sulfate/be commonly called as.
Summary of the invention
The above-mentioned defect that the present invention exists separately in order to overcome existing ethylene waste lye treatment process, provide after a kind of wet oxidation neutralizing treatment ethylene waste lye the method for reclaim(ed) sulfuric acid sodium therefrom.This invention can reduce the saltiness of waste lye, and the impact that can reduce or avoid wet oxidation to process the follow-up biochemical treatment of high salt pair in 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 the method for reclaim(ed) sulfuric acid sodium therefrom.Particularly, the method comprises: (1), under the wet oxidation condition, carries out wet oxidation with air or oxygen to it, obtains oxidation solution; (2) oxidation solution is neutralized, obtained neutralizer; (3) adopt the crystallization from neutralizer of evaporative crystallization method to go out the anhydrous sodium sulphate containing water entrainment; (4) the part mother liquid evaporation returns to neutralisation unit, and the part mother liquid evaporation goes biochemical treatment; (5) anhydrous sodium sulphate containing water entrainment is carried out to drying, obtain the anhydrous sodium sulphate product.
In step (1), the ethylene waste lye oxidizing temperature is to be greater than the scope interior (pressure is on hold-up vapour pressure at each temperature) of 150～250 ℃.
In step (3), crystallization adopts the method for vacuum evaporating crystalization directly from neutralizer, to obtain moisture anhydrous sodium sulphate crystallization, obtains the anhydrous sodium sulphate product after drying, i.e. Sodium sulfate anhydrous.min(99).When the crystalline product quality can not meet the demands, by mother liquid evaporation, send biochemical treatment.
Gained Sodium sulfate anhydrous.min(99) quality can reach or, higher than the requirement of II class salable product in industrial anhydrous sodium sulfate quality standard (GB/T 6009-2003), the rate of recovery of whole process sodium is greater than 80%, and the quantity discharged of salt reduces approximately 80%.
The preferred embodiment of the present invention:
The condition of step (1) wet oxidation: the wet oxidation temperature requirement of ethylene waste lye is for being greater than 150 ℃～250 ℃, reaction pressure is to be greater than saturated vapor pressure at each temperature more than 20%, guarantee enough residence time and oxygen partial pressure so that sodium sulphite fully is converted into sodium sulfate.Different wet type oxidizing temperatures require the minimum residence time:
The high ethylene waste lye for Sodium sulfhydrate content, complete oxidation can make its pH value be reduced to acidity, be subject 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.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.
In step (2) and pH control: neutralization reaction is at strong stirring or pass into pressurized air and carry out under stirring, with the CO that guarantees that solution mixes, generates
2fully discharge.The neutralizer pH that goes out reactor is controlled at 3.5～5.5, and for reaching higher anhydrous sodium sulphate product hierarchy, more excellent scope is 4.5～5.1.Neutralizer is processed and is removed impurity through sedimentation.
The high ethylene waste lye for 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 with in sodium hydroxide and unnecessary acidity, because the price of sodium carbonate is higher than sodium hydroxide, and uses sodium carbonate can increase sodium carbonate foreign matter content in sodium sulfate.Sodium sulfhydrate
Step (3) crystallization mode: the wet oxidation temperature, when being greater than 150 ℃～250 ℃, can adopt evaporative crystallization directly to reclaim the anhydrous sodium sulphate product in neutralizer.
The processing of step (4) evaporative crystallization mother liquor: part is got back to neutralisation unit, and part is gone biochemical treatment.The pH value of evaporative crystallization mother liquor is controlled at below 9, and the pH of evaporative crystallization mother liquor reaches at 8.5～9 o'clock, returns to neutralisation unit.The color of mother liquid evaporation, COD are removed biochemistry after surpassing certain value, 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, after the experiment through limited, have the ability to determine this value fully.The basic reason of controlling step (4) is: when evaporative crystallization gained Sodium sulfate anhydrous.min(99) can not meet the quality product requirement, no longer return to neutralisation unit, but mother liquid evaporation is gone to 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, there is new meaning.For reclaim(ed) sulfuric acid sodium, the report of the existing reclaim(ed) sulfuric acid sodium of other several industries, but have no report 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 processed and have all been carried out preferably:
For wet oxidation operation, carried out preferably for the residence time under differing temps and pressure.The operational condition that the wet oxidation of existing different enterprises is processed is as follows:
The operational condition difference that the wet oxidation of the different enterprises of table 3 is processed
Ethylene waste lye after deodorization goes biochemical will the neutralization before, but neutralization gets final product to pH 7～9.Due to Na in ethylene waste lye
2cO
3content higher than Na in mirabilite ore, bittern
2cO
3content, in it and the pH of the pH of terminal saltcake solution when also various conventional sodium sulfate is produced.Remove the carbonate in waste lye, will be reduced to pH lower.The present invention will be preferably 3.5～5.5 with terminal pH in oxidation solution, and more excellent is 4.5-5.1.
Crystallization mode to gained neutralizer after neutralization after wet oxidation in 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, in general sodium sulfate production, be again gained crystallization nitre to be got back to the evaporative crystallization operation after freezing and crystallizing, the present invention gets back to the oxidation solution neutralisation unit by its part and carries out neutralization operation.
The invention has the beneficial effects as follows:
Ethylene waste lye after deodorization is further processed, reclaim(ed) sulfuric acid sodium, can reduce the quantity discharged of waste lye, reduce or avoid wet oxidation to process the impact of the follow-up biochemical treatment of high salt pair in 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 processed reduces, and the saltiness of freezing and crystallizing mother liquor reduces greatly, all makes the biochemical treatment difficulty greatly reduce.By implementing optimal conditions of the present invention, can make the sodium sulfate good product quality reclaimed, the method such as need not burn and can reach " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product and above index.
The accompanying drawing explanation
Fig. 1 is that the ethene alkali lye through being greater than after 150 ℃～250 ℃ wet oxidations are processed reclaims the schematic flow sheet of anhydrous sodium sulphate through evaporative crystallization.
Embodiment
In embodiment, use the ethylene waste lye after certain enterprise's oil removing removes the gred to consist of (mass percent): NaOH17.9%, Na
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.
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 neutralizes pH4.64 with the vitriol oil, and neutralizer adopts vacuum evaporating crystalization, the part mother liquid evaporation removes biochemistry, and evaporative crystallization is dried to Sodium sulfate anhydrous.min(99).The part mother liquid evaporation returns to 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; The freezing mother liquor amount of gained be reduced to approximately in and liquid measure 1/7, COD 1300mg/L, total dissolved solidss 34%.
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 due to 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 sodium carbonate causes descends and can return to 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, remove biochemistry afterwards.
Embodiment 2
This ethylene waste lye is not in the situation that dilute and pH regulator, through 180 ℃ of (6MPa) wet type air oxidation 5h, the gained oxidation solution neutralizes pH4.01 with the vitriol oil, and neutralizer adopts vacuum evaporating crystalization, the part mother liquid evaporation removes biochemistry, and evaporative crystallization is dried to Sodium sulfate anhydrous.min(99).The part mother liquid evaporation returns to 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-T6009-2003 industrial anhydrous sodium sulfate " II class salable product standard; The freezing mother liquor amount of gained be reduced to approximately in and liquid measure 1/7, COD 900mg/L, total dissolved solidss 34%.
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 neutralizes pH4.70 with the vitriol oil, and neutralizer adopts vacuum evaporating crystalization, the part mother liquid evaporation removes biochemistry, and evaporative crystallization is dried to Sodium sulfate anhydrous.min(99).The part mother liquid evaporation returns to 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-T6009-2003 industrial anhydrous sodium sulfate " II class salable product standard; The freezing mother liquor amount of gained be reduced to approximately in and liquid measure 1/7, COD 600mg/L, total dissolved solidss 34%.
Claims (7)
1. process ethylene waste lye the method for reclaim(ed) sulfuric acid sodium therefrom for one kind, the method comprises:
(1) under the wet oxidation condition, with air or oxygen, it is carried out to wet oxidation, obtain oxidation solution;
Wherein, the condition of wet oxidation: the wet oxidation temperature requirement of ethylene waste lye is for being greater than 150 ℃～250 ℃, and reaction pressure is to be greater than saturated vapor pressure at each temperature more than 20%, and different wet type oxidizing temperatures require the minimum residence time as follows
(2) oxidation solution is neutralized, obtained neutralizer; Wherein, neutralization reaction is at strong stirring or pass into pressurized air and carry out under stirring, and the neutralizer pH that goes out reactor is controlled at 3.5～5.5;
(3) adopt the crystallization from neutralizer of evaporative crystallization method to go out the anhydrous sodium sulphate containing water entrainment;
(4) the part mother liquid evaporation returns to neutralisation unit, and the part mother liquid evaporation goes biochemical treatment;
(5) anhydrous sodium sulphate containing water entrainment is carried out to drying, obtain the anhydrous sodium sulphate product.
2. according to the described method of claim 1, in step (3), crystallization adopts the method for vacuum evaporating crystalization directly from neutralizer, to obtain moisture anhydrous sodium sulphate crystallization.
3. method according to claim 1, the neutralizer pH that goes out reactor in step (2) is controlled at 4.5～5.1.
4. according to the described method of claim 1, in step (2), adopt the vitriol oil to be neutralized.
5. according to the described method of claim 1, the high ethylene waste lye for Sodium sulfhydrate content is neutralized with sodium hydroxide in step (2).
6. according to the described method of claim 1 or 5, the high ethylene waste lye for Sodium sulfhydrate content, first with sodium hydroxide, regulate ethylene waste lye pH value and carry out again oxidation in step (1), in step (2), adopt sodium hydroxide or the vitriol oil to be neutralized.
7. method according to claim 6, the high ethylene waste lye for Sodium sulfhydrate content, in step (1), oxidation divides two sections, regulate the pH value of intermediate oxidation liquid with sodium hydroxide between the two-stage oxidizing reaction member, in step (2), adopt sodium hydroxide or the vitriol oil to be neutralized.
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| CN1162571A (en) * | 1996-01-31 | 1997-10-22 | 日本石油化学株式会社 | Wet oxidizing process |
| CN1257102A (en) * | 1998-12-16 | 2000-06-21 | 中国石油化工集团公司 | Process for treating waste lye of refining oil products in petroleum refining industry |
| 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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| CN1162571A (en) * | 1996-01-31 | 1997-10-22 | 日本石油化学株式会社 | Wet oxidizing process |
| CN1257102A (en) * | 1998-12-16 | 2000-06-21 | 中国石油化工集团公司 | Process for treating waste lye of refining oil products in petroleum refining industry |
| 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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