CN102452769B - Processing method for waste alkali liquor in ethylene unit - Google Patents
Processing method for waste alkali liquor in ethylene unit Download PDFInfo
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- CN102452769B CN102452769B CN 201010526713 CN201010526713A CN102452769B CN 102452769 B CN102452769 B CN 102452769B CN 201010526713 CN201010526713 CN 201010526713 CN 201010526713 A CN201010526713 A CN 201010526713A CN 102452769 B CN102452769 B CN 102452769B
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- liquid
- ethylene waste
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- 239000002699 waste material Substances 0.000 title claims abstract description 78
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical group C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000005977 Ethylene Substances 0.000 title claims abstract description 56
- 239000003513 alkali Substances 0.000 title abstract description 8
- 238000003672 processing method Methods 0.000 title abstract 2
- 238000000034 method Methods 0.000 claims abstract description 48
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 46
- 230000003647 oxidation Effects 0.000 claims abstract description 45
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 45
- 239000007788 liquid Substances 0.000 claims abstract description 42
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 34
- 230000008014 freezing Effects 0.000 claims abstract description 22
- 238000007710 freezing Methods 0.000 claims abstract description 22
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 238000002425 crystallisation Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 198
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 21
- 235000011152 sodium sulphate Nutrition 0.000 claims description 21
- 230000008025 crystallization Effects 0.000 claims description 14
- 230000001590 oxidative effect Effects 0.000 claims description 12
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 claims description 12
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims description 11
- 238000006386 neutralization reaction Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 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
- 238000010790 dilution Methods 0.000 abstract description 5
- 239000012895 dilution Substances 0.000 abstract description 5
- 230000003472 neutralizing effect Effects 0.000 abstract description 5
- 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 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 15
- 239000000047 product Substances 0.000 description 11
- 229960003010 sodium sulfate Drugs 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- 229940056729 sodium sulfate anhydrous Drugs 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 6
- 150000003839 salts Chemical class 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
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000003546 flue gas Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 235000017550 sodium carbonate Nutrition 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 238000005516 engineering process Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- -1 mercaptan Chemical class 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
- 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
- 239000007795 chemical reaction product Substances 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
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 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
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 206010023126 Jaundice Diseases 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
- 239000013078 crystal Substances 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
- 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
- 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
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 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)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a processing method for waste alkali liquor in an ethylene unit, wherein the method comprises the following steps: (1), performing wet oxidation on waste alkali liquor with air or oxygen under wet oxidation conditions to obtain oxidation liquid; (2), neutralizing the oxidation liquid to obtain neutralized liquid; (3), crystallizing out sodium sulfate decahydrate from the neutralized liquid by a freezing crystallization method; (4), performing biochemical treatment on frozen mother liquor; (5), drying the sodium sulfate decahydrate to obtain anhydrous sodium sulfate products. The method solves the technical problem that waste alkali liquor of ethylene after being processed by deodorization, dilution and biochemical treatment still contains high-salt which can cause an impact to the biochemical treatment system. The method can be applied in fields like petrochemical, chemical engineering, environment protection, comprehensive utilization of the resources and light industries.
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 freeze crystallization crystallization from neutralizer to go out sodium sulfate; (4) freezing mother liquor carries out biochemical treatment.
In step (1), oxidizing temperature is 110～250 ℃ scope interior (pressure is on hold-up vapour pressure at each temperature).
In step (3), crystallization adopts freeze crystallization crystallization from neutralizer to go out sal glauberi.Obtain the anhydrous sodium sulphate product after the sal glauberi drying, i.e. Sodium sulfate anhydrous.min(99).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 85%, and namely the quantity discharged of salt reduces about 85%.
Preferred implementation:
The condition of step (1) wet oxidation: the wet oxidation temperature requirement of ethylene waste lye is 115 ℃～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.Be subjected to the restriction of wet oxidation reaction equipment matter, may require the branch two-stage oxidizing and according to the pH value of Sodium sulfhydrate content control intermediate oxidation liquid.The present invention requires to regulate the pH value with sodium hydroxide between the two-stage oxidizing reaction member.
Step (3) crystallization mode: the wet oxidation temperature adopts the sal glauberi in the freezing and crystallizing recovery neutralizer in the time of 110 ℃～250 ℃, again sal glauberi is carried out drying, obtains the anhydrous sodium sulphate product, i.e. Sodium sulfate anhydrous.min(99).
The essential distinction of the present invention and prior art is, for the treatment process of ethylene waste lye, reclaims sodium sulfate on existing wet oxidation basis, has 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.
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.
The invention has the beneficial effects as follows: the 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.
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, Cr1.2mg/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, be specifically described by embodiment.
Embodiment 1
This ethylene waste lye is under the situation of not diluting with pH regulator, and through 120 ℃ of (6MPa) wet type air oxidation 8h, gained oxidation liquid is with the vitriol oil pH5.46 that neutralizes, and neutralizer is through freezing and crystallizing, and freezing mother liquor removes biochemistry, and crystallizing and drying becomes Sodium sulfate anhydrous.min(99).Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 93.76%, meets " GB-T6009-2003 industrial anhydrous sodium sulfate " III class salable product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/3, COD 2900mg/L, total dissolved solidss 9%.
Embodiment 2
This ethylene waste lye is under the situation of not diluting with pH regulator, and through 150 ℃ of (4.5MPa) wet type dioxygen oxidation 6h, gained oxidation liquid is with the vitriol oil pH5.03 that neutralizes, and neutralizer is through freezing and crystallizing, and freezing mother liquor removes biochemistry.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 97.24%, 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 1/3, COD 900mg/L, total dissolved solidss 7%.
Embodiment 3
This ethylene waste lye is under the situation of not diluting with pH regulator, and through 160 ℃ of (6MPa) wet type air oxidation 5h, gained oxidation liquid is with the vitriol oil pH4.64 that neutralizes, and neutralizer is through freezing and crystallizing, and freezing mother liquor removes biochemistry.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 99.05%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class salable product standard (because color jaundice); During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/3, COD 450mg/L, total dissolved solidss 6%.
Embodiment 4
This ethylene waste lye is under the situation of not diluting with pH regulator, and through 180 ℃ of (6MPa) wet type air oxidation 5h, gained oxidation liquid is with the vitriol oil pH4.01 that neutralizes, and neutralizer is through freezing and crystallizing, and freezing mother liquor removes biochemistry.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 98.08%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " II class acceptable end product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/3, COD 300mg/L, total dissolved solidss 6%.
Embodiment 5
This ethylene waste lye is under the situation of not diluting with pH regulator, and through 210 ℃ of (6MPa) wet type dioxygen oxidation 2h, gained oxidation liquid is with the vitriol oil pH4.70 that neutralizes, and neutralizer is through freezing and crystallizing, and freezing mother liquor removes biochemistry.Gained Sodium sulfate anhydrous.min(99) sodium sulphate content is 99.13%, meets " GB-T 6009-2003 industrial anhydrous sodium sulfate " I class acceptable end product standard; During the freezing mother liquor amount of gained is reduced to approximately and liquid measure 1/3, COD 220mg/L, total dissolved solidss 6%.
Description of drawings
Fig. 1 is the ethene alkali lye after handling through 110 ℃～250 ℃ wet oxidations reclaims anhydrous sodium sulphate through freezing and crystallizing schematic flow sheet.
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 ethylene waste lye oxidizing temperature is that pressure is on hold-up vapour pressure at each temperature in 110～250 ℃ the scope;
(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 freeze crystallization crystallization from neutralizer to go out sal glauberi, obtain anhydrous sodium sulphate after the sal glauberi drying;
(4) freezing mother liquor carries out biochemical treatment.
2. method according to claim 1, the condition of wet oxidation in step (1): the wet oxidation temperature of ethylene waste lye is 115 ℃～250 ℃, more than 20%, different wet type oxidizing temperatures require the minimum residence time to be to reaction pressure greater than at each temperature saturated vapor pressure:
3. method according to claim 1 goes out the neutralizer pH control of reactor 4.5～5.1 in step (2).
4. method according to claim 1 adopts the vitriol oil to neutralize in step (2).
5. method according to claim 1 for the high ethylene waste lye of Sodium sulfhydrate content, neutralizes with sodium hydroxide in step (2).
6. method according to claim 1 for the high ethylene waste lye of Sodium sulfhydrate content, is regulated ethylene waste lye pH value with sodium hydroxide earlier and is carried out oxidation again in step (1), adopts sodium hydroxide or the vitriol oil to neutralize in step (2).
7. according to claim 1 or 6 described methods, for the high ethylene waste lye of Sodium sulfhydrate content, oxidation divides two sections in the step (1), regulates the pH value of intermediate oxidation liquid between the two-stage oxidizing reaction member with sodium hydroxide, adopts sodium hydroxide or the vitriol oil to neutralize in step (2).
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