CN106315930A - Method for regenerating and recycling ethylene waste alkali liquor - Google Patents
Method for regenerating and recycling ethylene waste alkali liquor Download PDFInfo
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- CN106315930A CN106315930A CN201510346558.XA CN201510346558A CN106315930A CN 106315930 A CN106315930 A CN 106315930A CN 201510346558 A CN201510346558 A CN 201510346558A CN 106315930 A CN106315930 A CN 106315930A
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- bipolar membrane
- membrane electrodialysis
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- lye
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- 238000000034 method Methods 0.000 title claims abstract description 105
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000002699 waste material Substances 0.000 title claims abstract description 57
- 239000005977 Ethylene Substances 0.000 title claims abstract description 55
- 239000003513 alkali Substances 0.000 title claims abstract description 26
- 238000004064 recycling Methods 0.000 title abstract description 7
- 230000001172 regenerating effect Effects 0.000 title abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 269
- 239000012528 membrane Substances 0.000 claims abstract description 71
- 238000000909 electrodialysis Methods 0.000 claims abstract description 70
- 230000008569 process Effects 0.000 claims abstract description 64
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 41
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 27
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 21
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 20
- 238000001914 filtration Methods 0.000 claims abstract description 17
- 230000003647 oxidation Effects 0.000 claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 17
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000001117 sulphuric acid Substances 0.000 claims description 18
- 235000011149 sulphuric acid Nutrition 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 17
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 10
- 229910001948 sodium oxide Inorganic materials 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- 239000010865 sewage Substances 0.000 claims description 8
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 8
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 8
- 238000006477 desulfuration reaction Methods 0.000 claims description 7
- 230000023556 desulfurization Effects 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000009279 wet oxidation reaction Methods 0.000 claims description 7
- -1 hydrogen Sodium oxide Chemical class 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 5
- 238000007670 refining Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 4
- 238000007599 discharging Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 238000005336 cracking Methods 0.000 abstract description 15
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 abstract description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 abstract description 9
- 235000011152 sodium sulphate Nutrition 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 230000007547 defect Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000007788 liquid Substances 0.000 description 26
- 239000011734 sodium Substances 0.000 description 15
- 239000007789 gas Substances 0.000 description 13
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 11
- 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 9
- 238000006243 chemical reaction Methods 0.000 description 8
- 230000008859 change Effects 0.000 description 7
- 238000005265 energy consumption Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000011069 regeneration method Methods 0.000 description 6
- 229910052708 sodium Inorganic materials 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052979 sodium sulfide Inorganic materials 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000003518 caustics Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000005751 Copper oxide Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 229910000431 copper oxide Inorganic materials 0.000 description 2
- 230000003009 desulfurizing effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000004537 pulping Methods 0.000 description 2
- 210000000952 spleen Anatomy 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- 101100058599 Arabidopsis thaliana BPM2 gene Proteins 0.000 description 1
- RJBLRLUDKHMVTM-UHFFFAOYSA-L C(=O)=O.C([O-])([O-])=O.[Na+].[Na+] Chemical compound C(=O)=O.C([O-])([O-])=O.[Na+].[Na+] RJBLRLUDKHMVTM-UHFFFAOYSA-L 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 238000009303 advanced oxidation process reaction Methods 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009993 causticizing Methods 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- PANBYUAFMMOFOV-UHFFFAOYSA-N sodium;sulfuric acid Chemical compound [Na].OS(O)(=O)=O PANBYUAFMMOFOV-UHFFFAOYSA-N 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229930195735 unsaturated hydrocarbon Natural products 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
- Water Treatment By Electricity Or Magnetism (AREA)
Abstract
The invention relates to a method for regenerating and recycling ethylene waste alkali liquor, which comprises the following technological processes in sequence: oil removal treatment, oxidation treatment, filtration treatment and bipolar membrane electrodialysis treatment. The method adopts two-chamber type bipolar membrane and three-chamber type bipolar membrane electrodialysis to treat the ethylene waste alkali liquor in sequence, can convert sodium carbonate into carbon dioxide and sodium hydroxide while recovering the remaining sodium hydroxide, and convert sodium sulfate into sulfuric acid and sodium hydroxide, so that the obtained 8-15% sodium hydroxide solution can be directly returned to the ethylene cracking gas alkali washing device for recycling, the material consumption of the ethylene cracking gas alkali washing device is reduced, the production cost is reduced, and the defects that the prior art is low in recovered alkali concentration and difficult to directly recycle are overcome.
Description
Technical field
The invention belongs to oil-refining chemical field, relate to the Regeneration Treatment of ethylene waste lye, be also suitable for liquid simultaneously
The process of the sulfur-containing waste lyes such as state hydrocarbon alkali cleaning spent lye.
Background technology
In oil-refining chemical production process, the strong base solution such as sodium hydroxide of the most commonly used about 8% is washed
CO in method removing natural gas, liquid hydrocarbon or the ethylene cracking gas washed2、H2The sour gas such as S,
Thus produce substantial amounts of alkali-washing waste liquid (sour gas alkali-washing waste liquid).Except containing residue in sour gas alkali-washing waste liquid
NaOH outside, possibly together with in alkaline cleaning procedure generate Na2S、Na2CO3Deng inorganic salt.Simultaneously because
The processes such as the heavy constituent condensation occurred in alkali cleaning and unsaturated hydro carbons condensation, make substantial amounts of Organic substance enter useless
In alkali liquor, it is contained therein with forms such as oil slick, dispersed oil and emulsus oil.Therefore, sour gas alkali-washing waste liquid
Improvement relate to removing oily substance, go the asking of the several respects such as comprehensive utilization of sulphide removal and residue alkali
Topic.
Process for sour gas alkali-washing waste liquid both at home and abroad develops substantial amounts of method, and these methods can be classified as
Innoxious and the big class of resource two.
What innoxious process for treating application was wider has acidifying-vaporizing extract process and all kinds of oxidizing process.
Acidifying-vaporizing extract process is once commonly used to process in China's the eighties from the external ethylene unit introduced and splits
Vent one's spleen alkali-washing waste liquid.First cracking gas alkali-washing waste liquid is acidified by the method with concentrated sulphuric acid, and being re-fed into stripper will
H2S、CO2Etc. being stripped off sending torch to burn.Although this method technique is simple, high treating effect, but
It is the seriously corroded to equipment, produces secondary pollution simultaneously.The method is abandoned the most both at home and abroad at present
With.
Oxidizing process is that the sulfide in sour gas alkali-washing waste liquid is converted by the Oxidation by various oxidants
For harmless thiosulfate or sulfate etc..Difference according to the oxidant used and process technique again may be used
To be divided into air oxidation process, wet air oxidation, chlorine oxidation process, advanced oxidation processes and catalysis oxidation
Method etc..The advantage of these methods is that processing speed is fast and thorough, will not produce secondary pollution, but it lacks
Point is complex process, long flow path, equipment investment is big, operating cost is high.Wet type in current this kind of method is empty
Gas oxidizing process technology is more ripe, and Application comparison is extensive.But the waste liquid after Chu Liing also needs to through neutralizing, life
Change processes could qualified discharge.
The recycling treatment of sour gas alkali-washing waste liquid be initially pass it through simple oil removal treatment after for making
Slurry papermaking.Due to NaOH and Na in sour gas alkali-washing waste liquid2S is having in soda pulping process cooking liquor
Effect composition, therefore can be used for pulping and paper-making by the sour gas alkali-washing waste liquid after oil removing.The shortcoming of this method
It is that the oily substance in spent lye is generally difficult to Ex-all, with abnormal flavour, finally affects paper quality.
It addition, certain enterprise domestic once used H2S neutralisation reclaims in ethylene cracking gas alkali-washing waste liquid
Sodium sulfide.This technique can utilize ethylene cracking gas alkali-washing waste liquid to produce Na2S.But cannot be to it
In Na2CO3Reclaiming, the waste liquid of discharge need nonetheless remain for acid adding and neutralizes, and Na2The matter of S product
Measure the highest.
United States Patent (USP) US 4981556 describes one and " utilizes copper oxide preparation without the technique of sulfur alkali liquor ".
Sodium carbonate is first changed into sodium hydroxide with causticizing process by this patent, then with in the solution after copper oxide and causticization
Sodium sulfide reaction generates sodium hydroxide and copper sulfide.Copper sulfide regenerates oxygen with rotary furnace calcining after filtering
Change copper to recycle.But this patent copper sulfide regenerative process produces SO2, cause secondary pollution.
Chinese patent CN1789162A proposes the Regeneration Treatment of a kind of ethylene cracking gas alkali-washing waste liquid
Technique.This technique uses transition metal oxide and alkaline earth oxide to be split by ethylene unit after oil removing respectively
Vent one's spleen the Na in alkali-washing waste liquid2S and Na2CO3It is converted into NaOH, makes ethylene waste lye be regenerated.Should
The advantage of patent is to have carried out regenerating completely by ethylene cracking gas alkali-washing waste liquid, enables to return ethylene
Cracking alkaline cleaner recycles.But, this patent the most specifically proposes the copper sulfide of sweetening process generation and sinks
The processing method formed sediment.
Chinese patent CN102815815A is respectively adopted the metal-oxides such as CuO and CaO as desulfurizing agent
With caustic, spent lye being carried out desulfurization and causticization regeneration, desulfurization precipitation processes through wet oxidation process and is converted into
Sulfate, then generates metal oxide desulfurizer recycling utilization with alkaline reaction, and caustic precipitation passes through
Calcination and regeneration is that caustic recycles.The method treatment effect is preferable, it is achieved that desulfurizing agent pollution-free again
Give birth to and recycle.
Chinese patent CN102452673A discloses a kind of method reclaiming sodium sulfate from ethylene waste lye,
Ethylene waste lye after first wet oxidation process is processed by the method is neutralized, and then uses evaporative crystallization method
Reclaim anhydrous sodium sulfate product.
Wei Yanxin (" bipolar membrane electrodialysis method processes typical case's wastewater from chemical industry research ", China Science & Technology University
Ph.D. Dissertation, 2012) propose to use the hydrogen in bipolar membrane electrodialysis technology recovery ethylene waste lye
Sodium oxide, when electrolyte concentration is 0.20~0.30mol/L, and the initial concentration of alkali is 0.10~0.25mol/L
Low energy consumption and high current efficiency can be obtained.Additionally, want to obtain high current efficiency and relatively low energy consumption,
Electric current density selects 30~60mA/cm2Scope.Under optimal experiment condition, laboratory scale
After running 2h on equipment, the naoh concentration regenerating recovery from spent lye reaches 0.11mol/L, process
Cost about reclaims every kilogram sodium hydroxide and needs 0.97 dollar, and a small amount of oil in spent lye is to NaOH
Regeneration is almost no impact, and result shows, utilizes bipolar membrane electrodialysis technology to regenerate back from spent lye
It is feasible for receiving sodium hydroxide.Its shortcoming is that the alkali concn reclaimed is relatively low, only 0.44%, it is difficult to meet and follow
The requirement that ring utilizes, this research simultaneously is not mentioned and the sodium carbonate in ethylene waste lye and sodium sulfate being converted
For carbon dioxide, sulphuric acid and sodium hydroxide.
Zhang Ni (" research of bipolar membrane electrodialysis cleaning production organic acid ", HeFei University of Technology's master's degree
Paper, 2008) formic acid in BP-A two chamber-type bipolar membrane electrodialysis recovery oxalic acid abstraction waste liquor is proposed,
This research paper result of study shows 20~80mA/cm2Current density range in, the electrodialysis of carbonic acid
Energy consumption difference 20.1~96.3kwh/kg, it is clear that use BP-C-A tri-Room type bipolar membrane electrodialysis to process second
The energy consumption of alkene spent lye will be the highest.
Gold can bravely wait (the industrial applications research of BPM2 type bipolar membrane device sodium sulfate alkaline, water process skill
Art volume 39 the 7th phase, Vol.39No.7, in July, 2013,81-83) use BP-C-A tri-compartment type double
Pole EDBM sodium sulfate preparing hydrogen sodium oxide, uses BPM2-2500 type equipped with 60 groups, effective face
Long-pending total 15m2Equipment, preset 600A/m2(total current 150A) carries out under constant current operation, and electric current is imitated
Rate is 70%, produce alkali energy consumption be 1800kWh/t, produce alkali integrated cost be 2135 yuan/ton, less than 2300~
The cost of the conventional ion embrane method of 2500 yuan/ton.
Summary of the invention
For the defect of prior art, it is an object of the invention to provide a kind of economical and effective, without additional component
The New Method for Processing of ethylene waste lye, the method utilizes ethylene waste lye preparing hydrogen sodium oxide, sulphuric acid and dioxy
Changing carbon, sodium hydroxide solution returns ethene cracking gas alkaline cleaner and recycles, and sulphuric acid, carbon dioxide are comprehensive
Utilize or sell as side-product, thoroughly realizing the recycling treatment of this strand of spent lye, reduce efflux wastewater
Discharge capacity, and the salt rejection rate of waste water is greatly improved.
A kind of method for reclaiming of ethylene waste lye, including following technical process:
(1) oil removal treatment: use the oily substance in gravitational separation process and/or extraction removing spent lye,
Described oily substance includes oil slick, dispersed oil and oil emulsion;
(2) oxidation processes: use oxidizing process that the ethylene waste lye after oil removing is carried out desulfurization process, should
Sulfide in spent lye is converted into sulfate;
(3) filtration treatment: use the float in Filtration removing ethylene waste lye and solid precipitation;
(4) bipolar membrane electrodialysis processes: use two chamber-type bipolar membrane electrodialysis-filtration-three room type Bipolar Membrane
Spent lye after filtering is processed by electrodialysis, first, uses two chamber-type bipolar membrane electrodialysis device to reclaim
Remaining sodium hydroxide in spent lye, is converted into sodium hydroxide and dioxy by the sodium carbonate in this spent lye simultaneously
Changing carbon, obtain metabisulfite solution, carbon dioxide uses sodium bicarbonate solution and desalted water to wash and be dried successively
Refined recovery;Then, use three Room type bipolar membrane electrodialysis devices that metabisulfite solution is converted into sulphuric acid and hydrogen
Sodium oxide, processes, by two chamber-type and three Room type bipolar membrane electrodialysis, the sodium hydroxide solution merging obtained and directly returns
Return ethylene alkali-washing device to recycle;
The water part, salt room of described three Room type bipolar membrane electrodialysis devices is as two chamber-type bipolar membrane electrodialysis
The alkali room water inlet of device, remainder is discharged into sewage farm.
In step (4), described two chamber-type bipolar membrane electrodialysis device is BP-C configuration, described three Room types
Bipolar membrane electrodialysis device is BP-A-C configuration.
In step (4), during described two chamber-type bipolar membrane electrodialysis, electric current density be preferably 600~
1200A/m2。
In step (4), during described two chamber-type bipolar membrane electrodialysis, the pH of salt room discharging be 2.0~
4.4。
In step (4), during described three Room type bipolar membrane electrodialysis, electric current density be 800~
1500A/m2。
In step (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and sulphuric acid quality is dense
Degree is 7.8%~8.5%.
In step (4), described CO 2 refining reclaim time sodium bicarbonate solution mass concentration be 1%~
15%.
In step (2), described oxidation processes is wet oxidation process, and oxidizing temperature is 200~260 DEG C,
Partial pressure of oxygen is 0.5~2MPa, and oxidant is oxygen, and the time of staying is 1~3h.
The present invention, with ethylene waste lye preparing hydrogen sodium oxide, sulphuric acid and carbon dioxide, achieves ethylene comprehensively and gives up
The minimizing of alkali liquor, resource, compared with prior art, this technology mainly has the advantage that
1. in bipolar membrane electrodialysis processing procedure, initially with two chamber-type bipolar membrane electrodialysis device to useless
Alkali liquor processes, it is possible to electricity acidifying spent lye, while reclaiming residual hydrogen sodium oxide therein, by it
In sodium carbonate be converted into sodium hydroxide and carbon dioxide, CO 2 refining reclaims subsequently, and as by-product
Product comprehensively utilize;The raw material of three follow-up Room type bipolar membrane electrodialysis devices can be made to be mainly sodium sulfate simultaneously
Solution, it is to avoid electrodialysis energy consumption required in the presence of sodium carbonate, thus reduce the purpose of energy consumption.So
After, use three Room type bipolar membrane electrodialysis devices that filtrate is further processed, reclaim sulphuric acid and hydroxide
Sodium.Finally, hydrogen-oxygen two chamber-type bipolar membrane electrodialysis device and three Room type bipolar membrane electrodialysis devices prepared
Change sodium solution merging return ethylene alkali-washing device to recycle.
2. in bipolar membrane electrodialysis processing procedure, the salt room outlet part of three Room type bipolar membrane electrodialysis devices
It is allocated as the alkali room for two chamber-type and three Room type bipolar membrane electrodialysis devices to intake, has no effect on produced hydrogen-oxygen
Changing recycling of sodium, remainder is discharged into sewage farm.
3. using the part salt room discharging of three Room bipolar membrane electrodialysis devices as two Room bipolar membrane electrodialysis and three
The alkali room charging of room bipolar membrane electrodialysis so that the discharge capacity of efflux wastewater can reduce by more than 85%, with
Time spent lye in sodium carbonate and sodium sulfate owing to being converted into carbon dioxide, sodium hydroxide and sulphuric acid, hydrogen-oxygen
The form changing sodium reclaims and is removed so that salt content therein is down to less than 0.5%, and salt rejection rate reaches
More than 90%, solve a discharge difficult problem for the ethylene waste lye of high saliferous in ethylene production, favorably
In the stable operation of follow-up biological sewage treatment device, it is more beneficial for carrying out of follow-up reusing sewage further.
In sum, the present invention uses two chamber-type bipolar membrane electrodialysis device and three Room type Bipolar Membrane electric osmoses successively
Analysis apparatus processes ethylene waste lye, while reclaiming remaining sodium hydroxide, it is possible to be converted into by sodium carbonate
Carbon dioxide and sodium hydroxide, sodium sulfate is converted into sulphuric acid and sodium hydroxide, obtains the hydrogen-oxygen of 8%~15%
Change sodium solution can directly return ethene cracking gas alkaline cleaner and recycle, and reduces ethene cracking gas alkali cleaning
The supplies consumption of device, thus reduce production cost, alkali concn is low, be difficult to straight to overcome prior art recovery
Connect the shortcoming recycled;The present invention uses 1%~20% sodium bicarbonate solution and desalted water to wash also successively
It is dried to refine and has reclaimed the GHG carbon dioxide discharged in two Room bipolar membrane electrodialysis processing procedures, pure
Degree is more than 99.5%, it is achieved that the reduction of discharging of carbon dioxide, overcomes prior art and can not reclaim carbon dioxide
Shortcoming.
It addition, after the present invention uses oxidation technology to be sodium sulfate by oxidizing sodium sulphide, then use Bipolar Membrane electric osmose
Analysis PROCESS FOR TREATMENT prepares 2%~15% sulphuric acid, it is achieved that in ethylene waste lye, the resource of institute's sulfur compound is returned
Receive, comprehensively utilized or sell as side-product, it is possible to improving product is worth, obtain certain economic effect
Benefit.
Detailed description of the invention
Embodiments of the invention are as follows:
Embodiment 1:
(1) oil removal treatment: use the oily substance in gravitational separation process removing spent lye, oily substance bag
Include oil slick, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously
Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3:
0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 260 DEG C, partial pressure of oxygen is
2MPa, reaction time is 1h.After reaction terminates, S in spent lye2-Concentration is 0mg/L, desulfurization degree
It is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration
Spent lye after filtration carries out electrodialysis process, and electric current density is 600A/m2, salt room middle outlet feed liquid
PH is 4.4, reclaims the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously
Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this
1% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure
Degree is 99.5%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure
Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 800A/m2, by sulphuric acid
Sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis
Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed
And, mensuration volume is 7.20L, and naoh concentration is 8.0%, meets and returns ethene cracking gas alkaline cleaner
The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously
Sulphuric acid volume in dialyser acid room is 1.47L, and sulfuric acid concentration is 8.5%.
Finally, the most final volume processing water outlet in three type electrodialyzer salt rooms, Room is 1.19L, and salt content is down to
0.43%, wastewater discharge reduces 88.1%, and salt rejection rate is 94.5%.
Embodiment 2
(1) oil removal treatment: using the oily substance in extraction removing spent lye, oily substance includes floating
Oil, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously
Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3:
0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 220 DEG C, partial pressure of oxygen is
1MPa, reaction time be 2h.After reaction terminates, the S of spent lye2-Concentration 0mg/L, desulfurization
Rate is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration
Spent lye after filtration carries out electrodialysis process, and electric current density is 1200A/m2, salt room middle outlet feed liquid
PH is 4.0, reclaims the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously
Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this
15% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure
Degree is 99.6%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure
Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 1500A/m2, by sulfur
Acid sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis
Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed
And, mensuration volume is 6.95L, and naoh concentration is 8.3%, meets and returns ethene cracking gas alkaline cleaner
The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously
Sulphuric acid volume in dialyser acid room is 1.61L, and sulfuric acid concentration is 7.8%.
Finally, the most final volume processing water outlet of three Room type electrodialyzer salt room water outlets is 1.28L, salt content
Being down to 0.03%, wastewater discharge reduces 87.2%, and salt rejection rate is 99.8%.
Embodiment 3
(1) oil removal treatment: use the oily substance in gravitational separation process and extraction removing spent lye, oil
Class material includes oil slick, dispersed oil and oil emulsion.
(2) oxidation processes: use wet oxidation process that the ethylene waste lye after 10L oil removing is located continuously
Reason, mainly comprising as NaOH:0.253mol/L, Na of ethylene waste lye2S:0.135mol/L, Na2CO3:
0.526mol/L, salt content 7.85%, oxidant is O2, oxidizing reaction temperature is 200 DEG C, partial pressure of oxygen is
2MPa, reaction time is 3h.After reaction terminates, the S of spent lye2-Concentration 0mg/L, desulfurization degree
It is 100%.
(3) filtration treatment: filter the spent lye after oxidation, remove float therein and solid precipitation.
(4) bipolar membrane electrodialysis processes: use the two chamber-type bipolar membrane electrodialysis device pair of BP-C configuration
Spent lye after filtration carries out electrodialysis process, and electric current density is 800A/m2, salt room middle outlet feed liquid
PH is 4.0.Reclaim the sodium hydroxide in spent lye, the sodium carbonate in this spent lye is converted into hydrogen-oxygen simultaneously
Change sodium and carbon dioxide, obtain metabisulfite solution.The carbon dioxide warp successively will released during this
10% sodium bicarbonate solution and desalted water reclaim after washing and be dried refinement treatment, and chromatographic determination carbon dioxide is pure
Degree is 99.5%.
Then, after the salt room i.e. metabisulfite solution of middle outlet feed liquid is carried out filtration treatment, use BP-A-C structure
Three Room type bipolar membrane electrodialysis devices of type carry out electrodialysis process, and electric current density is 1000A/m2, by sulfur
Acid sodium solution is converted into sulphuric acid and sodium hydroxide solution.
Wherein, three water parts, type bipolar membrane electrodialysis salt room, Room are as the alkali of two chamber-type bipolar membrane electrodialysis
Room intakes, and remainder is discharged into sewage farm.
After process completes, the sodium hydroxide solution that two chamber-type electrodialyzer and three Room type electrodialyzers prepare is closed
And, mensuration volume is 7.22L, and naoh concentration is 8.0%, meets and returns ethene cracking gas alkaline cleaner
The needs recycled, directly return ethylene alkali-washing device and recycle;Measure three Room type Bipolar Membrane electricity simultaneously
Sulphuric acid volume in dialyser acid room is 1.57L, and sulfuric acid concentration is 8.0%.
Finally, the volume of three Room type electrodialyzer salt room water outlets is 1.22L, and salt content is down to 0.03%, useless
Water discharge capacity reduces by 89.2%, and salt rejection rate is 99.8%.
Claims (10)
1. the method for reclaiming of an ethylene waste lye, it is characterised in that include following technical process:
(1) oil removal treatment: use the oily substance in gravitational separation process and/or extraction removing spent lye,
Described oily substance includes oil slick, dispersed oil and oil emulsion;
(2) oxidation processes: use oxidizing process that the ethylene waste lye after oil removing is carried out desulfurization process, should
Sulfide in spent lye is converted into sulfate;
(3) filtration treatment: use the float in Filtration removing ethylene waste lye and solid precipitation;
(4) bipolar membrane electrodialysis processes: use two chamber-type bipolar membrane electrodialysis-filtration-three room type Bipolar Membrane
Spent lye after filtering is processed by electrodialysis, first, uses two chamber-type bipolar membrane electrodialysis device to reclaim
Remaining sodium hydroxide in spent lye, is converted into sodium hydroxide and dioxy by the sodium carbonate in this spent lye simultaneously
Changing carbon, obtain metabisulfite solution, carbon dioxide uses sodium bicarbonate solution and desalted water to wash and be dried successively
Refined recovery;Then, use three Room type bipolar membrane electrodialysis devices that metabisulfite solution is converted into sulphuric acid and hydrogen
Sodium oxide, processes, by two chamber-type and three Room type bipolar membrane electrodialysis, the sodium hydroxide solution merging obtained and directly returns
Return ethylene alkali-washing device to recycle;
The water part, salt room of described three Room type bipolar membrane electrodialysis devices is as two chamber-type bipolar membrane electrodialysis
The alkali room water inlet of device, remainder is discharged into sewage farm.
The method for reclaiming of ethylene waste lye the most according to claim 1, it is characterised in that step
Suddenly in (4), described two chamber-type bipolar membrane electrodialysis device is BP-C configuration, described three Room type Bipolar Membrane
Electrodialysis plant is BP-A-C configuration.
The method for reclaiming of ethylene waste lye the most according to claim 2, it is characterised in that step
Suddenly, in (4), during described two chamber-type bipolar membrane electrodialysis, electric current density is respectively 600~1200A/m2。
4. according to the method for reclaiming of the ethylene waste lye described in any one of claim 1-3, its feature
Be, in step (4), during described two chamber-type bipolar membrane electrodialysis, the pH of salt room discharging be 2.0~
4.4。
5. according to the method for reclaiming of the ethylene waste lye described in Claims 2 or 3, it is characterised in that
In step (4), during described three Room type bipolar membrane electrodialysis, electric current density is 800~1500A/m2。
The method for reclaiming of ethylene waste lye the most according to claim 4, it is characterised in that step
Suddenly, in (4), during described three Room type bipolar membrane electrodialysis, electric current density is 800~1500A/m2。
The method for reclaiming of ethylene waste lye the most according to claim 5, it is characterised in that step
Suddenly in (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and h 2 so 4 concentration is
7.8%~8.5%.
The method for reclaiming of ethylene waste lye the most according to claim 6, it is characterised in that step
Suddenly in (4), the sodium hydroxide mass concentration of described recovery is 8.0%~8.3%, and h 2 so 4 concentration is
7.8%~8.5%.
9., according to the method for reclaiming of the ethylene waste lye described in any one of claim 1-3, its feature exists
In, in step (4), described CO 2 refining reclaim time sodium bicarbonate solution mass concentration be 1%~
15%.
The method for reclaiming of ethylene waste lye the most according to claim 1, it is characterised in that step
Suddenly in (2), described oxidation processes is wet oxidation process, and oxidizing temperature is 200~260 DEG C, and oxygen divides
Pressure is 0.5~2MPa, and oxidant is oxygen, and the time of staying is 1~3h.
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CN111135603A (en) * | 2019-12-31 | 2020-05-12 | 大连汉诺工程技术有限公司 | Waste alkali treatment method |
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CN112358079A (en) * | 2020-10-23 | 2021-02-12 | 锦州泰丰精细化工有限公司 | Regeneration process of sulfur-containing waste alkali liquor |
CN113716809A (en) * | 2021-09-09 | 2021-11-30 | 南方创业(天津)科技发展有限公司 | Alkali residue wastewater treatment and alkali recovery method |
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CN111135603A (en) * | 2019-12-31 | 2020-05-12 | 大连汉诺工程技术有限公司 | Waste alkali treatment method |
CN111778061A (en) * | 2020-08-05 | 2020-10-16 | 伯尔菲特沧州科技中心 | Method and system for regenerating light hydrocarbon desulfurization alcohol alkali liquor |
CN112358079A (en) * | 2020-10-23 | 2021-02-12 | 锦州泰丰精细化工有限公司 | Regeneration process of sulfur-containing waste alkali liquor |
CN113716809A (en) * | 2021-09-09 | 2021-11-30 | 南方创业(天津)科技发展有限公司 | Alkali residue wastewater treatment and alkali recovery method |
CN113716809B (en) * | 2021-09-09 | 2022-12-27 | 南方创业(天津)科技发展有限公司 | Alkali residue wastewater treatment and alkali recovery method |
CN114212931A (en) * | 2021-11-18 | 2022-03-22 | 华东理工大学 | Ethylene alkaline residue wet oxidation alkaline wastewater quality-divided crystallization treatment method |
CN114212931B (en) * | 2021-11-18 | 2023-12-29 | 华东理工大学 | Wet oxidation alkaline waste water aqueous crystallization treatment method for ethylene alkali slag |
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