CN101962246B - Method for treating and recycling MTO process wastewater - Google Patents
Method for treating and recycling MTO process wastewater Download PDFInfo
- Publication number
- CN101962246B CN101962246B CN2009101573137A CN200910157313A CN101962246B CN 101962246 B CN101962246 B CN 101962246B CN 2009101573137 A CN2009101573137 A CN 2009101573137A CN 200910157313 A CN200910157313 A CN 200910157313A CN 101962246 B CN101962246 B CN 101962246B
- Authority
- CN
- China
- Prior art keywords
- water
- mto
- wastewater treatment
- processing wastewater
- treatment process
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims abstract description 83
- 230000008569 process Effects 0.000 title claims abstract description 45
- 239000002351 wastewater Substances 0.000 title claims abstract description 32
- 238000004064 recycling Methods 0.000 title abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 88
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 33
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 18
- 238000001223 reverse osmosis Methods 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 150
- 239000012528 membrane Substances 0.000 claims description 30
- 238000012545 processing Methods 0.000 claims description 27
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 13
- 239000003513 alkali Substances 0.000 claims description 12
- 238000005273 aeration Methods 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 10
- 239000010865 sewage Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- -1 polypropylene Polymers 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 229920002678 cellulose Polymers 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 238000005374 membrane filtration Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000004743 Polypropylene Substances 0.000 claims description 5
- 239000012510 hollow fiber Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 239000010802 sludge Substances 0.000 claims description 5
- 239000004697 Polyetherimide Substances 0.000 claims description 4
- 230000000844 anti-bacterial effect Effects 0.000 claims description 4
- 239000003899 bactericide agent Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- 230000005611 electricity Effects 0.000 claims description 4
- 230000001590 oxidative effect Effects 0.000 claims description 4
- 229920002492 poly(sulfone) Polymers 0.000 claims description 4
- 229920001601 polyetherimide Polymers 0.000 claims description 4
- 229920000098 polyolefin Polymers 0.000 claims description 4
- 238000012546 transfer Methods 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000000084 colloidal system Substances 0.000 claims description 2
- 239000005446 dissolved organic matter Substances 0.000 claims description 2
- 238000005189 flocculation Methods 0.000 claims description 2
- 230000016615 flocculation Effects 0.000 claims description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 150000002825 nitriles Chemical class 0.000 claims description 2
- 239000013618 particulate matter Substances 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 230000000737 periodic effect Effects 0.000 claims 1
- 238000010926 purge Methods 0.000 claims 1
- 230000001954 sterilising effect Effects 0.000 claims 1
- 238000004659 sterilization and disinfection Methods 0.000 claims 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 16
- 239000003245 coal Substances 0.000 abstract description 12
- 239000006227 byproduct Substances 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 8
- 150000001336 alkenes Chemical class 0.000 abstract description 7
- 239000003345 natural gas Substances 0.000 abstract description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001502 supplementing effect Effects 0.000 abstract 3
- 238000001311 chemical methods and process Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 abstract 1
- 239000002253 acid Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000003921 oil Substances 0.000 description 8
- 230000002000 scavenging effect Effects 0.000 description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 7
- 238000004140 cleaning Methods 0.000 description 7
- 230000004907 flux Effects 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 5
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 238000003889 chemical engineering Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000011010 flushing procedure Methods 0.000 description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 4
- 150000002430 hydrocarbons Chemical class 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003020 moisturizing effect Effects 0.000 description 4
- 229920013655 poly(bisphenol-A sulfone) Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 3
- 239000004695 Polyether sulfone Substances 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 229920002647 polyamide Polymers 0.000 description 3
- 229920006393 polyether sulfone Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- 241000282326 Felis catus Species 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229920002873 Polyethylenimine Polymers 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000035800 maturation Effects 0.000 description 2
- 230000000050 nutritive effect Effects 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000004576 sand Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920001747 Cellulose diacetate Polymers 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 229920012266 Poly(ether sulfone) PES Polymers 0.000 description 1
- NNLVGZFZQQXQNW-ADJNRHBOSA-N [(2r,3r,4s,5r,6s)-4,5-diacetyloxy-3-[(2s,3r,4s,5r,6r)-3,4,5-triacetyloxy-6-(acetyloxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6s)-4,5,6-triacetyloxy-2-(acetyloxymethyl)oxan-3-yl]oxyoxan-2-yl]methyl acetate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](OC(C)=O)[C@H]1OC(C)=O)O[C@H]1[C@@H]([C@@H](OC(C)=O)[C@H](OC(C)=O)[C@@H](COC(C)=O)O1)OC(C)=O)COC(=O)C)[C@@H]1[C@@H](COC(C)=O)O[C@@H](OC(C)=O)[C@H](OC(C)=O)[C@H]1OC(C)=O NNLVGZFZQQXQNW-ADJNRHBOSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- MGIYRDNGCNKGJU-UHFFFAOYSA-N isothiazolinone Chemical compound O=C1C=CSN1 MGIYRDNGCNKGJU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AIDQCFHFXWPAFG-UHFFFAOYSA-N n-formylformamide Chemical compound O=CNC=O AIDQCFHFXWPAFG-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920001643 poly(ether ketone) Polymers 0.000 description 1
- 229920003208 poly(ethylene sulfide) Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920006380 polyphenylene oxide Polymers 0.000 description 1
- 229920012287 polyphenylene sulfone Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000004627 regenerated cellulose Substances 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000001174 sulfone group Chemical group 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a method for treating and recycling byproduct water of a production process for converting an oxygen-containing compound into olefin, and relates to the technical field of process wastewater treatment and recycle of coal chemical industry and natural gas chemical industry. The combined process can effectively remove organic small molecular substances in the process byproduct water, the removal rate of COD in the wastewater can reach over 90 percent according to the pretreatment process, and the pretreated wastewater can meet the water quality requirement of circulating water supplementing water and boiler supplementing water after ultra-filtration and reverse osmosis treatment respectively or is used for supplementing water in the MTO process or other chemical processes. The method has the advantages of stable and reliable treatment effect, low treatment cost and simple and feasible operation, and is easy to realize industrialized application.
Description
[technical field]
The present invention relates to field of waste water treatment, particularly the Manufacturing Alkene from Natural Gas in the olefin hydrocarbon making by coal in the coal chemical technology, the gas chemical industry's technology, the water treatment of technique by-product and the reuse method in the MTO technology.
[background technology]
The low-carbon alkene such as ethene, propylene is important Organic Chemicals, has a very important role in modern oil and chemical industry.The source of ethene and propylene mainly is the hydrocarbon vapours cracking traditionally, and raw material mainly is petroleum naphtha.Three world oil crisis since 20 century 70s cause International Crude Oil to go up, and the production cost of alkene is constantly soaring.Under this background, the new way of impelling people to seek further to develop non-oil resource has greatly promoted Coal Chemical Industry and gas chemical industry's development, and the requirement of developing new Non oil-based route olefin production is day by day urgent.And the research and development of preparing low carbon olefinic hydrocarbon with methanol (MTO) process then are novel technical route producing Chemicals from non-oil resource.Along with the day by day maturation of coal or natural gas via synthetic gas methanol technology, MTO becomes a production line that receives much concern.
The chemical equation of ethene processed and propylene and thermal effect should be take methyl alcohol as raw material:
2CH
3OH→C
2H
4+2H
2 Δ O， ℃4
3CH
3OH→C
3H
6+3H
2 Δ
℃4
It is generally acknowledged that this technique is that methyl alcohol at first dewaters and is dme (DME), continues dehydration and generates the low-carbon alkene that comprises ethene and propylene; Only methanol dehydration generates the DME process, and DME per ton needs water consumption steam (0.8MPa) approximately 1.4 tons, approximately 100 tons of recirculated cooling waters (≤3 ℃), thereby this technique belongs to high water consumption technique.Simultaneously, because MTO technique itself is a highly heat release, high dehydration reaction, whole technique by-product water usually accounts for and flows out more than 50% of gross weight of material stream, and a large amount of heat of generation also needs a large amount of recirculated water heat exchange in the reaction process.If prepare methyl alcohol take coal and Sweet natural gas as raw material, adopt ripe operational path then one ton of methyl alcohol of every production need approximately 10 tons of water consumptions, so large-scale Coal Chemical Engineering Project year water consumption usually up to several ten million cubic metres, ton product water consumption is approximately more than ten tons.China belongs to lack of water country, and most of northern area is the extreme lack of water, and water resources is restricting further developing of enterprise.Along with the day by day maturation of MTO technology, produce increase and national increasing to the water resources protection dynamics to water demand, also will limit to a certain extent and hinder the MTO project implementation.Whether unimpeded core technology mainly concentrates on the MTO process to route to be related to olefin hydrocarbon making by coal (comprising coal through methanol-to-olefins, natural gas via methanol-to-olefins, dme alkene processed), and determine investment that MTO technique becomes oily project at coal whether one of them important factor fetch water exactly and can processing wastewater fully utilize.
For the MTO operational path, the wastewater treatment scheme that Lurgi company adopts is: water can be used as the technique generating steam, and excessive water then can supply agriculture production after being used as dedicated processes.
The mixture that the MTO technique of UOP/Hydro is left reactor enters separator after by a custom-designed charging/effluent exchanger.In separator, most water and unreacted methyl alcohol are removed.Hydro carbons is separated from the oxygenatedchemicals recycle stream by fractionation, and oxygenatedchemicals is removed in the compression section.Technologic improvement mainly concentrates on and how to reduce the energy for MTO, reduce the aspects such as process cost, and water-related main improvement comprises two aspects: (1) utilizes thick methanol-to-olefins, thick methyl alcohol except anhydrating or impurity is just sent into MTO technology, does not therefore need the rectifying group of the preparation high purity methanol of complex and expensive.For the processing of by-product water, Uop Inc.'s patent (US5914433) proposes to utilize scheme: the one, the by-product water that the MTO operation produces is directly delivered to the synthetic gas production process, and need not remove hydrocarbon and oxygenatedchemicals; The 2nd, with the excessive water of MTO operation part, produce the 2-isopropyl ether by the propylene etherificate, these measures have all been saved significantly investment and have been reduced process cost.(2) mention in the US Patent No. 6444869 and will contain methane and the light olefin cut partly is back to conversion reaction zone, methane replaces water as thinner, thereby has reduced the disadvantageous effect of water to catalyst stability and life-span.Wherein, demethanizing tower adopts 1 revolution adsorption technology with pressure that methane and water are removed from reactant, has saved investment.But the use of these methods all needs to build according to full scale plant the actual needs of geographical position and peripheral facilities, suits measures to local conditions, realizes the comprehensive utilization of technique by-product water.
Chinese patent application CN101139117A and CN101139118A disclose a kind of waste water treatment process that contains methyl alcohol and dme, its concrete grammar is: the waste water that will contain methyl alcohol and dme, after the pressurization and the stripping tower heat exchange of purifying waste water, then enter stripping tower, the gaseous mixture such as methyl alcohol that the stripping tower cat head produces enter return tank after heat exchange, a part is returned the stripping tower cat head as backflow; It is outer or as the raw material of MTO device that another part is delivered to device; Go out to purify waste water at the bottom of the stripping tower tower, with deliver to outside the device after the wastewater heat exchange that contains methyl alcohol and dme, the total content of purify waste water middle methyl alcohol and dme behind stripping is not more than 100ppm, can satisfy sewage-farm influent quality requirement, but biochemical treatment and reuse is not reported in the patent.
Above-mentioned foreign patent mainly is to consider that from technique itself technique self needs the reuse situation of water spot, but because MTO technique itself is the process that an alkene and water constantly produce, when the water circuit of technique own reach stable after, still have large water gaging and discharge, above-mentioned patent is not all processed reuse for remaining processing wastewater; And thereby Chinese patent application mainly is to reclaim the method for large amount of organic the processing wastewater so that processing wastewater is purified to the requirement into sewage work from steam stripped angle, as for having no report in follow-up processing and the reuse method patent.Thereby, the present document announcement of also not finding the unnecessary by-product water treatment of relevant MTO technique and reuse.
[summary of the invention]
For the deficiencies in the prior art, the invention provides a kind of processing wastewater advanced treatment of MTO device generation and the technology method of reuse.Use the technique by-product water that obtains after the art breading of the present invention can reach middle low-pressure boiler supplementary feed water quality requirement; This Technology has advantages of that processing efficiency is high, running cost is low, easy handling and be easy to realize industrial applications.
The present invention adopts following technical scheme: a kind of MTO processing wastewater treatment process, comprise the steps: the first step, and process MTO technique stripping and purify waste water, may further comprise the steps: transfer alkali, aeration, sedimentation and filtration; Second step enters biochemical system with the product water of the first step and carries out aerobic treatment; In the 3rd step, the product water of second step enters the ultrafiltration membrance filter system, removes colloid, suspended substance and particulate matter; In the 4th step, the product water in the 3rd step enters reverse osmosis membrane system and further removes dissolved organic matter and mineral ion, and the product water in above-mentioned the 4th step is reuse water.The product water in above-mentioned the 4th step also can satisfy middle low-pressure boiler moisturizing requirement, especially can be used for the moisturizing of waste heat boiler or the heat-exchange system of MTO device.
The stripping tower of the present invention water quality characteristic of purifying waste water is: wastewater temperature is 25～45 ℃, and pH is 4～9, COD
CrBe 400～1000mg/L, main organism kinds comprises the mixture of organic substance such as methyl alcohol, dme, acetic acid, ethanol, methylethylketone, propionic acid, and wherein methanol content is 50～100mg/L, and acetic acid content is 100～500mg/L, and it is 30～400 μ s/cm etc. that electricity is led;
In the first step, the purify waste water alkali lye that arranges on transfer line of stripping tower adds entrance, flocculation agent dosing mouth and line mixer and carries out dosing and mix, and adopts NaOH to regulate the pH of above-mentioned processing wastewater to 8-10; The mode that adopts known aeration method and conventional sedimentation to filter is carried out aeration and precipitation, and the delivery turbidity after the sedimentation is less than 1NTU.Accent alkali aeration and sedimentation device of the present invention mainly comprises two functions: one for transferring alkali aeration mixing, two to be precipitate and separate.Waste water mixes through aeration first in coagulative precipitation tank: the aeration rate residence time is 5～40 minutes, and the hydromechanics residence time is preferably 10～20 minutes; Then enter the settling region and carry out sedimentation, the hydromechanics residence time is 30～90 minutes herein, and optimum is 50～70 minutes.
Aerobic process control condition of the present invention comprises that mainly dwell time of sewage is 4～24h, and optimum is 6～18h; The dissolved oxygen span of control is 1～5mg/L in the sewage, and optimum is 1.5～4.5mg/L; The sludge concentration span of control is 1.5～3.5g/L, and optimum is 2～3g/L.
Ultrafiltration membrance filter system of the present invention (comprising immersion membrane filtration system) can adopt hollow fiber film assembly, tubular membrane component, rolled membrane module, curtain type film assembly and plate and frame module, and optimum is polysulfone hollow fiber ultrafiltration membrane system and curtain type film assembly.
The material of above-mentioned membrane module comprises cellulose family and derivatived cellulose, polysulfones, polyimide PI, polyetherimide PEI, polyvinylidene difluoride (PVDF) class PVDF, polypropylene nitrile PAN, polyvinylchloride class and polyolefins.
Wherein, cellulose family and derivative thereof mainly comprise regenerated cellulose RCE, nitrocellulose CN, Cellulose diacetate CA and cellulosetri-acetate CTA, vinyl cellulose EC.
Polysulfones mainly comprises bisphenol-a polysulfone PSF, polyethersulfone PES, phenolic polyether sulphone PES-C and polyetherketone PEK-C, Polyphenylene Sulfone diformamide PSA, contains phthalazine biphenyl structure poly (aryl ether sulfone ketone) PPESK, poly (arylene ether nitrile) ketone PPENK and copolyether sulfone PPBES.
Polyolefins mainly comprises polythene PE, polypropylene PP and the derivative of the two thereof.
Above-mentioned ultra-filtration membrane aperture is less than 0.2 μ m, and preferred 0.01～0.1 μ m, optimum are 0.05～0.1 μ m; The operation scheme of hyperfiltration membrane assembly comprises cross flow filter technique and dead-end filtration technique, and wherein dead-end filtration technique can realize go-and-retum every water inlet, and optimum is cross-flow technique; Can realize disperseing to wash, strengthening washing and soaking the periodical operation of washing in the automatic and manual operational process of hyperfiltration membrane assembly, wherein disperse to wash and can realize alternately water inlet of two ends, the water inlet cycle was respectively 30～120 minutes, and optimum is 45～90 minutes; Backwashing time is 5～30 seconds; Operating flux in the ultrafiltration operational process is 50～1000L/m
2H, optimum are 100～300L/m
2H; The reinforcement of ultra-filtration membrane is washed and immersion is washed in the process mainly take the soda acid dosing as main;
Wherein, acid mainly comprises: HCl, oxalic acid, citric acid, nitric acid, sulfuric acid and with composite clean-out system of EDTA etc.;
Alkali mainly comprises: NaClO, NaOH etc. and the composite clean-out system that forms with EDTA thereof etc.;
Organism class clean-out system such as methyl alcohol, ethanol and vinyl glycol monomethyl butyrates etc.), this is invented described ultra-filtration membrane cleaning way and has comprised online and off-line cleaning operation, the operations such as gas is cleaned, steam-water mixing is washed are preferably steam-water mixing and wash technological process.
The membrane module of reverse osmosis filtration system of the present invention mainly adopts polyamide composite film and various hydrophilic modifying thereof the antipollution RO membrane module of (mainly comprising the modification of sulfonation, carboxylated and PVA coating etc.), wherein reverse osmosis counterdie material mainly comprises functional high molecule material and polyolefine and the polyolefinic derivative that contains aromatic ring and fragrant heterocycle structure, as: PSF, PES, PPO, PEI, PP, PE, PAN, PVDF, the RO film operating flux in this technological process is 20～60L/m
2H, optimum are 30～50L/m
2H; The system recoveries rate of RO device is controlled at 60～90%, and optimum is 70-80%; Cleaning interval is 30～120 days, and optimum is 45～90 days; The pH of reverse osmosis operational process is controlled to be 7.0～9.5, and optimum is 7.5～9.0; Adopt in the RO During Process of Long-term Operation and alternately add non oxidizing bactericide (such as Flocide380, Trsea380, isothiazolinone), alternately the timed interval is 3～20 days, and optimum is 5～10 days.
The present invention has following beneficial effect:
1, technique of the present invention can be to coal chemical engineering equipment, and especially the stripping in the MTO device is purified waste water and processed, and (main water quality comprises: COD can to satisfy one-level qualified discharge standard after pre-treatment and biochemical treatment
Cr＜60mg/L, BOD
5＜20mg/L, petroleum-type＜10mg/L, ammonia nitrogen＜15mg/L, SS＜20mg/L etc.);
2, the product water of technique of the present invention behind biochemical treatment-ultrafiltration membrance filter satisfies the circulating cooling make-up water standard (main water quality comprises: COD
Cr＜60mg/L, BOD
5＜5mg/L, Fe＜0.5mg/L, Mn＜0.2mg/L, TP＜1mg/L etc.), can be used for circulating cooling make-up water, especially the MTO device circulating cooling make-up water of coal chemical engineering equipment;
3, the product water water quality of the biochemical treatment-ultrafiltration membrance filter in the technique of the present invention-reverse osmosis membrane filtration satisfies middle low-pressure boiler moisturizing water quality requirement (main water quality comprises: COD
Mn≤ 2mg/L, Fe≤0.03mg/L, Cu≤0.005mg/L, oil≤0.3mg/L, SiO
2≤ 0.02mg/L etc.), can be used for the boiler replenishing water water quality requirement that the reaction superfluous heat removes in coal chemical engineering equipment itself, especially the MTO device.
[description of drawings]
Fig. 1 is schematic flow sheet of the present invention, among the figure: 1, pretreatment unit; 2, biochemical unit; 3, ultrafiltration system; 4, reverse osmosis system.
[embodiment]
Below in conjunction with description of drawings of the present invention detailed process of the present invention.
MTO technique by-product water is purified waste water through the redundance behind the stripping and enter biochemical treatment unit 2 (biochemical treatment comprises the aerobic treatment process of catalytic oxidation, BAF etc.) behind the pretreatment unit 1 of accent alkali, aeration, sedimentation and filtration, water outlet enters ultra-filtration membrane treatment system 3 through the second pond precipitate and separate is laggard, ultrafiltration system produces the reverse osmosis system 4 that water can be used as circulating cooling make-up water or penetration depth processing, the dense water of reverse osmosis system 4 is back to the biochemical treatment unit, and RO produces water and can be used as the middle low-pressure boiler moisturizing.
Embodiment 1
The main water quality characteristics of MTO technique stripping tower bottom purified water: the temperature of purifying waste water is 3 ℃, and pH is 5, COD
CrBe 400mg/L, methanol content is 50mg/L, and acetic acid content is 100mg/L, and it is 100 μ s/cm etc. that electricity is led; This waste water enters the aerobic biochemical reactor after the nutritive equilibrium of biochemical treatment, the residence time is 8h, and dissolved oxygen is 3mg/L in the sewage, and sludge concentration is 1.6g/L.
Laggard to enter the aperture be the PVDF hollow fiber ultrafiltration membrane system of 0.05 μ m to waste water behind the aerobic treatment through the sedimentation of second pond sand filtering device, adopts the mode of cross flow filter to move, and the operating flux of ultra-filtration membrane is 100L/m
2H after the two ends flooding time is spaced apart 45 minutes, adds first behind the alkali dispersion of acid adding and washes operation, and soda acid dosing scavenging period is 10 seconds, carries out afterwards proceeding normal operation behind 5 seconds the flushing operation; This process reruns and carries out soda acid after 10 times and soak and strengthen cleaning operation; The soda acid soak time is 10 minutes, carries out afterwards 5 seconds flushing operation.This ultrafiltration system continuously operation carried out the steam-water mixing cleaning operation one time after 15 days, and scavenging period is 10 minutes.
Ultrafiltration system produces water and enter the RO membrane filtration system after the topping-up pump supercharging, and it is the polyamide composite film of PES that reverse osmosis membrane assembly adopts the ultrafiltration counterdie, and the operating flux of film system is designed to 20L/m
2H, the rate of recovery of RO system is 70%, RO water inlet pH regulator is 8.0, the cycle of operation of RO system is 90 days, RO film system carries out alkali respectively afterwards, acid soak is washed, the RO system carries out low pressure operation 2h, soaks 4h under the atmosphere of scavenging solution cyclical operation moves continuously 4 all after dates and carries out entering normal operating condition after the scavenging solution displacement with ultrafiltration product water, and the RO system alternately added non oxidizing bactericide in 5 days in interval in normal course of operation.
RO after treatment produces water water quality: Fe＜0.04mg/L; Copper≤0.01mg/L; Oil is 0.23mg/L; COD
MnBe 1.34mg/L; SiO
2Be 0.01mg/L; Specific conductivity 8.0 μ s/cm; Dissolved oxygen is 7.6mg/L.
Embodiment 2
MTO technique stripping tower bottom purified water water quality characteristics: the temperature of purifying waste water is 40 ℃, and pH is 8, COD
CrBe 600mg/L, methanol content is 100mg/L, and acetic acid content is 500mg/L, and it is 800 μ s/cm etc. that electricity is led; This waste water enters the aerobic biochemical reactor after the nutritive equilibrium of biochemical treatment, dwell time of sewage is 10h, and dissolved oxygen is 4.5mg/L in the sewage, and sludge concentration is 3.5g/L.
Laggard to enter the aperture be the PES hollow fiber ultrafiltration membrane system of 0.2 μ m to aerobic treatment by the sedimentation of second pond sand filtering device, adopts the mode of cross flow filter to move, and the operating flux of ultra-filtration membrane is 300L/m
2H, after the two ends flooding time was spaced apart 30 minutes, operation was washed in the dispersion that adds the alkali acid adding, and soda acid dosing scavenging period is 12 seconds, carries out afterwards proceeding normal operation behind 8 seconds the flushing operation; This process reruns and carries out soda acid after 15 times and soak and strengthen cleaning operation; The soda acid soak time is 10 minutes, carries out afterwards 5 seconds flushing operation.This ultrafiltration system operation was carried out the steam-water mixing cleaning operation one time after 20 days, and scavenging period is 20 minutes.
Ultrafiltration system produces water as the water inlet of RO membrane filtration system, and it is the polyamide composite film of PSF that reverse osmosis membrane assembly adopts counterdie, and the operating flux of film system is designed to 50L/m
2H, the rate of recovery of RO system is 80%, RO water inlet pH regulator is 8.5, the cycle of operation of RO system is 60 days, RO film system carries out alkali respectively afterwards, acid soak is washed, the RO system carries out low pressure operation 2h, soaks 4h under the atmosphere of scavenging solution cyclical operation moves continuously 4 all after dates and carries out entering normal operating condition after the scavenging solution displacement with ultrafiltration product water, and the RO system alternately added non oxidizing bactericide in 10 days in interval in normal course of operation.
RO after treatment produces water water quality: Fe＜0.04mg/L; Copper≤0.01mg/L; Oil is 0.28mg/L; COD
MnBe 1.17mg/L; SiO
2Be 0.01mg/L; Specific conductivity is 9.3 μ s/cm; Dissolved oxygen is 10.4mg/L.
Claims (13)
1. a MTO processing wastewater treatment process is characterized in that comprising the steps: the first step, processes MTO technique stripping and purifies waste water, and may further comprise the steps: transfer alkali, aeration, sedimentation and filtration; Second step enters biochemical system with the product water of the first step and carries out aerobic treatment; In the 3rd step, the product water of second step enters the ultrafiltration membrance filter system, removes colloid, suspended substance and particulate matter; In the 4th step, the product water in the 3rd step enters reverse osmosis membrane system and further removes dissolved organic matter and mineral ion, and the product water in above-mentioned the 4th step is reuse water,
Wherein, the described stripping water quality characteristic of purifying waste water is: wastewater temperature is 25～45 ℃, and pH is 4～9, COD
CrBe 400～1000mg/L, main organism kinds comprises methyl alcohol, dme, acetic acid, ethanol, methylethylketone and propionic acid mixture, and wherein methanol content is 50～100mg/L, and acetic acid content is 100～500mg/L, and it is 30～400 μ s/cm that electricity is led.
2. MTO processing wastewater treatment process according to claim 1, it is characterized in that: the purify waste water alkali lye that arranges on transfer line of stripping tower adds entrance, flocculation agent dosing mouth and line mixer and carries out dosing and mix, and adopts NaOH to regulate the pH of above-mentioned processing wastewater to 8-10; Carry out aeration and precipitation, the delivery turbidity after the sedimentation is less than 1NTU.
3. MTO processing wastewater treatment process according to claim 1, it is characterized in that: the dwell time of sewage of the aerobic unit in the second step is 4～24h; Dissolved oxygen is 1～5mg/L; The sludge concentration span of control is 1.5～3.5g/L.
4. MTO processing wastewater treatment process according to claim 3, it is characterized in that: the dwell time of sewage of aerobic unit is 6～18h; The dissolved oxygen span of control is 1.5～4.5mg/L in the sewage; The sludge concentration span of control is 2～3g/L.
5. MTO processing wastewater treatment process according to claim 1 is characterized in that: the form of hyperfiltration membrane assembly employing hollow fiber film assembly, tubular membrane component, rolled membrane module, curtain type film assembly or the plate and frame module of the ultrafiltration membrance filter system in the 3rd step.
6. MTO processing wastewater treatment process according to claim 5 is characterized in that: the ultra-filtration membrane of ultra-filtration membrane employing cellulose family, derivatived cellulose, polysulfones, polyimide, polyetherimide, polyvinylidene difluoride (PVDF) class, polypropylene nitrile, polyvinyl chloride or polyolefins.
7. according to claim 6 or 5 described MTO processing wastewater treatment processs, it is characterized in that the ultra-filtration membrane aperture is 0.01～0.1 μ m.
8. MTO processing wastewater treatment process according to claim 1 is characterized in that: the ultra-filtration membrane operation scheme of the ultrafiltration system in the 3rd step comprises cross flow filter mode or dead-end filtration mode.
9. MTO processing wastewater treatment process according to claim 8, it is characterized in that: the cross flow filter mode of ultra-filtration membrane or dead-end filtration mode are all carried out go-and-retum every water inlet, disperse successively to wash, strengthen washing and soaking the periodical operation of washing in the operational process.
10. it is characterized in that according to claim 9 or 8 described MTO processing wastewater treatment processs: the operation that gas is cleaned or steam-water mixing is washed is adopted in the periodic purge operation in the ultra-filtration membrane operational process.
11. MTO processing wastewater treatment process according to claim 1 is characterized in that: the reverse osmosis membrane filtration system in the 4th step adopts conventional reverse osmosis membrane or antipollution RO film.
12. MTO processing wastewater treatment process according to claim 1 is characterized in that: adopt non oxidizing bactericide to carry out the impact sterilization operation in the reverse osmosis membrane filtration system operational process in the 4th step.
13. a MTO processing wastewater treatment process is characterized in that: according to the described treatment process of one of the claims 1-12, the product water after the processing directly enters the compensating water system of middle low-pressure boiler.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101573137A CN101962246B (en) | 2009-07-24 | 2009-07-24 | Method for treating and recycling MTO process wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009101573137A CN101962246B (en) | 2009-07-24 | 2009-07-24 | Method for treating and recycling MTO process wastewater |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101962246A CN101962246A (en) | 2011-02-02 |
| CN101962246B true CN101962246B (en) | 2013-01-02 |
Family
ID=43515338
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2009101573137A Active CN101962246B (en) | 2009-07-24 | 2009-07-24 | Method for treating and recycling MTO process wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101962246B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2984874B1 (en) * | 2011-12-23 | 2014-01-10 | Degremont | PROCESS FOR TREATING INDUSTRIAL OR URBAN WASTEWATER FOR REUSE, AND INSTALLATION FOR CARRYING OUT SAID METHOD |
| JP5547224B2 (en) * | 2012-03-14 | 2014-07-09 | 株式会社東芝 | Membrane filtration system |
| CN103496800A (en) * | 2013-10-10 | 2014-01-08 | 浙江汉蓝环境科技有限公司 | Method for deeply treating high-concentration nitrogen-containing chemical wastewater |
| CN105271585A (en) * | 2014-06-11 | 2016-01-27 | 中国石油化工股份有限公司 | Method for processing wastewater generated in a process for preparing butadiene through oxidative dehydrogenation of industrial butylene |
| CN104071910B (en) * | 2014-06-25 | 2016-01-20 | 江苏久吾高科技股份有限公司 | Liquid dewaxing deoiling method and device at the bottom of MTO/MTP product separation tower tower |
| CN111003895B (en) * | 2019-12-27 | 2022-04-15 | 南京工业大学 | MTO chemical wastewater membrane method zero-discharge treatment process and waste salt resource utilization technology |
| CN111003896A (en) * | 2019-12-27 | 2020-04-14 | 南京工业大学 | Multi-membrane integrated near-zero emission treatment process for MTO (methanol to olefin) high-concentration organic wastewater |
| CN112546865B (en) * | 2020-11-30 | 2025-07-08 | 上海凯鑫分离技术股份有限公司 | Recycling process and recycling system for purified water in process of preparing olefin from methanol |
-
2009
- 2009-07-24 CN CN2009101573137A patent/CN101962246B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN101962246A (en) | 2011-02-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101962246B (en) | Method for treating and recycling MTO process wastewater | |
| CN101962235B (en) | Method for high temperature wastewater treatment and reuse in MTO process | |
| CN103224305B (en) | Treatment method of wastewater containing dimethylamine | |
| CN102358651B (en) | Advanced treatment process for fermented pharmaceutical wastewater | |
| CN103803752B (en) | Treatment method of wastewater with high salinity and high organic matters | |
| CN102659283B (en) | Process for treating and recovering dye industrial wastewater | |
| CN106396234A (en) | Zero-discharge treatment method for reverse osmosis concentrated water | |
| CN103922549B (en) | A kind of coal gasification waste water treatment and reuse method and device thereof | |
| CN105417775A (en) | Reverse osmosis membrane treating and recycling method for printing and dyeing wastewater | |
| CN105217861A (en) | A kind for the treatment of process of reverse osmosis concentrated water | |
| CN103626352A (en) | Advanced treatment and recycling process and apparatus for sewage reaching standard | |
| CN103663849A (en) | Method for treating papermaking wastewater based on combined process including integrated membrane technology and advanced oxidation technology | |
| CN103755092A (en) | Novel textile dyeing and finishing waste water deep treatment and recycling method | |
| CN101376551A (en) | Method for processing process waste water of ethylene preparation by ethanol dehydration | |
| CN103771641A (en) | Advanced treatment and reuse method of nitrochlorobenzene wastewater | |
| CN111875180A (en) | Coal chemical industry wastewater zero-discharge integrated treatment system and method | |
| CN105399249A (en) | Advanced municipal sewage treatment device and method | |
| CN117049755B (en) | Reclaimed water recycling treatment process for coal gas wastewater | |
| CN219044900U (en) | High temperature coal tar hydrogenation effluent treatment plant | |
| CN103787539B (en) | A kind of method of membrane separation nitro-chlorobenzene hot wastewater | |
| CN203959992U (en) | A kind of coal gasification waste water treatment and reuse device | |
| CN116216964B (en) | Method and system for treating industrial wastewater in membrane production | |
| CN216863920U (en) | Urea production waste liquid treatment device | |
| CN207227223U (en) | A kind of processing of gasification of poor coal waste water and recycle device | |
| CN216997948U (en) | Preparation of Ternary Orientation Technology System for Wastewater Regeneration and Utilization of New Water |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |