CN105170199A - Regeneration method for deep oxidation catalyst of coal gasification waste water - Google Patents
Regeneration method for deep oxidation catalyst of coal gasification waste water Download PDFInfo
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- CN105170199A CN105170199A CN201510602448.5A CN201510602448A CN105170199A CN 105170199 A CN105170199 A CN 105170199A CN 201510602448 A CN201510602448 A CN 201510602448A CN 105170199 A CN105170199 A CN 105170199A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- 239000003245 coal Substances 0.000 title claims abstract description 42
- 239000002351 wastewater Substances 0.000 title claims abstract description 42
- 238000002309 gasification Methods 0.000 title claims abstract description 40
- 230000003647 oxidation Effects 0.000 title claims abstract description 31
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 31
- 238000011069 regeneration method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 62
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000967 suction filtration Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000003960 organic solvent Substances 0.000 claims abstract description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 18
- 238000009418 renovation Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
- 230000002779 inactivation Effects 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002808 molecular sieve Substances 0.000 claims description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 9
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000002904 solvent Substances 0.000 claims description 5
- 229910002012 Aerosil® Inorganic materials 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000012670 alkaline solution Substances 0.000 claims description 4
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910052787 antimony Inorganic materials 0.000 claims description 2
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 239000011135 tin Substances 0.000 claims description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000011701 zinc Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 abstract 2
- 239000003513 alkali Substances 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 6
- 230000008929 regeneration Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 238000003889 chemical engineering Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- WBJXZTQXFVDYIZ-UHFFFAOYSA-N [Sb].[N+](=O)(O)[O-] Chemical compound [Sb].[N+](=O)(O)[O-] WBJXZTQXFVDYIZ-UHFFFAOYSA-N 0.000 description 1
- -1 aerobic/anaerobic Substances 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- DBRMBYFUMAFZOB-UHFFFAOYSA-N molybdenum nitric acid Chemical compound [Mo].[N+](=O)(O)[O-] DBRMBYFUMAFZOB-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a regeneration method for a deep oxidation catalyst of coal gasification waste water. The regeneration method comprises the following steps that firstly, an inactivated catalyst is steeped into a selected organic solvent and subjected to ultrasonic treatment for 5-60 min, and the treated catalyst is dried in an oven at 80-120 DEG C after suction filtration separation is conducted; secondly, the dried catalyst is steeped into a prepared alkali solution with the mass fraction of 2-10%, ultrasonic treatment is conducted for 5-60 min, washing in pure water is conducted until the pH ranges from 7 to 8, and roasting is conducted after drying in the oven. The regeneration method for the deep oxidation catalyst of the coal gasification waste water is simple, the technological process is short, and the inactivated catalyst can be repeatedly regenerated.
Description
Technical field
The invention belongs to coal chemical industrial waste water processing technology field, be specifically related to the renovation process of the waste water advanced oxidation treatment catalyst of coal gasification course.
Background technology
China has abundant coal resources, how to be cleaned, is used efficiently, is one of scientific research personnel's priority research areas always.At present, coal gasification is the major way of coal high-efficiency comprehensive utilization, but coal can produce a large amount of high pollution waste water in gasification, and mainly containing phenol, tar, aliphatic and aromatic compound etc., pollutant levels are high, complicated component, and intractability is larger.
The gasification furnace used in current Coal Gasification Project mainly contains lurgi gasifier, shell stove, Texaco stove, multi nozzle of gasification furnace etc., and the waste water composition that different gasification furnace produces is not identical.The processing technological flow of existing coal gasification waste water mainly includes pretreatment, biological treatment and advanced treating three steps.Pretreatment generally adopts physico-chemical process such as ammonia still process dephenolize, air supporting gravity oil-removing, coagulating sedimentation to remove the toxic or inhibiting composition of microorganism in biological treatment; Biological treatment mainly adopts the techniques such as activated sludge, aerobic/anaerobic, SBR to be further processed waste water; The indexs such as the waste water COD after biochemical treatment, colourity, ammonia nitrogen are generally difficult to reach national grade one discharge standard, also need can discharge after further processing.
Recently, country is more and more higher to the environmental requirement of Coal Gasification Project, and it is not enough that a lot of Coal Chemical Engineering Project waste water only reaches national grade one discharge standard.In the face of real situations such as shortage of water resources, environmental carrying capacity are limited, how research makes coal gasification waste water utilize through advanced treating Posterior circle, and really realizing the target of Coal Chemical Engineering Project wastewater zero discharge, is the direction of industry scientific research personnel effort from now on.
Method at present for coal gasification waste water advanced treating has charcoal absorption, biofilter, UF membrane, catalytic oxidation etc., and in wherein charcoal absorption method, regenerating active carbon power consumption is comparatively large, and after regeneration, adsorption capacity declines; Biofilter cost is low, but treatment effeciency is lower, easily has secondary pollution; UF membrane cost is higher, and film easily blocks, and requires higher to influent quality, limits the scope of application.This several method above-mentioned is that pollutant is carried out physical transfer in essence, does not make it disappear, also needs follow-up harmless treatment.
Catalytic oxidation can make the organic pollution in waste water under the effect of catalyst through being degraded to inorganic matter, inherently eliminates organic pollution, has comprehensive advantage.The oxidation technology mainly catalytic ozonation of current report, namely in the presence of a catalyst, passes into ozone in coal gasification waste water, and make organic pollutant degradation be carbon dioxide, but this technology needs the ozone of at substantial, cost is relatively high.
Adopt effective catalyst, directly under the effect of air, carrying out degraded rapidly to the organic pollution in waste water after coal gasification biochemical treatment is one of waste water advanced oxidation technology with bright application prospect.For improving the catalyst market competitiveness, reduce catalyst cost, how effective regeneration catalyst determines that can this technology the key factor of Rapid Popularization.
Summary of the invention
In view of this, the present invention is intended to the renovation process proposing a kind of coal gasification waste water deep oxidation catalyst.
For achieving the above object, technical scheme of the present invention is achieved in that
A renovation process for coal gasification waste water deep oxidation catalyst, comprises the steps,
1) catalyst after inactivation is immersed in selected organic solvent, ultrasonic process 5-60min, after suction filtration is separated, by catalyst 80 ~ 120 DEG C of oven dry in an oven processed; Preferably, bake out temperature is 100 DEG C;
2) by the catalyst after drying, to immerse the mass fraction prepared be in 2-10% alkaline solution, ultrasonic process 5-60min, and be 7-8 with pure water to pH, in an oven after 80 ~ 120 DEG C of oven dry, carry out roasting, preferably, bake out temperature is 100 DEG C.
Preferably, described step 1) in catalyst be prepared from by the following method, be dissolved in after a) slaine being mixed by a certain percentage in solvent, be prepared into the mixed solution that mass fraction is 1-15%; Mixed solution is at room temperature stirred and places 6-12h;
B) carrier being immersed the mass fraction prepared is in the acid solution of 2-10%, ultrasonic process 5-60min, is 6-7 with pure water to pH, 80 ~ 120 DEG C of dry for standby in an oven; Preferably, bake out temperature is 100 DEG C;
C) by step 1) mixed solution and the step 2 that prepare) carrier after process is according to mass ratio (0.8 ~ 1.2): (0.8 ~ 1.2) mix, standing 1-24h, in an oven 80 ~ 120 DEG C of oven dry, then high-temperature roasting; Preferably, be 1:1 in mass ratio; Bake out temperature is 100 DEG C.
Preferably, described a) in soluble metallic salt be one or more in zinc, indium, ammonium, iron, copper, manganese, bismuth, nickel, cobalt, molybdenum, tin, ammonium, gallium, cerium, antimony, the nitrate of cadmium, sulfate, carbonate, chloride, vanadate, solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride; Described step b) in carrier be one in aerosil, ZSM-5 molecular sieve, S-1 molecular sieve, TS-1 molecular sieve, Woelm Alumina, acid solution is the one in sulfuric acid, nitric acid, hydrochloric acid; Described step c) in the temperature of high-temperature roasting be 300 ~ 800 DEG C, the time is 1 ~ 36h.
Preferably, described step 1) in organic solvent be one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride.
Preferably, described step 1) in, the mass ratio of the catalyst after described organic solvent and inactivation is (1 ~ 10): 1.
Preferably, described step 2) in, described alkaline solution is one or more in NaOH, potassium hydroxide, ammoniacal liquor, tetraethyl ammonium hydroxide, TPAOH, TBAH, n-butylamine.
Preferably, described step 2) in, described sintering temperature is 300 ~ 800 DEG C, and roasting time is 1 ~ 48h.
Relative to prior art, the renovation process of a kind of coal gasification waste water deep oxidation catalyst of the present invention, has following advantage:
1) coal gasification waste water deep oxidation catalyst renovation process of the present invention is simple, and technological process is short, can repeat regeneration to decaying catalyst.
2) in catalyst regeneration process of the present invention, various solvent all can recycle, and avoids the secondary pollution of catalyst regeneration process.
Detailed description of the invention
The present invention is described in detail below in conjunction with embodiment.
Embodiment 1
A preparation method for coal gasification waste water deep oxidation catalyst, comprises the steps:
1) zinc nitrate, indium nitrate, ammonium tungstate are dissolved in methyl alcohol after mixing with mol ratio 0.2:0.4:0.4, are prepared into the mixed solution that mass fraction is 1%, mixed solution are at room temperature stirred and places 6h.
2) aerosil being immersed the mass fraction prepared is in the sulfuric acid solution of 2%, ultrasonic process 5min, is 6-7 with pure water to pH, in an oven dry for standby at 100 DEG C.
3) by step 1) mixed solution and the step 2 that prepare) carrier after process mix according to mass ratio 1:1, leaves standstill 1h, oven dry at 100 DEG C in an oven, then 300 DEG C of roasting 1h in Muffle furnace.
As above the renovation process of coal gasification waste water deep oxidation catalyst prepared of method, comprises the steps,
1) the catalyst 20g after inactivation is immersed in 20g methyl alcohol, ultrasonic process 5min, after suction filtration is separated, by the catalyst 100 DEG C of oven dry in an oven processed;
2) by the 20g catalyst after drying, to immerse the 20g mass fraction prepared be in 2% sodium hydroxide solution, ultrasonic process 5min, and be 7-8 with pure water to pH, in an oven after 100 DEG C of oven dry, in Muffle furnace, at 300 DEG C, roasting time is 1h.
Embodiment 2
A preparation method for coal gasification waste water deep oxidation catalyst, comprises the steps:
1) copper nitrate, cadmium nitrate, chromic nitrate are dissolved in ethanol after mixing with mol ratio 0.4:0.3:0.3, are prepared into the mixed solution that mass fraction is 15%, mixed solution are at room temperature stirred and places 12h.
2) ZSM-5 molecular sieve being immersed the mass fraction prepared is in the hydrochloric acid solution of 10%, ultrasonic process 60min, is 6-7 with pure water to pH, in an oven dry for standby at 100 DEG C.
3) by step 1) mixed solution and the step 2 that prepare) carrier after process mix according to mass ratio 1:1, leaves standstill 24h, oven dry at 100 DEG C in an oven, then 800 DEG C of roasting 36h in Muffle furnace.
As above the renovation process of coal gasification waste water deep oxidation catalyst prepared of method, comprises the steps,
1) the catalyst 20g after inactivation is immersed in 200g ethanol, ultrasonic process 60min, after suction filtration is separated, by the catalyst 100 DEG C of oven dry in an oven processed;
2) by the 20g catalyst after drying, to immerse the 200g mass fraction prepared be in 10% sodium hydroxide solution, ultrasonic process 60min, and be 7-8 with pure water to pH, in an oven after 100 DEG C of oven dry, in Muffle furnace, at 800 DEG C, roasting time is 48h.
Embodiment 3
A preparation method for coal gasification waste water deep oxidation catalyst, comprises the steps:
1) nitric acid molybdenum, manganese nitrate, nitric acid antimony, ferric nitrate are dissolved in isopropyl alcohol after mixing with mol ratio 0.4:0.4:0.1:0.1, are prepared into the mixed solution that mass fraction is 10%, mixed solution are at room temperature stirred and places 6h.
2) TS-1 molecular sieve being immersed the mass fraction prepared is in the hydrochloric acid solution of 5%, ultrasonic process 30min, is 6-7 with pure water to pH, 95 DEG C of dry for standby in an oven.
3) by step 1) mixed solution and the step 2 that prepare) carrier after process mix according to mass ratio 1:1, standing 12h, in an oven 105 DEG C of oven dry, then 600 DEG C of roasting 24h in Muffle furnace.
As above the renovation process of coal gasification waste water deep oxidation catalyst prepared of method, comprises the steps,
1) the catalyst 20g after inactivation is immersed in 100g ethanol, ultrasonic process 30min, after suction filtration is separated, by the catalyst 100 DEG C of oven dry in an oven processed;
2) by the 20g catalyst after drying, to immerse the 100g mass fraction prepared be in 5% ammonia spirit, ultrasonic process 30min, and be 7-8 with pure water to pH, in an oven after 100 DEG C of oven dry, in Muffle furnace, at 600 DEG C, roasting time is 24h.
Embodiment 4
A preparation method for coal gasification waste water deep oxidation catalyst, comprises the steps:
1) cobalt nitrate, nickel nitrate are dissolved in methyl alcohol after mixing with mol ratio 0.4:0.6, are prepared into the mixed solution that mass fraction is 10%, mixed solution are at room temperature stirred and places 6h.
2) S-1 molecular sieve being immersed the mass fraction prepared is in the salpeter solution of 5%, ultrasonic process 30min, is 6-7 with pure water to pH, 100 DEG C of dry for standby in an oven.
3) by step 1) mixed solution and the step 2 that prepare) carrier after process mix according to mass ratio 1:1, standing 12h, in an oven 100 DEG C of oven dry, then 600 DEG C of roasting 24h in Muffle furnace.
As above the renovation process of coal gasification waste water deep oxidation catalyst prepared of method, comprises the steps,
1) the catalyst 20g after inactivation is immersed in 100g isopropyl alcohol, ultrasonic process 30min, after suction filtration is separated, by the catalyst 100 DEG C of oven dry in an oven processed;
2) the 20g catalyst after oven dry being immersed the 100g mass fraction prepared is in 8% TPAOH solution, ultrasonic process 30min, be 7-8 with pure water to pH, in an oven 100 DEG C dry after, in Muffle furnace, at 600 DEG C, roasting time is 24h.
Embodiment 5
A preparation method for coal gasification waste water deep oxidation catalyst, comprises the steps:
1) copper nitrate is dissolved in glycerine, is prepared into the mixed solution that mass fraction is 8%, mixed solution is at room temperature stirred and places 10h.
2) aerosil being immersed the mass fraction prepared is in the hydrochloric acid solution of 10%, ultrasonic process 30min, is 6-7 with pure water to pH, 105 DEG C of dry for standby in an oven.
3) by step 1) mixed solution and the step 2 that prepare) carrier after process mix according to mass ratio 1:1, standing 10h, in an oven 105 DEG C of oven dry, then 400 DEG C of roasting 10h in Muffle furnace.
As above the renovation process of coal gasification waste water deep oxidation catalyst prepared of method, comprises the steps,
1) the catalyst 20g after inactivation is immersed in 100g glycerine, ultrasonic process 30min, after suction filtration is separated, by the catalyst 100 DEG C of oven dry in an oven processed;
2) by the 20g catalyst after drying, to immerse the 50g mass fraction prepared be in 10% TBAH solution, ultrasonic process 30min, and be 7-8 with pure water to pH, in an oven after oven dry, in Muffle furnace, at 400 DEG C, roasting time is 12h.
Coal gasification waste water deep oxidation catalyst 50g being placed in volume is 400ml tubular reactor, pumping into COD is waste water after the coal gasification biochemical treatment of 300ppm, flow is 200ml/min, in waste water, pass into air, air velocity is 30ml/min, starts reaction under normal temperature and pressure, the COD value of detection reaction device water outlet, when COD value stops reaction higher than during 100ppm, be judged to be inactivation, the service life of record fresh catalyst.Inactivation regenerates the service life of the catalyst after recording the 10th regeneration for 10 times afterwards repeatedly, and result is as shown in table 1.
The catalyst service life of the different embodiment of table 1
| Numbering | Fresh catalyst life-span (h) | Regenerate 10 rear catalysts life-span (h) |
| Embodiment 1 | 82 | 40 |
| Embodiment 2 | 78 | 65 |
| Embodiment 3 | 81 | 63 |
| Embodiment 4 | 79 | 57 |
| Embodiment 5 | 80 | 46 |
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (7)
1. a renovation process for coal gasification waste water deep oxidation catalyst, is characterized in that: comprise the steps,
1) catalyst after inactivation is immersed in selected organic solvent, ultrasonic process 5-60min, after suction filtration is separated, by catalyst 80 ~ 120 DEG C of oven dry in an oven processed; Preferably, bake out temperature is 100 DEG C;
2) by the catalyst after drying, to immerse the mass fraction prepared be in 2-10% alkaline solution, ultrasonic process 5-60min, and be 7-8 with pure water to pH, in an oven after 80 ~ 120 DEG C of oven dry, carry out roasting, preferably, bake out temperature is 100 DEG C.
2. the renovation process of coal gasification waste water deep oxidation catalyst according to claim 1, it is characterized in that: described step 1) in catalyst be prepared from by the following method, a) be dissolved in after slaine being mixed by a certain percentage in solvent, be prepared into the mixed solution that mass fraction is 1-15%; Mixed solution is at room temperature stirred and places 6-12h;
B) carrier being immersed the mass fraction prepared is in the acid solution of 2-10%, ultrasonic process 5-60min, is 6-7 with pure water to pH, 80 ~ 120 DEG C of dry for standby in an oven; Preferably, bake out temperature is 100 DEG C;
C) by step 1) mixed solution and the step 2 that prepare) carrier after process is according to mass ratio (0.8 ~ 1.2): (0.8 ~ 1.2) mix, standing 1-24h, in an oven 80 ~ 120 DEG C of oven dry, then high-temperature roasting; Preferably, be 1:1 in mass ratio; Bake out temperature is 100 DEG C.
3. the renovation process of coal gasification waste water deep oxidation catalyst according to claim 2, it is characterized in that: described a) in soluble metallic salt be one or more in zinc, indium, ammonium, iron, copper, manganese, bismuth, nickel, cobalt, molybdenum, tin, ammonium, gallium, cerium, antimony, the nitrate of cadmium, sulfate, carbonate, chloride, vanadate, solvent is one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride; Described step b) in carrier be one in aerosil, ZSM-5 molecular sieve, S-1 molecular sieve, TS-1 molecular sieve, Woelm Alumina, acid solution is the one in sulfuric acid, nitric acid, hydrochloric acid; Described step c) in the temperature of high-temperature roasting be 300 ~ 800 DEG C, the time is 1 ~ 36h.
4. the renovation process of the coal gasification waste water deep oxidation catalyst according to claim 1 or 3, is characterized in that: described step 1) in organic solvent be one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride.
5. the renovation process of the coal gasification waste water deep oxidation catalyst according to claim 1 or 3, is characterized in that: described step 1) in, the mass ratio of the catalyst after described organic solvent and inactivation is (1 ~ 10): 1.
6. the renovation process of the coal gasification waste water deep oxidation catalyst according to claim 1 or 3, it is characterized in that: described step 2) in, described alkaline solution is one or more in NaOH, potassium hydroxide, ammoniacal liquor, tetraethyl ammonium hydroxide, TPAOH, TBAH, n-butylamine.
7. the renovation process of the coal gasification waste water deep oxidation catalyst according to claim 1 or 3, is characterized in that: described step 2) in, described sintering temperature is 300 ~ 800 DEG C, and roasting time is 1 ~ 48h.
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| CN107115867A (en) * | 2017-06-22 | 2017-09-01 | 中国天辰工程有限公司 | A kind of preparation method of the catalyst of ozone oxidation organic exhaust gas |
| CN112221489A (en) * | 2020-11-18 | 2021-01-15 | 西安凯立新材料股份有限公司 | Regeneration method of gold carbon catalyst for preparing VCM |
| CN115945228A (en) * | 2022-12-12 | 2023-04-11 | 巴斯夫公司 | Regeneration method for preparing 1,4-butynediol catalyst through alkyne hydroformylation reaction |
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