CN105170135A - Preparing method for deep oxidation catalyst of coal gasification waste water - Google Patents
Preparing method for deep oxidation catalyst of coal gasification waste water Download PDFInfo
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- CN105170135A CN105170135A CN201510599257.8A CN201510599257A CN105170135A CN 105170135 A CN105170135 A CN 105170135A CN 201510599257 A CN201510599257 A CN 201510599257A CN 105170135 A CN105170135 A CN 105170135A
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Abstract
The invention provides a preparing method for a deep oxidation catalyst of coal gasification waste water. The preparing method comprises the following steps that firstly, metal salt is mixed according to a certain proportion, then dissolved into a solvent and prepared into a mixed solution with the mass fraction of 1-15%, and the mixed solution is stirred and placed for 6-12 min at the room temperature; secondly, a carrier is steeped into a prepared acid solution with the mass fraction of 2-10%, subjected to ultrasonic treatment for 5-60 min, washed with pure water until pH ranges from 6 to 7, and dried in an oven for standby use; thirdly, the mixed solution prepared in the firstly step and the carrier treated in the second step are mixed according to the mass ratio of (0.8-1.2):(0.8-1.2), subjected to standing for 1-24 h, dried in the oven and then roasted at high temperature; preferably, the mass ratio is 1:1. Under the action of the catalyst, organic pollutants can be greatly reduced as long as air is introduced into the waste water, and the catalyst is low in cost and good in regenerability.
Description
Technical field
The invention belongs to coal chemical industrial waste water processing technology field, be specifically related to the preparation method 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.
At present, the processing technological flow of 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 active carbon adsorption, biofilter, UF membrane, catalytic oxidation etc., and wherein in active carbon adsorption method, carbon, C regeneration 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.
Summary of the invention
In view of this, the present invention is intended to the preparation method proposing a kind of coal gasification waste water deep oxidation catalyst, under the effect of this catalyst, only need in waste water and pass into air and organic pollution significantly can be reduced, and catalyst is with low cost, regenerability is good, reaction can be carried out at normal temperatures and pressures smoothly, and engineering amplification difficulty is less, has very bright application prospect.
For achieving the above object, technical scheme of the present invention is achieved in that a kind of preparation method of coal gasification waste water deep oxidation catalyst, comprises the steps:
1) 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;
2) 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;
3) 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 mixing in mass ratio, bake out temperature is 100 DEG C.
Preferably, described step 1) 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.
Preferably, described step 1) in slaine be the mixture of zinc nitrate, indium nitrate, ammonium tungstate three, the mol ratio of three is (0.15 ~ 0.25): (0.3 ~ 0.5): (0.3 ~ 0.5); Preferably, mol ratio 0.2:0.4:0.4.
Preferably, described step 1) in slaine be the mixture of copper nitrate, cadmium nitrate, chromic nitrate three, the mol ratio of three is (0.3 ~ 0.5): (0.25 ~ 0.35): (0.25 ~ 0.35); Preferably, mol ratio 0.4:0.3:0.3.
Preferably, described step 1) in slaine be the mixture of nitric acid molybdenum, manganese nitrate, nitric acid antimony, ferric nitrate, the mol ratio of four is (0.3 ~ 0.5): (0.3 ~ 0.5): (0.05 ~ 0.15): (0.05 ~ 0.15); Preferably, mol ratio 0.4:0.4:0.1:0.1.
Preferably, described step 1) in slaine be cobalt nitrate, the mixture of both nickel nitrates, both mol ratios are (0.3 ~ 0.5): (0.5 ~ 0.7); Preferably, mol ratio 0.4:0.6.
Preferably, described step 1) in solvent be one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride.
Preferably, described step 2) in carrier be one in aerosil, ZSM-5 molecular sieve, S-1 molecular sieve, TS-1 molecular sieve, Woelm Alumina.
Preferably, described step 2) in acid solution be one in sulfuric acid, nitric acid, hydrochloric acid.
Preferably, described step 3) in, the temperature of high-temperature roasting is 300 ~ 800 DEG C, and the time is 1 ~ 36h.
Relative to prior art, the preparation method of a kind of coal gasification waste water deep oxidation catalyst of the present invention, has following advantage:
1) catalyst preparing of coal gasification waste water deep oxidation prepared of the present invention is simple, and technological process is short, with low cost.
2), under the effect of the catalyst prepared in the present invention, coal gasification waste water organic pollution can be degraded rapidly at normal temperatures and pressures, and course of reaction only need pass into air, avoids in By Ozone a large amount of energy consumptions prepared needed for ozone, has good economic outlook.
3) in catalyst preparation process of the present invention, various solvent all can recycle, and avoids the secondary pollution of catalyst production 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.
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.
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.
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.
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.
Evaluating catalyst
Catalyst 20g embodiment one ~ embodiment five prepared is placed in there-necked flask, putting into 200mlCOD is waste water after the coal gasification biochemical treatment of 300ppm, air is passed in waste water, air velocity is 30ml/min, reaction is stopped after reaction 5min, detect now COD content in waste water, result is as shown in table 1.
The different embodiment prepared catalyst of table 1 is to coal gasification waste water COD removal effect
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 (10)
1. a preparation method for coal gasification waste water deep oxidation catalyst, is characterized in that: comprise the steps:
1) be dissolved in after soluble metallic salt 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;
2) 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;
3) 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 mixing in mass ratio, bake out temperature is 100 DEG C.
2. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, is characterized in that: described step 1) 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.
3. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, it is characterized in that: described step 1) in slaine be the mixture of zinc nitrate, indium nitrate, ammonium tungstate three, the mol ratio of three is (0.15 ~ 0.25): (0.3 ~ 0.5): (0.3 ~ 0.5); Preferably, mol ratio 0.2:0.4:0.4.
4. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, it is characterized in that: described step 1) in slaine be the mixture of copper nitrate, cadmium nitrate, chromic nitrate three, the mol ratio of three is (0.3 ~ 0.5): (0.25 ~ 0.35): (0.25 ~ 0.35); Preferably, mol ratio 0.4:0.3:0.3.
5. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, it is characterized in that: described step 1) in slaine be the mixture of nitric acid molybdenum, manganese nitrate, nitric acid antimony, ferric nitrate, the mol ratio of four is (0.3 ~ 0.5): (0.3 ~ 0.5): (0.05 ~ 0.15): (0.05 ~ 0.15); Preferably, mol ratio 0.4:0.4:0.1:0.1.
6. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, it is characterized in that: described step 1) in slaine be cobalt nitrate, the mixture of both nickel nitrates, both mol ratios are (0.3 ~ 0.5): (0.5 ~ 0.7); Preferably, mol ratio 0.4:0.6.
7. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, is characterized in that: described step 1) in solvent be one or more in methyl alcohol, ethanol, isopropyl alcohol, the tert-butyl alcohol, glycerine, ethylene glycol, carbon tetrachloride.
8. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, is characterized in that: described step 2) in carrier be one in aerosil, ZSM-5 molecular sieve, S-1 molecular sieve, TS-1 molecular sieve, Woelm Alumina.
9. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, is characterized in that: described step 2) in acid solution be one in sulfuric acid, nitric acid, hydrochloric acid.
10. the preparation method of coal gasification waste water deep oxidation catalyst according to claim 1, is characterized in that: described step 3) in, the temperature of high-temperature roasting is 300 ~ 800 DEG C, and the time is 1 ~ 36h.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106582777A (en) * | 2016-12-27 | 2017-04-26 | 郑州天舜电子技术有限公司 | Catalyst for treating coked phenol wastewater and preparation method of catalyst |
| CN106881090A (en) * | 2017-03-20 | 2017-06-23 | 中国天辰工程有限公司 | A kind of ozone catalytic oxidation catalyst method of modifying |
| 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 |
| CN107961789A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | The preparation method of O composite metallic oxide catalyst and thus obtained catalyst and the method for application and O3 catalytic oxidation |
| CN109529867A (en) * | 2018-10-25 | 2019-03-29 | 南京工业大学 | Efficient catalyst for treating tail water in coal chemical industry and preparation method thereof |
| CN110280254A (en) * | 2018-11-21 | 2019-09-27 | 湖北工业大学 | A kind of catalyst and its preparation method and application handling methylene blue dye wastewater |
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| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
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- 2015-09-18 CN CN201510599257.8A patent/CN105170135A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101601998A (en) * | 2009-06-11 | 2009-12-16 | 浙江省环境保护科学设计研究院 | A kind of Preparation of catalysts method that is used for treating high-concentration organic wastewater through catalytic oxidation |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107961789A (en) * | 2016-10-19 | 2018-04-27 | 中国石油化工股份有限公司 | The preparation method of O composite metallic oxide catalyst and thus obtained catalyst and the method for application and O3 catalytic oxidation |
| CN106582777A (en) * | 2016-12-27 | 2017-04-26 | 郑州天舜电子技术有限公司 | Catalyst for treating coked phenol wastewater and preparation method of catalyst |
| CN106881090A (en) * | 2017-03-20 | 2017-06-23 | 中国天辰工程有限公司 | A kind of ozone catalytic oxidation catalyst method of modifying |
| CN106881090B (en) * | 2017-03-20 | 2019-08-02 | 中国天辰工程有限公司 | A kind of ozone catalytic oxidation catalyst method of modifying |
| 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 |
| CN109529867A (en) * | 2018-10-25 | 2019-03-29 | 南京工业大学 | Efficient catalyst for treating tail water in coal chemical industry and preparation method thereof |
| CN110280254A (en) * | 2018-11-21 | 2019-09-27 | 湖北工业大学 | A kind of catalyst and its preparation method and application handling methylene blue dye wastewater |
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