CN103523891A - Method for realizing catalytic wet oxidation of wastewater containing organic substances - Google Patents
Method for realizing catalytic wet oxidation of wastewater containing organic substances Download PDFInfo
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- CN103523891A CN103523891A CN201210225882.2A CN201210225882A CN103523891A CN 103523891 A CN103523891 A CN 103523891A CN 201210225882 A CN201210225882 A CN 201210225882A CN 103523891 A CN103523891 A CN 103523891A
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- 239000002351 wastewater Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 35
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 13
- 238000009279 wet oxidation reaction Methods 0.000 title abstract description 22
- 239000000126 substance Substances 0.000 title abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000002071 nanotube Substances 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 7
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 7
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 7
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 7
- 229910052707 ruthenium Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 5
- 239000010815 organic waste Substances 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 abstract description 21
- 229910000510 noble metal Inorganic materials 0.000 abstract description 8
- 239000004408 titanium dioxide Substances 0.000 abstract description 6
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 abstract description 2
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 229910001882 dioxygen Inorganic materials 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 12
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 12
- -1 acrylic nitrile Chemical class 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 239000010970 precious metal Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 239000004480 active ingredient Substances 0.000 description 7
- 239000010936 titanium Substances 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005470 impregnation Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 230000015556 catabolic process Effects 0.000 description 4
- 239000012018 catalyst precursor Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000002638 heterogeneous catalyst Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000002815 homogeneous catalyst Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229910018879 Pt—Pd Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 210000002318 cardia Anatomy 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000007810 chemical reaction solvent Substances 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000012809 cooling fluid Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000011363 dried mixture Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a method for realizing catalytic wet oxidation of wastewater containing organic substances, which mainly solves the problem that high-concentration organic wastewater is difficult to treat in the prior art. The technical scheme of the method comprises the following step: by taking noble metal loaded nano titanium dioxide as a catalyst, enabling organic wastewater to be in contact with the catalyst in a high-pressure reaction kettle for 30-120 minutes under the conditions that the reaction temperature is 120-260 DEG C and the oxygen gas pressure is 1-10 MPa, wherein the used catalyst comprises the following components in parts by weight: A) 97-99.8 parts of titanium dioxide nanotube, and B) 0.2-3 parts of at least one of Ru, Pd, Pt, Au or Rh loaded on the nanotube. Thus, the problem is well solved; and the method can be used for industrial production of organic wastewater treatment.
Description
Technical field
The present invention relates to a kind of method containing organism Catalytic Wet Air Oxidation for Wastewater.
Background technology
The characteristic that water is nontoxic owing to having, cheap etc., in chemical process, be often used as the uses such as reaction solvent, medium or cooling fluid, therefore, in application process, water quality has inevitably been subject to destruction, and flourish along with chemical industry, water pollution is ascendant trend year by year, and wherein toxic organic compound is particularly serious to the pollution of water body.This pollutant have quantity discharged large, pollute the features such as wide and difficult for biological degradation, serious threat, to human lives, is also restricting the development of chemical industry simultaneously.
Wet oxidation is that grown up by American scientist Zimmermann the 1950's a kind of processes oxidation technology poisonous, harmful, high concentrated organic wastewater effectively.This method is under high temperature (125～320 ℃), high pressure (0.5～20MPa) condition, take air or pure oxygen as oxygenant, in liquid phase, organic pollutant is oxidized to CO
2chemical process with the inorganicss such as water or small organic molecule.For improving wet oxidation efficiency, reducing reaction conditions, rise the seventies in last century, adds efficient, the stable catalyzer designing for waste water composition, thereby developed Catalytic Wet Oxidation technology on traditional wet oxidation basis.According to the classification of catalyzer, Catalytic Wet Oxidation is divided into homogeneous phase and heterogeneous catalyst wet oxidation two classes.Although homogeneous catalyst has the advantages such as activity is high, speed of response is fast,, because catalyzer is dissolved in waste water, waste water has been caused to secondary pollution, need to carry out the sedimentation of metal ion and reclaim, thereby make technical process become complicated, improve the cost of wastewater treatment.Be different from homogeneous catalyst, the advantage such as heterogeneous catalyst has easily separated, reusable, has simplified the operating process of wet oxidation.Studying efficient, stable catalyzer has become the focus of heterogeneous catalyst wet oxidation.At present the heterogeneous catalyst of research can be divided into three kinds of copper system, composite oxides and noble metal carrier catalysts.Although copper system and composite oxide catalysts have good catalytic activity, in reaction process, active ingredient is stripping inevitably, causes catalyst activity to reduce, can not life-time service; Although noble metal catalyst cost is higher, it still can stable existence under harsh reaction conditions, and oxidation activity is very high.
It is carrier that patent CN1317070C discloses a kind of RE CeO 2, and one or more in precious metal Ru, Pt, Pd, Rh or Au are the preparation method of the wet oxidizing catalyst of catalyst activity component.The standby CeO 2 supporting wet oxidizing catalyst of this legal system has shown good activity in processing high density, organic wastewater with difficult degradation thereby.Yet ceria supports can not stable existence under harsh reaction conditions, the stripping of carrier will impel coming off of noble metal active component, causes the activity decreased of noble metal catalyst.
Summary of the invention
When technical problem to be solved by this invention is existing Catalytic Wet Oxidation skill cardia high density containing organic wastewater, there is the problem that catalyst activity is low, a kind of new method containing organism Catalytic Wet Air Oxidation for Wastewater is provided.When the method has advantages of the high density of processing containing organic wastewater, catalyst activity is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method containing organism Catalytic Wet Air Oxidation for Wastewater, take containing organic waste water is raw material, in temperature of reaction, it is 120～260 ℃, oxygen pressure is under 1～10MPa condition, make waste water contact 30～120min with catalyzer, the organic cod content after reaction in waste water can reduce more than 99%, and wherein catalyzer used comprises following component in parts by weight: the A) titania nanotube of 97～99.8 parts; With the B carrying thereon) 0.2～3 part select at least one in Ru, Pd, Pt, Au or Rh.
In technique scheme, in parts by weight, select at least one the consumption preferable range in Ru, Pd, Pt, Au or Rh be 0.2～1 part.
The preparation method of the wet oxidizing catalyst that the present invention adopts is as follows:
(1) take the NaOH solution of anatase-type nanometer titanium dioxide powder and 1～10mol/L is raw material, at 100～180 ℃ of temperature, adopts hydrothermal method to prepare titania nanotube precursor; Described carrier precursor washing is to neutral, dry, obtain titania nanotube;
(2) titanium dioxide nano-tube support be impregnated in precious metal salt solution, noble metal support amount is 0.2～3%, and dipping time is 12～24h, dry afterwards;
(3) dried mixture roasting 2～5h in air atmosphere, in the muffle furnace of 300～600 ℃, obtains wet oxidizing catalyst presoma; By described presoma, at 300～600 ℃, reductase 12～5h in hydrogen atmosphere, obtains titania nanotube supporting wet oxidizing catalyst.
Precious metal of the present invention is at least one in Ru, Pd, Pt, Au or Rh.
In metal oxide catalyst carrier, the metal oxide of Al, Hf, Ti and Zr can be in supercritical water stable existence, therefore can choose titanium dioxide as the carrier of wet oxidizing catalyst.It is support of the catalyst that the present invention chooses titania nanotube, not only utilized its higher hydrothermal stability, meanwhile, the characteristic of the high-ratio surface that it has, can make the noble metal nano particles high dispersing of preparation at carrier titanium dioxide surface, improve the oxidation activity of catalyzer.Experimental data confirms that this catalyzer has advantages of high reactivity, high stability in processing high density, organic wastewater with difficult degradation thereby.Take 1L autoclave as reactor, choose the industrial acrylic nitrile waste water that acrylic acid wastewater that COD is 28600mg/L and COD are 29600mg/L, catalyzer of the present invention is carried out to wet oxidation investigation.In temperature of reaction, it is 120～260 ℃, total pressure is 1～10MPa, after reaction 30～120min, the COD clearance of acrylic acid wastewater and industrial acrylic nitrile waste water reaches respectively 99.2% and 99.4%, organic waste water after processing can be realized direct discharge, proves a kind of effective method of organism Catalytic Wet Air Oxidation for Wastewater that contains that the present invention is to provide.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, proof is carrier and all not strippings of active ingredient in wet oxidation process, embody the good stability of catalyzer, obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
[embodiment 1]
Take anatase-type nanometer titanium dioxide powder and NaOH solution is raw material, adopts hydrothermal method, in 1L autoclave, the NaOH of 20g nano titanium dioxide powder and 500mL (10mol/L) solution is mixed, and stirs 48h at 100 ℃.Mixed solution is after centrifugation, and solid sediment with the HCl solution washing of 1mol/L once, then is washed with distilled water to neutrality, and the support precursor obtaining is dry 24h in 100 ℃ of baking ovens, makes titania nanotube; By 5g titania nanotube incipient impregnation in containing 0.3750g RuCl
3﹒ nH
212h in the aqueous solution of O, then in 100 ℃ of baking ovens dry 12h, the catalyst precursor obtaining reduces 3h under 350 ℃ of hydrogen atmospheres, makes Ru/TiO
2catalyzer WAO-01.In 1L autoclave, with 4g Ru/TiO
2for catalyzer, process the acrylic acid wastewater that 600mL COD is 28600mg/L, at 200 ℃, under oxygen pressure 5MPa, reaction 60min, COD clearance is 98.2%; Process the industrial acrylic nitrile waste water that 600mL COD is 29600mg/L, at 240 ℃, under the condition of oxygen pressure 8MPa, reaction 80min, COD clearance is 97.6%.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, prove carrier and all not strippings of active ingredient in wet oxidation process.
[embodiment 2]
In 1L autoclave, the NaOH of 20g nano titanium dioxide powder and 500mL (1mol/L) solution is mixed, stir 48h at 180 ℃.Mixed solution is after centrifugation, and solid sediment with the HCl solution washing of 1mol/L once, then is washed with distilled water to neutrality, and the support precursor obtaining is dry 24h in 100 ℃ of baking ovens, makes titania nanotube; By 5g titania nanotube incipient impregnation in containing 0.1150g PdCl
2the aqueous solution in 12h, dry 12h in 100 ℃ of baking ovens, the catalyst precursor obtaining reduces 3h under 550 ℃ of hydrogen atmospheres, makes Pd/TiO
2catalyzer WAO-02.In 1L autoclave, with 4g Pd/TiO
2for catalyzer, process the acrylic acid wastewater that 600mL COD is 28600mg/L, at 250 ℃, under oxygen pressure 8MPa, reaction 120min, COD clearance is 96.6%; Process the industrial acrylic nitrile waste water that 600mL COD is 29600mg/L, at 260 ℃, under the condition of oxygen pressure 10MPa, reaction 120min, COD clearance is 97.3%.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, prove carrier and all not strippings of active ingredient in wet oxidation process.
[embodiment 3]
In 1L autoclave, the NaOH solution of 20g nano titanium dioxide powder and 500mL 6mol/L is mixed, stir 48h at 130 ℃.Mixed solution is after centrifugation, and solid sediment with the HCl solution washing of 1mol/L once, then is washed with distilled water to neutrality, and the support precursor obtaining is dry 24h in 100 ℃ of baking ovens, makes titania nanotube; By 5g titania nanotube incipient impregnation in containing 0.1250g H
2ptCl
6the aqueous solution in 12h, then in 100 ℃ of baking ovens after dry 12h, the catalyst precursor obtaining reduces 3h under 600 ℃ of hydrogen atmospheres, makes Pt/TiO
2catalyzer WAO-03.In 1L autoclave, with 4g Pt-Pd/TiO
2for catalyzer, process the acrylic acid wastewater that 600mL COD is 28600mg/L, at 160 ℃, under oxygen pressure 4MPa, reaction 30min, COD clearance is 98.8%; Process the industrial acrylic nitrile waste water that 600mL COD is 29600mg/L, at 220 ℃, under the condition of oxygen pressure 6MPa, reaction 60min, COD clearance is 97.8%.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, prove carrier and all not strippings of active ingredient in wet oxidation process.
[embodiment 4]
Titania nanotube in 5g embodiment 3 be impregnated in to the RuCl containing 0.1250g
3﹒ nH
2o and 0.025g H
2ptCl
6the aqueous solution in, at room temperature after incipient impregnation 12h, dry 12h in 100 ℃ of baking ovens, the catalyst precursor obtaining reduces 3h under 350 ℃ of hydrogen atmospheres, makes Ru-Pt/TiO
2catalyzer WAO-04.In 1L autoclave, with 4g Ru-Pt/TiO
2for catalyzer, process the acrylic acid wastewater that 600mL COD is 28600mg/L, at 200 ℃, under oxygen pressure 5MPa, reaction 60min, COD clearance is 98.7%; Process the industrial acrylic nitrile waste water that 600mL COD is 29600mg/L, at 240 ℃, under the condition of oxygen pressure 8MPa, reaction 80min, COD clearance is 98.1%.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, prove carrier and all not strippings of active ingredient in wet oxidation process.
[embodiment 5-8]
Embodiment 5,6,7,8 catalyzer preparation conditions and wet oxidation reaction condition are identical with embodiment 4, and the precious metal salt solution of just selecting is different, and specifically the results are shown in Table 1 for formula and wet oxidation.Utilize ICP to detect reacted waste water, in acrylic acid wastewater and industrial acrylic nitrile waste water, the fignal center of Ti and M (M is precious metal) all do not detected, prove carrier and all not strippings of active ingredient in wet oxidation process.
[comparative example 1]
According to CN1317070C patent description, prepared RuO
2/ CeO
2catalyzer.Concrete preparation method is as follows: with Ce (NO
3)
3﹒ 6H
2o and NH
3﹒ H
2o is raw material, adopts coprecipitation method, by Ce (NO
3)
3solution drops to NH
3﹒ H
2in O, 100 ℃ of dry 24h under air atmosphere, then under 350 ℃ of air atmospheres, roasting 7h, makes CeO
2carrier; By 5g CeO
2carrier impregnation is in containing 0.3073g RuCl
3﹒ nH
2in the aqueous solution of O, room temperature dipping 10h, dry under 110 ℃ of air atmospheres, roasting 7h under 300 ℃ of air atmospheres, makes RuO
2/ CeO
2catalyzer WAO-09.
[comparative example 2]
CeO with preparation in comparative example 1
2for carrier, by 4g CeO
2impregnated in 0.2523g H
2ptCl
6﹒ 6H
2in the aqueous solution of O, under room temperature, flood after 12h, dry under 110 ℃ of air atmospheres, then under 300 ℃ of hydrogen atmospheres, reduce 3h, make Pt/CeO
2catalyzer WAO-10.
Feature of the present invention is to utilize TiO
2the hydrothermal stability of nanotube and high-ratio surface characteristic, invented a kind of with noble metal support TiO
2nano tube catalyst is processed the method for high density, high toxicity, organic wastewater with difficult degradation thereby for wet oxidation.
Table 1 different catalysts Pyrogentisinic Acid's waste water and vinyl cyanide trade effluent wet oxidation result
Claims (2)
1. the method containing organism Catalytic Wet Air Oxidation for Wastewater, take containing organic waste water is raw material, in temperature of reaction, it is 120～260 ℃, oxygen pressure is under 1～10MPa condition, make waste water contact 30～120min with catalyzer, organic cod content after reaction in waste water can reduce more than 99%, and wherein catalyzer used comprises following component in parts by weight: the A) titania nanotube of 97～99.8 parts; With the B carrying thereon) 0.2～3 part select at least one in Ru, Pd, Pt, Au or Rh.
2. according to claim 1 containing the method for organism Catalytic Wet Air Oxidation for Wastewater, it is characterized in that in parts by weight, select at least one the consumption in Ru, Pd, Pt, Au or Rh be 0.2～1 part.
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Cited By (10)
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| CN105347573A (en) * | 2015-12-10 | 2016-02-24 | 浙江奇彩环境科技有限公司 | Treatment method for pyridine wastewater |
| CN105597740A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method thereof |
| CN106045000A (en) * | 2016-07-11 | 2016-10-26 | 上海应用技术学院 | Wet-oxidation treatment method of wastewater generated in wood cooking processing process |
| CN106582705A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Heterogeneous wet oxidation catalyst |
| CN107335454A (en) * | 2017-08-28 | 2017-11-10 | 安徽大学 | Load type Pd3Preparation and application of Cl cluster catalyst |
| CN107552046A (en) * | 2016-07-01 | 2018-01-09 | 中国科学院大连化学物理研究所 | Treatment of acrylic acid waste water by catalytic wet oxidation catalyst and its preparation method and application |
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| CN111333169A (en) * | 2020-03-05 | 2020-06-26 | 上海耀嵘环保科技有限公司 | Catalytic wet oxidation treatment method for organic wastewater |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105597740B (en) * | 2014-11-20 | 2018-04-06 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidizing catalyst and preparation method thereof |
| CN105597740A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Heterogeneous catalysis wet oxidation catalyst and preparation method thereof |
| CN106582705A (en) * | 2015-10-14 | 2017-04-26 | 中国石油化工股份有限公司 | Heterogeneous wet oxidation catalyst |
| CN106582705B (en) * | 2015-10-14 | 2019-08-06 | 中国石油化工股份有限公司 | Multiphase wet oxidation catalyst |
| CN105347573A (en) * | 2015-12-10 | 2016-02-24 | 浙江奇彩环境科技有限公司 | Treatment method for pyridine wastewater |
| CN107552046A (en) * | 2016-07-01 | 2018-01-09 | 中国科学院大连化学物理研究所 | Treatment of acrylic acid waste water by catalytic wet oxidation catalyst and its preparation method and application |
| CN106045000A (en) * | 2016-07-11 | 2016-10-26 | 上海应用技术学院 | Wet-oxidation treatment method of wastewater generated in wood cooking processing process |
| CN107335454A (en) * | 2017-08-28 | 2017-11-10 | 安徽大学 | Load type Pd3Preparation and application of Cl cluster catalyst |
| CN107335454B (en) * | 2017-08-28 | 2020-07-24 | 安徽大学 | Load type Pd3Preparation and application of Cl cluster catalyst |
| CN109465008A (en) * | 2018-11-19 | 2019-03-15 | 厦门大学 | A kind of catalytic wet oxidation catalyst and its preparation method and application |
| CN109465008B (en) * | 2018-11-19 | 2020-09-15 | 厦门大学 | A kind of catalytic wet oxidation catalyst and its preparation method and application |
| CN111018089A (en) * | 2019-11-08 | 2020-04-17 | 康纳新型材料(杭州)有限公司 | Catalytic wet oxidation treatment method for propylene oxide wastewater |
| CN111333169A (en) * | 2020-03-05 | 2020-06-26 | 上海耀嵘环保科技有限公司 | Catalytic wet oxidation treatment method for organic wastewater |
| CN113880217A (en) * | 2021-09-30 | 2022-01-04 | 中化环境科技工程有限公司 | Method for treating nitrogenous heterocyclic pesticide wastewater |
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