CN103041810A - Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method - Google Patents
Cellulosic ethanol wastewater treatment catalyst, preparation method thereof and wastewater treatment method Download PDFInfo
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- CN103041810A CN103041810A CN201110313287XA CN201110313287A CN103041810A CN 103041810 A CN103041810 A CN 103041810A CN 201110313287X A CN201110313287X A CN 201110313287XA CN 201110313287 A CN201110313287 A CN 201110313287A CN 103041810 A CN103041810 A CN 103041810A
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Abstract
The invention relates to a cellulosic ethanol wastewater treatment catalyst, a preparation method of the catalyst and a wastewater treatment method. Nanometer TiO2 is used as a carrier in the cellulosic ethanol wastewater treatment catalyst; the cellulosic ethanol wastewater treatment catalyst contains the following active components in parts by mass: 0.35-0.8% of precious metal element and 1-10% of rare-earth metal element, wherein the precious metal element is one or more than one of Pt, Pd, Ru and Rh, the rare-earth metal element used as an assistant is one or more than one of La, Ce, Pr and Nd, and the mass ratio of the rare-earth metal element to the precious metal element is 3-15. The catalyst provided by the invention is used in the cellulosic ethanol wastewater catalytic wet oxidation treatment process and has the advantages of high catalytic activity, low reaction temperature and the like.
Description
Technical field
The present invention relates to a kind of catalyst and preparation method and application of cellulose ethanol wastewater treatment, special cellulose ethanol Catalytic Wet Air Oxidation for Wastewater is processed catalyst and preparation method and application.
Background technology
Cellulose ethanol makes by the preliminary treatment fermenting and producing take fibers such as stalk, crops as raw material.Because the cellulose ethanol production process is complicated, industrial water and displacement are all very high, and the waste water that produces in the process is the organic wastewater of a kind of high concentration, high suspended matter, high content of salt, generally are acid, are the topmost pollution sources of ethanol industry.Therefore, the processing of cellulose ethanol waste water has become a key factor of restriction cellulose ethanol large-scale production.
At present, the processing method of organic wastewater mainly contains bioanalysis, enrichment firing method and wet oxidation process.Cellulose ethanol waste water for high concentration, the ubiquitous problem of bioanalysis is wastewater dilution to a lower concentration just can need to be processed, and activated sludge process is wanted further lignin-sludge, has increased cost investment, and the mushroom in the anaerobic process is difficult to control to condition sensitives such as temperature.
According to one's analysis, produce one ton of ethanol and will produce waste water about 25 tons, the fuel cost that adopts the enrichment firing method to consume is quite surprising, and the waste gas of burning produces secondary pollution, needs further to process.In the technology of processing high concentration hard-degraded organic waste water, comparatively advanced is Wet Oxidation Process, this technical equipment is taken up an area little, secondary pollution is few, but need to operate under higher temperature and pressure, and the researcher was by adding an amount of catalyst in reaction system in the last few years, reduced reaction activity, make the catalysis wet-type oxidation technology condition be tending towards gentle, accelerated reaction speed, reduced cost of investment.The core of this technology is the development of the catalyst of high activity and stability.
CN1292304A disclosed " being used for rare earth based loaded catalyst of wet oxidation and preparation method thereof ", a kind of Ti-Ce-Bi non-precious metal catalyst for CWO and preparation method thereof is provided, to reduce the catalyst cost, but the reaction temperature that this catalyst requires is higher, the acetic acid model reaction after 230 ℃ of next hours the acetic acid clearance reach 96%.
CN1358567A disclosed " a kind of copper-based catalysts of processing industrial wastewater for CWO and preparation method thereof ", a kind of copper-based catalysts that CWO is processed industrial wastewater that is applicable to is provided, oxide by Cu and Zn, Mg or Ni and Cr, Al or Fe and rare earth metal forms, do not contain noble metal, focus on the difficult loss of heavy metal copper in the catalyst, reaction is after 2 hours under for some waste water certain condition, and the loss concentration of Cu is very low.But this catalyst preparation process is complicated, is unfavorable for large-scale industrial application.
CN1498860A disclosed " a kind of CWO is processed photoresists waste water catalyst and application thereof " adopts noble metal and rare-earth metal catalyst with high catalytic activity, and the applied catalysis Wet Oxidation Process is processed photoresists waste water.The bullion content of this catalyst is high, and the catalyst cost is high, and the reaction temperature of choosing and pressure are all higher, 250 ~ 270 ℃ of temperature, and pressure 5.0 ~ 7.0MPa has improved requirement and cost of investment to reaction unit so greatly.
CN1524613A disclosed " high activity wet oxidizing catalyst take material with carbon element as carrier and preparation method thereof ", provide the high bullion content of a kind of activity the low and wet oxidizing catalyst take material with carbon element as carrier, noble metal dosage is 0.25 ~ 0.5wt%, and all the other are carbon.Be 250 ~ 280 ℃ in reaction temperature, during initial pressure 4.3MPa, the COD clearance is up to 91.3%.But reaction temperature and pressure are higher, and material with carbon element catalyst preparation process more complicated, are unfavorable for the industrial applications of catalyst.
CN1669643A disclosed " rare earth composite oxide catalyst in catalytic wet oxidation process and preparation method thereof " provides a kind of ZrO of solid powdery
2And CeO
2Composite oxide catalysts and preparation method thereof, this catalyst has good activity for the little molecule organic wastewater that contains high-concentration hardly-degradable, the digestion of metallic ion amount is very little, but this catalyst is at 230 ℃, when stagnation pressure was 5MPa, the COD clearance reached 87%, and reaction temperature and pressure are higher, cost of investment is large, and powder catalyst is unfavorable for industrial applications.
CN101185887A disclosed " Catalysts and its preparation method that is used for wet-type oxidation technology " proposes a kind of γ-Al
2O
3The supporting wet oxidizing catalyst of supported rare earth metal oxide and transition metal greatly reduces the catalyst cost.This catalyst Pyrogentisinic Acid waste water has good treatment effect, but cellulose ethanol waste water is not had catalytic activity.
CN1672786A disclosed " RE CeO 2 supporting wet oxidizing catalyst and preparation method thereof " proposes a kind of MO that the organic matter such as difficult degradation organic acid is active and stability is high that processes
x/ CeO
2Catalysts and its preparation method, this catalyst can reduce the wet oxidation reaction condition, improves conversion rate.But its noble-metal-supported amount is 1 ~ 3wt%, is difficult to reduce the catalyst cost.
CN102039128A disclosed " waste water wet oxidation process Catalysts and its preparation method ", biological inhibition when mainly solving sulfur-containing waste water and processing, the COD clearance is not high and the problem of complex process or cyanide wastewater exist when processing can not process simultaneously the problem of other organic pollution and secondary pollution in the waste water.By adopting a kind of waste water wet oxidation to process catalyst, comprise that in parts by weight 90～99.9 parts are selected from TiO
2, Al
2O
3, SiO
2Or ZrO
2In at least a oxide carrier; With carry thereon 0.1～10 part and be selected from least a metal among Pt, Pd, Ru, Ir or the Rh or oxide and 0.01～5 part of technical scheme that is selected from least a oxide in Bi, Ba, Mg, B, V, Mo or the rare earth and solved preferably this problem, can be used in the industrial treatment of industrial organic waste water.The bullion content of this catalyst is high, and the catalyst cost is high, and unsatisfactory to the treatment effect of cellulose ethanol production wastewater.
CN1084496 disclosed " the trade effluent wet oxidation that contains high-enriched organics and ammonia purifies ", it is to be supported in TIO by noble metal component (Pt, Pd, Ru, Ir, one of Rh) and rare earth element that catalyst is provided
2Upper composition, the present invention adopts the technology of preparing of double activated component total immersion stain or minute dipping.The catalyst of making is higher than single noble metal catalyst oxidation activity, and bullion content low (0.3～1% percentage by weight) can be managed air speed at (2.0 o'clock at higher position
-1) the lower use, the clearance of CODcr is reached more than 98.5%, NH
3-N clearance reaches more than 99.6%, therefore can improve wastewater purification efficiency and reduce the purification expense.But the treatment effect when this catalyst is used the cellulose ethanol wastewater treatment is unsatisfactory, illustrates that its catalyst forms and be unwell to the processing cellulose ethanol production wastewater.
Cellulose ethanol production wastewater has complicated components, solid solution object height, salt content high, when using existing wet oxidizing catalyst, perhaps effect is unsatisfactory, and perhaps reaction condition is comparatively harsh, perhaps need use the higher noble metal catalyst of bullion content, cost improves.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of cellulose ethanol wastewater treatment catalyst and preparation method and application, it is low that catalyst of the present invention has bullion content, and the cellulose ethanol purification efficiency is high, the catalyst low cost and other advantages.
Cellulose ethanol wastewater treatment catalyst of the present invention, take nano titanium oxide as carrier, the catalyst activity component is one or more among precious metal element Pt, Pd, Ru, the Rh, auxiliary agent is one or more among rare-earth metals La, Ce, Pr, the Nd, each component is take the mass fraction of element as precious metal element 0.35% ~ 0.8%, thulium is 1% ~ 10%, and the mass ratio of thulium and precious metal element is 3～15.Best group becomes: precious metal element is 0.5% ~ 0.65%, and thulium is 6% ~ 8%, and the mass ratio of thulium and precious metal element is 4～10.
In the cellulose ethanol wastewater treatment catalyst of the present invention, nano titanium oxide is anatase structured, and average particulate diameter is 10～80nm, can use the commercial goods, or by the preparation of this area conventional method.
The preparation method of cellulose ethanol wastewater treatment catalyst of the present invention comprises: be carrier with nanometer titanium dioxide forming, then adopt infusion process carried noble metal element and thulium.
The processing method of cellulose ethanol production wastewater, adopt the CWO method, use cellulose ethanol wastewater treatment catalyst of the present invention, reaction temperature is 150 ~ 260 ℃, and the reaction gross pressure is 0.3 ~ 6.0MPa, mixing speed 0 ~ 300r/min, reaction time is 0.5 ~ 3h, take air or oxygen-enriched air as oxide isolation, wherein the introducing amount of oxygen is 1～3 times of the required theoretical requirement of waste water complete oxidation, is preferably 1.1～1.8 times.Preferred operating condition is: temperature 180-200 ℃, and pressure 1.5 ~ 3.5MPa, reaction time 1 ~ 2h.Can adopt the continuous operation type reactor, also can adopt intermittently operated formula reactor.When adopting the continuous operation type reactor, fixed bed reactors can be adopted, also fluidized-bed reactor can be adopted.When adopting intermittently operated formula reactor, the mass volume ratio of catalyst and organic wastewater is 1 ~ 10 g catalyst/L waste water.
Catalyst of the present invention adopts suitable carrier, uses a small amount of noble metal active component, and with the rare earth element of relatively large ratio, this catalyst has very high purified treatment performance to cellulose ethanol production wastewater, reduces simultaneously the catalyst cost of knowing clearly.Specifically, catalyst of the present invention and preparation method and application's method have the following advantages:
1, in the cellulose ethanol Catalytic Wet Air Oxidation for Wastewater technique, adopt the catalyst of the present invention can decrease reaction temperature and pressure, fast reaction speed reduces and processes energy consumption, reduces equipment investment;
2, owing to adopt nanoscale TiO
2Raw material is made carrier material, cooperate simultaneously suitable noble metal active component and the thulium auxiliary agent of higher proportion, in the lower situation of noble metal active constituent content, have higher catalytic activity, greatly reduce the consumption of noble metal, reduced the catalyst cost;
3, catalyst of the present invention does not in use have efflorescence, argillization phenomenon, and reactor water outlet ICP-MS analyzes measurement result and shows that the stripping quantity of metal ion is very little, and catalyst has good stability;
4, Catalyst Production of the present invention is simple for process, and equipment investment cost is low, can adopt the industrial continuous fixed-bed reactor of generally using, and has wide practical use.
The specific embodiment
The concrete preparation process of cellulose ethanol wet oxidation waste water catalyst for catalytic oxidation of the present invention is as follows:
1, with Nano titanium dioxide Material Addition binding agent, peptizing agent, auxiliary agent and water, through extrusion molding on the screw rod banded extruder after mixing, mediating, dry, roasting obtains catalyst carrier;
2, with equi-volume impregnating with TiO
2Carrier impregnation is in the mixed solution that contains thulium compound and precious metal element chemical combination compound, and dip time is 0.1 ~ 1h, then obtains final catalyst through super-dry and roasting.
3, in the above-mentioned catalyst preparation process, the drying of step (1) is at 60 ~ 120 ℃ of drying 6 ~ 12h, and roasting is at 300 ~ 600 ℃ of roasting 5 ~ 8h.Binding agent wherein is generally one or more in boehmite, silica, natural clay, paraffin, starch, the polyvinyl alcohol etc., and consumption of binder is generally 7% ~ 35% of Nano titanium dioxide quality of materials; Peptizing agent is generally one or more in nitric acid, hydrochloric acid, formic acid, the acetic acid, and the peptizing agent consumption is generally 1% ~ 10% of Nano titanium dioxide quality of materials; Auxiliary agent is generally any one or more than one combination in the polybasic carboxylic acids such as oxalic acid, tartaric acid, citric acid, maleic acid and sesbania powder and the top polybasic carboxylic acid of mentioning, and auxiliary dosage is generally 2% ~ 15% of Nano titanium dioxide quality of materials; Water consumption is generally 35% ~ 55% of Nano titanium dioxide quality of materials.
In the above-mentioned catalyst preparation process, the drying of step (2) is at 60 ~ 120 ℃ of drying 6 ~ 12h, and roasting is at 300 ~ 600 ℃ of lower roasting 5 ~ 8h.
Give further instruction below by specific embodiment to technology of the present invention, but catalyst of the present invention is not limited to embodiment, percentage wherein is mass fraction.Utilizing ICP-MS that the ion stripping is carried out in water outlet measures.
(1) preparation of catalyst
Embodiment 1(catalyst carrier of the present invention and preparation)
The preparation of catalyst carrier TOS-1: with 40g nano titanium oxide (average grain diameter 30nm) and boehmite 12.5g, 65% nitric acid 2.5g, distilled water 25g, sesbania powder 1.5g mediates, and carries out extruded moulding at double screw banded extruder and processes, shaping carrier was dried in the shade in air 24 hours, 120 ℃ of lower oven dry 12 hours again 500 ℃ of roastings 12 hours, make cylindric TiO
2Carrier TOS-1.
Embodiment 2(reference catalyst carrier and preparation)
The preparation of catalyst carrier TOS-2: with 40g non-nano titanium dioxide (conventional titanic oxide material, average grain diameter is about 450nm) and boehmite 12.5g, 65% nitric acid 2.5g, distilled water 25g, sesbania powder 1.5g, mediate, carry out extruded moulding at double screw banded extruder and process, shaping carrier was dried in the shade in air 24 hours, 120 ℃ of lower oven dry 12 hours, 500 ℃ of roastings 12 hours, make cylindric TiO again
2Carrier TOS-2.
Embodiment 3(reference catalyst and preparation)
With equi-volume impregnating with the TOS-2 carrier impregnation in the mixed aqueous solution that cerous nitrate and chloroplatinic acid are made into, loading is Ce4%, Pt0.6%, dip time is 0.1h, in the air of certain humidity, dried in the shade 20 hours afterwards, then 120 ℃ of oven dry 12 hours in the baking oven of air atmosphere place Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere at last, obtain the catalyst A-1 for CWO cellulose ethanol waste water.With identical method, take TOS-1 as carrier, preparation Ce1%, the catalyst A of Pt2%-2.
Embodiment 4(catalyst of the present invention and preparation)
Take TOS-1 as carrier, additive method obtains catalyst B with embodiment 3.
Embodiment 5(catalyst of the present invention and preparation)
With equi-volume impregnating with the TOS-1 carrier impregnation in the mixed aqueous solution that lanthanum nitrate and ruthenic chloride are made into, loading is La5%, Ru0.8%, dip time is 0.2h, in the air of certain humidity, dried in the shade 20 hours afterwards, then 120 ℃ of oven dry 12 hours in the baking oven of air atmosphere place Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere at last, obtain the catalyst C for CWO cellulose ethanol waste water.
Embodiment 6(catalyst of the present invention and preparation)
With equi-volume impregnating with the TOS-1 carrier impregnation in the mixed aqueous solution that praseodymium nitrate and radium chloride are made into, loading is La4%, Rh0.8%, dip time is 0.2h, in the air of certain humidity, dried in the shade 20 hours afterwards, then 120 ℃ of oven dry 12 hours in the baking oven of air atmosphere place Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere at last, obtain the catalyst D for CWO cellulose ethanol waste water.
(2) test for the CWO of cellulosic ethanol waste liquid
Cellulose ethanol waste water quality: COD is 129000mg/L, total molten solid 96900mg/L[is that water-soluble total solid material comprises salt and dissolved organic matter], total extract 316 mg/L, petroleum-type 0mg/L, vegetable and animals oils 316 mg/L, ammonia nitrogen 38.8mg/L, volatile phenol 600 mg/L, BOD68600mg/L, sulfate radical 9290 mg/L, total salt 9.8%.
Embodiment 7(reactivity worth embodiment)
Investigate different catalysts to the impact of water treatment effect.In the autoclave of 2L, do not add or add catalyst 1g, add again 400ml cellulose ethanol waste liquid, close the autoclave leak test, determine to be heated to 200 ℃ ± 2 ℃ after airtight, fill oxygen to stagnation pressure 3.5MPa, begin to stir, mixing speed 300r/min, take out liquid behind the reaction 1.5h, test COD, detecting catalyst is active.The result is as shown in table 1.
Table 1 catalyst raw material is on the impact of water treatment effect
| Catalyst | Nothing | A-1 | A-2 | B | C | D |
| COD clearance (%) | 26.52 | 57.48 | 90.32 | 95.17 | 94.48 | 94.56 |
Find out from upper table 1, the COD clearance of the wet oxidation of catalyst-free is minimum, only have 26.52%, the A-1 catalyst is because the non-nano raw material that uses, catalytic effect to cellulose ethanol waste water is relatively poor, although and A-2 has used catalyst carrier of the present invention, because cooperating, component is not suitable for, use higher precious metal element also not obtain desirable reactivity worth.And B, C, three kinds of catalyst activities of D are higher, and the COD clearance of cellulose ethanol waste water has all been reached about 95%.
Embodiment 8
Investigate reaction temperature and pressure to the impact of water treatment effect.In the autoclave of 2L, add catalyst B 1g, add again 400ml cellulose ethanol waste liquid, close the autoclave leak test, determine to be heated to uniform temperature after airtight, fill oxygen to certain pressure, begin to stir mixing speed 300r/min, take out liquid behind the reaction 1.5h, test COD, detecting catalyst is active.The result is as shown in table 2.
Table 2 reaction temperature is on the impact of water treatment effect
| Reaction temperature (℃) | 150 | 180 | 200 | 220 |
| Reaction gross pressure (MPa) | 2.1 | 2.9 | 3.5 | 4.2 |
| COD clearance (%) | 80.50 | 89.63 | 94.17 | 95.36 |
Found out that by table 2 increase with temperature, pressure, the COD clearance increases gradually, what still then increase more than 200 ℃ is not obvious.
In like manner, utilize above-mentioned other noble metals and rare earth metal salt solutions to carry out load, can prepare equally the CWO catalyst for cellulose ethanol waste water, realize the present invention.
Can be learnt that by above embodiment the catalyst that the present invention develops has higher catalytic activity, and bullion content is low, the interpolation of rare earth element has increased the stable and active of catalyst, and further reduces cost.The Catalyst Production of the present invention's development is simple in addition, and equipment investment is low, and preferably prospects for commercial application is arranged.
Claims (10)
1. cellulose ethanol wastewater treatment catalyst, it is characterized in that: the cellulose ethanol wastewater treatment catalyst is take nano titanium oxide as carrier, the catalyst activity component is one or more among precious metal element Pt, Pd, Ru, the Rh, auxiliary agent is one or more among rare-earth metals La, Ce, Pr, the Nd, each component is take the mass fraction of element as precious metal element 0.35% ~ 0.8%, thulium is 1% ~ 10%, and the mass ratio of thulium and precious metal element is 3～15.
2. according to catalyst claimed in claim 1, it is characterized in that each component take the mass fraction of element as: precious metal element is as 0.5% ~ 0.65%, and thulium is 6% ~ 8%, and the mass ratio of thulium and precious metal element is 4～10.
3. according to catalyst claimed in claim 1, it is characterized in that: nano titanium oxide is anatase structured, and average particulate diameter is 10～80nm.
4. the processing method of a cellulose ethanol production wastewater, adopt the CWO method, it is characterized in that right to use requires the described catalyst of 1 to 3 arbitrary claim, reaction temperature is 150 ~ 260 ℃, the reaction gross pressure is 0.3 ~ 6.0MPa, reaction time is 0.5 ~ 3h, and take air or oxygen-enriched air as oxide isolation, wherein the introducing amount of oxygen is 1～3 times of the required theoretical requirement of waste water complete oxidation.
5. in accordance with the method for claim 4, it is characterized in that: reaction temperature is 180-200 ℃, and the reaction gross pressure is 1.5 ~ 3.5MPa, and the reaction time is 1 ~ 2h, and the introducing amount of oxygen is 1.1～1.8 times of the required theoretical requirement of waste water complete oxidation.
6. in accordance with the method for claim 4, it is characterized in that: cellulose ethanol production wastewater is processed and is adopted the continuous operation type reactor, perhaps adopts intermittently operated formula reactor.
7. the preparation method of the described catalyst of claim 1 is characterized in that: be carrier with nanometer titanium dioxide forming, then adopt infusion process carried noble metal element and thulium.
8. in accordance with the method for claim 7, it is characterized in that comprising the steps: (1) with Nano titanium dioxide Material Addition binding agent, peptizing agent, auxiliary agent and water, through moulding after mixing, mediating, dry, roasting obtains catalyst carrier; (2) with equi-volume impregnating with TiO
2Then carrier impregnation obtains final catalyst through super-dry and roasting in the mixed solution that contains thulium compound and precious metal element chemical combination compound.
9. in accordance with the method for claim 8, it is characterized in that: the drying of step (1) is at 60 ~ 120 ℃ of drying 6 ~ 12h, roasting is at 300 ~ 600 ℃ of roasting 5 ~ 8h, binding agent wherein is among a kind of or several in boehmite, silica, natural clay, paraffin, starch, the polyvinyl alcohol, peptizing agent is one or more in nitric acid, hydrochloric acid, formic acid, the acetic acid, and auxiliary agent is to be selected from any one or more than one combination in the polybasic carboxylic acid of oxalic acid, tartaric acid, citric acid, maleic acid or sesbania powder and the above-mentioned polybasic carboxylic acid.
10. in accordance with the method for claim 8, it is characterized in that: the drying of step (2) is that roasting is at 300 ~ 600 ℃ of lower roasting 5 ~ 8h at 60 ~ 120 ℃ of drying 6 ~ 12h.
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Cited By (5)
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|---|---|---|---|---|
| CN104437667A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Ring-gear-shaped heterogeneous catalyzed wet oxidation catalyst as well as preparation method and application of catalyst |
| CN104667920A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Noble metal catalyst for catalytic wet oxidation and preparation method thereof |
| CN104667918A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Noble metal catalyst for catalytic wet oxidation and preparation method thereof |
| CN104667993A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalyst carrier material, catalyst carrier and preparation method thereof |
| CN112573734A (en) * | 2020-12-01 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Environment-friendly discharge method of ammonia nitrogen wastewater in regeneration and recycling process of etching solution |
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| CN102039128A (en) * | 2009-10-13 | 2011-05-04 | 中国石油化工股份有限公司 | Catalytic wet oxidation catalyst for wastewater and preparation method thereof |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104437667A (en) * | 2013-09-24 | 2015-03-25 | 中国石油化工股份有限公司 | Ring-gear-shaped heterogeneous catalyzed wet oxidation catalyst as well as preparation method and application of catalyst |
| CN104667920A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Noble metal catalyst for catalytic wet oxidation and preparation method thereof |
| CN104667918A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Noble metal catalyst for catalytic wet oxidation and preparation method thereof |
| CN104667993A (en) * | 2013-11-29 | 2015-06-03 | 中国石油化工股份有限公司 | Catalyst carrier material, catalyst carrier and preparation method thereof |
| CN104667920B (en) * | 2013-11-29 | 2017-05-17 | 中国石油化工股份有限公司 | Noble metal catalyst for catalytic wet oxidation and preparation method thereof |
| CN112573734A (en) * | 2020-12-01 | 2021-03-30 | 苏州美源达环保科技股份有限公司 | Environment-friendly discharge method of ammonia nitrogen wastewater in regeneration and recycling process of etching solution |
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|---|---|
| CN103041810B (en) | 2014-10-15 |
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