CN103041810B - 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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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
It is raw material that cellulose ethanol be take the fibers such as stalk, crops, by pretreatment fermenting and producing, makes.Because cellulose ethanol production process is complicated, industrial water and displacement are all very high, and the waste water producing in process is the organic wastewater of a kind of high concentration, high suspended matter, high content of salt, are generally 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 combustion method and wet oxidation process.Cellulose ethanol waste water for high concentration, the ubiquitous problem of bioanalysis is wastewater dilution to lower concentration just can need to be processed, and activated sludge process is wanted further lignin-sludge, has increased cost investment, and mushroom in anaerobic process is to condition sensitives such as temperature, be difficult to control.
According to one's analysis, produce one ton of ethanol and will produce the waste water of 25 tons of left and right, the fuel cost that adopts enrichment combustion method to consume is quite surprising, and the waste gas of burning generation secondary pollution, need further process.In processing the technology of 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 under higher temperature and pressure, operate, and researcher by adding appropriate catalyst in reaction system in the last few years, reduced reaction activity, make 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 " 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 catalyst cost, but the reaction temperature that this catalyst requires is higher, acetic acid model reaction after 230 ℃ of next hours 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, not containing noble metal, focusing on heavy metal copper in catalyst is difficult for running off, under for some waste water certain condition, react after 2 hours, 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 catalyst and application thereof for photoresists waste water ", adopts noble metal and the rare-earth metal catalyst with high catalytic activity, and applied catalysis Wet Oxidation Process is processed photoresists waste water.The bullion content of this catalyst is high, and 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 so greatly to the requirement of reaction unit and cost of investment.
CN1524613A disclosed " high activity wet oxidizing catalyst that the material with carbon element of take is carrier and preparation method thereof ", provide the high bullion content of a kind of activity low and take the wet oxidizing catalyst that material with carbon element is carrier, noble metal dosage is 0.25 ~ 0.5wt%, and all the other are carbon.In reaction temperature, be 250 ~ 280 ℃, during initial pressure 4.3MPa, COD clearance is up to 91.3%.But reaction temperature and pressure are higher, and material with carbon element catalyst preparation process more complicated, be 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 containing high-concentration hardly-degradable, digestion of metallic ion amount is very little, but this catalyst is at 230 ℃, when stagnation pressure is 5MPa, COD clearance reaches 87%, and reaction temperature and pressure are higher, cost of investment is large, and powder catalyst is unfavorable for industrial applications.
CN101185887A disclosed " for the Catalysts and its preparation method of 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 catalyst cost.This catalyst Pyrogentisinic Acid waste water has good treatment effect, but cellulose ethanol waste water is not had to catalytic activity.
CN1672786A disclosed " RE CeO 2 supporting wet oxidizing catalyst and preparation method thereof ", proposes a kind of organic matter activity and high MO of stability such as difficult degradation organic acid of processing
x/ CeO
2catalysts and its preparation method, this catalyst can reduce wet oxidation reaction condition, improves conversion rate.But its noble-metal-supported amount is 1 ~ 3wt%, be difficult to reduce 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 problem that can not simultaneously process other organic pollution and secondary pollution in waste water existing when COD clearance is not high and the problem of complex process or cyanide wastewater process.By adopting a kind of waste water wet oxidation to process catalyst, in parts by weight, comprise that 90～99.9 parts are selected from TiO
2, Al
2o
3, SiO
2or ZrO
2in at least one oxide carrier; With carry thereon 0.1～10 part and be selected from least one metal in Pt, Pd, Ru, Ir or Rh or oxide and 0.01～5 part of technical scheme that is selected from least one oxide in Bi, Ba, Mg, B, V, Mo or 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 catalyst cost is high, and unsatisfactory to the treatment effect of cellulose ethanol production wastewater.
CN1084496 disclosed " the trade effluent wet oxidation containing 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 manage air speed at (2.0 o'clock at higher position
-1) lower use, can make the clearance of CODcr reach more than 98.5%, NH
3-N clearance reaches more than 99.6%, therefore can improve wastewater purification efficiency and reduce purification expense.But treatment effect when this catalyst is used cellulose ethanol wastewater treatment is unsatisfactory, illustrates that its catalyst forms and be unwell to processing cellulose ethanol production wastewater.
Cellulose ethanol production wastewater has complicated components, solid solution object height, salt content high, while using existing wet oxidizing catalyst, or effect is unsatisfactory, or reaction condition is comparatively harsh, or need to 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 cellulose ethanol purification efficiency is high, catalyst low cost and other advantages.
Cellulose ethanol wastewater treatment catalyst of the present invention, take nano titanium oxide as carrier, catalyst activity component is one or more in precious metal element Pt, Pd, Ru, Rh, auxiliary agent is one or more in rare-earth metals La, Ce, Pr, Nd, it is precious metal element 0.35% ~ 0.8% that each component be take the mass fraction of element, 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 cellulose ethanol wastewater treatment catalyst of the present invention, nano titanium oxide is anatase structured, and average particulate diameter is 10～80nm, can use 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: by nanometer titanium dioxide forming, be carrier, then adopt infusion process carried noble metal element and thulium.
The processing method of cellulose ethanol production wastewater, adopt CWO method, use cellulose ethanol wastewater treatment catalyst of the present invention, reaction temperature is 150 ~ 260 ℃, and 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, and wherein the introduction volume 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 ℃, pressure 1.5 ~ 3.5MPa, reaction time 1 ~ 2h.Can adopt continuous operation type reactor, also can adopt intermittently operated formula reactor.While adopting continuous operation type reactor, fixed bed reactors can be adopted, also fluidized-bed reactor can be adopted.While 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 the catalyst cost of knowing clearly simultaneously.Specifically, catalyst of the present invention and preparation method and application's method have the following advantages:
1, in cellulose ethanol Catalytic Wet Air Oxidation for Wastewater technique, adopt catalyst of the present invention can significantly reduce reaction temperature and pressure, fast reaction speed, reduces and processes energy consumption, reduces equipment investment;
2, owing to adopting nanoscale TiO
2raw material is made carrier material, the thulium auxiliary agent that simultaneously coordinates suitable noble metal active component and higher proportion, in the situation that noble metal active constituent content is lower, has higher catalytic activity, greatly reduce the consumption of noble metal, reduced catalyst cost;
3, catalyst of the present invention in use, does not have efflorescence, argillization phenomenon, and reactor water outlet ICP-MS analyzes measurement result and shows, 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 generally continuous fixed-bed reactor of application, 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,, by Nano titanium dioxide Material Addition binding agent, peptizing agent, auxiliary agent and water, through extrusion molding on screw rod banded extruder after mixing, mediating, dry, roasting obtains catalyst carrier;
2, with equi-volume impregnating by TiO
2carrier impregnation is in the mixed solution containing thulium compound and precious metal element chemical combination compound, and dip time is 0.1 ~ 1h, then through super-dry and roasting, obtains final catalyst.
3, in above-mentioned catalyst preparation process, being dried as at 60 ~ 120 ℃ of dry 6 ~ 12h of step (1), roasting is at 300 ~ 600 ℃ of roasting 5 ~ 8h.Binding agent is wherein generally one or more in boehmite, silica, natural clay, paraffin, starch, 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, acetic acid, and peptizing agent consumption is generally 1% ~ 10% of Nano titanium dioxide quality of materials; Auxiliary agent be generally the polybasic carboxylic acids such as oxalic acid, tartaric acid, citric acid, maleic acid and sesbania powder and the polybasic carboxylic acid mentioned above in any one or more than one combination, 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 above-mentioned catalyst preparation process, being dried as at 60 ~ 120 ℃ of dry 6 ~ 12h of step (2), roasting is roasting 5 ~ 8h at 300 ~ 600 ℃.
Below by specific embodiment, to technology of the present invention, give further instruction, but catalyst of the present invention is not limited to embodiment, percentage is wherein mass fraction.Utilize ICP-MS to carry out ion stripping mensuration to water outlet.
(1) preparation of catalyst
Embodiment 1(catalyst carrier of the present invention and preparation)
The preparation of catalyst carrier TOS-1: by 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 processing on double screw banded extruder, shaping carrier is dried in the shade in air 24 hours, at 120 ℃, dry 12 hours, then 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: by 40g non-nano titanium dioxide (conventional titanic oxide material, average grain diameter is 450nm left and right) and boehmite 12.5g, 65% nitric acid 2.5g, distilled water 25g, sesbania powder 1.5g, mediate, on double screw banded extruder, carry out extruded moulding processing, shaping carrier is dried in the shade in air 24 hours, dry 12 hours at 120 ℃, 500 ℃ of roastings 12 hours, make cylindric TiO again
2carrier TOS-2.
Embodiment 3(reference catalyst and preparation)
With equi-volume impregnating by 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, dry in the shade 20 hours afterwards, then in the baking oven of air atmosphere 120 ℃ dry 12 hours, be finally placed in Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere, obtain catalyst A-1 for CWO cellulose ethanol waste water.By identical method, take TOS-1 as carrier, preparation Ce1%, catalyst A-2 of Pt2%.
Embodiment 4(catalyst of the present invention and preparation)
Take TOS-1 as carrier, and additive method, with embodiment 3, obtains catalyst B.
Embodiment 5(catalyst of the present invention and preparation)
With equi-volume impregnating by 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, dry in the shade 20 hours afterwards, then in the baking oven of air atmosphere 120 ℃ dry 12 hours, be finally placed in Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere, obtain the catalyst C for CWO cellulose ethanol waste water.
Embodiment 6(catalyst of the present invention and preparation)
With equi-volume impregnating by 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, dry in the shade 20 hours afterwards, then in the baking oven of air atmosphere 120 ℃ dry 12 hours, be finally placed in Muffle furnace 500 ℃ of roastings 3 hours under air atmosphere, obtain the catalyst D for CWO cellulose ethanol waste water.
(2) for the CWO of cellulosic ethanol waste liquid, test
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 the impact of different catalysts on water treatment effect.In the autoclave of 2L, do not add or add catalyst 1g, add again 400ml cellulose ethanol waste liquid, close autoclave leak test, determine after airtight and be heated to 200 ℃ ± 2 ℃, fill oxygen to stagnation pressure 3.5MPa, start to stir, mixing speed 300r/min, after reaction 1.5h, take out liquid, test COD, detecting catalyst is active.Result is as shown in table 1.
The impact of table 1 catalyst raw material on 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 |
From upper table 1, find out, the COD clearance of the wet oxidation of catalyst-free is minimum, only have 26.52%, A-1 catalyst is due to the non-nano raw material using, catalytic effect to cellulose ethanol waste water is poor, although and A-2 has been used catalyst carrier of the present invention, be not suitable for because component coordinates, use higher precious metal element also not obtain desirable reactivity worth.And B, C, tri-kinds of catalyst activities of D are higher, and the COD clearance of cellulose ethanol waste water has all been reached to 95% left and right.
Embodiment 8
Investigate reaction temperature and the impact of pressure on water treatment effect.In the autoclave of 2L, add catalyst B 1g, then add 400ml cellulose ethanol waste liquid, close autoclave leak test, determine after airtight and be heated to uniform temperature, fill oxygen to certain pressure, start to stir mixing speed 300r/min, after reaction 1.5h, take out liquid, test COD, detecting catalyst is active.Result is as shown in table 2.
The impact of table 2 reaction temperature on 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 |
By table 2, found out, with temperature, pressure, increase, COD clearance increases gradually, but 200 ℃ of above increase 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.
By above embodiment, can be learnt, the catalyst that the present invention develops has higher catalytic activity, and bullion content is low, and the interpolation of rare earth element has increased stability and the activity of catalyst, and further reduces costs.The Catalyst Production of the present invention's development is simple in addition, and equipment investment is low, has good prospects for commercial application.
Claims (10)
1. a cellulose ethanol wastewater treatment catalyst, it is characterized in that: it is carrier that cellulose ethanol wastewater treatment catalyst be take the nano titanium oxide that average particulate diameter is 10～80nm, catalyst activity component is one or more in precious metal element Pt, Pd, Ru, Rh, auxiliary agent is one or more in rare-earth metals La, Ce, Pr, Nd, it is precious metal element 0.35%～0.8% that each component be take the mass fraction of element, 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 element mass fraction as: 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.
3. according to catalyst claimed in claim 1, it is characterized in that: nano titanium oxide is anatase structured.
4. the processing method of a cellulose ethanol production wastewater, adopt CWO method, it is characterized in that right to use requires the catalyst described in 1 to 3 arbitrary claim, reaction temperature is 150～260 ℃, reaction gross pressure is 0.3～6.0MPa, reaction time is 0.5～3h, take air or oxygen-enriched air as oxide isolation, and wherein the introduction volume 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 ℃, reaction gross pressure is 1.5～3.5MPa, and the reaction time is 1～2h, and the introduction volume 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 adopted continuous operation type reactor, or adopt intermittently operated formula reactor.
7. the preparation method of catalyst described in claim 1, is characterized in that: by nanometer titanium dioxide forming, be carrier, 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: that (1) is by 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 by TiO
2carrier impregnation, in the mixed solution containing thulium compound and precious metal element chemical combination compound, then obtains final catalyst through super-dry and roasting.
9. in accordance with the method for claim 8, it is characterized in that: being dried as at 60～120 ℃ of dry 6～12h of step (1), roasting is at 300～600 ℃ of roasting 5～8h, binding agent is wherein in a kind of or several in boehmite, silica, natural clay, paraffin, starch, polyvinyl alcohol, peptizing agent is one or more in nitric acid, hydrochloric acid, formic acid, 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 above-mentioned polybasic carboxylic acid.
10. in accordance with the method for claim 8, it is characterized in that: being dried as at 60～120 ℃ of dry 6～12h of step (2), roasting is roasting 5～8h at 300～600 ℃.
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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 |
| CN104667993B (en) * | 2013-11-29 | 2017-06-20 | 中国石油化工股份有限公司 | catalyst carrier material, catalyst carrier and preparation method thereof |
| CN104667918B (en) * | 2013-11-29 | 2017-08-22 | 中国石油化工股份有限公司 | Noble metal catalyst for CWO 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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| 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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| CN1084496A (en) * | 1992-09-22 | 1994-03-30 | 中国科学院大连化学物理研究所 | Contain high-enriched organics and ammonia industrial sewage wet oxidation cleaning catalyst |
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