CN1166573C - Non-noble-metal catalyst for treating industrial sewage and its preparing process - Google Patents
Non-noble-metal catalyst for treating industrial sewage and its preparing process Download PDFInfo
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- CN1166573C CN1166573C CNB011036893A CN01103689A CN1166573C CN 1166573 C CN1166573 C CN 1166573C CN B011036893 A CNB011036893 A CN B011036893A CN 01103689 A CN01103689 A CN 01103689A CN 1166573 C CN1166573 C CN 1166573C
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Abstract
The present invention relates to a non noble metal catalyst for processing industrial waste water by wet-type catalytic oxidation, which has main components of copper, aluminium, zinc, manganese, chromium and rare earth metal oxides. The weight percentage of the components according to oxide content meets the following requirements: 30 to 50% of CuO or MnO, 30 to 50% of Zno or Cr2O3, 10 to 30% of Al2O3 and 2 to 10% of rare earth oxide. Salt containing various kinds of metal is used as a raw material for preparing the non noble metal catalyst by a coprecipitation method. The non noble metal catalyst has higher catalysis efficiency and stability, and various metal components are not easy to run off. Thus, toxic industrial waste water or the industrial waste water with difficultly oxidized pollutants containing phenol, surface active agents, etc. can be effectively processed.
Description
Technical field
The present invention relates to a kind of non-precious metal catalyst and method for making thereof that catalytic wet oxidation is handled trade effluent that be used for.Specifically having provided a kind of main component is the catalyzer of the oxide compound of metal oxides such as copper, aluminium, zinc, manganese, chromium and a part of rare earth metal.The present invention also provides described Preparation of catalysts method, and in certain embodiments as the investigation and the comparison of catalytic efficiency, catalyzer of the present invention has higher catalytic efficiency and stable preferably, and its various metal components are difficult for running off.
Background technology
Catalytic wet oxidation (Catalytic Wet Air Oxidation, be called for short CWAO) promptly utilizes molecular oxygen (air or pure oxygen), at high temperature, high pressure, under the effect of catalyzer, under liquid-phase condition to waste water in organism carry out deep oxidation, change into CO at last
2And water, organonitrogen is transformed into N
2, organophosphorus, organosulfur are transformed into corresponding PO
4 3-And SO
4 2-COD falls
Cr(chemical oxygen demand (COD)) and other content of harmful, thus reach the emission standard of waste water.Catalytic wet oxidation is compared with other sewage disposal technologies, and many advantages are arranged, and is particularly suitable for handling high density, difficult degradation, as coking, printing and dyeing, agricultural chemicals, medicine, petrochemical complex, waste water such as paper making pulp.Though especially concentration is high, but also do not reach burning concentration, perhaps owing to there is secondary pollution to be not suitable for burning.The phenols that perhaps contains bio-toxicity, aldehydes or organic amine when being not suitable for biochemical treatment again, then more can demonstrate its advantage.In recent years, CWAO technical development very fast is subjected to paying attention to widely, and some achievements in research have reached the practical stage.
But be applied in the actually operating of the skilful water treatment of industry at catalytic wet oxidation, because its reaction requirement condition is relatively harsher, higher to equipment requirements, one-time investment is big, has therefore limited its development.The desired condition of catalytic wet oxidation generally is: temperature is 160-280 ℃, pressure 2-9MPa.If the good catalyzer of use properties in the wet oxidation process then can reduce the temperature and pressure of processing, and can obtain better effect.Therefore, develop excellent property, low-cost effective catalyst is that the catalytic wet oxidation technology is introduced to the market, pushes industrialized key to.
Catalyzer on catalytic wet oxidation is used at present can be divided into two kinds, and a kind of is noble metal catalyst, and a kind of is non-precious metal catalyst.The former is the supported catalyst that contains platinum metals, and the latter is the catalyzer that contains different transition metal, and forefathers have done a large amount of research.Jiang Yi etc. have done some researchs [ball border science 11.5 (1989) 34-37] to noble metal catalyst, have developed the catalyzer that supports platinum metals with conductor oxidate, to the COD in the coking chemical waste water
CrAmmonia nitrogen removal efficient is higher, but the catalyzer cost is very high, and industry is beyond affordability.
Non-precious metal catalyst mainly is the transition metal metal, copper for example, iron, the oxide compound of metals such as manganese and composite oxides.For non-precious metal catalyst, not only to investigate its catalytic efficiency, also to investigate its leachability, the serious catalyzer of loss of active component does not have prospects for commercial application.The for example Cu-Mn-Fe-O (USP 4062772) that introduces of United States Patent (USP), and the Cu-Mn-Fe-O (USP 4072608) that has added metal Bi is exactly typical composite oxide catalysts.This catalyzer is used for transaction module compound butanone, has also obtained more satisfactory effect.Janez Levec its article (Applied Catalysis, 63,1990, the catalyzer of the Cu-Al-Zn-O system of L1～L5) mention is handled at a certain temperature, makes crystalline structure change spinel structure into.In the opposition of transaction module compound phenol, be 130 ℃ at reaction conditions, P
O2During=0.3Mpa, find the catalyzer under 870 ℃ of conditions, handle catalytic effect best, but above both does not study the losing issue of activity of such catalysts component, particularly copper.
People such as A.Alejandre research (Applied Catalysis B:Enviromental 16 (1988) 53-6) CuO/r-Al of treatment of different temperature
2O
3As catalyst treatment simulating pollution thing phenol, also obtained certain effect.But in the process of reaction the loss of copper has taken place, concentration reaches 25～70mg/l, and along with the loss of metallic copper in the catalyzer, the catalyst ability also has very big loss.
Guest's moon scape, Zhu Wanpeng etc. mention them with coprecipitation method synthetic Cu-Ce System Catalyst at its article of delivering (environmental science 20 (1999,3) 42-45), have obtained COD in the experiment of handling H-acid waste water
CrRemoval effect more than 90%.The pH value of solution was that the concentration of cupric ion in 6.5 reaction solutions is 20.5mg/L after reaction finished.The pool second place, the article of Jiang Zhanpeng etc. [environmental science 21 (2000,7) 82-85] has carried out seminar to the loss of its catalyzer, analyzed reason, the conclusion that obtains is the loss of cupric ion and the composition of catalyzer, preparation condition, crystal formation, the pH value of reaction solution, reaction conditionss etc. all have relation.But no matter fixed is any condition to its catalyzer, reach pollutent high processing clearance, and its ketone ionic runs off and all can't avoid.Copper from loss concentration all about 10mg/L, though bigger improvement had been arranged than former various catalyzer, but still do not reach the 2mg/L of national secondary discharge standard, along with the loss of metallic copper in the catalyzer, the catalyst ability also has a lot of losses certainly.
Summary of the invention
The purpose of this invention is to provide a kind of non-precious metal catalyst, this catalyzer is used for catalytic wet oxidation processing trade effluent and has higher catalytic efficiency and stable preferably.And the cost that this catalyzer does not contain noble metal catalyst is low, and easy being suitable for of preparation method used in industry.
To achieve these goals, the non-precious metal catalyst that is used to handle trade effluent of the present invention it is characterized in that being made up of the oxide compound of Cu or Mn, Zn or Cr, Al and rare earth metal, and each component with the composition calculated by content of oxides weight percent is:
CuO or MnO:30-50%, ZnO or Cr
2O
3: 30-50%, Al
2O
3: 10-30%, rare-earth oxide: 2-10%.
In above-mentioned non-precious metal catalyst, it is characterized in that each component with the composition calculated by content of oxides weight percent is:
CuO or MnO:35-40%, ZnO or Cr
2O
3: 40-45%, Al
2O
3: 15-25%, rare-earth oxide: 2-6%.
In above-mentioned non-precious metal catalyst, it is characterized in that rare earth metal be among La, Ce, Pr, Nd or the Pm one or more.
In addition, the preparation method who is used to handle the non-precious metal catalyst of trade effluent of the present invention is characterized in that by following step:
(1) utilize coprecipitation method, the solution the soluble salt that contains as the metallic element of catalyst component is mixed with is added drop-wise in the precipitation agent, stirs fast simultaneously, and titration finishes the back and guarantees mother liquor pH＞9; Obtain throw out;
(2) sediment separate out washs with deionized water, obtains not having the precipitation of hydroxide of the various metals of sodium ion;
(3) at high temperature the roasting throw out obtains catalyzer.
In above-mentioned preparation method, it is characterized in that the soluble salt of described metallic element is its nitrate, vitriol, muriate or oxalate.
In above-mentioned preparation method, it is characterized in that (1) used precipitation agent is a sodium carbonate solution, its precipitin reaction was carried out under 50-90 ℃ 4-36 hour.
In above-mentioned preparation method, it is characterized in that sediment separate out carries out with the vacuum filtration method, behind no sodium ion, obtain the exsiccant throw out through deionized water wash in 80-120 ℃ of following drying.
In above-mentioned preparation method, it is characterized in that 400-1000 ℃ of following roasting throw out 2-12 hour.
In above-mentioned preparation method, it is characterized in that 600-800 ℃ of following roasting throw out 6-10 hour.
Specifically, the Preparation of catalysts method is as follows:
The soluble salt of metallic copper, aluminium, zinc, chromium, manganese, for example nitrate, vitriol, hydrochloride or oxalate are mixed with certain density solution, add La
2(NO
3)
3And/or Ce
2(NO
3)
3Deng the salt of rare earth metal, allow its dissolving fully, slowly splash into then and fill excessive 1.0mol/LNa
2CO
3In the beaker of solution, constantly stir simultaneously.And pH and uses heating in water bath greater than 9 when keeping titration to finish.Precipitation and mother liquor at room temperature aging 12～36 hours.Behind aging the end, precipitation is separated with mother liquor, with deionized water repeatedly washing under the condition of vacuum filtration, its sodium ion of flush away with the method for vacuum filtration.Precipitation is extruded into the bar of Φ 3, dries in air, under 110 ℃ temperature dry 2-4 hour again, it was standby to obtain the exsiccant throw out.
The precipitation that composition is mainly various oxyhydroxide is placed on roasting in the muffle furnace, and maturing temperature is 400～1000 ℃, and optimum calcination temperature is 500～900 ℃.Roasting time is 2～12 hours.
The catalytic activity of the catalyzer after the roasting can be tested with catalytic wet oxidation and be estimated, and selects for use to contain exemplary compounds such as phenol, sulphosalicylic acid, Sodium dodecylbenzene sulfonate and sodium laurylsulfonate in the waste water.
Specifically, can in the autoclave of 100ml, add catalyzer, add the certain density model waste water thing solution of preparation in advance again.Close autoclave then, leak test injects the air of certain pressure under the situation of guaranteeing not leak, and begins to stir after being heated to certain temperature, and anti-temperature is 100～260 ℃.Behind the reaction certain hour reaction solution is emitted, test its COD
Cr, according to COD
CrClearance investigate the catalytic activity of catalyzer.To reacted solution copper test ionic content optionally, investigate the loss of catalyzer simultaneously.
Embodiment
Give further instruction below by embodiment to technology of the present invention.
Embodiment 1: Preparation of catalysts (I) is got the Na that 550ml concentration is 1.0mol/L
2CO
3Solution, placing bath temperature is 70 ℃ water bath, heats 20 minutes.Get the Cu (NO of 1.0mol/L
3)
2Solution 100ml, the Zn (NO of 1.0mol/L
3)
2Solution 110ml gets the Al (NO of 0.5mol/L
3)
3Solution 75ml transfers in the beaker, mixes.Take by weighing La
2(NO
3)
3.6H
2O crystal 2 .0g is dissolved in the mixed salts solution.Stir, wait to dissolve complete back slowly being added drop-wise to and fill Na with separating funnel
2CO
3In the beaker of solution, stir fast simultaneously.Titration finishes pH that the back guarantees mother liquor greater than 9, and allows precipitation and the mother liquor diel that wears out together.
Separate precipitation with the vacuum filtration machine aging back with mother liquor, and wash flush away foreign ion four times with deionized water under the condition of vacuum filtration.Precipitation is squeezed the bar of Φ 3, dry in air, under 110 ℃ temperature dry 2 hours again, it was standby to obtain the exsiccant throw out, and composition mainly is oxyhydroxide and a part of combination water of various salt.
The throw out of obtaining roasting in muffle furnace, the maturing temperature of selection are 700 ℃, and the treatment time is 8 hours.The catalysis punishment A that obtains is ground into 60-80 order powder and waits until later catalytic wet oxidation experiment.
Embodiment 2: Preparation of catalysts (II)
Remove and use La
2(NO
3)
36H
2O crystal 1.0g and Ce
2(NO
3)
36H
2O crystal 1.14g replaces La
2(NO
3)
36H
2O crystal 2 .0g is with the Mn (NO of 1.0mol/L
3)
2Solution 100ml replaces the Cu (NO of 1.0mol/L
3)
2Solution 100ml, selecting maturing temperature in muffle furnace is 900 ℃, the treatment time is beyond 6 hours, with embodiment 1 identical preparation catalyst B.
Embodiment 3: Preparation of catalysts (III)
Remove Cr with 1.0mol/L
2O
3Solution 130ml replaces the Zn (NO of 1.0mol/L
3)
2Solution 110ml is with the AlCl of 0.5mol/L
3Solution 50ml replaces the Al (NO of 0.5mol/L
3)
3Beyond the solution 75ml, with embodiment 1 identical preparation catalyzer C.
Embodiment 4: for the catalytic wet oxidation experiment of phenol solution
In the FDX-01 of 100ml type autoclave, add 1 synthetic catalyst A of example 0.8g, add the certain density model compound phenol solution that 40ml prepares in advance again, original solution COD
CrBe 4710.6mg/L.Close autoclave then, leak test, injecting certain total pressure under the situation of guaranteeing not leak is the air of 2.5MPa, promptly oxygen partial pressure is 0.5MPa.Begin to stir after being heated to certain temperature, temperature regulating device is the GDK-4 temperature controller, and alr mode is that the permanent-magnet reciprocating formula stirs.Temperature of reaction is 120-200 ℃.React and after 2 hours reaction solution is emitted, test its COD
Cr, according to COD
CrClearance investigate the catalytic activity of catalyzer.Simultaneously can investigate the loss of catalyzer to reacted solution copper test ionic content optionally.
The warm formula catalytic oxidation treatment of table-1 phenol is 40ml air stagnation pressure 2.5Mpa as a result
| Temperature (℃) | Time (h) | Catalyzer | Stoste pH | Reaction back pH | Stoste COD cr (mg/L) | Reaction back COD cr (mg/L) | COD clearance (%) |
| 120 | 2 | 0.8g | 6.0 | 6.0 | 4710.6 | 3403.7 | 27.7％ |
| 140 | 2 | 0.8g | 6.0 | 6.0 | 4710.6 | 1481.5 | 68.5％ |
| 160 | 2 | 0.8g | 6.0 | 6.0 | 4710.6 | 409.4 | 91.3％ |
| 180 | 2 | 0.8g | 6.0 | 6.0 | 4710.6 | 309.4 | 93.0％ |
Reaction conditions is the same, and the solution of adding is phenol, original solution COD
CrBe 4710.6ml/L, but do not add catalyzer.Temperature of reaction is 120-200 ℃.Experimental result is compared with the result who adds catalyzer.
The warm formula oxide treatment of table-2 phenol is 40ml air stagnation pressure 2.5Mpa as a result
| Temperature (℃) | Time (h) | Catalyzer | Stoste pH | Reaction back pH | Stoste COD cr (mg/L) | Reaction back COD cr (mg/L) | COD clearance (%) |
| 120 | 2 | Do not have | 6.0 | 5.4 | 4710.6 | 4451.1 | 5.5％ |
| 140 | 2 | Do not have | 6.0 | 4.7 | 4710.6 | 3772.5 | 19.9％ |
| 160 | 2 | Do not have | 6.0 | 3.0 | 4710.6 | 1057.9 | 77.5％ |
| 180 | 2 | Do not have | 6.0 | 3.5 | 4710.6 | 379.2 | 92.0％ |
| 200 | 2 | Do not have | 6.0 | 4.0 | 4710.6 | 159.7 | 96.6％ |
Embodiment 5: for the catalyzed oxidation experiment of Sodium dodecylbenzene sulfonate solution
Reaction conditions is with embodiment 4, and the solution that (adding catalyst B 0.8g) adds is Sodium dodecylbenzene sulfonate, original solution COD
CrBe 4368.8mg/L.Temperature of reaction is 180-260 ℃.
The catalytic wet oxidation result 40ml air stagnation pressure 2.5Mpa of table-3 Sodium dodecylbenzene sulfonatees
| Temperature (℃) | Time (h) | Catalyzer | Stoste pH | Reaction back pH | Stoste COD cr (mg/L) | Reaction back COD cr (mg/L) | COD clearance (%) |
| 160 | 2 | 0.8g | 9.3 | 9.3 | 4368.8 | 1189.2 | 72.8％ |
| 180 | 2 | 0.8g | 9.3 | 9.0 | 4368.8 | 1834.1 | 58.0％ |
| 200 | 2 | 0.8g | 9.3 | 9.0 | 4368.8 | 2144.3 | 50.3％ |
| 220 | 2 | 0.8g | 9.3 | 9.0 | 4368.8 | 2085.9 | 52.3％ |
| 240 | 2 | 0.8g | 9.3 | 8.8 | 4368.8 | 1657.0 | 62.1％ |
| 260 | 2 | 0.8g | 9.3 | 8.8 | 4368.8 | 1411.4 | 67.7％ |
Reaction conditions is the same, and the solution that (not adding catalyzer) adds is former COD
CrBe the Sodium dodecylbenzene sulfonate of 4144.3ml/L, experimental result is compared with the result who adds catalyzer.
The warm formula oxide treatment of table-4 Sodium dodecylbenzene sulfonatees is 40ml air stagnation pressure 2.5Mpa as a result
| Temperature (℃) | Time (h) | Catalyzer | Stoste pH | Reaction back pH | Stoste COD cr (mg/L) | Reaction back COD cr (mg/L) | COD clearance (%) |
| 160 | 2 | Do not have | 9.3 | 9.3 | 4144.3 | 4374.0 | 0.91％ |
| 180 | 2 | Do not have | 9.3 | 9.0 | 4144.3 | 3653.3 | 11.8％ |
| 200 | 2 | Do not have | 9.3 | 9.0 | 4144.3 | 3115.5 | 24.8％ |
| 220 | 2 | Do not have | 9.3 | 8.2 | 4144.3 | 2697.2 | 32.8％ |
| 240 | 2 | Do not have | 9.3 | 7.5 | 4144.3 | 2159.3 | 51.1％ |
Comparative Examples 1:
The method synthetic catalyst that is provided according to reference [1].
Get the Na that 550ml concentration is 1.0mol/L
2CO
3Solution.Get the Cu (NO of 1.0mol/L
3)
2Solution 100ml, the Zn (NO of 1.0mol/L
3)
2Solution 110ml gets the Al of 0.5mol/L
2(NO
3)
3Solution 75ml transfers in the beaker, mixes back slowly being added drop-wise to separating funnel and fills Na
2CO
3In the beaker of solution, continue fast simultaneously to stir.Titration finishes pH that the back guarantees mother liquor greater than 9, and allows precipitation and the mother liquor diel that wears out together.
Separate precipitation with the vacuum filtration machine aging back with mother liquor, and wash flush away foreign ion four times with deionized water under the condition of vacuum filtration.Precipitation is squeezed the bar of Φ 3, in air, dries, again 110 " under the temperature of C dry 2 hours, it is standby to obtain the exsiccant throw out, and composition mainly is oxyhydroxide and a part of combination water of various salt.
The throw out of obtaining roasting in muffle furnace, the maturing temperature of selection are that 870 ℃ of treatment times are 8 hours.The catalyzer that obtains consists of Cu-Al-Zn-O, and wherein CuO is 42%, and ZnO is 47%, Al
2O
3Be 10%.The catalyzer that obtains is ground into 60～80 order powder waits until later experiment.
Comparative Examples 2
In the FDX-01 of 100ml type autoclave, add the Embodiment B synthetic catalyst B 0.8g of institute, add the Sodium dodecylbenzene sulfonate that 40ml prepares in advance again, original solution COD
CrBe 4368.8mg/L.Close autoclave then, leak test, injecting certain total pressure under the situation of guaranteeing not leak is the air of 2.5Mpa, promptly oxygen partial pressure is 0.5Mpa.Begin to stir after being heated to certain temperature, temperature regulating device is the GDK-4 temperature controller, and alr mode is that the permanent-magnet reciprocating formula stirs.Temperature of reaction is 200 ℃.React and after 2 hours reaction solution is emitted, test its COD
Cr
Reaction conditions is the same, and the solution of adding is former COD
CrConcentration is the Sodium dodecylbenzene sulfonate of 4144.5mg/L.But the catalyzer that adds is 1 synthetic catalyzer of Comparative Examples 0.8g.
Can see under relatively mild condition by reaction result.200 ℃ of air stagnation pressures of temperature of reaction 2.5Mpa, catalyzer of the present invention has advantages of high catalytic activity to the Sodium dodecylbenzene sulfonate of difficult degradation, its catalytic elimination rate reaches 50.3%, and the catalytic elimination rate of the Catalysts Cu-Al-Zn-O of bibliographical information had only 27.4% in the past.
Table-5 contrast experiments' one data (200 ℃ of air stagnation pressures of temperature of reaction 2.5Mpa)
| Project | Original solution COD cr (mg/L) | Reaction back COD cr (mg/L) | CODcr clearance (%) | Original solution pH | Reaction back pH |
| Catalyst B | 4368.8 | 2144.3 | 50.3％ | 9.3 | 9.0 |
| Cu-Al-Zn-O | 4144.3 | 3009.5 | 27.4％ | 9.3 | 8.5 |
Research and comparison that the stability of 3 pairs of catalyzer of Comparative Examples in reaction is carried out:
Is 200 ℃ at embodiment 3 used catalyzer C in temperature of reaction as table-6, and reaction is two hours under the condition of air stagnation pressure 2.5Mpa, surveys the wherein concentration of cupric ion.Copper ion concentration is below 0.5mg/L.With comparing of former various bibliographical informations, the copper of loss is considerably less.
The experimental result that table-6 cupric ions run off
| Temperature of reaction (℃) | Reaction times (h) | The material of reaction | Stoste pH | Reaction back pH | COD clearance (%) | The concentration of loss copper (mg/L) in the reaction solution |
| 140 | 2.0 | Sodium dodecylbenzene sulfonate | 9.3 | 9.0 | 92.3％ | ＜0.1 |
| 200 | 2.0 | Sodium dodecylbenzene sulfonate | 9.3 | 9.0 | 50.9％ | 0.1 |
| 260 | 2.0 | Sodium dodecylbenzene sulfonate | 9.3 | 8.8 | 67.7％ | 0.3 |
| 160 | 2.0 | Phenol | 6.4 | 6.0 | 91.3％ | ＜0.1 |
Can be learnt by above embodiment and Comparative Examples: catalyzer of the present invention and the former non-precious metal catalyst of reporting comparatively speaking have advantages of high catalytic activity.Particularly lower in temperature, COD when not having the existing of catalyzer
CrUnder the low-down situation of clearance, use the raising COD that catalyzer of the present invention can be by a relatively large margin
CrClearance.The present invention helps reducing catalytic wet oxidation again and reacts needed temperature, and conditions such as pressure help applying of its technology.Catalyzer of the present invention is high catalytic activity effectively, and to the compound of some difficult degradations, effect is more obvious especially, makes the technical finesse of application catalytic wet oxidation contain Stability Analysis of Structures, and the waste water of difficult degradation public property becomes possibility.
In addition, heavy metal is difficult for running off in the catalyzer of the present invention.Be applied in the existing problem of catalytic wet oxidation at non-precious metal catalyst, the loss of catalyst activity component is the major cause that the cheap non-precious metal catalyst of check prince is applied.The catalyzer that the present invention developed still has stability preferably under the High Temperature High Pressure of catalyzed reaction.
Claims (8)
1. non-precious metal catalyst that is used to handle trade effluent it is characterized in that being made up of the oxide compound of Cu or Mn, Zn or Cr, Al and rare earth metal, and each component with the composition calculated by content of oxides weight percent is:
CuO or MnO:30-50%,
ZnO or Cr
2O
3: 30-50%,
Al
2O
3：10-30％，
Rare-earth oxide: 2-10%.
2. non-precious metal catalyst according to claim 1 is characterized in that each component with the composition calculated by content of oxides weight percent is:
CuO or MnO:35-40%,
ZnO or Cr
2O
3: 40-45%,
Al
2O
3：15-25％，
Rare-earth oxide: 2-6%.
3. non-precious metal catalyst according to claim 1 and 2, it is characterized in that rare earth metal be among La, Ce, Pr, Nd or the Pm one or more.
4. preparation method who is used to handle the non-precious metal catalyst of trade effluent is characterized in that by following step:
(1) utilizes coprecipitation method, the solution that the soluble salt that contains as the metallic element of catalyst component is mixed with, be added drop-wise in the precipitation agent, stir fast simultaneously, titration finishes the back and guarantees mother liquor pH＞9, obtain throw out, used precipitation agent is a sodium carbonate solution, and its precipitin reaction was carried out under 50-90 ℃ 4-36 hour;
(2) sediment separate out washs with deionized water, obtains not having the precipitation of hydroxide of the various metals of sodium ion;
(3) at high temperature the roasting throw out obtains catalyzer.
5. preparation method according to claim 4 is characterized in that the soluble salt of described metallic element is its nitrate, vitriol, muriate or oxalate.
6. preparation method according to claim 4 is characterized in that sediment separate out carries out with the vacuum filtration method, behind no sodium ion, obtains exsiccant throw out in 80-120 ℃ of following drying through deionized water wash.
7. preparation method according to claim 4 is characterized in that 400-1000 ℃ of following roasting throw out 2-12 hour.
8. preparation method according to claim 7 is characterized in that 600-800 ℃ of following roasting throw out 6-10 hour.
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|---|---|---|---|
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|---|---|---|---|
| CNB011036893A CN1166573C (en) | 2001-02-09 | 2001-02-09 | Non-noble-metal catalyst for treating industrial sewage and its preparing process |
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