CN102451713B - Catalyst for treating industrial wastewater, and preparation method thereof - Google Patents
Catalyst for treating industrial wastewater, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for treating industrial wastewater. According to the catalyst, active carbon is adopted as a carrier, Cu-Zn-Pt is adopted as an active component, wherein the weight of the active metal component (calculated as the element) is 2-20% of the total weight of the catalyst, the weight of the Cu is 1-15% of the total weight of the catalyst, the weight of the Zn is 0.1-5% of the total weight of the catalyst, and the weight of the Pt is 0.01-1% of the total weight of the catalyst. The preparation method of the catalyst comprises: firstly preparing a high temperature active carbon carrier with a temperature of 350-700 DEG C under the protection of inert gas, then carrying out impregnating or spraying and dipping on the high temperature active carbon carrier by using an impregnating solution containing the active metal component, such that the catalytic active component is rapidly loaded on the active carbon carrier. According to the catalyst prepared by the method of the present invention, the active metal component content is high, the distribution is uniform, the catalyst does not easily loss in the wastewater, and the three metals are adopted as the active component of the catalyst, such that advantages of high catalytic activity, good application effect and simple preparation process are provided.
Description
Technical field
The present invention relates to a kind of Catalysts and its preparation method of processing industrial wastewater, relate to specifically a kind of trimetallic catalyst of processing industrial wastewater and preparation method thereof.
Background technology
Increasingly stringent along with global environmental regulation, the control index request of sewage qualified discharge is more and more higher, under this form, waste water treatment by catalytic oxidation more and more obtains people's attention and employing, as the CWO of high-concentration sewage, catalytic and oxidative electrolysis technology, photochemical catalytic oxidation, advanced oxidation etc.In waste water catalytic oxidation process, the catalyst that preparation has high-activity component, high strength, high stability becomes the key that waste water catalytic oxidation technology is applied undoubtedly.
Waste water catalyst for catalytic oxidation is mainly divided into homogeneous catalyst and heterogeneous solid catalyst two classes.
Homogeneous catalyst mainly comprises producing Fenton reagent, the Fe of oxygen radical
3+, Cu
2+, the metal ion such as cobalt and manganese etc., effect by means of these homogeneous catalysts, organic component in waste water, sulfide, ammonia nitrogen etc. are oxidized into low molecular acid (or low mass molecule alcohol, carbon dioxide etc.), sulfate or thiosulfate, nitrogen etc. by oxide isolations such as air, oxygen, ozone, hydrogen peroxide, make waste water reach the processing intent of decarburization, desulfurization and denitrogenation.Homogeneous oxidation catalyst preparation and use procedure are comparatively simple, generally can directly select the slaines such as iron, copper, cobalt, manganese be made into the aqueous solution or directly put in handled waste water, and in the water outlet after processing, discharge or regenerate after recycle.The oxidation of employing homogeneous catalysis, because metal active constituent can fully dissolve and disperse in waste water, generally can reach comparatively stable water treatment effect, but exist that reagent consumption is large, operating cost is high, the serious problems such as metal loss and secondary pollution, cause its application to be subject to larger restriction.
Heterogeneous solid catalyst is mainly that to take active carbon, molecular sieve, aluminium oxide, titanium dioxide etc. be carrier, with one or more in alkali metal, alkaline-earth metal, transition metal or Pt, Pd noble metal, makees the catalyst that active component forms.Because active carbon wide material sources, specific area are large, organic component and sulfide etc. is had to the higher characteristics such as adsorption capacity, therefore at present for the heterogeneous solid catalyst of wastewater treatment, mostly select active carbon as carrier.And the preparation of the catalyst of corresponding supported active metal is main, adopts dipping or spray method, be about to containing the salt of active metal oxide is water-soluble or organic solvent in, form uniform solution or colloid, absorbent charcoal carrier after carrying out washing treatment is immersed or directly on absorbent charcoal carrier, is sprayed, then make catalyst prod through standing, dry, high temperature sintering, cooling, washing, the process such as dry.
And some high concentration hard-degraded organic waste water concentration for burning is too low, but exceeded the concentration range of biochemical treatment; For this kind of waste water, wet air oxidation is a kind of very attractive treatment technology.Wet air oxidation can be defined as under HTHP with organic matter or inorganic matter in air or oxygen aqueous oxidizing.Typical wet oxidation condition is 180 ℃～315 ℃ of temperature, pressure 2MPa～15MPa; Time of staying l5min～120min; COD (COD) clearance is approximately 75%～90%; Insoluble organic matter is converted to little molecule dissolved organic matter, and then further oxidation, finally changes into carbon dioxide and water, and do not have NO
x, SO
2, HCl ， bioxin, the discharge of furans and dust.But due to the severe reaction conditions of wet air oxidation, corresponding cost of investment and operating cost are relatively high, therefore finding suitable catalyst becomes the key of CWO technology to reduce reaction condition.
The noble metal catalyst supporting is at present administered in sewage and is had successful application in catalytic wet oxidation technique, but such catalyst used carrier overwhelming majority is TiO
2.Also having some is the catalyst for catalytic wet oxidation about zirconium compounds.
US2003166987 is with Pt, Pd, and Rh, Ru, Re, Os noble metal is as active component, take Ce-Zr-M as carrier (M is Ti, V, Fe, Co, Cr, Ni, Au, a kind of and several in Pt and Cu), and the content of Zr in carrier is 0～20%.CN1919452A, CN1876232A propose respectively a kind of carried by active carbon iron oxide and copper oxide catalyst, and its preparation process is the sodium hydroxide solution Immesion active carbon 24h with 10%; Filtration, deionized water washing are to neutral; Hydrochloric acid solution Immesion active carbon 24h with 1: 1; Filtration, deionized water washing are to neutral; Dry at 110～120 ℃; Preparation 1.0%～25%FeCl
3or 0.2～0.3mol/L Cu (NO
3)
2solution, adds above-mentioned active carbon to stir 1h; Soak 24h; The Fe of activated carbon surface is removed in deionized water washing
3+; Dry 6h at 110～120 ℃; At 260～270 ℃, activate 12h.With this catalyst, process at normal temperatures coking phenol containing waste water, can obtain 94% COD removal effect.
US6623648 and CN1370618A propose a kind of oxidation catalyst and preparation method thereof, with tin compound, activated carbon surface is improved, adopt again infusion process by transition metal, alkali metal, alkaline-earth metal, if Rn, Al, Sn, Pb, Se, Zn, Fe, Cr and Pd even load are to absorbent charcoal carrier, after the processing such as drying, sintering, make oxidation catalyst.By this oxidation catalyst Treatment of Cyanide-containing Wastewater under ozone condition, can obtain good COD and chromaticity removing effect.
Yet by above catalyst soakage or the analysis that sprays preparation method are shown, this conventional method for preparing catalyst exists low, uniformly dispersed poor, the problem such as active metal easily runs off, raw materials utilization rate is low, preparation process is loaded down with trivial details and the time is long of activity component load quantity.And due to the inequality of absorbent charcoal carrier pore-size distribution, determined that the dispersiveness of institute's supported active metal has inequality; For removing the impurity in absorbent charcoal carrier micropore, carry out pickling, alkali cleaning and deionized water washing repeatedly in addition, make that the catalyst preparation process time is long, expense is high, also have the series of problems such as follow-up environmental protection etc.And adopt at present base metal as the catalyst of active component, and the active problem on the low side of ubiquity, adopts noble metal as active component, although solved this problem, the cost of its catalyst will improve greatly.
Summary of the invention
For the deficiencies in the prior art, the object of the invention is to provide a kind of catalytic activity high, a kind of trimetallic catalyst of processing industrial wastewater that effect is good and preparation method thereof.
The present invention processes the catalyst of industrial wastewater, take active carbon as carrier, take Cu-Zn-Pt as active component, active metal component (in element) accounts for 2%～20% of total catalyst weight, wherein Cu accounts for 1%～15% of total catalyst weight, Zn accounts for 0.1%～5% of total catalyst weight, and Pt accounts for 0.01%～1% of total catalyst weight.
The present invention also provides the preparation method of above-mentioned wastewater treatment catalyst, comprises the steps:
(1) maceration extract that preparation contains active metal component;
(2) under inert gas shielding, preparation temperature is 350～700 ℃, is preferably the high temperature active charcoal carrier of 400～500 ℃;
(3) with the maceration extract that contains active metal component prepared by step (1), spray or the high temperature active charcoal carrier of impregnation steps (2), active metal component loads on the absorbent charcoal carrier of step (2);
(4) active carbon after supported active metal is made catalyst finished product through cooling, wash and being dried.
The maceration extract of the active metal component described in step (1) is selected from the solution containing mantoquita, zinc salt and platiniferous, and wherein mantoquita comprises all soluble copper salts such as copper chloride, copper nitrate, copper sulphate, is preferably copper nitrate; Zn salt comprises all soluble zinc salts such as zinc chloride, zinc nitrate, zinc sulfate; Be preferably zinc nitrate; Pt is chloroplatinic acid.Maceration extract is the solution that simultaneously contains three kinds of active metal components, or preparation contains Cu salt and Zn salt respectively hybrid infusion solution and platinum acid chloride solution, or three kinds of maceration extracts that contain respectively different activities metal component of configuration.Can adopt and flood three kinds of active components simultaneously, also can step impregnation active component.Also can be first impregnating metal copper and metallic zinc simultaneously, then impregnating metal platinum.While repeatedly flooding, before each dipping, active carbon being warming up to 350～700 ℃, can be also active carbon to be risen to high temperature while flooding first, and follow-up dipping is normal temperature dipping.
Active carbon described in step (2) can be selected conventional granular activated carbon commodity, as all kinds of wood activated charcoals, active fruit shell carbon, active carbon from coal etc.; Also can select with wooden material, mineral material, plastics and discarded object, as the various activated carbon products through traditional preparation method's acquisition such as timber, wood chip, charcoal, coconut husk, fruit stone, shell, coal, gangue, petroleum coke, asphalt, polyvinyl chloride, polypropylene, organic resin, damaged tire, excess sludge.The preparation of wherein said high temperature active charcoal carrier can be carried out by the temperature-fall period after the activation that adopts conventional method for preparation of active carbon; Also can, under the protection of inert gas, above-mentioned conventional active carbon commodity be carried out carrying out under secondary high-temperature heat treated.
Impregnation method described in step (3) can be to spray or conventional dipping.The weight concentration of maceration extract while spraying (take active metal salt quality) is 1%～30%, is preferably 5%～25%; During conventional dipping, the concentration of maceration extract is 5%～50%.Be preferably 8%～40%.The dipping of active metal component maceration extract on high temperature active charcoal carrier or to spray the processing time be 10～300 seconds, is preferably 30～150 seconds.
Cooling described in step (4), washing and drying process all can adopt ordinary skill in the art means.The object of washing is to utilize deionized water to wash out in active carbon carrier hole and surperficial impurity, and described baking temperature is 60～130 ℃, and be 0.5～6h drying time.
The principle that method for preparing catalyst of the present invention adopts is: under more than 350 ℃ high temperature, the surface pore structure of active carbon is almost in uniform open configuration, can pass larger-diameter metal ion or the hydrated ion with catalytic activity, and make on metal ion or the hydrated ion quick adsorption seeing through and the endoporus that is deposited on active carbon, mesopore and large hole surface, to reach high-load, high speed load, increase adhesion, to reduce the object running off.Simultaneous high temperature, the impurity in active carbon hole is effectively removed, and has exempted the washing process of numerous and diverse pickling, alkali cleaning and deionized water.And adopt three kinds of metals as the active component of catalyst, synergy due to three kinds of active components, use a small amount of noble metal just can make catalyst there is the high activity that is equal to precious metal oxidation catalyst, and added metallic zinc, can make catalyst there is the highly active while, can improve the service life of catalyst again, catalyst of the present invention is used in while processing waste water, can react at normal temperatures.
The specific embodiment
Below in conjunction with specific embodiment, further illustrate the inventive method and effect.
Embodiment 1
Take 8gCu (NO
3)
2, 3gZn (NO
3)
2be dissolved in the deionized water of 500mL with 1.0g platinum acid chloride solution (Pt content 10%, lower same), after fully stirring, form solution as catalyst impregnating solution A, be placed in one with the closed container of nitrogen protection.
Selecting commercially available coconut husk granular activated carbon is catalyst carrier, and the main character of active carbon is: moisture content 5.8%, specific area 928m
2/ g, average pore size 0.88nm, iodine sorption value 700mg/g, grain graininess 3mm.Take this kind of active carbon 50g and be placed in tubular type electric heater, under nitrogen protection, with the programming rate of 15～20 ℃/min, be heated to 420 ℃.Active carbon is moved to rapidly in the closed container that catalyst impregnating solution A is housed to standing 3min.Along with the rapid decline of temperature, the complete load of active component in catalyst impregnating solution A and depositing on absorbent charcoal carrier.After being cooled to room temperature, take out active carbon, then with distilled water washing three times, place in baking oven and after 100～110 ℃ of dry 1h, make catalyst finished product.Catalyst is numbered E-1, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Embodiment 2
The preparation process of catalyst is with embodiment 1, and difference is 10gCu (Cl)
2, 1g ZnSO
4be dissolved in the deionized water of 200mL with 0.6g chloroplatinic acid, heating activated carbon temperature is 450 ℃.Catalyst is numbered E-2, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Embodiment 3
The preparation process of catalyst is with embodiment 1, and difference is 16CuSO
4, 1.5g Zn (NO
3)
2be dissolved in the deionized water of 200mL with 0.6g chloroplatinic acid, heating activated carbon temperature is 380 ℃.Catalyst is numbered E-3, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Embodiment 4
Take 10gCu (NO
3)
2with 3g Zn (NO
3)
2be dissolved in the deionized water of 150mL, after fully stirring, form solution as catalyst impregnating solution B1, be placed in one with the closed container of nitrogen protection.
Take in the deionized water that 0.8g chloroplatinic acid is dissolved in 150mL, after fully stirring, form solution as catalyst impregnating solution B2, be placed in one with the closed container of nitrogen protection.
Selecting commercially available apricot shell granular active carbon is catalyst carrier, and the main character of active carbon is: moisture content 6.2%, specific area 780m
2/ g, average pore size 10A, iodine sorption value 690mg/g, grain graininess 3mm.Take this kind of active carbon 15g and be placed in tubular type electric heater, under nitrogen protection, with the programming rate of 15～20 ℃/min, be heated to 550 ℃.Active carbon is moved to rapidly in the closed container that catalyst impregnating solution B1 is housed to standing 2.5min.Along with the rapid decline of temperature, the complete load of the copper nitrate in catalyst impregnating solution B1 and zinc nitrate and depositing on absorbent charcoal carrier.After being cooled to room temperature, take out active carbon, then repeat aforesaid operations process, by the complete load of the chloroplatinic acid in maceration extract B2 with deposit on absorbent charcoal carrier, then with distilled water washing three times, place in baking oven and after 100～110 ℃ of dry 1h, make catalyst finished product.Catalyst is numbered E-4, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Embodiment 5
Take 12g Cu (NO
3)
2be dissolved in the deionized water of 100mL, after fully stirring, form solution as catalyst impregnating solution B1, be placed in one with the closed container of nitrogen protection.
Take 3g 3g Zn (Cl)
2be dissolved in the deionized water of 100mL, after fully stirring, form solution as catalyst impregnating solution B2, be placed in one with the closed container of nitrogen protection.
Take in the deionized water that 1.2g chloroplatinic acid is dissolved in 150mL, after fully stirring, form solution as catalyst impregnating solution B3, be placed in one with the closed container of nitrogen protection.
Selecting commercially available apricot shell granular active carbon is catalyst carrier, and the main character of active carbon is: moisture content 6.2%, specific area 780m
2/ g, average pore size 10A, iodine sorption value 690mg/g, grain graininess 3mm.Take this kind of active carbon 15g and be placed in tubular type electric heater, under nitrogen protection, with the programming rate of 15～20 ℃/min, be heated to 550 ℃.Active carbon is moved to rapidly in the closed container that catalyst impregnating solution B1 is housed to standing 2.5min.Along with the rapid decline of temperature, copper nitrate in catalyst impregnating solution B1 is by load completely and deposit on absorbent charcoal carrier.After being cooled to room temperature, take out active carbon, repeat again aforesaid operations process, by in the zinc chloride in maceration extract B2 and B3 solution the complete load of chloroplatinic acid and deposit on absorbent charcoal carrier, then with distilled water washing three times, place in baking oven and after 100～110 ℃ of dry 1h, make catalyst finished product.Catalyst is numbered E-4, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Comparative example 1
The preparation process of catalyst is with embodiment 1, and difference is 30Cu (NO
3)
2, 10Zn (NO
3)
2be dissolved in the deionized water of 200mL with 1.5g chloroplatinic acid, normal temperature dipping twice, dry and 400 ℃ of roastings 2 hours after dipping.Catalyst is numbered C-1, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Comparative example 2
The preparation process of catalyst is with embodiment 1, and difference is 20Zn (Cl)
2be dissolved in the deionized water of 200mL with 1.0g chloroplatinic acid.Catalyst is numbered C-2, and the composition of this catalyst is in Table 1, and evaluation result is in Table 2.
Comparative example 3
Take 10Cu (NO
3)
2be dissolved in the deionized water of 200mL, after fully stirring, form solution as catalyst impregnating solution C.
Selecting commercially available coconut husk granular activated carbon is catalyst carrier, and the main character of active carbon is: moisture content 5.8%, specific area 928m
2/ g, average pore size 8.8A, iodine sorption value 700mg/g, grain graininess 3mm.Take this kind of active carbon 15g, the sodium hydroxide solution that is placed in 50ml 10% floods 24 hours; Filter activity charcoal; By deionized water washing, filtered several times, until filtrate is neutral; Be placed in baking oven and carry out being dried 1 hour at 110～150 ℃; After taking-up as catalyst carrier active carbon D.
The catalyst impregnating solution C preparing is joined to catalyst carrier with in active carbon D, fully stir 1 hour; Standing immersion 24 hours; By deionized water, wash, remove by filter the Cu of activated carbon surface
2+; Be placed in baking oven and carry out being dried 6 hours at 110～150 ℃; Be placed in again tube type resistance furnace and at 260～270 ℃, activate 12 hours; After being cooled to room temperature, take out, make Activated Carbon with Cu catalyst.Catalyst is numbered the composition of this catalyst of C-3 in Table 1, and evaluation result is in Table 2.
Catalyst packing, in fluidized-bed reactor, be take to ozone as oxide isolation, certain oil plant is processed continuously containing phenol, sulfur-containing waste water.Major pollutants COD 1200mg/L, S in waste water
2-280mg/L, volatile phenol 180mg/L.The condition of oxidation processes is: normal temperature, and oxidation time 1.5 hours, ozone consumption is 25mg/L.
Table 1 catalyst forms (percetage by weight)
| Cu | Zn | Pt | |
| E-1 | 4.35 | 1.67 | 0.18 |
| E-2 | 7.71 | 0.78 | 0.11 |
| E-3 | 10.1 | 0.84 | 0.11 |
| E-4 | 5.78 | 1.71 | 0.14 |
| E-5 | 6.77 | 2.34 | 0.21 |
| C-1 | 17.34 | 5.84 | 0.25 |
| C-2 | 14.1 | 0 | 0.18 |
| C-3 | 4.95 | 0 | 0 |
The evaluation result of table 2 catalyst
| COD(mg/L) | S 2-(mg/L) | Volatile phenol (mg/L) | |
| E-1 | 70 | 0.19 | 0.20 |
| E-2 | 69 | 0.16 | 0.18 |
| E-3 | 65 | 0.20 | 0.16 |
| E-4 | 71 | 0.16 | 0.13 |
| E-5 | 68 | 0.18 | 0.14 |
| C-1 | 90 | 1.0 | 0.61 |
| C-2 | 96 | 1.5 | 0.80 |
| C-3 | 108 | 1.2 | 1.65 |
Claims (8)
1. an oil plant is containing the processing method of phenol, sulfur-containing waste water, by Catalyst packing in fluidized-bed reactor, take ozone as oxide isolation, oil plant is processed continuously containing phenol, sulfur-containing waste water, wherein said catalyst be take active carbon as carrier, it is characterized in that: catalyst be take Cu-Zn-Pt as active component, active metal component accounts for 2%～20% of total catalyst weight in element, wherein Cu accounts for 1%～15% of total catalyst weight, Zn accounts for 0.1%～5% of total catalyst weight, and Pt accounts for 0.01%～1% of total catalyst weight.
2. in accordance with the method for claim 1, it is characterized in that the preparation method that described catalyst adopts comprises the steps:
(1) maceration extract that preparation contains active metal component;
(2) under inert gas shielding, preparation temperature is the high temperature active charcoal carrier of 350～700 ℃;
(3) with the maceration extract that contains active metal component prepared by step (1), spray or the high temperature active charcoal carrier of impregnation steps (2), active metal component loads on the absorbent charcoal carrier of step (2);
(4) active carbon after supported active metal is made catalyst finished product through cooling, wash and being dried.
3. in accordance with the method for claim 2, it is characterized in that: method for preparing catalyst step (1) maceration extract is the solution that simultaneously contains three kinds of active metal components, or preparation contains Cu salt and Zn salt respectively hybrid infusion solution and platinum acid chloride solution, or three kinds of maceration extracts that contain respectively different activities metal component of configuration.
4. it is characterized in that in accordance with the method for claim 2: method for preparing catalyst step (2) preparation temperature under inert gas shielding is the high temperature active charcoal carrier of 400～500 ℃.
5. it is characterized in that in accordance with the method for claim 3: mantoquita comprises copper chloride, copper nitrate or copper sulphate; Zn salt comprises zinc chloride, zinc nitrate or zinc sulfate.
6. it is characterized in that in accordance with the method for claim 2: the dipping of active metal component maceration extract on high temperature active charcoal carrier or to spray the processing time be 10～300 seconds in method for preparing catalyst step (3).
7. it is characterized in that in accordance with the method for claim 6: flooding or spraying the processing time is 30～150 seconds.
8. in accordance with the method for claim 2, it is characterized in that: the baking temperature in method for preparing catalyst step (4) is 60～130 ℃, be 0.5～6h drying time.
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| CN103055894B (en) * | 2012-12-28 | 2014-12-10 | 邓世碧 | Catalyst for deoxygenation of calcium carbide furnace gas and method preparation thereof |
| CN104258803B (en) * | 2013-09-04 | 2017-01-11 | 赵世怀 | Method for preparing carbon monoxide filtering material |
| CN103586083A (en) * | 2013-10-10 | 2014-02-19 | 安徽工程大学 | Preparation method of nonhomogeneous Fenton reagent |
| CN104001512B (en) * | 2014-06-10 | 2016-03-02 | 中昊(大连)化工研究设计院有限公司 | A kind of non-mercury catalyst for the preparation of vinyl chloride and its preparation method and application |
| CN105174418A (en) * | 2015-10-13 | 2015-12-23 | 中国石油化工股份有限公司 | Method for treating oil-containing sewage in refined oil depot by catalytic oxidation |
| CN110642365B (en) * | 2019-11-11 | 2021-10-12 | 浙江晶立捷环境科技有限公司 | Method for advanced treatment of wastewater by subcritical oxidation technology |
| CN111203179A (en) * | 2020-01-15 | 2020-05-29 | 清创人和生态工程技术有限公司 | Preparation method and application of renewable phenol-containing organic wastewater catalytic adsorption material |
| CN115888629A (en) * | 2022-12-21 | 2023-04-04 | 重庆工商大学 | Composite adsorbent for advanced treatment of coking wastewater and preparation method thereof |
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