CN103521242A - Heterogeneous catalysis wet oxidation catalyst taking volcanic rock as carrier and preparation method thereof - Google Patents
Heterogeneous catalysis wet oxidation catalyst taking volcanic rock as carrier and preparation method thereof Download PDFInfo
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- CN103521242A CN103521242A CN201210225874.8A CN201210225874A CN103521242A CN 103521242 A CN103521242 A CN 103521242A CN 201210225874 A CN201210225874 A CN 201210225874A CN 103521242 A CN103521242 A CN 103521242A
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Abstract
The invention relates to a catalyst for treating industrial organic wastewater by a heterogeneous catalysis wet oxidation process and a preparation method thereof, which are mainly used for solving the problem of low COD removal rate in the prior art. The heterogeneous catalysis wet oxidation catalyst taking volcanic rock as a carrier comprises the following components in parts by weight: A: 97.5-99.7 parts of volcanic rock and B loaded on A: 0.3-2.5 parts of at least one precious metal of Ru, Pd, Pt and Au. By adopting the catalyst and the preparation method thereof, the problem is perfectly solved, and the catalyst can be used for treating industrial organic wastewater.
Description
Technical field
The present invention relates to a kind of heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier and preparation method thereof of take.
Background technology
Wet oxidation is grow up the fifties in last century a kind of under the condition of high pressure-temperature, adopts simple substance--oxygen is processed method poisonous, harmful, high concentrated organic wastewater.20 century 70s are developed CWO on the basis of wet oxidation, improve waste water treatment efficiency, reduce reaction condition.CWO technology can be processed separately waste water, also can be used as the pretreatment of biochemical treatment, by wet oxidation, reduces the COD of waste water, removes the poisonous and hazardous material of biochemical bacterium, improves the biodegradability of waste water.On the other hand; along with energy-saving and cost-reducing pressure continues to increase; environmental protection is controlled more and more stricter; the waste water that organic concentration is higher adopts incinerator burning disposal to cause energy consumption and environmental protection dual-pressure to device; CWO technology can largely replace waster water incinerator; reduce energy consumption, make device wastewater treatment meet environmental requirement.
The research of early stage CWO agent mainly concentrates on homogeneous catalyst, homogeneous catalyst there is active high, the advantage such as reaction speed is fast but due to catalyst be dissolved in useless in, cause secondary pollution, need subsequent treatment, improved the cost of wastewater treatment.Heterogeneous catalysis aqua becomes study hotspot in recent years, and heterogeneous catalyst mainly contains noble metal and the large class of metal oxide two, and wherein noble metal carrier catalyst has higher catalytic activity and stability, and this type of catalyst is greatly mainly with TiO at present
2, ZrO
2, CeO
2or their composite oxides are carrier, Ru, Rh, Pd, Ir, Pt, Au are loaded on above-mentioned carrier, but high this type of catalyst cost that causes of noble metal self price is higher.So be necessary prior art to improve.
For precious metal catalyst Wet Oxidation Process patent, disclose as follows:
CN1084496A，CN1121322A
In above patent, catalyst cost is high, and catalytic activity and stability all undesirable.
Summary of the invention
One of technical problem to be solved by this invention is the low problem of heterogeneous catalysis wet oxidation reaction COD clearance in prior art, and a kind of new heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier of take is provided.This catalyst has advantages of that for after heterogeneous catalysis wet oxidation reaction COD clearance is high.Two of technical problem to be solved by this invention is to provide the corresponding preparation method of a kind of catalyst used with one of technical solution problem.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind ofly take the heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier, in parts by weight, comprise following component:
A:97.5～99.7 part volcanic rock; With carry thereon
B:0.3～2.5 part are selected from least one noble metal in Ru, Pd, Pt, Au.
In technique scheme, the consumption preferable range of parts by weight volcanic rock of take is 98.5～99.7 parts; The consumption preferable range that is selected from least one noble metal in Ru, Pd, Pt, Au is 0.5～2.0 part.
For solve the problems of the technologies described above two, the technical solution used in the present invention is as follows: a kind of preparation method of take the heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier, comprises the following steps:
A) aequum is selected at least one the salt wiring solution-forming in Ru, Pd, Pt, Au
;
B) adopt infusion process by solution
in active principle be carried on the volcanic rock carrier of aequum, drying, makes catalyst precursor at 350～600 ℃ of roasting 3～7h afterwards;
C) by catalyst precursor at 300～650 ℃ with hydrogen reducing 2～6h with obtain catalyst finished product.
Heterogeneous catalysis wet oxidizing catalyst of the present invention is being reaction temperature: 240-290 ℃ for the treatment of industrial wastewater general technology condition, reaction pressure: 6.0-9.0MPa, gas-liquid volume ratio (being the volume ratio of oxygen and industrial wastewater): carry out under 100-200 condition.
Volcanic rock is natural formation, and the advantage of its high-specific surface area, high porosity is conducive to the dispersed and catalyst stability of noble metal; The advantage that its vapour lock is little, is conducive to liquid and can disperses well film forming, increase gas-liquid two-phase contact area, thereby gas-liquid two-phase carries out abundant mass transfer, heat transfer; Its high temperature high voltage resistant, corrosion resistant advantage, be conducive to all kinds of operating modes and process various complicated waste water; Its Main Ingredients and Appearance of volcanic rock is silicon, aluminium, calcium, sodium, magnesium, titanium, manganese, iron, nickel, cobalt and molybdenum etc. in addition, some of them element itself just has purification function to water quality, so supported active noble metal is processed waste water and had composite purification function on volcanic rock.In the selected heterogeneous catalysis wet oxidation of the present invention, its COD clearance is up to 96.2%, compares other carriers, and COD clearance has raising in various degree, has obtained good technique effect.
Below by embodiment, the present invention is further elaborated.
The specific embodiment
[embodiment 1]
1.98g volcanic rock be impregnated in to the RuCl containing 0.052g
3in solution.At room temperature flood 6h, dry 16h in the baking oven of 110 ℃, obtains catalyst precursor at 450 ℃ of roasting 5h of muffle furnace afterwards subsequently, finally at 400 ℃, with hydrogen reducing 4h, obtains catalyst finished product.
In the above-described embodiments, heterogeneous catalysis wet oxidation reaction being investigated to identical appreciation condition is:
Reactor: fixed bed reactors, 22 millimeters of internal diameters, 800 millimeters of reactor length
Filler amount of fill: 300ml
Reaction temperature: 290 ℃
Reaction pressure: 9.0MPa
Industrial organic waste water COD:15000mg/l
Gas-liquid volume ratio: 150
Product is measured COD value with the COD of Hach company analyzer, and the COD value that records the rear organic industrial sewage of reaction is 975mg/l, and COD clearance is 93.5%.
[embodiment 2-4]
In embodiment 2-4, each step is identical with embodiment 1, and just noble metal kind is different from load capacity.Actual conditions with the results are shown in table 1.
[comparative example 1]
Ti (the SO of preparation 0.2mol/l
4)
2solution 100ml and 0.6mol/l ammoniacal liquor 500mL.Adopt titanium sulfate and ammoniacal liquor co-precipitation to generate titanium hydroxide, through filtering, wash, drying, and TiO is made in roasting at 800 ℃
2carrier.
By 1.98g TiO
2impregnated in containing 0.052g RuCl
3in the aqueous solution.At room temperature flood 6h, dry 16h in the baking oven of 110 ℃, obtains catalyst precursor at 450 ℃ of roasting 5h of muffle furnace afterwards subsequently, finally at 400 ℃, with hydrogen reducing 4h, obtains catalyst finished product.
In above-mentioned comparative example, heterogeneous catalysis wet oxidation reaction investigated to identical appreciation condition be:
Reactor: fixed bed reactors, 22 millimeters of internal diameters, 800 millimeters of reactor length
Filler amount of fill: 300ml
Reaction temperature: 290 ℃
Reaction pressure: 9.0MPa
Industrial organic waste water COD: 15000mg/l
Gas-liquid volume ratio: 150
[comparative example 2-4]
In comparative example 2-4, each step is identical with comparative example 1, and just noble metal type is different from bearer type.Actual conditions with the results are shown in table 1.
[comparative example 5]
The ZrOCl of preparation 0.2mol/L
28H
2ce (the NO of O and 0.2mol/L
3)
36H
2o mixed solution 100ml and 0.6mol/l ammoniacal liquor 500mL.Adopt zirconates, cerium salt and ammoniacal liquor co-precipitation to generate gel precipitate, through filtering, wash, drying, and CeO is made in roasting at 900 ℃
2-zrO
2complex carrier.
By 1.98g CeO
2-zrO
2complex carrier impregnated in the RuCl containing Ru0.052g
3in solution.At room temperature flood 6h, dry 16h in the baking oven of 110 ℃, obtains catalyst precursor at 450 ℃ of roasting 5h of muffle furnace afterwards subsequently, finally at 400 ℃, with hydrogen reducing 4h, obtains catalyst finished product.
In above-mentioned comparative example, heterogeneous catalysis wet oxidation reaction investigated to identical appreciation condition be:
Reactor: fixed bed reactors, 22 millimeters of internal diameters, 800 millimeters of reactor length
Filler amount of fill: 300ml
Reaction temperature: 290 ℃
Reaction pressure: 9.0MPa
Industrial organic waste water COD:15000mg/l
Gas-liquid volume ratio: 150
[comparative example 6-8]
In comparative example 6-8, each step is identical with comparative example 5, and just noble metal type is different from bearer type.Actual conditions with the results are shown in table 1.
COD clearance under table 1 different carriers
Claims (3)
1. the heterogeneous catalysis wet oxidizing catalyst that the volcanic rock of take is carrier, comprises following component in parts by weight:
A:97.5～99.7 part volcanic rock; With carry thereon
B:0.3～2.5 part are selected from least one noble metal in Ru, Pd, Pt, Au.
2. according to claim 1ly take the heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier, it is characterized in that take that the consumption of parts by weight volcanic rock is 98.5～99.7 parts; The consumption that is selected from least one noble metal in Ru, Pd, Pt, Au is 0.5～2.0 part.
3. preparation method of take the heterogeneous catalysis wet oxidizing catalyst that volcanic rock is carrier according to claim 1, comprises the following steps:
A) aequum is selected at least one the salt wiring solution-forming in Ru, Pd, Pt, Au
;
B) adopt infusion process by solution
in active principle be carried on the volcanic rock carrier of aequum, drying, makes catalyst precursor at 350～600 ℃ of roasting 3～7h afterwards;
C) by catalyst precursor at 300～650 ℃ with hydrogen reducing 2～6h with obtain catalyst finished product.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105600909A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalytic wet oxidation treatment method for organic waste water |
| CN107224974A (en) * | 2017-07-14 | 2017-10-03 | 河北科技大学 | α‑Fe2O3The preparation method and applications of/volcanic rock catalyst |
| CN107282085A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Waste water wet oxidizing catalyst |
| CN107866260A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of wet oxidation waste water |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105600909A (en) * | 2014-11-20 | 2016-05-25 | 中国石油化工股份有限公司 | Catalytic wet oxidation treatment method for organic waste water |
| CN105600909B (en) * | 2014-11-20 | 2019-06-11 | 中国石油化工股份有限公司 | The method of catalytic wet oxidation processing organic wastewater |
| CN107282085A (en) * | 2016-04-13 | 2017-10-24 | 中国石油化工股份有限公司 | Waste water wet oxidizing catalyst |
| CN107282085B (en) * | 2016-04-13 | 2020-01-03 | 中国石油化工股份有限公司 | Wet oxidation catalyst for waste water |
| CN107866260A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | The catalyst of wet oxidation waste water |
| CN107866260B (en) * | 2016-09-26 | 2020-06-09 | 中国石油化工股份有限公司 | Catalyst for wet oxidation of waste water |
| CN107224974A (en) * | 2017-07-14 | 2017-10-03 | 河北科技大学 | α‑Fe2O3The preparation method and applications of/volcanic rock catalyst |
| CN107224974B (en) * | 2017-07-14 | 2019-10-29 | 河北科技大学 | α-Fe2O3The preparation method and applications of/volcanic rock catalyst |
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Application publication date: 20140122 |