CN103521222B - Heterogeneous catalysis wet oxidizing catalyst and preparation method thereof - Google Patents

Heterogeneous catalysis wet oxidizing catalyst and preparation method thereof Download PDF

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CN103521222B
CN103521222B CN201210225872.9A CN201210225872A CN103521222B CN 103521222 B CN103521222 B CN 103521222B CN 201210225872 A CN201210225872 A CN 201210225872A CN 103521222 B CN103521222 B CN 103521222B
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catalyst
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tio
heterogeneous catalysis
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CN103521222A (en
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郑育元
汪国军
郭宗英
陈航宁
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a kind of by a kind of heterogeneous catalysis wet oxidizing catalyst of Heterogeneous Catalytic Wet Oxidation process and preparation method thereof, mainly solve the low problem with poor stability of COD clearance in prior art.The present invention, by adopting a kind of heterogeneous catalysis wet oxidizing catalyst, comprises following component with weight parts: A) 98.0 ~ 99.7 parts of complex carriers; With carry B thereon) 0.3 ~ 2.0 part of at least one noble metal be selected from Ru, Pd, Pt or Au; Wherein complex carrier, comprises following component by weight percentage: a) TiO of 35 ~ 55% 2; B) ZrO of 25 ~ 45% 2; C) CeO of 15 ~ 35% 2and preparation method thereof technical scheme, solve this problem preferably, can be used in the process of industrial wastewater.

Description

Heterogeneous catalysis wet oxidizing catalyst and preparation method thereof
Technical field
The present invention relates to a kind of heterogeneous catalysis wet oxidizing catalyst and preparation method thereof.
Background technology
Late 1970s, CWO is developed on the basis of Wet Oxidation Process, become CO by the organic matter in sewage and containing N, S harmful substance through oxidation Decomposition 2, N 2, SO 4 =and H 2the innocuous substances such as O.CWO technology can process waste water separately, also as the pretreatment of biochemical treatment, by wet oxidation, can reduce the COD of waste water, remove the poisonous and hazardous material of biochemical bacterium, improve the biodegradability of waste water.On the other hand; along with energy-saving and cost-reducing pressure continues to increase; environmental protection controls more and more stricter; the waste water that organic concentration is higher adopts incinerator burning disposal can cause energy consumption and environmental protection dual-pressure to device; CWO technology largely can 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, improve the cost of wastewater treatment.Heterogeneous catalyst 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 both composite oxides between them are carrier, by Ru, Rh, Pd, Ir, Pt, Au load on above-mentioned carrier, but noble metal price is high, therefore many prior aries are studied carrier, ites is desirable to develop the active catalyst had both with cost.
Such as: it is that the catalyst of carrier is for water technology that patent CN1278771C prepares with CeO2-TiO2; Patent CN1317070C is that catalyst using CeO2 as carrier is to process small molecular organic acid.In above publication, catalyst activity is all good, but it is all very short to investigate the time to catalyst stability, verifies that above-mentioned catalyst is active after use is more than 48h through us and obviously decline, in addition, waste water handled in above-mentioned patent mostly is small molecular organic acid class, lacks popularity.
Summary of the invention
One of technical problem to be solved by this invention is the low problem with poor stability of heterogeneous catalysis wet oxidation reaction COD clearance in prior art, provides a kind of new heterogeneous catalysis wet oxidizing catalyst.This catalyst is used in heterogeneous catalysis wet oxidation reaction, has the high and advantage that stability is high of COD clearance in industrial wastewater.Two of technical problem to be solved by this invention is to provide a kind of preparation method corresponding with one of technical solution problem used catalyst.
For one of solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of heterogeneous catalysis wet oxidizing catalyst, comprises following component with weight parts:
A) 98.0 ~ 99.7 parts of complex carriers: with carry thereon
B) 0.3 ~ 2.0 part is selected from least one noble metal in Ru, Pd, Pt or Au;
Wherein complex carrier, comprises following component by weight percentage:
A) TiO of 35 ~ 55% 2;
B) ZrO of 25 ~ 45% 2;
C) CeO of 15 ~ 35% 2.
In technique scheme, the consumption preferable range of at least one noble metal be selected from Ru, Pd, Pt or Au with weight parts is 0.5 ~ 1.5 part; In complex carrier, TiO by weight percentage 2consumption preferable range be 40 ~ 50%; ZrO 2consumption preferable range be 30 ~ 40%; CeO 2consumption preferable range be 20 ~ 30%.
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 heterogeneous catalysis wet oxidizing catalyst, comprises the following steps:
A) the cerium salt of aequum, zirconates, titanium salt mixed solution and ammoniacal liquor co-precipitation are generated gelatinous mass, make TiO through vacuum filtration, washing, oven dry, 600 ~ 900 DEG C of roasting 3 ~ 8h 2-ZrO 2-CeO 2carrier;
B) aequum is selected from least one salt wiring solution-forming in Ru, Pd, Pt, Au ;
C) adopt infusion process by solution in active principle be carried on the TiO of aequum 2-ZrO 2-CeO 2on carrier, drying, obtains catalyst precursor at 300 ~ 800 DEG C of roasting 2 ~ 7h afterwards;
D) catalyst precursor is obtained finished catalyst with hydrogen reducing 2 ~ 5h at 300 ~ 600 DEG C.
Heterogeneous catalysis wet oxidizing catalyst of the present invention is being reaction temperature: 240-290 DEG C for the treatment of industrial wastewater general technology condition, reaction pressure: 6.0-9.0MPa, gas-liquid volume ratio (i.e. the volume ratio of oxygen and industrial wastewater): carry out under 100-200 condition.
Detitanium-ore-type TiO 2during as wet oxidizing catalyst carrier, its specific surface is higher, is beneficial to active component at its Dispersion on surface, shortcoming be noble metal and its conjugation more weak, the easy stripping of noble metal after the washing away of waste water; ZrO 2although intensity is guaranteed, match problem with noble metal; CeO 2vector stabilisation is better, but lower to the clearance of small molecular organic acid.Carrier selected by the present invention is through certain proportioning composition TiO 2-ZrO 2-CeO 2complex carrier, its have high-ratio surface, good stability, good with conjugation with all kinds of noble metal matching, compared with other carriers can efficiently process all kinds of waste water.Adopt catalyst of the present invention for the treatment of industrial wastewater, after reaction 48h, its COD clearance can reach 97.5%, and the good stability of catalyst, achieves good technique effect.
Below by embodiment, the present invention is further elaborated.
Detailed description of the invention
[embodiment 1]
Preparation 0.8mol/lTi (SO 4) 2, 0.4mol/l ZrOCl 28H 2ce (the NO of O and 0.2mol/l 3) 36H 2the mixed solution 100ml of O and 0.6mol/l ammoniacal liquor 500mL.Adopt cerium salt, zirconates, titanium salt mixed solution and ammoniacal liquor co-precipitation to generate gelatinous mass, make TiO through vacuum filtration, washing, oven dry, 800 DEG C of roasting 4h 2-ZrO 2-CeO 2carrier.
By 1.98gCeO 2+impregnated in containing 0.052gRuCl 3in the aqueous solution.At room temperature flood 15h, subsequently dry 8h in the baking oven of 110 DEG C, obtain catalyst precursor at muffle furnace 450 DEG C of roasting 5h afterwards, finally at 400 DEG C, obtain finished catalyst with hydrogen reducing 4h.
In the above-described embodiments, investigating identical appreciation condition to above-mentioned heterogeneous catalysis wet oxidation reaction is:
Reactor: fixed bed reactors, internal diameter 22 millimeters, reactor length 800 millimeters
Filler amount of fill: 300ml
Reaction temperature: 260 DEG C
Reaction pressure: 7.0MPa
Gas-liquid volume ratio: 150
Organic wastewater type: acrylic acid industrial wastewater COD:30000mg/l
Sulphur ammonium industrial wastewater COD:50000mg/l
Product Hach company COD analyzer measures COD value.
[embodiment 2 ~ 8]
In embodiment 2 ~ 8, each step is identical with embodiment 1, and just complex carrier element mol ratio, noble metal kind and proportioning are different from waste water type.Actual conditions with the results are shown in table 1.
[comparative example 1]
Ce (the NO of preparation 0.2mol/l 3) 36H 2o solution 100ml and 0.6mol/l ammoniacal liquor 500mL, adopts with Ce (NO 3) 36H 2o and ammoniacal liquor co-precipitation generate gel precipitation, and through filtering, washing, dry, and roasting 5h makes CeO at 500 DEG C 2carrier.
By 1.98gCeO 2impregnated in containing 0.052gRuCl 3in the aqueous solution.At room temperature flood 15h, subsequently dry 8h in the baking oven of 110 DEG C, obtain catalyst precursor at muffle furnace 450 DEG C of roasting 5h afterwards, finally at 400 DEG C, obtain finished catalyst with hydrogen reducing 4h.
In above-mentioned comparative example, investigating identical appreciation condition to above-mentioned heterogeneous catalysis wet oxidation reaction is:
Reactor: fixed bed reactors, internal diameter 22 millimeters, reactor length 800 millimeters
Filler amount of fill: 300ml
Reaction temperature: 260 DEG C
Reaction pressure: 7.0MPa
Gas-liquid volume ratio: 150
Organic wastewater type: acrylic acid industrial wastewater COD:30000mg/l
Sulphur ammonium industrial wastewater COD:50000mg/l
[comparative example 2 ~ 4]
In comparative example 2 ~ 4, each step is identical with comparative example 1, just noble metal kind and waste water type difference.Actual conditions with the results are shown in table 1.
[comparative example 5]
Ce (the NO of preparation 0.2mol/l 3) 36H 2ti (the SO of O and 0.8mol/l 4) 2mixed solution 100ml and 0.6mol/l ammoniacal liquor 500mL.Adopt titanium salt, cerium and ammoniacal liquor co-precipitation to generate gel precipitate, through filtering, washing, dry, and CeO is made in roasting at 800 DEG C 2-tiO 2complex carrier.
By 1.98gCeO 2-tiO 2complex carrier impregnated in containing 0.052gRuCl 3in the aqueous solution.At room temperature flood 15h, subsequently dry 8h in the baking oven of 110 DEG C, obtain catalyst precursor at muffle furnace 450 DEG C of roasting 5h afterwards, finally at 400 DEG C, obtain finished catalyst with hydrogen reducing 4h.
In above-mentioned comparative example, investigating identical appreciation condition to above-mentioned heterogeneous catalysis wet oxidation reaction is:
Reactor: fixed bed reactors, internal diameter 22 millimeters, reactor length 800 millimeters
Filler amount of fill: 300ml
Reaction temperature: 260 DEG C
Reaction pressure: 7.0MPa
Gas-liquid volume ratio: 150
Organic wastewater type: acrylic acid industrial wastewater COD:30000mg/l
Sulphur ammonium industrial wastewater COD:50000mg/l
[comparative example 6 ~ 8]
In comparative example 6 ~ 8, each step is identical with comparative example 5, just noble metal kind and waste water type difference.Actual conditions with the results are shown in table 1.
[comparative example 9]
Ce (the NO of preparation 0.2mol/l 3) 36H 2the ZrOCl of O and 0.52mol/l 28H 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, washing, dry, and CeO is made in roasting at 800 DEG C 2-zrO 2complex carrier.
By 1.98gCeO 2-zrO 2complex carrier impregnated in containing 0.052gRuCl 3in the aqueous solution.At room temperature flood 15h, subsequently dry 8h in the baking oven of 110 DEG C, obtain catalyst precursor at muffle furnace 450 DEG C of roasting 5h afterwards, finally at 400 DEG C, obtain finished catalyst with hydrogen reducing 4h.
In above-mentioned comparative example, investigating identical appreciation condition to above-mentioned heterogeneous catalysis wet oxidation reaction is:
Reactor: fixed bed reactors, internal diameter 22 millimeters, reactor length 800 millimeters
Filler amount of fill: 300ml
Reaction temperature: 260 DEG C
Reaction pressure: 7.0MPa
Gas-liquid volume ratio: 150
Organic wastewater type: acrylic acid industrial wastewater COD:30000mg/l
Sulphur ammonium industrial wastewater COD:50000mg/l
[comparative example 10 ~ 12]
In comparative example 10 ~ 12, each step is identical with comparative example 9, just noble metal kind and waste water type difference.Actual conditions with the results are shown in table 1.
COD clearance under table 1 different carriers

Claims (2)

1. a heterogeneous catalysis wet oxidizing catalyst, comprises following component with weight parts:
A) 98.0 ~ 99.7 parts of complex carriers; With carry thereon
B) 0.3 ~ 2.0 part is selected from least one noble metal in Ru, Pd, Pt or Au;
Wherein complex carrier, comprises following component by weight percentage:
A) TiO of 35 ~ 55% 2;
B) ZrO of 25 ~ 45% 2;
C) CeO of 15 ~ 35% 2;
Described catalyst adopts the method preparation comprised the following steps:
A) the cerium salt of aequum, zirconates, titanium salt mixed solution and ammoniacal liquor co-precipitation are generated gelatinous mass, make TiO through vacuum filtration, washing, oven dry, 600 ~ 900 DEG C of roasting 3 ~ 8h 2-ZrO 2-CeO 2carrier;
B) aequum is selected from least one salt wiring solution-forming I in Ru, Pd, Pt, Au;
C) infusion process is adopted the active principle in solution I to be carried on the TiO of aequum 2-ZrO 2-CeO 2on carrier, drying, obtains catalyst precursor at 300 ~ 800 DEG C of roasting 2 ~ 7h afterwards;
D) catalyst precursor is obtained finished catalyst with hydrogen reducing 2 ~ 5h at 300 ~ 600 DEG C.
2. heterogeneous catalysis wet oxidizing catalyst according to claim 1, is characterized in that the consumption of at least one noble metal be selected from Ru, Pd, Pt or Au with weight parts is 0.5 ~ 1.5 part; In complex carrier, TiO by weight percentage 2consumption be 40 ~ 50%; ZrO 2consumption be 30 ~ 40%; CeO 2consumption be 20 ~ 30%.
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CN105084505B (en) * 2014-05-14 2017-10-27 中国石油化工股份有限公司 The method that multiphase wet oxidation handles industrial wastewater
CN105268435B (en) * 2014-07-24 2019-01-25 中国石油化工股份有限公司 Heterogeneous catalysis wet oxidizing catalyst
CN106582705B (en) * 2015-10-14 2019-08-06 中国石油化工股份有限公司 Multiphase wet oxidation catalyst
CN105854900A (en) * 2016-04-27 2016-08-17 厦门大学 Catalytic wet oxidation catalyst applied to harmless treatment of ammonia-nitrogen wastewater and preparation method thereof
CN105879922A (en) * 2016-05-19 2016-08-24 四川福思达生物技术开发有限责任公司 Molybdenum disulfide modified catalytic wet oxidation catalyst and preparation method thereof
CN107552046A (en) * 2016-07-01 2018-01-09 中国科学院大连化学物理研究所 Treatment of acrylic acid waste water by catalytic wet oxidation catalyst and its preparation method and application
CN108067225B (en) * 2016-11-11 2020-06-09 中国石油化工股份有限公司抚顺石油化工研究院 Preparation method of catalytic wet oxidation catalyst and organic wastewater treatment method
CN111135823B (en) * 2020-01-14 2021-06-11 厦门大学 Wet oxidation catalyst and preparation method and application thereof
CN114425319B (en) * 2020-10-15 2023-08-04 中国石油化工股份有限公司 Wet oxidation catalyst and preparation method thereof
CN116371404B (en) * 2023-04-18 2023-11-07 中国科学院兰州化学物理研究所 Catalytic wet oxidation catalyst and preparation method and application thereof

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