CN114832859B - CVOCs purifying catalyst and preparation method thereof - Google Patents

CVOCs purifying catalyst and preparation method thereof Download PDF

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Publication number
CN114832859B
CN114832859B CN202210637473.7A CN202210637473A CN114832859B CN 114832859 B CN114832859 B CN 114832859B CN 202210637473 A CN202210637473 A CN 202210637473A CN 114832859 B CN114832859 B CN 114832859B
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catalyst
preparation
ruthenium
auxiliary agent
mass ratio
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CN114832859A (en
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吴忠标
赵叶民
高珊
奚超
刘学炎
莫建松
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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Zhejiang Tianlan Environmental Protection Technology Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
    • B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8659—Removing halogens or halogen compounds
    • B01D53/8662—Organic halogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8678—Removing components of undefined structure
    • B01D53/8687—Organic components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/462—Ruthenium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J33/00—Protection of catalysts, e.g. by coating
    • B01J35/23—
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/20—Halogens or halogen compounds
    • B01D2257/206—Organic halogen compounds
    • B01D2257/2064—Chlorine
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters

Abstract

The invention relates to a CVOCs purifying catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-polyethylene imidazole complex and a catalyst auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain the catalyst; the silicon-containing auxiliary agent is obtained by carrying out a first stirring reaction on methyltriethoxysilane, tetraethoxysilane and alcohol in a water phase, then sequentially adding acid and n-butyl titanate to carry out a second stirring reaction, and then carrying out solid-liquid separation and second roasting. The preparation method provided by the invention realizes the preparation of the catalyst with high water resistance by adopting a specific preparation process, can continuously and efficiently adsorb and catalyze the target compound, and prevents the deactivation and failure of the catalyst; meanwhile, migration, aggregation and growth of metal ions in the high-temperature roasting process can be inhibited.

Description

CVOCs purifying catalyst and preparation method thereof
Technical Field
The invention relates to the field of waste gas treatment, in particular to a CVOCs purifying catalyst and a preparation method thereof.
Background
At present, the chlorine-containing volatile organic compounds (Chlorinated Volatile Organic Compounds, CVOCs) are one of volatile organic compounds (Volatile Organic Compounds, VOCs) and have wide application in the industries of medicines, leather, paint, printing, dye, rubber, chemical industry and the like. CVOCs have the characteristics of high chemical stability, low biodegradability, strong fat solubility and the like. CVOCs have serious hazard, and the human body can cause diseases such as reduced immune level, central nervous system dysfunction and the like after long-time exposure to the CVOCs; in addition, CVOCs are also important precursors that cause ozone and PM2.5 concentrations in the atmosphere to exceed standard.
On the other hand, CVOCs such as chlorobenzene or chlorophenol are important precursors of dioxin which is a primary carcinogen, and are commonly existing in smoke discharged by industries such as household garbage and medical waste incineration, steel smelting, heating and power supply and the like. In recent years, with the year by year importance of ecological environment protection in China and the arrival of people to beautiful life, the acceleration of waste gas treatment construction, especially CVOCs treatment engineering construction, is one of important means for improving the environmental air quality in China. The method can not only realize the reduction of CVOCs pollutants, but also reduce the generation of byproduct dioxin, thereby achieving the purpose of harmlessness and having extremely high environmental, social and economic values.
The catalytic oxidation technology is one of the most effective and economical methods for treating CVOCs, and particularly aims to realize the directional removal of pollutants by reducing the reaction activation energy under the action of a catalyst so as to enable target pollutants to undergo oxidation-reduction reaction on the surface of the catalyst. The technology has the advantages of low energy consumption, high efficiency, less secondary pollution and the like.
As CN110038407a discloses a method for purifying an exhaust gas containing hydrogen chloride gas and organic chlorine compound gas, comprising the steps of: and introducing the mixed gas of the waste gas and the air into a graphite preheater for preheating, then introducing a shell side of a heat exchanger to perform heat exchange and heating with high-temperature gas from a fixed bed reactor, then introducing the high-temperature gas into the fixed bed reactor for catalytic oxidation reaction, introducing the reacted high-temperature gas into a tube side of the heat exchanger for heat exchange and cooling, introducing the cooled gas into a spray scrubber for absorbing acid gas, and then introducing the gas into a gas-liquid separator for directly discharging. According to the method, a fixed bed reactor catalytic oxidation method is adopted, waste gas containing hydrogen chloride gas and organic chlorine compound gas is efficiently treated at low cost, mixed gas is preheated through a graphite preheater, dew point corrosion of HCl gas to pipelines and a heat exchanger is reduced, high-temperature tail gas after catalytic oxidation and the waste gas to be treated are subjected to heat exchange through the heat exchanger, reaction heat is fully utilized, and good economic benefits are achieved.
CN102698751a is a catalyst for low-temperature catalytic combustion elimination of chlorine-containing volatile organic compounds, which mainly comprises a transition metal oxide-cerium oxide composite oxide carrier and ruthenium oxide supported by the carrier, wherein the transition metal element is Ti, mn, co, fe, cu, ni. Air serving as an oxidant is taken into the reactor, so that the chlorine-containing volatile organic compounds are converted into carbon dioxide, hydrogen chloride and chlorine, and the tail gas after complete combustion can be absorbed by adopting dilute alkali solution and then is exhausted. The catalyst has high catalytic activity, strong chlorine poisoning resistance and long service life, and is particularly suitable for eliminating chlorine-containing organic compounds by low-temperature catalytic combustion.
But currently, when treating CVOCs, this technique presents the following challenges: firstly, the low conversion rate of CVOCs and CO when purifying high concentration of CVOCs are caused by weaker catalyst performance 2 The generation rate is not high, so that the treated tail gas is difficult to meet the pollutant emission standard; secondly, the catalyst is difficult to realize directional adsorption, catalysis and removal of CVOCs under high water vapor content, so that the purification efficiency is forced to be difficult to meet the industrial requirements.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a CVOCs purifying catalyst and a preparation method thereof, and solves the problems that the existing catalyst has poor treatment effect on organic chlorine-containing gas under high water vapor content and the purifying efficiency does not reach the standard.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a catalyst for purifying CVOCs, the method comprising the steps of: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-polyethylene imidazole complex and a catalyst auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain the catalyst;
the silicon-containing auxiliary agent is obtained by carrying out a first stirring reaction on methyltriethoxysilane, tetraethoxysilane and alcohol in a water phase, then sequentially adding acid and n-butyl titanate to carry out a second stirring reaction, and then carrying out solid-liquid separation and second roasting.
The preparation method provided by the invention realizes the preparation of the catalyst with high water resistance by adopting a specific preparation process, can continuously and efficiently adsorb and catalyze the target compound, and prevents the deactivation and failure of the catalyst; meanwhile, the preparation method provided by the invention can also inhibit migration, aggregation and growth of noble metal ions in the high-temperature roasting process.
In the invention, the content of the high water vapor is more than or equal to 5 percent, preferably 5 to 10 percent of the water vapor in the organic chlorine-containing gas.
In the invention, the solid-liquid separation can be performed by aging, drying and other operations sequentially.
In the present invention, the acid may be hydrochloric acid, nitric acid, sulfuric acid, or the like.
As a preferred technical scheme of the invention, the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing stirring is (50-200): 1, for example, 50:1, 60:1, 70:1, 80:1, 90:1, 100:1, 110:1, 120:1, 130:1, 140:1, 150:1, 160:1, 170:1, 180:1, 190:1 or 200:1 and the like can be adopted, but the invention is not limited to the listed values, and other non-listed values in the range are also satisfactory.
Preferably, the mass ratio of the catalyst promoter to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing stirring is (3-8): 1, for example, may be 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1, 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1 or 8:1, but not limited to the values listed, and other values not listed in the range also meet the requirements.
Preferably, the catalyst promoter comprises 1 or at least 2 of copper oxide, cobaltosic oxide, cerium oxide or manganese oxide, such as a combination of copper oxide and cobaltosic oxide, a combination of cerium oxide and manganese oxide or a combination of copper oxide and cerium oxide, etc.
Preferably, the mixing and stirring time is 1-3h, for example, but not limited to, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.8h, 1.9h, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h or 3h, etc., and other non-enumerated values in this range are also acceptable.
In a preferred embodiment of the present invention, the first firing temperature may be 300 to 500 ℃, for example, 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, or 500 ℃, etc., but not limited to the above-mentioned values, and other values not mentioned in the above range are also acceptable.
Preferably, the time of the first roasting is 2-5h, for example, 2h, 2.1h, 2.2h, 2.3h, 2.4h, 2.5h, 2.6h, 2.7h, 2.8h, 2.9h, 3h, 3.1h, 3.2h, 3.3h, 3.4h, 3.5h, 3.6h, 3.7h, 3.8h, 3.9h, 4h, 4.1h, 4.2h, 4.3h, 4.4h, 4.5h, 4.6h, 4.7h, 4.8h, 4.9h or 5h, etc., but not limited to the recited values, other non-recited values in the range are also suitable.
In a preferred embodiment of the present invention, the mass ratio of methyltriethoxysilane to tetraethyl orthosilicate in the preparation process of the silicon-containing additive is (3-6): 1, for example, 3:1, 3.1:1, 3.2:1, 3.3:1, 3.4:1, 3.5:1, 3.6:1, 3.7:1, 3.8:1, 3.9:1, 4:1, 4.1:1, 4.2:1, 4.3:1, 4.4:1, 4.5:1, 4.6:1, 4.7:1, 4.8:1, 4.9:1, 5:1, 5.1:1, 5.2:1, 5.3:1, 5.4:1, 5.5:1, 5.6:1, 5.8:1, 5.9:1, or 6:1 may be, but not limited to the above numerical values, and the numerical values do not meet the other requirements.
Preferably, the mass ratio of the alcohol to the methyltrimethoxy in the preparation process of the silicon-containing auxiliary agent is (5-10): 1, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1 or 10:1, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
Preferably, the mass ratio of the alcohol to the water in the preparation process of the silicon-containing auxiliary agent is (2-5): 1, for example, may be 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5:1, etc., but not limited to the listed values, and other non-listed values in the range also meet the requirements.
Preferably, the addition amount of the acid in the preparation process of the silicon-containing auxiliary agent is 0.5-2% of the addition amount of the water, for example, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.1%, 1.2%, 1.3%, 1.4%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9% or 2%, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
In the present invention, the acid may be an organic acid or an inorganic acid, and may be acetic acid, sulfuric acid, hydrochloric acid, nitric acid, or the like.
Preferably, the molar concentration of the acid in the preparation process of the silicon-containing auxiliary agent is 9-12mol/L, for example, 9mol/L, 9.2mol/L, 9.4mol/L, 9.6mol/L, 9.8mol/L, 10mol/L, 10.2mol/L, 10.4mol/L, 10.6mol/L, 10.8mol/L, 11mol/L, 11.2mol/L, 11.4mol/L, 11.6mol/L, 11.8mol/L or 12mol/L and the like can be used, but the silicon-containing auxiliary agent is not limited to the recited values, and other non-recited values in the range are also satisfactory.
Preferably, the mass ratio of the n-butyl titanate to the methyltriethoxysilane in the preparation process of the silicon-containing auxiliary agent is (1-5): 1, for example, may be 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3:1, 3.2:1, 3.4:1, 3.6:1, 3.8:1, 4:1, 4.2:1, 4.4:1, 4.6:1, 4.8:1 or 5:1, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
In a preferred embodiment of the present invention, the time of the first stirring reaction in the preparation process of the silicon-containing auxiliary agent is 0.5-1h, for example, 0.5h, 0.55h, 06.h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
Preferably, the time of the second stirring reaction in the preparation process of the silicon-containing auxiliary agent is 0.5-1h, for example, 0.5h, 0.55h, 06.h, 0.65h, 0.7h, 0.75h, 0.8h, 0.85h, 0.9h, 0.95h or 1h, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
In a preferred embodiment of the present invention, the second firing temperature in the preparation of the silicon-containing auxiliary agent is 300 to 600 ℃, for example, 300 ℃, 320 ℃, 340 ℃, 360 ℃, 380 ℃, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, or the like, but not limited to the above-mentioned values, and other values not mentioned in the above range are also within the above range.
Preferably, the second roasting time in the preparation process of the silicon-containing auxiliary agent is 2-6h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8h or 6h, and the like, but is not limited to the listed values, and other non-listed values in the range are also suitable.
As a preferable technical scheme of the invention, the ruthenium-polyethylene-imidazole complex is obtained by carrying out a third stirring reaction on polyethylene-imidazole, ruthenium precursor and liquid phase.
In the present invention, the polyvinylimidazole can be referred to as: jose-Maria, sansinena, jerzy, et al effects of Axial Coordination of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a Nonprecious Catalyst for Oxygen Reduction [ J ]. Journal of Physical Chemistry C,2014,118 (33), 19139-19149.
Preferably, the mass ratio of the polyvinylimidazole to the ruthenium precursor in the preparation process of the ruthenium polyvinylimidazole complex is (5-20): 1, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, 15:1, 15.5:1, 16:1, 16.5:1, 17:1, 17.5:1, 18:1, 18.5:1, 19:1, 19.5:1 or 20:1 may be, but not limited to the values listed, and other non-listed values within the range are also satisfactory.
Preferably, the liquid phase in the preparation process of the ruthenium-polyethylene imidazole complex comprises water and alcohol in a mass ratio of (1-3): 1, for example, the mass ratio may be 1:1, 1.1:1, 1.2:1, 1.3:1, 1.4:1, 1.5:1, 1.6:1, 1.7:1, 1.8:1, 1.9:1, 2:1, 2.1:1, 2.2:1, 2.3:1, 2.4:1, 2.5:1, 2.6:1, 2.7:1, 2.8:1, 2.9:1 or 3:1, but not limited to the listed values, and other non-listed values in the range are also consistent with the requirements.
In the present invention, the alcohol may be methanol, ethanol, glycerol, ethylene glycol, or the like.
Preferably, the mass ratio of the alcohol to the polyvinylimidazole in the preparation process of the ruthenium polyvinylimidazole complex is (5-10): 1, for example, may be 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, but not limited to the recited values, other non-recited values within the range also conform to the requirements.
Preferably, the ruthenium precursor in the preparation process of the ruthenium-polyethylene imidazole complex comprises 1 or at least 2 of ruthenium chloride, nitrosyl ruthenium nitrate or hexa-ammonium ruthenium trichloride.
Preferably, the time of the third stirring reaction in the preparation process of the ruthenium-polyethylene imidazole complex is 0.5-2h, for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, 1.1h, 1.2h, 1.3h, 1.4h, 1.5h, 1.6h, 1.7h, 1.8h, 1.9h or 2h, etc., but not limited to the listed values, and other non-listed values in the range are also satisfactory.
According to the preparation method, the catalyst, the sol, the coating auxiliary agent and the water are mixed and ball-milled to obtain a coating material, the coating material is coated on the surface of a carrier, and then the catalyst is dried and third baked to obtain the monolithic catalyst.
Preferably, the sol comprises a nanosilicon sol.
Preferably, the coating aid comprises 1 or a combination of at least 2 of cetyltrimethylammonium bromide, polyethylene glycol, sodium dodecyl sulfate.
In the invention, the molecular weight of the polyethylene glycol is less than or equal to 400.
Preferably, the mass ratio of the catalyst to the sol is (9.5-10.5): 1, for example, it may be 9.5:1, 9.55:1, 9.6:1, 9.65:1, 9.7:1, 9.75:1, 9.8:1, 9.85:1, 9.9:1, 9.95:1, 10:1, 10.05:1, 10.1:1, 10.15:1, 10.2:1, 10.25:1, 10.3:1, 10.35:1, 10.4:1, 10.45:1 or 10.5:1, etc., but is not limited to the values recited, and other values not recited in this range are also satisfactory.
Preferably, the mass ratio of the catalyst to the coating auxiliary agent is (5-10): 1, for example, it may be 5:1, 5.2:1, 5.4:1, 5.6:1, 5.8:1, 6:1, 6.2:1, 6.4:1, 6.6:1, 6.8:1, 7:1, 7.2:1, 7.4:1, 7.6:1, 7.8:1, 8:1, 8.2:1, 8.4:1, 8.6:1, 8.8:1, 9:1, 9.2:1, 9.4:1, 9.6:1, 9.8:1 or 10:1, etc., but is not limited to the recited values, and other non-recited values within the range are also satisfactory.
Preferably, the mass ratio of water to catalyst is (5-15): 1, which may be, for example, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 10.5:1, 11:1, 11.5:1, 12:1, 12.5:1, 13:1, 13.5:1, 14:1, 14.5:1, or 15:1, etc., but is not limited to the recited values, and other non-recited values within this range are also acceptable.
Preferably, the ball milling time is 2-5h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, etc., but not limited to the recited values, and other non-recited values in the range are also satisfactory.
Preferably, the drying temperature is 120 to 220 ℃, for example, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃, 170 ℃, 175 ℃, 180 ℃, 185 ℃, 190 ℃, 195 ℃, 200 ℃, 205 ℃, 210 ℃, 215 ℃, 220 ℃, or the like, but not limited to the recited values, and other non-recited values within the range are also satisfactory.
Preferably, the drying time is 2-8h, for example, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h, 5h, 5.2h, 5.4h, 5.6h, 5.8h, 6h, 6.2h, 6.4h, 6.6h, 6.8h, 7h, 7.2h, 7.4h, 7.6h, 7.8h or 8h, but not limited to the recited values, other non-recited values within the range are also satisfactory.
The temperature of the third firing is preferably 300 to 500 ℃, and may be 300 ℃, 310 ℃, 320 ℃, 330 ℃, 340 ℃, 350 ℃, 360 ℃, 370 ℃, 380 ℃, 390 ℃, 400 ℃, 410 ℃, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃, 480 ℃, 490 ℃, 500 ℃, or the like, for example, but not limited to the recited values, and other non-recited values within the range are also satisfactory.
Preferably, the third roasting time is 1-5h, for example, but not limited to 1h, 1.2h, 1.4h, 1.6h, 1.8h, 2h, 2.2h, 2.4h, 2.6h, 2.8h, 3h, 3.2h, 3.4h, 3.6h, 3.8h, 4h, 4.2h, 4.4h, 4.6h, 4.8h or 5h, and other non-enumerated values in the range are also satisfactory.
As a preferable technical scheme of the invention, the preparation method comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyethylene imidazole complex and a catalyst auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain the catalyst, mixing and ball-milling the catalyst, sol, a coating auxiliary agent and water to obtain a coating material, coating the coating material on the surface of a carrier, and then drying and third roasting to obtain an integral catalyst;
the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing and stirring is (50-200): 1; the mass ratio of the catalyst auxiliary agent to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing and stirring is (3-8) 1; the catalyst promoter comprises 1 or a combination of at least 2 of copper oxide, cobaltosic oxide, cerium oxide or manganese oxide; the mixing and stirring time is 1-3h; the temperature of the first roasting is 300-500 ℃ and the time is 2-5h; the sol comprises nano silica sol; the coating auxiliary agent comprises 1 or at least 2 of hexadecyl trimethyl ammonium bromide, polyethylene glycol and sodium dodecyl sulfate; the mass ratio of the catalyst to the sol is (9.5-10.5): 1; the mass ratio of the catalyst to the coating auxiliary agent is (5-10): 1; the mass ratio of the water to the catalyst is (5-15) 1; the ball milling time is 2-5h; the drying temperature is 120-220 ℃ and the drying time is 2-8h; the temperature of the third roasting is 300-500 ℃ and the time is 1-5h;
the silicon-containing auxiliary agent is obtained by mixing methyltriethoxysilane, ethyl orthosilicate, alcohol and water for a first stirring reaction, sequentially adding acid and n-butyl titanate for a second stirring reaction, and then carrying out solid-liquid separation and second roasting; the mass ratio of the methyltriethoxysilane to the tetraethoxysilane is (3-6) 1; the mass ratio of the ethanol to the methyltrimethoxy is (5-10): 1; the mass ratio of the ethanol to the water is (2-5) 1; the addition amount of the acid is 0.5-2% of the addition amount of the water; the mass concentration of the acid is 9-12mol/L; the mass ratio of the n-butyl titanate to the methyltriethoxysilane is (1-5) 1; the time of the first stirring reaction is 0.5-1h; the second stirring reaction time is 0.5-1h; the temperature of the second roasting is 300-600 ℃ and the time is 2-6h;
the ruthenium-polyvinyiimidazole complex is obtained by carrying out a third stirring reaction on polyvinyiimidazole, ruthenium precursor and liquid phase; the mass ratio of the polyvinyl imidazole to the ruthenium precursor is (5-20): 1; the liquid phase comprises water and alcohol with the mass ratio of (1-3) being 1; the mass ratio of the alcohol to the polyvinyl imidazole is (5-10): 1; the ruthenium precursor comprises 1 or a combination of at least 2 of ruthenium chloride, ruthenium nitrosylnitrate or ruthenium hexammoniate; the time of the third stirring reaction is 0.5-2h.
In a second aspect, the invention provides a CVOCs purifying catalyst, which is obtained by adopting the preparation method as described in the first aspect and is used for treating organic chlorine-containing gas with water vapor content of more than or equal to 5%.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the preparation method provided by the invention, the polyethylene imidazole is introduced to effectively inhibit migration, aggregation and growth of noble metal components in the high-temperature roasting process, so that the ruthenium components after roasting are uniformly distributed on the surface of the catalyst in the form of microparticles, and a sufficient number of catalytic active sites in unit volume are ensured, and thus, the catalyst has higher catalytic efficiency and stability.
(2) According to the preparation method provided by the invention, the silicon-titanium phase is introduced and matched with the polyethylenimine, so that the catalyst has high water resistance, water poisoning is prevented, and the surface energy of the catalyst is promoted to continuously and efficiently adsorb and catalyze target compounds.
(3) The integral catalyst provided by the invention can effectively solve the problems of difficult treatment of high-concentration CVOCs waste gas and the like, realize the directional removal of target pollutants, and ensure higher CVOCs conversion rate and CO 2 Yield, CVOCs conversion rate is more than or equal to 98%, CO 2 The yield is more than or equal to 98 percent.
Detailed Description
For a better illustration of the present invention, which is convenient for understanding the technical solution of the present invention, exemplary but non-limiting examples of the present invention are as follows:
example 1
The embodiment provides a preparation method of a CVOCs purifying catalyst, which comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyethylene imidazole complex and a catalyst auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain the catalyst, mixing and ball-milling the catalyst, sol, a coating auxiliary agent and water to obtain a coating material, coating the coating material on the surface of a carrier, and then drying and third roasting to obtain an integral catalyst;
the specific adoption is as follows: (1) 30g of methyltriethoxysilane and 10g of tetraethoxysilane are dissolved in ethanol (180 g), 50g of water is added and fully mixed, 0.5g of hydrochloric acid (12 mol/L) is slowly added dropwise, stirring is carried out for 0.5h, 60g of n-butyl titanate is added, stirring is carried out slowly for 0.5h, ageing is carried out for 12h, the product is collected, the product is dried for 5h at 120 ℃ in an oven, and finally the product is baked for 3h at 450 ℃ in a muffle furnace, thus obtaining the silicon-containing auxiliary agent.
(2) 10g of polyvinylimidazole and 1g of ruthenium trichloride are fully dissolved in 100g of ethanol, stirred for 30 minutes, then 200g of deionized water is added, and stirring is continued for 1 hour, so that a ruthenium-polyvinylimidazole complex solution is prepared.
(3) 200g of a silicon-containing auxiliary agent was added to the obtained ruthenium-polyethylene imidazole complex solution of step (2), and 4g of cerium oxide was added thereto, stirred for 2 hours, then dried at 150℃for 5 hours, and calcined at 450℃for 3 hours, to obtain a powdery catalyst.
(4) Adding 20g of a powder catalyst into 100g of deionized water, adding 2g of nano silica sol, 1g of sodium dodecyl sulfate and 1g of polyethylene glycol (molecular weight is 300), and ball milling for 2 hours to prepare slurry; the honeycomb cordierite carrier was then immersed in the slurry, the slurry remaining in the channels was removed by blowing off with ear-washing balls, dried at 120 ℃ for 4 hours, and then calcined at 450 ℃ for 3 hours, to obtain a monolithic catalyst capable of purifying CVOCs.
Example 2
The embodiment provides a preparation method of a CVOCs purifying catalyst, which comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyethylene imidazole complex and a catalyst auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain the catalyst, mixing and ball-milling the catalyst, sol, a coating auxiliary agent and water to obtain a coating material, coating the coating material on the surface of a carrier, and then drying and third roasting to obtain an integral catalyst;
the specific adoption is as follows: (1) 40g of methyltriethoxysilane and 10g of tetraethoxysilane are dissolved in ethanol (300 g), 80g of water is added and fully mixed, 0.8g of hydrochloric acid (12 mol/L) is slowly added dropwise, stirring is carried out for 0.5h, 100g of n-butyl titanate is added, stirring is carried out slowly for 0.5h, aging is carried out for 12h, the product is collected, the product is dried for 5h at 120 ℃ in an oven, and finally the product is baked for 3h at 450 ℃ in a muffle furnace, thus obtaining the silicon-containing auxiliary agent.
(2) 10g of polyvinyl imidazole and 1g of hexaammonium ruthenium trichloride are fully dissolved in 100g of ethanol, stirred for 30 minutes, then 100g of deionized water is added, and stirring is continued for 1 hour, so that a ruthenium-polyvinyl imidazole complex solution is prepared.
(3) 100g of a silicon-containing auxiliary agent was added to the ruthenium-polyethylene imidazole complex solution obtained in the step (2), and 4g of copper oxide was added thereto, stirred for 2 hours, then dried at 150℃for 5 hours, and calcined at 450℃for 3 hours, to obtain a powdery catalyst.
(4) Adding 20g of a powder catalyst into 100g of water, adding 2g of nano silica sol and 2g of sodium dodecyl sulfate, and ball milling for 2 hours to prepare slurry; the honeycomb cordierite carrier was then immersed in the slurry, the slurry remaining in the channels was removed by blowing off with ear-washing balls, dried at 120 ℃ for 4 hours, and then calcined at 450 ℃ for 3 hours, to obtain a monolithic catalyst capable of purifying CVOCs.
Example 3
The embodiment provides a preparation method of a CVOCs purifying catalyst, which comprises the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-containing polyethylene imidazole complex and a catalyst auxiliary agent, then carrying out solid-liquid separation and first roasting to obtain the catalyst, mixing and ball-milling the catalyst, sol, a coating auxiliary agent and water to obtain a coating material, coating the coating material on the surface of a carrier, and then drying and third roasting to obtain an integral catalyst;
the specific adoption is as follows: (1) 50g of methyltriethoxysilane and 15g of tetraethoxysilane are dissolved in ethanol (300 g), 80g of water is added and fully mixed, 1g of hydrochloric acid (12 mol/L) is slowly added dropwise, stirring is carried out for 0.5h, 120g of n-butyl titanate is added, stirring is carried out slowly for 0.5h, aging is carried out for 12h, the product is collected, the product is dried for 5h at 120 ℃, and finally the product is baked for 3h at 450 ℃ in a muffle furnace, thus obtaining the silicon-containing auxiliary agent.
(2) 10g of polyvinyl imidazole and 2g of ruthenium nitrosylnitrate are fully dissolved in 100g of ethanol, stirred for 30 minutes, then 100g of deionized water is added, and stirring is continued for 1 hour, so that a ruthenium-polyvinyl imidazole complex solution is prepared.
(3) 100g of a silicon-containing auxiliary agent was added to the ruthenium-polyethylene imidazole complex solution obtained in the step (2), and 8g of manganese oxide was added thereto, stirred for 2 hours, then dried at 150℃for 5 hours, and calcined at 480℃for 2 hours, to obtain a powdery catalyst.
(4) Adding 20g of a powder catalyst into 100g of deionized water, adding 2g of nano silica sol and 2g of polyethylene glycol (molecular weight is 400), and ball milling for 2 hours to prepare slurry; and immersing the honeycomb mullite carrier into the slurry, taking out the slurry which is remained in the pore channels and is blown out by using the ear-washing balls, drying for 5 hours at 100 ℃, and roasting for 1 hour at 500 ℃ to obtain the monolithic catalyst capable of purifying CVOCs.
Example 4
The only difference in example 1 is that the preparation of the ruthenium polyethylenimine complex is carried out under carbon monoxide atmosphere.
Example 5
The only difference from example 1 is that the ruthenium polyethylenimine complex is not added during mixing.
Example 6
The only difference from example 1 is the substitution of ruthenium precursor for ruthenium carbonyl.
Example 7
The only difference from example 1 is that no n-butyl titanate was added.
Example 8
The difference from example 1 is only that no silicon-containing auxiliary agent is added during the mixing and stirring.
Example 9
The only difference from example 1 is the addition of cobalt nitrate in an amount equivalent to the ruthenium precursor during the preparation of the ruthenium polyvinylimidazole complex.
Application example 1
The catalysts obtained in examples 1 to 9 and the catalysts obtained in examples A2 and B2 of CN111135816A were subjected to a combustion treatment of methylene chloride having a steam content of 7% and chlorobenzene having a steam content of 7%, the treatment results are shown in tables 1 and 2, wherein Table 1 shows the treatment results of methylene chloride and Table 2 shows the treatment results of chlorobenzene.
The polyvinylimidazoles used in the above examples are described in the references: jose-Maria, sansinena, jerzy, et al effects of Axial Coordination of the Metal Center on the Activity of Iron Tetraphenylporphyrin as a Nonprecious Catalyst for Oxygen Reduction [ J ]. Journal of Physical Chemistry C,2014,118 (33), 19139-19149.
TABLE 1
CVOCs conversion/% CO 2 Yield/%
Example 1 99％ 99％
Example 2 100％ 99％
Example 3 100％ 100％
Example 4 93％ 92％
Example 5 64％ 42％
Example 6 94％ 93％
Example 7 71％ 61％
Example 8 80％ 78％
Example 9 84％ 65％
CN111135816a example A2 65％ 63％
CN111135816a example B2 69％ 71％
TABLE 2
In the above table, the CVOCs conversion was calculated as (content of chlorine-containing organic gas in the feed gas-content of chlorine-containing organic gas in the post-combustion gas)/content of chlorine-containing organic gas in the feed gas, CO 2 The rate of formation is calculated as the carbon dioxide content of the post-combustion gas/the chlorine-containing organic gas content of the feed gas.Specifically, if the invention is applied to combustion treatment of methylene dichloride containing water vapor, the CVOCs conversion rate is calculated by the method of (the methylene dichloride content in the feed gas-the methylene dichloride content in the gas after combustion)/the methylene dichloride content in the feed gas, and CO 2 The yield was calculated as the carbon dioxide content in the gas after combustion/the methylene chloride content in the feed gas. When the combustion treatment is carried out on chlorobenzene containing water vapor, the CVOCs conversion is calculated as (content of chlorobenzene in the feed gas-content of chlorobenzene in the post-combustion gas)/content of chlorobenzene in the feed gas, CO 2 The yield was calculated as carbon dioxide content in the post-combustion gas 6/chlorobenzene content in the feed gas.
According to the results, the preparation method provided by the invention realizes the preparation of the catalyst with high water resistance by adopting a specific preparation process, can continuously and efficiently adsorb and catalyze the target compound, and prevents the deactivation and failure of the catalyst; meanwhile, the preparation method provided by the invention can also inhibit migration, aggregation and growth of noble metal ions in the high-temperature roasting process.
It is stated that the detailed structural features of the present invention are described by the above embodiments, but the present invention is not limited to the above detailed structural features, i.e., it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be apparent to those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope of the present invention and the scope of the disclosure.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited to the specific details of the above embodiments, and various simple modifications can be made to the technical solution of the present invention within the scope of the technical concept of the present invention, and all the simple modifications belong to the protection scope of the present invention.
In addition, the specific features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various possible combinations are not described further.
Moreover, any combination of the various embodiments of the invention can be made without departing from the spirit of the invention, which should also be considered as disclosed herein.

Claims (22)

1. A method for preparing a catalyst for purifying CVOCs, which is characterized by comprising the following steps: mixing and stirring a silicon-containing auxiliary agent, a ruthenium-polyethylene imidazole complex and a catalyst auxiliary agent, and then carrying out solid-liquid separation and first roasting to obtain a catalyst;
the silicon-containing auxiliary agent is obtained by mixing methyltriethoxysilane, ethyl orthosilicate, alcohol and water for a first stirring reaction, sequentially adding acid and n-butyl titanate for a second stirring reaction, and then carrying out solid-liquid separation and second roasting;
the mass ratio of the silicon-containing auxiliary agent to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing and stirring is (50-200): 1; the mass ratio of the catalyst auxiliary agent to the ruthenium precursor in the ruthenium-polyethylene imidazole complex in the mixing and stirring is (3-8) 1; the catalyst promoter comprises 1 or a combination of at least 2 of copper oxide, cobaltosic oxide, cerium oxide or manganese oxide; the temperature of the first roasting is 300-500 ℃; the first roasting time is 2-5h; the mass ratio of the methyltriethoxysilane to the tetraethoxysilane in the preparation process of the silicon-containing auxiliary agent is (3-6) 1; the mass ratio of the n-butyl titanate to the methyltriethoxysilane in the preparation process of the silicon-containing auxiliary agent is (1-5) 1; the temperature of the second roasting is 300-600 ℃; the second roasting time is 2-6h;
mixing and ball milling the catalyst, sol, coating auxiliary agent and water to obtain a coating material, coating the coating material on the surface of a carrier, and drying and third roasting to obtain an integral catalyst; the temperature of the third roasting is 300-500 ℃; the third roasting time is 1-5h.
2. The method of claim 1, wherein the mixing is for a period of 1 to 3 hours.
3. The preparation method according to claim 1, wherein the mass ratio of the alcohol to methyltriethoxysilane in the preparation of the silicon-containing auxiliary is (5-10): 1.
4. The preparation method according to claim 1, wherein the mass ratio of the alcohol to the water in the preparation process of the silicon-containing auxiliary agent is (2-5): 1.
5. The method of claim 1, wherein the acid is added in an amount of 0.5 to 2% of the water during the preparation of the silicon-containing auxiliary agent.
6. The method of claim 1, wherein the molar concentration of acid in the preparation of the silicon-containing auxiliary is 9-12mol/L.
7. The method of claim 1, wherein the first stirring reaction is for a period of time ranging from 0.5 to 1 hour.
8. The process of claim 1, wherein the second stirring reaction is carried out for a period of time ranging from 0.5 to 1 hour.
9. The preparation method of claim 1, wherein the ruthenium-polyvinylimidazole complex is obtained by performing a third stirring reaction on polyvinylimidazole, a ruthenium precursor and a liquid phase;
the liquid phase in the preparation process of the ruthenium-polyethylene imidazole complex comprises water and alcohol with the mass ratio of (1-3): 1.
10. The method according to claim 9, wherein the mass ratio of the polyvinylimidazole to the ruthenium precursor in the preparation of the ruthenium polyvinylimidazole complex is (5-20): 1.
11. The process according to claim 9, wherein the mass ratio of the alcohol to the polyvinylimidazole in the preparation of the ruthenium polyvinylimidazole complex is (5-10): 1.
12. The method of claim 9, wherein the ruthenium precursor comprises 1 or a combination of at least 2 of ruthenium chloride, ruthenium nitrosylnitrate, or ruthenium hexammoniumtrichloride during the preparation of the ruthenium polyvinylimidazole complex.
13. The process according to claim 9, wherein the time for the third stirring reaction during the preparation of the ruthenium polyethylenimine complex is 0.5 to 2 hours.
14. The method of manufacturing of claim 1, wherein the sol comprises a nanosilica sol.
15. The method of claim 1, wherein the coating aid comprises 1 or a combination of at least 2 of cetyltrimethylammonium bromide, polyethylene glycol, and sodium dodecyl sulfate.
16. The process according to claim 1, wherein the mass ratio of the catalyst to the sol is from (9.5 to 10.5): 1.
17. The process according to claim 1, wherein the mass ratio of the catalyst to the coating auxiliary is (5-10): 1.
18. The process according to claim 1, wherein the mass ratio of water to catalyst in the preparation of the monolithic catalyst is (5-15): 1.
19. The method of claim 1, wherein the ball milling is performed for a period of 2 to 5 hours.
20. The method of claim 1, wherein the drying temperature is 120-220 ℃.
21. The method of claim 1, wherein the drying time is 2 to 8 hours.
22. A catalyst for purifying CVOCs, which is obtained by the preparation method according to any one of claims 1 to 21 and is used for treating organic chlorine-containing gases with a water vapor content of not less than 5%.
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