CN110665495A - Honeycomb catalyst adhesive system and preparation method thereof - Google Patents

Honeycomb catalyst adhesive system and preparation method thereof Download PDF

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Publication number
CN110665495A
CN110665495A CN201910974689.0A CN201910974689A CN110665495A CN 110665495 A CN110665495 A CN 110665495A CN 201910974689 A CN201910974689 A CN 201910974689A CN 110665495 A CN110665495 A CN 110665495A
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CN
China
Prior art keywords
parts
pug
honeycomb catalyst
adhesive
solvent
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201910974689.0A
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Chinese (zh)
Inventor
梁材
杨强
刘桐李
周健
熊丽仙
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CHENGDU DONGFANG KWH ENVIRONMENTAL PROTECTION CATALYSTS Co Ltd
Original Assignee
CHENGDU DONGFANG KWH ENVIRONMENTAL PROTECTION CATALYSTS Co Ltd
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Priority to CN201910974689.0A priority Critical patent/CN110665495A/en
Publication of CN110665495A publication Critical patent/CN110665495A/en
Pending legal-status Critical Current

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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/30Tungsten
    • B01J35/56
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B01J37/0018Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)

Abstract

The invention relates to the technical field of catalysts, and discloses a honeycomb catalyst adhesive system, which comprises: inorganic powders, binders, solvents to dissolve the binders, surfactants and other additives. According to the honeycomb catalyst adhesive system and the preparation method thereof, the glycol and the water are mixed to serve as a solvent, so that the mixing of solid powder and liquid is intensified, the mixing speed is accelerated, and more uniform mixed pug is obtained, so that the problem of inconsistent flow of the pug in the area can be solved, the problem of wall starving or blocking is solved, the pug has good fluidity, the defects of starving or material breaking and the like cannot occur, and the defects of distortion, collapse and deformation and the like cannot occur due to high strength of an extrusion-molded honeycomb structure, and meanwhile, carton sealing, wrapping and drying are not needed, so that the workload caused by sealing and removing sealing is avoided on one hand; on the other hand, complete drying can be directly finished at one time, and the production flow is simplified.

Description

Honeycomb catalyst adhesive system and preparation method thereof
Technical Field
The invention relates to the technical field of catalysts, in particular to a honeycomb catalyst adhesive system and a preparation method thereof.
Background
The powder materials such as titanium dioxide and the like are combined with an adhesive system to manufacture the honeycomb SCR denitration catalyst, so that the adhesive system is compatible with a ceramic material, and the sufficient fluidity and dispersibility of mud can be ensured in the mixing process; in addition, the green compact preforms formed from the powder and binder system should have sufficient strength for subsequent processing, the binder formulation to meet these requirements is complex, many different formulations have been disclosed in the prior art, usually cellulose ethers and polyethylene glycols, solvents using water, in combination with fine titanium dioxide, and the like, and the powder mixtures, in addition to the binder, contain additives such as surfactants, lubricants and dispersants which act as processing aids to enhance wetting and thereby produce a homogeneous batch, and thin wall and high density honeycomb green preforms made using current binder systems have low strength, are easily deformed, and are prone to wall plugging and defects.
The existing method, through prolonging the mixing and kneading time, or increasing the steps of adding and stirring solid powder and liquid powder or adjusting the adding sequence, and using the aging, pre-extruding or aging combined with the pre-extruding process, etc., the green strength is improved, and is more suitable for processing into thin-wall honeycomb body, although the above process has the capability of producing thin-wall and high-density honeycomb body, the whole production process becomes complicated and long, the production efficiency is reduced, generally kneading and mixing takes about 2-5 hours, aging and pre-extruding process takes about 24 hours, and because the green preform has lower strength, in the drying process, only the carton can be used for independently packaging and sealing the green preform, the labor intensity is very large, long-time drying is carried out at low temperature, generally 7-14 days is required, and the carton needs to be removed and then secondary drying is carried out, the drying process step can be completed finally. In general, a binder system with water as a solvent is easy to cause uneven discharging of pug when a green blank preform is extruded, and particularly, after firing, the product has internal material breakage, so that the strength of the product is greatly reduced, mainly because the solid powder and the binder system are not thoroughly mixed, the pug has uneven properties, so that the flowability of the green blank during the extrusion of the pug is uneven, and the material breakage phenomenon occurs in the core of the final product. In view of the foregoing inconvenience in the art, there is a need for a binder system that can be conveniently mixed with a liquid system and fired into a qualified honeycomb SCR denitration catalyst, while avoiding the problems of reduced monomer strength, shortened operating life, etc. caused by wall deformation or wall starvation, and thus a honeycomb catalyst binder system and a method for preparing the same are proposed to solve the above-mentioned problems.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a honeycomb catalyst adhesive system and a preparation method thereof, which have the advantages of avoiding the reduction of the monomer strength caused by wall deformation or wall starvation and the like, and solve the problem of the reduction of the monomer strength caused by wall deformation or wall starvation.
(II) technical scheme
In order to achieve the purpose of avoiding the reduction of the strength of the monomer caused by wall deformation or wall starvation, the invention provides the following technical scheme: a honeycomb catalyst adhesive system comprising: inorganic powders, binders, solvents to dissolve the binders, surfactants and other additives.
Preferably, the solvent for dissolving the adhesive is composed of water and glycol, and the ratio of glycol to water in the solvent for dissolving the adhesive is 1: 1-2: 1, the inorganic powder component is composed of a sinterable inorganic powder material.
Preferably, the binder is selected from any one of methylcellulose or derivatives thereof, polyethylene glycol and mixtures thereof, the surfactant is selected from any one of stearic acid, oleic acid and mixtures thereof, and the additive comprises any one of pH regulators and the like selected from ammonia, monoethanolamine and lactic acid.
Preferably, the feed comprises the following raw materials in parts by weight: 100 parts of inorganic solid powder, 0.5-10 parts of adhesive, at least 0.1 part of V2O5 precursor solution, at least 0.1 part of WO3 precursor solution, 0.1-10 parts of surfactant, 1-20 parts of other additives and 5-50 parts of solvent.
Preferably, the feed comprises the following raw materials in parts by weight: 100 parts of inorganic solid powder, 0.5-5 parts of adhesive, at least 0.1 part of V2O5 precursor solution, at least 0.1 part of WO3 precursor solution, 0.1-3 parts of surfactant, 2-10 parts of other additives and 10-40 parts of solvent.
Preferably, the inorganic solid powder comprises titanium dioxide, especially anatase titanium dioxide produced by a sulfuric acid process.
A method of preparing a honeycomb catalyst adhesive comprising the steps of:
1) uniformly mixing, kneading and milling the inorganic powder and the adhesive to fully mix and contact the inorganic powder and the adhesive so as to obtain pug with better plasticity;
2) the pug with better plasticity is molded through a die, so that the pug with better plasticity is molded into a green body prefabricated body, and the molding is to extrude the pug with better plasticity through a screw vacuum extruder and a specially designed die to be molded into a honeycomb green body prefabricated product;
3) after the pug with better plasticity is molded by a die, the pug with better plasticity is placed in hot air drying equipment for sufficient drying, and the drying is finished after the temperature is controlled below 117 ℃ for 20-60 hours.
(III) advantageous effects
Compared with the prior art, the invention provides a honeycomb catalyst adhesive system and a preparation method thereof, and the honeycomb catalyst adhesive system has the following beneficial effects:
1. according to the honeycomb catalyst adhesive system and the preparation method thereof, the ethylene glycol and the water are mixed to serve as a solvent, so that the mixing of solid powder and liquid is intensified, the mixing speed is accelerated, and the more uniform mixed pug is obtained, so that the problem of inconsistent flow of the pug in the area can be solved, the problem of wall surface starving or blocking is solved, the pug has good fluidity, the defects of starving or material breakage and the like cannot occur, and the extruded honeycomb structure body has high strength and does not have the defects of distortion, collapse, deformation and the like; on the other hand, compared with the viscosity of an adhesive system obtained by only using water as a solvent to dissolve the adhesive, due to the addition of the glycol, the glycol and the water form a mixed solution which is used as the solvent to dissolve the adhesive, the viscosity can be greatly improved, the strength of the prepared green blank prefabricated product can be greatly improved, the complete drying can be directly completed by hot air at one time, the drying is not needed again after the sealing is removed, the equipment investment is reduced, meanwhile, the carton is not needed to be sealed and wrapped for drying, the workload caused by sealing and sealing removal is avoided, and the production flow is simplified.
2. According to the honeycomb catalyst adhesive system and the preparation method thereof, the ethylene glycol is added to form a mixture as a solvent after being mixed with the water, the boiling point of the ethylene glycol is 197 ℃, the saturated vapor pressure partial pressure of the ethylene glycol under normal pressure is very low, and simultaneously, due to the special properties of the ethylene glycol, the mixture has good water retention performance, after inorganic solid powder and the adhesive are mixed and extruded to form a green preform, the green preform is dried to remove low-temperature volatile substances, the slow and controlled evaporation speed is shown, the generation of cracks on the green preform is avoided, the drying period is greatly shortened, and the drying period from 7 to 14 days can be shortened to 20 to 60 hours.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first embodiment is as follows: a honeycomb catalyst adhesive system comprising: 1.5 parts by weight of a binder, 2 parts by weight of a V2O5 precursor solution, 8 parts by weight of a WO3 precursor solution, 0.5 part by weight of a surfactant, 5 parts by weight of other additives and 25 parts by weight of a solvent, wherein the inorganic powder component is composed of sinterable inorganic powder materials, the inorganic solid powder comprises titanium dioxide, in particular anatase titanium dioxide produced by a sulfuric acid process, the solvent for dissolving the binder is composed of water and ethylene glycol, the ratio of the ethylene glycol to the water in the solvent for dissolving the binder is 1.2:1, 100 parts by weight of the inorganic solid powder, the binder is selected from any one of methyl cellulose or a derivative thereof, polyethylene glycol and a mixture thereof, the surfactant is selected from any one of stearic acid, oleic acid and a mixture thereof, and the additive comprises any one of ammonia water, monoethanolamine and lactic acid and the like.
Example two: a honeycomb catalyst adhesive system comprising: 100 parts by weight of inorganic solid powder, 1 part by weight of binder, 0.6 part by weight of V2O5 precursor solution, 10 parts by weight of WO3 precursor solution, 1.5 parts by weight of surfactant, 8 parts by weight of other additives and 20 parts by weight of solvent, wherein the inorganic powder component is composed of sinterable inorganic powder materials, the inorganic solid powder comprises titanium dioxide, especially anatase titanium dioxide produced by a sulfuric acid method, the solvent for dissolving the binder is composed of water and ethylene glycol, the ratio of the ethylene glycol to the water in the solvent for dissolving the binder is 1.5:1, the binder is selected from any one of methyl cellulose or derivatives thereof, polyethylene glycol and mixtures thereof, the surfactant is selected from any one of stearic acid, oleic acid and mixtures thereof, and the additives comprise any one of ammonia water, monoethanolamine and lactic acid such as pH value regulator.
A method of preparing a honeycomb catalyst comprising the steps of:
1) uniformly mixing, kneading and mixing inorganic powder and an adhesive to fully mix and contact the inorganic powder and the adhesive, thereby obtaining pug with better plasticity;
2) the pug with better plasticity is molded through a die, so that the pug with better plasticity is molded into a green body prefabricated body, and the molding is to extrude the pug with better plasticity into a honeycomb green body prefabricated body through a screw vacuum extruder and a specially designed die;
3) after the pug with better plasticity is molded by a die, the pug with better plasticity is placed in hot air drying equipment for sufficient drying, and the drying is finished after the temperature is controlled below 117 ℃ for 20-60 hours.
The invention has the beneficial effects that: according to the honeycomb catalyst adhesive system and the preparation method thereof, the glycol and the water are mixed to serve as a solvent, so that the mixing of solid powder and liquid is intensified, the mixing speed is accelerated, and more uniform mixed pug is obtained, so that the problem of inconsistent flow of the pug can be solved, the problem of wall starving or blocking is solved, the pug has good fluidity, the defects of starving or material breaking and the like are avoided, and the defects of distortion, collapse, deformation and the like are avoided due to the high strength of the extrusion-molded honeycomb structure, and meanwhile, carton sealing, wrapping and drying are not needed, so that the workload caused by sealing and removing sealing is avoided on one hand; on the other hand, complete drying can be directly finished once without removing the seal and then drying again, the equipment investment is reduced, the production flow is simplified, hot air is directly used for drying, compared with the viscosity of a binder system obtained by dissolving the binder only by using water as a solvent without adding ethylene glycol, the ethylene glycol and the water form a mixed solution by adding the ethylene glycol, the binder is dissolved by using the solvent to form the binder, the viscosity can be greatly improved, the strength of the prepared green blank prefabricated product can be greatly improved, the mixture formed by mixing the ethylene glycol and the water is used as the solvent by adding the ethylene glycol, the boiling point of the ethylene glycol is 197 ℃, the saturated vapor pressure partial pressure of the ethylene glycol under normal pressure is very low, and simultaneously, due to the special property, the water retention performance of the green blank prefabricated product is good, after the green blank prefabricated product is formed by mixing and extruding the inorganic solid powder and the binder, when the low-temperature volatile matter is removed by drying treatment, slow and controlled evaporation speed can be shown, crack generation of a green preform is avoided, the drying period is greatly shortened from 7-14 days to 20-60 hours, and the problem of monomer strength reduction caused by wall surface deformation or wall surface material shortage is solved.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (7)

1. A honeycomb catalyst binder system, comprising: inorganic powders, binders, solvents to dissolve the binders, surfactants and other additives.
2. The honeycomb catalyst binder system of claim 1 wherein the solvent for dissolving the binder is comprised of water and glycol, the ratio of glycol to water in the solvent for dissolving the binder being 1: 1-2: 1, the inorganic powder component is composed of a sinterable inorganic powder material.
3. The honeycomb catalyst binder system according to claim 1 wherein the binder is selected from the group consisting of methylcellulose or its derivatives, polyethylene glycol and mixtures thereof, the surfactant is selected from the group consisting of stearic acid, oleic acid and mixtures thereof, and the additive comprises a PH adjuster or the like selected from the group consisting of ammonia, monoethanolamine and lactic acid.
4. The honeycomb catalyst adhesive system according to claim 1, comprising the following raw materials in parts by weight: 100 parts of inorganic solid powder, 0.5-10 parts of adhesive, at least 0.1 part of V2O5 precursor solution, at least 0.1 part of WO3 precursor solution, 0.1-10 parts of surfactant, 1-20 parts of other additives and 5-50 parts of solvent.
5. The honeycomb catalyst adhesive system according to claim 1, comprising the following raw materials in parts by weight: 100 parts of inorganic solid powder, 0.5-5 parts of adhesive, at least 0.1 part of V2O5 precursor solution, at least 0.1 part of WO3 precursor solution, 0.1-3 parts of surfactant, 2-10 parts of other additives and 10-40 parts of solvent.
6. Honeycomb catalyst binder system according to claim 1, characterised in that the inorganic solid powder comprises titanium dioxide, in particular anatase titanium dioxide produced by the sulphuric acid process.
7. A preparation method of a honeycomb catalyst adhesive is characterized by comprising the following steps:
1) uniformly mixing, kneading and milling the inorganic powder and the adhesive to fully mix and contact the inorganic powder and the adhesive so as to obtain pug with better plasticity;
2) the pug with better plasticity is molded through a die, so that the pug with better plasticity is molded into a green body prefabricated body, and the molding is to extrude the pug with better plasticity through a screw vacuum extruder and a specially designed die to be molded into a honeycomb green body prefabricated product;
3) after the pug with better plasticity is molded by a die, the pug with better plasticity is placed in hot air drying equipment for sufficient drying, and the drying is finished after the temperature is controlled below 117 ℃ for 20-60 hours.
CN201910974689.0A 2019-10-14 2019-10-14 Honeycomb catalyst adhesive system and preparation method thereof Pending CN110665495A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007652A1 (en) * 1997-08-08 1999-02-18 Corning Incorporated Improved method of forming and shaping plasticized mixtures and the green bodies made therefrom
WO2001049634A1 (en) * 1999-12-31 2001-07-12 Corning Incorporated Improved binder system for honeycomb ceramic bodies and a method for producing said honeycomb bodies
CN101502796A (en) * 2009-03-20 2009-08-12 无锡市宜刚耐火材料有限公司 Integral honeycomb selective catalytic reduction catalyst for flue gas denitration and method for preparing the same
WO2014073066A1 (en) * 2012-11-08 2014-05-15 イビデン株式会社 Honeycomb structure and manufacturing method thereof
CN103861653A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Modified titanium dioxide, ultrafine crystal ceramic powder, high-strength heat-engine plant denitration catalyst, and preparation methods of modified titanium dioxide, ultrafine crystal ceramic powder, and high-strength heat-engine plant denitration catalyst
CN109046320A (en) * 2018-07-09 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation process of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999007652A1 (en) * 1997-08-08 1999-02-18 Corning Incorporated Improved method of forming and shaping plasticized mixtures and the green bodies made therefrom
WO2001049634A1 (en) * 1999-12-31 2001-07-12 Corning Incorporated Improved binder system for honeycomb ceramic bodies and a method for producing said honeycomb bodies
CN101502796A (en) * 2009-03-20 2009-08-12 无锡市宜刚耐火材料有限公司 Integral honeycomb selective catalytic reduction catalyst for flue gas denitration and method for preparing the same
WO2014073066A1 (en) * 2012-11-08 2014-05-15 イビデン株式会社 Honeycomb structure and manufacturing method thereof
CN103861653A (en) * 2012-12-14 2014-06-18 上海郎特电力环保科技有限公司 Modified titanium dioxide, ultrafine crystal ceramic powder, high-strength heat-engine plant denitration catalyst, and preparation methods of modified titanium dioxide, ultrafine crystal ceramic powder, and high-strength heat-engine plant denitration catalyst
CN109046320A (en) * 2018-07-09 2018-12-21 上海纳米技术及应用国家工程研究中心有限公司 Preparation process of honeycomb catalyst for coal-fired power plant denitrating flue gas and products thereof and application

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Application publication date: 20200110