CN109305823A - A kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst - Google Patents

A kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst Download PDF

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Publication number
CN109305823A
CN109305823A CN201711133628.9A CN201711133628A CN109305823A CN 109305823 A CN109305823 A CN 109305823A CN 201711133628 A CN201711133628 A CN 201711133628A CN 109305823 A CN109305823 A CN 109305823A
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CN
China
Prior art keywords
catalytic cracking
spent catalyst
cracking spent
strength ceramic
ceramic granule
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Pending
Application number
CN201711133628.9A
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Chinese (zh)
Inventor
房师平
张宏哲
张志远
牟桂芹
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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China Petroleum and Chemical Corp
Sinopec Qingdao Safety Engineering Institute
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Application filed by China Petroleum and Chemical Corp, Sinopec Qingdao Safety Engineering Institute filed Critical China Petroleum and Chemical Corp
Priority to CN201711133628.9A priority Critical patent/CN109305823A/en
Publication of CN109305823A publication Critical patent/CN109305823A/en
Pending legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/04—Clay; Kaolin
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/131—Inorganic additives
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • C04B33/132—Waste materials; Refuse; Residues
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/009—Porous or hollow ceramic granular materials, e.g. microballoons
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3201—Alkali metal oxides or oxide-forming salts thereof
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P40/00—Technologies relating to the processing of minerals
    • Y02P40/60—Production of ceramic materials or ceramic elements, e.g. substitution of clay or shale by alternative raw materials, e.g. ashes

Abstract

The present invention provides a kind of high-strength ceramic granules prepared by catalytic cracking spent catalyst, it is made of catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent through mixing, stirring, balling-up, drying and roasting, wherein the weight ratio of catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent is 40-60:10-50:5-20:5-20, catalytic cracking spent catalyst powder is made by ball milling, and specific surface area is not less than 200m2/g.The present invention is using catalytic cracking spent catalyst as raw material, the solidification in haydite solidification process to heavy metal is utilized simultaneously, keep the leaching concentration of obtained high-strength ceramic granule heavy metal extremely low, realize catalytic cracking spent catalyst collaboration is innoxious and recycling, it not only solves the problems, such as that catalytic cracking spent catalyst pollutes environment, while having obtained the haydite with higher economic value.

Description

A kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst
Technical field
The present invention relates to solid waste resource recoveries to utilize field, and in particular to one kind is prepared by catalytic cracking spent catalyst High-strength ceramic granule.
Background technique
So that catalyst activity is accelerated decline by heavy metal pollution due to catalyst in catalytic cracking unit, leads to catalyst Reaction selectivity be deteriorated, need periodically to draw off a part of poising agent to guarantee the activity and selectivity water of catalyst in device Flat, this poising agent drawn off is known as catalytic cracking spent catalyst.Catalytic cracking spent catalyst activity is low, and containing a certain amount of Heavy metal, pollution is strong, and the random processing for not conforming to specification can constitute a serious threat to environment for human survival.
Many research institutions start with certain ingredients in dead catalyst as raw material and carry out benefit again both at home and abroad, this is not Environmental pollution is only reduced, and reduces product cost.Though there is many patents (such as CN104495924A, CN102586606) The method for describing the recovering rare earth from catalytic cracking spent catalyst is studied, but since the taste of wherein metals such as nickel, vanadium is low (general Content is in thousands of ppm), do not have the economic value of extraction, while a large amount of spent acid alkali etc. can be generated newly in sour treatment process Dangerous waste, therefore the method economic benefit and environmental benefit of recovering rare earth be not high.
These thinkings all think that rare earth, heavy metal and molecular sieve on catalytic cracking spent catalyst are all valuable objects Matter, consideration is all how to be recycled, if transformation thinking, the heavy metal in catalytic cracking spent catalyst is consolidated Change harmlessness disposing and product is made again later, as long as Leaching of Heavy Metals concentration is not exceeded in product, and production process environment is dirty Dye is controllable, just meets the requirement of National Hazard waste resource recovery.
Artificial porcelain granule is had excellent performance, and can be widely used for the row such as building, farmland, water conservancy, traffic, metallurgy, petroleum, gardens Industry, configurable concrete make the purposes such as roadbed material, filtrate, greening gardens, and not only function admirable, can more save a large amount of sand Stone resource, demand are big.
Summary of the invention
For haydite demand and catalytic cracking spent catalyst the characteristics of, the present invention provides one kind to be urged by catalytic cracking is useless The high-strength ceramic granule of agent preparation passes through addition clay, fluxing agent, foaming agent etc. using catalytic cracking spent catalyst as raw material Auxiliary material is prepared into high-strength ceramic granule, not only solves the problems, such as that catalytic cracking spent catalyst pollutes environment, being also obtained has The haydite of higher economic value.
A kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst, by catalytic cracking spent catalyst powder, clay, fluxing Agent and foaming agent are made through mixing, stirring, balling-up, drying and roasting, and the catalytic cracking spent catalyst powder, helps clay The weight ratio of flux and foaming agent is 40-60:10-50:5-20:5-20.
Preferably, the weight ratio of the catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent is 40-60: 30-50:15-20:10-20.
Preferably, the specific surface area of the catalytic cracking spent catalyst powder, which is greater than, is equal to 200m2/g。
Preferably, the catalytic cracking spent catalyst powder is to be made by ball milling.
Preferably, the cosolvent selects one or more of sodium hydroxide, calcium oxide and potassium hydroxide.
Preferably, the cosolvent selects potassium hydroxide.
Preferably, the foaming agent selects one of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus and hydrogen peroxide Or it is several.
Preferably, the foaming agent selects saleratus.
Technical characterstic for a better understanding of the invention is briefly described as follows technical principle and theoretical foundation of the invention:
It is a kind of hazardous waste there are heavy metals such as Ni, V, Sb in catalytic cracking spent catalyst, but catalytic cracking is given up and is catalyzed The main component of agent is SiO2、Al2O3Equal sieve and silica-sesquioxides and metal oxide, satisfaction prepare the component requirements of haydite.
The solidification of haydite can curing heavy metal, avoid the heavy metal pollution in catalytic cracking spent catalyst.Haydite is solid Change the mechanism of heavy metal: heavy metal element is in high-temperature sintering process, it may occur however that class matter enters Si-O bone with mutually replacing In frame network, becomes network and constitute body, to be firmly fixed in new mineral crystal structure, and clay ratio is to heavy metal Solidification have an impact, clay ratios are big, and Leaching of Heavy Metals concentration is generally smaller, and compression strength is bigger.
The technical effect directly brought by the technical proposal is that:
Using catalytic cracking spent catalyst as raw material, prepared by auxiliary materials such as addition clay, fluxing agent, foaming agents At high-strength ceramic granule, the solidification of haydite can curing heavy metal so that the leaching concentration of heavy metal is extremely low in haydite, to realize The collaboration of catalytic cracking spent catalyst is innoxious and recycling, not only solves asking for catalytic cracking spent catalyst pollution environment The haydite with higher economic value is also obtained in topic.
Specific embodiment
Combined with specific embodiments below, the present invention will be further described:
Embodiment 1:
High-strength ceramic granule using catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent as raw material, through mixing, stirring, Balling-up, drying and roasting are prepared.Wherein catalytic cracking spent catalyst powder is obtained by catalytic cracking spent catalyst through ball milling, Its specific surface area is 225m2/kg；Fluxing agent is sodium hydroxide；Foaming agent is sodium carbonate；Catalytic cracking spent catalyst powder glues Soil, sodium hydroxide, sodium carbonate weight ratio be 60:25:5:5, the nickel leaching concentration of the haydite being prepared is 0.11mg/L, is resisted Compressive Strength is 16MPa.
Embodiment 2:
High-strength ceramic granule using catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent as raw material, through mixing, stirring, Balling-up, drying and roasting are prepared.Wherein catalytic cracking spent catalyst powder is obtained by catalytic cracking spent catalyst through ball milling, Its specific surface area is 310m2/kg；Fluxing agent is calcium oxide；Foaming agent is sodium bicarbonate；Catalytic cracking spent catalyst powder glues Soil, sodium hydroxide, sodium carbonate weight ratio be 50:30:15:10, the nickel leaching concentration of the haydite being prepared is 0.08mg/L, Compression strength is 20MPa.
Embodiment 3:
High-strength ceramic granule using catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent as raw material, through mixing, stirring, Balling-up, drying and roasting are prepared.Wherein catalytic cracking spent catalyst powder is obtained by catalytic cracking spent catalyst through ball milling, Its specific surface area is 265m2/kg；Fluxing agent is potassium hydroxide；Foaming agent is hydrogen peroxide；Catalytic cracking spent catalyst powder glues Soil, sodium hydroxide, sodium carbonate weight ratio be 40:20:20:20, the nickel leaching concentration of the haydite being prepared is 0.21mg/L, Compression strength is 15MPa.
Embodiment 4:
High-strength ceramic granule using catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent as raw material, through mixing, stirring, Balling-up, drying and roasting are prepared.Wherein catalytic cracking spent catalyst powder is obtained by catalytic cracking spent catalyst through ball milling, Its specific surface area is 200m2/kg；Fluxing agent is sodium hydroxide；Foaming agent is potassium carbonate；Catalytic cracking spent catalyst powder glues Soil, sodium hydroxide, sodium carbonate weight ratio be 40:10:10:15, the nickel leaching concentration of the haydite being prepared is 0.23mg/L, Compression strength is 13MPa.
Embodiment 5:
High-strength ceramic granule using catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent as raw material, through mixing, stirring, Balling-up, drying and roasting are prepared.Wherein catalytic cracking spent catalyst powder is obtained by catalytic cracking spent catalyst through ball milling, Its specific surface area is 215m2/kg；Fluxing agent is potassium hydroxide；Foaming agent is saleratus；Catalytic cracking spent catalyst powder, Clay, sodium hydroxide, sodium carbonate weight ratio be 40:50:20:20, the nickel leaching concentration of the haydite being prepared is 0.05mg/ L, compression strength 25MPa.
Certainly, the above description is not a limitation of the present invention, and the present invention is also not limited to the example above, this technology neck The variations, modifications, additions or substitutions that the technical staff in domain is made within the essential scope of the present invention also should belong to of the invention Protection scope.

Claims (8)

1. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst, which is characterized in that the high-strength ceramic granule is by catalytic cracking Dead catalyst powder, clay, fluxing agent and foaming agent are made through mixing, stirring, balling-up, drying and roasting, and the catalysis is split The weight ratio for changing dead catalyst powder, clay, fluxing agent and foaming agent is 40-60:10-50:5-20:5-20.
2. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 1, which is characterized in that described Catalytic cracking spent catalyst powder, clay, fluxing agent and foaming agent weight ratio be 40-60:30-50:15-20:10-20.
3. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 1, which is characterized in that described The specific surface area of catalytic cracking spent catalyst powder, which is greater than, is equal to 200m2/g。
4. any high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 1 to 3, feature exist In the catalytic cracking spent catalyst powder is to be made by ball milling.
5. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 1, which is characterized in that described Cosolvent selects one or more of sodium hydroxide, calcium oxide and potassium hydroxide.
6. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 5, which is characterized in that described Cosolvent selects potassium hydroxide.
7. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 1, which is characterized in that described Foaming agent selects one or more of sodium carbonate, potassium carbonate, sodium bicarbonate, saleratus and hydrogen peroxide.
8. a kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst according to claim 7, which is characterized in that described Foaming agent selects saleratus.
CN201711133628.9A 2017-11-16 2017-11-16 A kind of high-strength ceramic granule prepared by catalytic cracking spent catalyst Pending CN109305823A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564400A (en) * 2019-09-24 2019-12-13 中石化石油工程技术服务有限公司 fracturing propping agent sintered by oil-based drilling cutting thermal desorption residues and preparation method thereof
CN114426429A (en) * 2020-09-02 2022-05-03 中国石油化工股份有限公司 Filling sand mixture, ceramsite filling sand, and preparation method and application thereof
CN114426837A (en) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 Micron-sized fracturing propping agent and preparation method thereof
RU2789299C1 (en) * 2022-08-10 2023-02-01 федеральное государственное автономное образовательное учреждение высшего образования "Самарский государственный экономический университет" Ceramic mass for manufacturing ceramic seismic resistant brick
CN116023119A (en) * 2021-10-26 2023-04-28 中国石油化工股份有限公司 Porous ceramic and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08119766A (en) * 1994-10-27 1996-05-14 Showa Shell Sekiyu Kk Porous ceramic sintered compact and its production
CN102126838A (en) * 2010-12-09 2011-07-20 江西赣锋锂业股份有限公司 Method for preparing light building material ceramsites by using lithium extraction slag of lithium mica
CN103922664A (en) * 2014-03-25 2014-07-16 江苏尼高科技有限公司 Lightweight partition plate produced by using oil refining waste catalyst and its preparation method
CN104446350A (en) * 2014-11-25 2015-03-25 沈阳建筑大学 Gangue lightweight aggregate ceramsite and preparation method thereof
CN106565274A (en) * 2016-11-21 2017-04-19 江苏建筑职业技术学院 Fiber enhanced ceramsite foamed concrete and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH08119766A (en) * 1994-10-27 1996-05-14 Showa Shell Sekiyu Kk Porous ceramic sintered compact and its production
CN102126838A (en) * 2010-12-09 2011-07-20 江西赣锋锂业股份有限公司 Method for preparing light building material ceramsites by using lithium extraction slag of lithium mica
CN103922664A (en) * 2014-03-25 2014-07-16 江苏尼高科技有限公司 Lightweight partition plate produced by using oil refining waste catalyst and its preparation method
CN104446350A (en) * 2014-11-25 2015-03-25 沈阳建筑大学 Gangue lightweight aggregate ceramsite and preparation method thereof
CN106565274A (en) * 2016-11-21 2017-04-19 江苏建筑职业技术学院 Fiber enhanced ceramsite foamed concrete and preparation method thereof

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110564400A (en) * 2019-09-24 2019-12-13 中石化石油工程技术服务有限公司 fracturing propping agent sintered by oil-based drilling cutting thermal desorption residues and preparation method thereof
CN110564400B (en) * 2019-09-24 2022-07-12 中石化石油工程技术服务有限公司 Fracturing propping agent sintered by oil-based drilling cutting thermal desorption residues and preparation method thereof
CN114426429A (en) * 2020-09-02 2022-05-03 中国石油化工股份有限公司 Filling sand mixture, ceramsite filling sand, and preparation method and application thereof
CN114426837A (en) * 2020-10-29 2022-05-03 中国石油化工股份有限公司 Micron-sized fracturing propping agent and preparation method thereof
CN114426837B (en) * 2020-10-29 2023-06-16 中国石油化工股份有限公司 Micron-sized fracturing propping agent and preparation method thereof
CN116023119A (en) * 2021-10-26 2023-04-28 中国石油化工股份有限公司 Porous ceramic and preparation method thereof
RU2789299C1 (en) * 2022-08-10 2023-02-01 федеральное государственное автономное образовательное учреждение высшего образования "Самарский государственный экономический университет" Ceramic mass for manufacturing ceramic seismic resistant brick

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