CN100465096C - Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material - Google Patents

Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material Download PDF

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CN100465096C
CN100465096C CNB2007100684330A CN200710068433A CN100465096C CN 100465096 C CN100465096 C CN 100465096C CN B2007100684330 A CNB2007100684330 A CN B2007100684330A CN 200710068433 A CN200710068433 A CN 200710068433A CN 100465096 C CN100465096 C CN 100465096C
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flyash
acid
coal series
series kaolin
kaolin rock
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CN101045543A (en
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夏枚生
叶瑛
邬黛黛
张平萍
陈雪刚
张孝彬
程继鹏
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

A process for preparing flaky aluminum oxide from coal kaolinite or powdered coal ash includes such steps as pulverizing, magnetic separation, high-temp calcining, extracting in acid to obtain Al salt, purifying, refining, crystallizing, shaping and pyrolyzing.

Description

A kind of is the method for feedstock production tabular alumina with coal series kaolin rock or flyash
Technical field
The present invention relates to coal series kaolin rock or Ash Utilization deep processing and utilization field, particularly a kind of is the method for feedstock production tabular alumina with coal series kaolin rock or flyash.
Background technology
Coal series kaolin rock and flyash are being used as cement, ceramic raw material, papermaking, coating and filler traditionally, in view of domestic and international market bauxite resource critical shortage, coal series kaolin rock and flyash also are used as the raw material of producing aluminum oxide in recent years, because of product orientation mainly is the low value-added product of some preliminary working, the utilization of resources is insufficient, economic benefit is not obvious at present.
Tabular alumina is except that the good physical and chemical performance with aluminum oxide itself, also because it is nano level or be bordering on nano level on thickness dimension, it on the radial dimension micron order, thereby have the dual nature of nano-powder and micro-powder concurrently, can combine with other active group is effective, be difficult for again reuniting; The flaky alumina purity height of synthetic, the face thickness rate is adjustable, and powder itself is close to water white transparency.In pearly pigment, makeup, automobile finish, filler and abrasive material field etc., huge application potential is arranged.
The technical difficult points of acidic process coal series kaolin rock or fly-ash Preparation tabular alumina is: 1) foreign ions such as the iron in the purification removal vat liquor, manganese, the particularly removal of iron ion, common method for removing iron as: technology such as extraction, ion-exchange, recrystallization, alkaline media deironing can not reach economical and effective deironing purpose; 2) the aluminum oxide crystalline form is difficult to control, and tabular alumina is used preparations such as molten-salt growth method, high-temperature sintering process, hydrothermal method, coating method, mechanical process usually, these method steps complexity usually, and processing condition are strict, and product purity is low, the cost height.
Summary of the invention
The purpose of this invention is to provide a kind of is the method for feedstock production tabular alumina with coal series kaolin rock or flyash.
With coal series kaolin rock or flyash is that the method for feedstock production tabular alumina is to be raw material with coal series kaolin rock or flyash, through pulverizing, magnetic separation, calcining, acidleach carry aluminium salt, pyrogenically prepared flake ultrafine aluminum oxide after purified, refining, the shaping, concrete steps are as follows:
1) with the oven dry of coal series kaolin rock or flyash, pulverize, dry magnetic separation then 550~850 ℃ of calcinings 1~4 hour down, is that 20~35% acid mixes with mass percent concentration, 100~250 ℃ of following lixiviates 1~4 hour; Filter or centrifugation, promptly get aluminum salt solution;
2) aluminum salt solution that step 1) is made is regulated pH to 3~5 with alkali, filters or centrifugation, obtains the purified aluminium salts solution;
3) with step 2) gained purified aluminium salts solution evaporation concentration is to saturated adding shaping agent, and by aluminium: the mol ratio of shaping agent is 1:50~300, is cooled to room temperature, separates out aluminium salt, after filtration or centrifugation, promptly gets and makes with extra care flaky aluminum salt; Mother liquid recycling.
4) the refining flaky aluminum salt of step 3) gained is put into the calcining furnace pyrolysis, be warming up to 400~500 ℃, be incubated 1~2 hour with the speed of 2~20 ℃/min; Speed with 100~200 ℃/min is warming up to 1000~1300 ℃ then, is incubated 1~2 hour, gets the flake ultrafine alumina product.
Described acid is hydrochloric acid, sulfuric acid or nitric acid.The shaping agent is formic acid, acetate, propionic acid, butyric acid or the compound between them.
The advantage that comparison had of the present invention and prior art is that preparation technology is simple, the operational condition gentleness, and raw material cheaply is easy to get, the mother liquor reusable edible, cost is low; The flake ultrafine aluminum oxide pattern of preparation is regular, particle diameter even, narrow particle size distribution, and the face thickness rate is big.
Embodiment
Of the present invention is the method for feedstock production tabular alumina with coal series kaolin rock or flyash, pH condition by the hierarchy of control, impurity major parts such as iron in the aluminium vat liquor, manganese, lead are removed with sedimentary form, again that purified aluminum salt solution evaporation concentration is extremely saturated, add precipitation agent, shaping agent, use the salting-out process recrystallization, obtain purified flaky aluminum salt.Used precipitation agent, shaping agent are same class organic acids, i.e. formic acid, acetate, propionic acid, butyric acid or the compound between them.
Of the present invention is the method for feedstock production tabular alumina with coal series kaolin rock or flyash, it is characterized in that to make with extra care flaky aluminum salt by temperature programming, dehydration and acid group and the aluminum oxide temperature rise rate of conversion stage is mutually controlled in high-temperature calcination respectively, the flake ultrafine alumina product.
The present invention is further described in conjunction with following example, but content of the present invention is not limited only to content related among the embodiment.
Embodiment 1
1) with coal series kaolin rock oven dry, to pulverize, dry magnetic separation then 550 ℃ of calcinings 4 hours down, is that 20% sulfuric acid mixes with mass percent concentration, 250 ℃ of following lixiviates 1 hour; Filter, promptly get alum liquor;
2) alum liquor that step 1) is made is regulated pH to 3 with sodium hydroxide, filters, and obtains the purification of sulphuric acids aluminum solutions;
3) with step 2) gained purification of sulphuric acids aluminum solutions evaporation concentration is to saturated, and by aluminium: the mol ratio of formic acid is that the ratio of 1:50 adds formic acid, is cooled to room temperature, separates out Tai-Ace S 150, and filtration promptly gets and makes with extra care sheet Tai-Ace S 150; Mother liquid recycling.
4) the refining sheet Tai-Ace S 150 of step 3) gained is put into the calcining furnace pyrolysis, be warming up to 400 ℃, be incubated 1 hour with the speed of 2 ℃/min; Speed with 100 ℃/min is warming up to 1000 ℃ then, is incubated 1 hour, gets the flake ultrafine alumina product.
Embodiment 2
1) with flyash oven dry, to pulverize, dry magnetic separation then 850 ℃ of calcinings 1 hour down, is that 35% nitric acid mixes with mass percent concentration, 100 ℃ of following lixiviates 4 hours; Centrifugation promptly gets aluminum nitrate solution;
2) aluminum nitrate solution that step 1) is made is regulated pH to 5 with sodium bicarbonate, and centrifugation obtains the purifying aluminum nitrate solution;
3) with step 2) gained purifying aluminum nitrate solution evaporation concentration is to saturated, and by aluminium: the mol ratio of acetate is the ratio adding acetate of 1:300, is cooled to room temperature, separates out aluminum nitrate, and centrifugation promptly gets and makes with extra care the sheet aluminum nitrate; Mother liquid recycling.
4) the refining sheet aluminum nitrate of step 3) gained is put into the calcining furnace pyrolysis, be warming up to 500 ℃, be incubated 2 hours with the speed of 20 ℃/min; Speed with 200 ℃/min is warming up to 1300 ℃ then, is incubated 2 hours, gets the flake ultrafine alumina product.
Embodiment 3
1) with coal series kaolin rock oven dry, pulverize, dry magnetic separation, then 650 ℃ of calcinings 3 hours down, with mass percent concentration be 30% mixed in hydrochloric acid, 125 ℃ of following lixiviates 4 hours; Filter, promptly get liquor alumini chloridi;
2) liquor alumini chloridi that step 1) is made is regulated pH to 5 with yellow soda ash, and centrifugation obtains the purification of chlorinated aluminum solutions;
3) with step 2) gained purification of chlorinated aluminum solutions evaporation concentration is to saturated, and by aluminium: the mol ratio of propionic acid is the ratio adding propionic acid of 1:50, is cooled to room temperature, separates out aluminum chloride, after filtration or centrifugation, promptly gets and makes with extra care sheet aluminum chloride, mother liquid recycling;
4) the refining sheet aluminum chloride of step 3) gained is put into calcining furnace, be warming up to 500 ℃, be incubated 2 hours with the speed of 2 ℃/min; Speed with 200 ℃/min is warming up to 1300 ℃ then, is incubated 1 hour, gets the flake ultrafine alumina product.
Embodiment 4
1) with coal series kaolin rock oven dry, to pulverize, dry magnetic separation then 750 ℃ of calcinings 1 hour down, is that 30% nitric acid mixes with mass percent concentration, 125 ℃ of following lixiviates 3.5 hours; Filter, promptly get aluminum nitrate solution;
2) pH of the aluminum nitrate solution that step 1) is made transfers to 3, filters or centrifugation, obtains the purifying aluminum nitrate solution;
3) with step 2) gained purifying aluminum nitrate solution evaporation concentration is to saturated, and by aluminium: butyro-mol ratio is the ratio adding butyric acid of 1:100, is cooled to room temperature, separates out aluminum nitrate, after filtration or centrifugation, promptly gets and makes with extra care sheet aluminum nitrate, mother liquid recycling;
4) the refining sheet aluminum nitrate aluminium of step 3) gained is put into calcining furnace, be warming up to 500 ℃, be incubated 1 hour with the speed of 20 ℃/min; Speed with 100 ℃/min is warming up to 1000 ℃ then, is incubated 2 hours, gets the flake ultrafine alumina product.
Embodiment 5
1) with coal series kaolin rock oven dry, to pulverize, dry magnetic separation then 850 ℃ of calcinings 1 hour down, is that 35% sulfuric acid mixes with mass percent concentration, 125 ℃ of following lixiviates 3.5 hours; Filter, promptly get alum liquor;
2) alum liquor that step 1) is made is regulated pH to 4 with sodium hydroxide, filters or centrifugation, obtains the purification of sulphuric acids aluminum solutions;
3) with step 2) gained purification of sulphuric acids aluminum solutions evaporation concentration is to saturated, and by aluminium: the mol ratio of propionic acid is that the ratio of 1:150 mol ratio adds propionic acid, is cooled to room temperature, separates out Tai-Ace S 150, and filtration promptly gets and makes with extra care sheet Tai-Ace S 150, mother liquid recycling;
4) the refining sheet Tai-Ace S 150 of step 3) gained is put into calcining furnace, be warming up to 500 ℃, be incubated 1.5 hours with the speed of 5 ℃/min; Speed with 200 ℃/min is warming up to 1200 ℃ then, is incubated 2 hours, gets the flake ultrafine alumina product.
Embodiment 6
1) with flyash oven dry, to pulverize, dry magnetic separation then 850 ℃ of calcinings 1 hour down, is that 35% sulfuric acid mixes with mass percent concentration, 125 ℃ of following lixiviates 3.5 hours; Filter, promptly get alum liquor;
2) alum liquor that step 1) is made is regulated pH to 4 with sodium hydroxide, filters or centrifugation, obtains the purification of sulphuric acids aluminum solutions;
3) with step 2) gained purification of sulphuric acids aluminum solutions evaporation concentration is to saturated, and by aluminium: the mol ratio of propionic acid is that the ratio of 1:150 adds propionic acid, is cooled to room temperature, separates out Tai-Ace S 150, and filtration promptly gets and makes with extra care sheet Tai-Ace S 150, mother liquid recycling;
4) the refining sheet Tai-Ace S 150 of step 3) gained is put into calcining furnace, be warming up to 500 ℃, be incubated 1.5 hours with the speed of 5 ℃/min; Speed with 200 ℃/min is warming up to 1200 ℃ then, is incubated 2 hours, gets the flake ultrafine alumina product.

Claims (3)

1. one kind is the method for feedstock production tabular alumina with coal series kaolin rock or flyash, it is characterized in that it is is raw material with coal series kaolin rock or flyash, through pulverizing, magnetic separation, calcining, acidleach carry aluminium salt, pyrogenically prepared flake ultrafine aluminum oxide after purified, refining, the shaping, concrete steps are as follows:
1) with the oven dry of coal series kaolin rock or flyash, pulverize, dry magnetic separation then 550~850 ℃ of calcinings 1~4 hour down, is that 20~35% acid mixes with mass percent concentration, 100~250 ℃ of following lixiviates 1~4 hour; Filter or centrifugation, promptly get aluminum salt solution;
2) aluminum salt solution that step 1) is made is regulated pH to 3~5 with alkali, filters or centrifugation, obtains the purified aluminium salts solution;
3) with step 2) gained purified aluminium salts solution evaporation concentration is to saturated adding shaping agent, and by aluminium: the mol ratio of shaping agent is 1:50~300, is cooled to room temperature, separates out aluminium salt, after filtration or centrifugation, promptly gets and makes with extra care flaky aluminum salt; Mother liquid recycling;
4) the refining flaky aluminum salt of step 3) gained is put into the calcining furnace pyrolysis, be warming up to 400~500 ℃, be incubated 1~2 hour with the speed of 2~20 ℃/min; Speed with 100~200 ℃/min is warming up to 1000~1300 ℃ then, is incubated 1~2 hour, gets the flake ultrafine alumina product.
2. as claimed in claim 1 a kind of be the method for feedstock production tabular alumina with coal series kaolin rock or flyash, it is characterized in that described acid is hydrochloric acid, sulfuric acid or nitric acid.
3. as claimed in claim 1 a kind of be the method for feedstock production tabular alumina with coal series kaolin rock or flyash, it is characterized in that described shaping agent is formic acid, acetate, propionic acid, butyric acid or the compound between them.
CNB2007100684330A 2007-05-08 2007-05-08 Method for preparing sheet alumina using coal series kaolin rock or flyash as raw material Expired - Fee Related CN100465096C (en)

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CN101775659B (en) * 2010-01-14 2011-11-23 陕西理工学院 Process for preparing mullite whisker or flaky alumina by using coal ash
CN101811712A (en) 2010-04-27 2010-08-25 中国神华能源股份有限公司 Method for preparing metallurgical-grade aluminum oxide by using fluid-bed fly ash
CN102020299B (en) * 2010-12-23 2012-10-24 南京航空航天大学 Method for producing industrial activated aluminum oxide from pulverized fuel ash
AU2012386620B2 (en) * 2012-08-01 2017-02-02 Obshestvo S Ogranichennoy Otvetstvennost'yu "Obedinennaya Kompania Rusal Inzhenerno-Tekhnologicheskiy Tsentr" Method for producing alumina
CN103480793A (en) * 2013-08-26 2014-01-01 安徽金岩高岭土科技有限公司 Precision-casting surface-layer sand powder processed from coal series kaolinite
CN106277002A (en) * 2016-08-18 2017-01-04 合肥信诺捷科节能服务有限公司 A kind of method preparing nano aluminium oxide

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961030A (en) * 1974-08-12 1976-06-01 Freeport Minerals Company Production of alumina from ores
CN1334240A (en) * 2000-07-14 2002-02-06 任忠胜 Process for preparing super-purity alumina from gaolinite (gaolin)
CN1623901A (en) * 2004-07-02 2005-06-08 郭长征 Novel process for producing alumina
CN1923695A (en) * 2006-09-15 2007-03-07 平朔煤炭工业公司 Method for preparing alumina from fly ash
CN1927716A (en) * 2006-08-29 2007-03-14 吉林大学 Preparation method of alumina

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3961030A (en) * 1974-08-12 1976-06-01 Freeport Minerals Company Production of alumina from ores
CN1334240A (en) * 2000-07-14 2002-02-06 任忠胜 Process for preparing super-purity alumina from gaolinite (gaolin)
CN1623901A (en) * 2004-07-02 2005-06-08 郭长征 Novel process for producing alumina
CN1927716A (en) * 2006-08-29 2007-03-14 吉林大学 Preparation method of alumina
CN1923695A (en) * 2006-09-15 2007-03-07 平朔煤炭工业公司 Method for preparing alumina from fly ash

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