CN106629803B - The method for producing calcium chloride and aluminium polychloride using high-calcium fly ass - Google Patents
The method for producing calcium chloride and aluminium polychloride using high-calcium fly ass Download PDFInfo
- Publication number
- CN106629803B CN106629803B CN201610894457.0A CN201610894457A CN106629803B CN 106629803 B CN106629803 B CN 106629803B CN 201610894457 A CN201610894457 A CN 201610894457A CN 106629803 B CN106629803 B CN 106629803B
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- Prior art keywords
- calcium
- fly ass
- hydrochloric acid
- dissolution
- temperature
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/20—Halides
- C01F11/24—Chlorides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/48—Halides, with or without other cations besides aluminium
- C01F7/56—Chlorides
Abstract
The invention discloses a kind of methods producing calcium chloride and aluminium polychloride using high-calcium fly ass.The present invention uses high-calcium fly ass and hydrochloric acid for raw material, goes out calcium chloride and aluminium polychloride product by technique productions such as gradually temperature raising, segmentation dissolutions.This method improves valuable metal comprehensive utilization ratio in high-calcium fly ass, reduces environmental pollution, has the advantages that raw material sources are wide, technological process is short, consuming little energy, good in economic efficiency.
Description
Technical field
The present invention relates to a kind of methods producing calcium chloride and aluminium polychloride using high-calcium fly ass, and it is comprehensive to belong to flyash
It closes and utilizes technical field.
Background technology
Flyash is the waste of coal-burning power plant's discharge, and current one of maximum industrial waste of discharge capacity in the world.
Since the quantity and scale in thermal power plant constantly expand, the sharp increase of flyash discharge capacity is resulted in.Recently as state
The aggravation of border performance source imbalance between supply and demand and the requirement more and more high to environmental protection, the powder treated for a long time as solid waste
Oneself causes the concern of countries in the world to coal ash, and is conducted extensive research to it, has made some progress.
High-calcium fly ass is a major class of flyash, accounts for about the 1/3 of flyash total amount, generally by calcium oxide content >=8%
Flyash be referred to as high-calcium fly ass, predominantly lignite and ub-bituminous coal burning gained.CaO improves intentionally for desulfurization in some power plant
Content, takes in stove while spraying into the measures such as pulverized limestone, and the flyash obtained in this way is also high-calcium fly ass.Flyash at present
Extract valuable metal research emphasis mainly extract aluminium, in flyash calcium and other elements concern and it is few, extracted
Calcium and other metallic elements are often treated as impurity in journey, and the method taken is to abandon calcium and the removal of other metallic elements.
It is actually rare for the report and patent of the extraction valuable metal of high-calcium fly ass, if extraction aluminium is not only uneconomical merely, also
It can cause the waste of other valuable metals.
Invention content
In view of the deficiencies of the prior art, the purpose of the present invention is to provide it is a kind of using high-calcium fly ass production calcium chloride and
The method of aluminium polychloride.The method of the present invention is simple, is skillfully constructed, and valuable metal substep in flyash can be made to be fully dissolved out, work
Skill flow is short, consuming little energy；Using present invention process, aoxidize 95% or more dissoluble rate of calcium, the dissolution rate 90% of aluminium oxide with
On, iron oxide dissolution rate can reach 95% or more.
The present invention uses gradually temperature raising to high-calcium fly ass, dissolving-out process is segmented, to realize the step by step arithmetic of calcium and aluminium.
It utilizes the difference of different material Dissolution behaviours, dissolves out calcium oxide at low temperature first, and aluminium oxide and iron oxide are dissolved out in high temperature,
Achieve the purpose that separation.
Technical scheme of the present invention is specifically described as follows.
The present invention provides a kind of method producing calcium chloride and aluminium polychloride using high-calcium fly ass, and specific steps are such as
Under：
(1) high-calcium fly ass and mixed in hydrochloric acid are subjected to low temperature dissolution, are once separated by solid-liquid separation after low temperature dissolution, once
Solution after separation produces calcium chloride product；Wherein：The mass percent concentration of the hydrochloric acid is 1%-5%, the temperature of low temperature
It it is 80 DEG C~100 DEG C, the mass ratio of high-calcium fly ass and hydrochloric acid is 1:3~1:5；
(2) high temperature dissolution is carried out with mixed in hydrochloric acid after the solid washing after first separation, is carried out after high temperature dissolution secondary solid
Liquid detaches, and the solution after secondary separation produces aluminium polychloride；Wherein：The mass percent concentration of the hydrochloric acid is 25%-
31%, the temperature of high temperature is 150 DEG C~195 DEG C, and the mass ratio of solid and hydrochloric acid after first separation is 1:3~1:5.
In above-mentioned steps (1), the temperature of the low temperature is 80~90 DEG C.
In above-mentioned steps (1), dissolution time is 0.5~4h, and the mass percent concentration of hydrochloric acid is 1%~3%.
In above-mentioned steps (2), the temperature of the high temperature is 160-175 DEG C.
In above-mentioned steps (2), dissolution time is 2~5h, and hydrochloric acid mass percent concentration is 28%~31%.
In the present invention, dissolution rate >=95% of calcium oxide after low temperature dissolution, digesting efficiency of alumina≤5%, iron oxide dissolution
Rate≤5%；The calcareous amount of Chlorine in Solutionization a concentration of 12%~40% after first separation；High temperature dissolution after digesting efficiency of alumina >=
90%, iron oxide dissolution rate >=95%.Chlorine in Solution aluminum amount a concentration of 15%~32% after secondary separation.Utilize this hair
The calcium chloride of the method production of bright offer reaches industrial chlorinations standard calcium (GB/T 26520-2011), the aluminium polychloride of production
Reach water process rank (GB/T 22627-2008) or Drinking Water rank (GB/T 15892-2009).
Compared with prior art, the method that the present invention uses has following advantage：
(1) present invention controls acid concentration and reaction temperature, effectively using gradually temperature raising, segmentation dissolving-out process by control
Ground has detached calcium constituent and aluminium element, can significantly shorten flow.
(2) process efficiency is high, and valuable metal in flyash can be made to be fully dissolved out, and aoxidizes 95% or more dissoluble rate of calcium, oxygen
The dissolution rate for changing aluminium ensures that iron oxide dissolution rate can reach 95% or more, and valuable metal comprehensive utilization ratio is high 90% or more,
Significantly improve economic benefit.
Specific implementation mode
Embodiment 1
Two 330MW units of Inner Mongolia Autonomous Region somewhere power plant generate about 1,920,000 tons of high-calcium fly ass every year, and ingredient is
CaO-8.3%, Al2O3- 44.43%, SiO2- 31.37%, Fe2O3- 1.95%, MgO-0.76%, igloss -10.68%, fine coal
Ash does not comprehensively utilize all into lime-ash stockyard.
Hydrochloric acid (the solid-liquid quality that the above high-calcium fly ass and mass percent concentration are 1% by method using the present invention
Than being 1:4) low temperature digestion series are mixed into, 80 DEG C, dissolution time 2h of leaching temperature is controlled, low temperature dissolves out the dissolution of calcium oxide
Rate reaches 97.8%, and the dissolution rate of aluminium oxide and iron oxide is respectively 1.7% and 2.3%.Dissolution afterchlorinate calcium solution concentration reaches
To 14.2%, calcium chloride solution can may be made as calcium chloride dihydrate or anhydrous calcium chloride product directly as product.First separation
Solid and matter percent concentration be 31% hydrochloric acid (solid-liquid mass ratio 1:3) high temperature digestion series, control dissolution are mixed into
The dissolution rate of 160 DEG C, dissolution time 4h of temperature, high temperature dissolution aluminium oxide reaches 94.7%, and total dissolution rate of iron oxide reaches
99.3%.Dissolution afterchlorinate aluminum solutions mass concentration reaches 25.4%, and liquor alumini chloridi can be made into after the pyrolysis that crystallizes, boils
Aluminium polychloride product.
Embodiment 2
About 3,000,000 tons of high calcium circulating fluid bed coal ash of the annual output of large enterprise of Shandong Province, ingredient CaO-
18.07%, Al2O3- 24.47%, SiO2- 36.80%, Fe2O3- 5.83%, MgO-3.27%, igloss -11.56%.
Hydrochloric acid that the high-calcium fly ass of mentioned component and mass percent concentration are 5% by method using the present invention (Gu
Liquid mass ratio 1:3) low temperature digestion series are mixed into, 80 DEG C, dissolution time 3h of leaching temperature is controlled, low temperature dissolves out calcium oxide
Dissolution rate reaches 98.2%, and the dissolution rate of aluminium oxide and iron oxide is respectively 1.52% and 2.2%.It is dense to dissolve out afterchlorinate calcium solution
Degree reaches 18%, and calcium chloride solution can may be made as calcium chloride dihydrate or anhydrous calcium chloride product directly as product.Primary point
From solid and mass percent concentration be 25wt% hydrochloric acid (solid-liquid mass ratio 1:5) high temperature digestion series are mixed into, are controlled
150 DEG C, dissolution time 3h of leaching temperature processed, dissolution rate 87%, dissolution afterchlorinate aluminum solutions concentration reaches 22%, by knot
Aluminium polychloride product is can be made into after brilliant, boiling pyrolysis.
Claims (1)
1. a kind of method producing calcium chloride and aluminium polychloride using high-calcium fly ass, which is characterized in that be as follows：
(1) high-calcium fly ass and mixed in hydrochloric acid are subjected to low temperature dissolution, are once separated by solid-liquid separation after low temperature dissolution, first separation
Solution afterwards produces calcium chloride product；Wherein：The mass percent concentration of the hydrochloric acid is 1%~3%, and the temperature of low temperature is 80
DEG C~100 DEG C, the mass ratio of high-calcium fly ass and hydrochloric acid is 1:3~1:5, dissolution time is 0.5~2h；
(2) solid after first separation carries out high temperature dissolution with mixed in hydrochloric acid, and secondary separation of solid and liquid is carried out after high temperature dissolution, secondary
Solution after separation produces aluminium polychloride；Wherein：The mass percent concentration of the hydrochloric acid is 25% or 28% or 31%, high
The temperature of temperature is 160 DEG C~195 DEG C, and the mass ratio of solid and hydrochloric acid after first separation is 1:3~1:5, dissolution time be 3~
5h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610894457.0A CN106629803B (en) | 2016-10-13 | 2016-10-13 | The method for producing calcium chloride and aluminium polychloride using high-calcium fly ass |
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|---|---|---|---|
| CN201610894457.0A CN106629803B (en) | 2016-10-13 | 2016-10-13 | The method for producing calcium chloride and aluminium polychloride using high-calcium fly ass |
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| Publication Number | Publication Date |
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| CN106629803A CN106629803A (en) | 2017-05-10 |
| CN106629803B true CN106629803B (en) | 2018-08-14 |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107601539B (en) * | 2017-08-08 | 2020-01-07 | 中国铝业股份有限公司 | Method for preparing polyaluminum chloride from sodium-silicon slag |
| CN110902704A (en) * | 2018-09-17 | 2020-03-24 | 中国科学院过程工程研究所 | Method for preparing polyaluminum chloride by using fluidized bed fly ash |
| CN110903104A (en) * | 2018-09-17 | 2020-03-24 | 中国科学院过程工程研究所 | Method for preparing foamed ceramic and co-producing calcium chloride and polyaluminium chloride by fluidized bed fly ash |
| CN110902709B (en) * | 2018-09-17 | 2021-05-14 | 中国科学院过程工程研究所 | Method for preparing calcium chloride by utilizing fluidized bed fly ash |
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| CN101172684B (en) * | 2007-10-09 | 2010-11-24 | 王贵明 | Method for industrial production of polymeric aluminum ferric chloride water purification agent with coal ash |
| CN103601228B (en) * | 2013-11-01 | 2015-06-24 | 青岛星火化工技术有限公司 | Method for preparation of chemical raw materials by use of fly ash as raw material |
| CN104876253B (en) * | 2015-05-15 | 2017-08-25 | 南阳东方应用化工研究所 | The processing method of calcium in high-calcium fly ass |
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