CN106477612B - A kind of method for preparing anhydrous calcium chloride using white clay and iron content by-product waste hydrochloric acid - Google Patents
A kind of method for preparing anhydrous calcium chloride using white clay and iron content by-product waste hydrochloric acid Download PDFInfo
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- CN106477612B CN106477612B CN201610840037.4A CN201610840037A CN106477612B CN 106477612 B CN106477612 B CN 106477612B CN 201610840037 A CN201610840037 A CN 201610840037A CN 106477612 B CN106477612 B CN 106477612B
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- Prior art keywords
- white clay
- hydrochloric acid
- calcium chloride
- iron content
- waste hydrochloric
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Classifications
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- 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
- C01F11/28—Chlorides by chlorination of alkaline-earth metal compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
The present invention relates to a kind of method for preparing anhydrous calcium chloride using white clay and iron content by-product waste hydrochloric acid, obtained anhydrous calcium chloride cost is very low, and process equipment is simple, easily operated popularization.The problem of because raw material is white clay and iron content by-product waste hydrochloric acid, can not only turning waste into wealth, and meeting to white clay and iron content by-product waste hydrochloric acid mass disposal, there is economic, society and environmental benefit well.
Description
Technical field
Present invention relates particularly to a kind of method for preparing anhydrous calcium chloride using white clay and iron content by-product waste hydrochloric acid, belong to ring
Border is protected and technical field of resource utilization.
Background technology
Soda ash is important basic chemical industry raw material, is widely used in the works such as metallurgy, chemical industry, weaving, papermaking, medicine and food
Industry.China mainly uses ammonia-soda process soda ash, annual production ten thousand t about more than 2000 at present, but at the same time to discharge alkaline residue and (be commonly called as
White clay) more than 600 ten thousand t (butt), plus accumulation over the years, substantial amounts of white clay, reasonably it cannot handle and utilize for a long time, not only make
Into the wasting of resources, and the substantial amounts of human and material resources of consumption, financial resources are managed, and appropriation of land, pollution environment, destroy ecological put down
Weighing apparatus.Due to the special nature that white clay has in itself, it, which is handled, utilizes difficulty very big, as the enhancing of environmental consciousness and white clay are stored up
The growing tension in place, the processing of white clay turn into urgent problem to be solved, it is necessary to which the processing for energetically exploring white clay utilizes skill
Art.
With the development of steel and iron industry and Surface Processing Industry, into making, metal surface is clean and tidy, improves steel table for pickling
Face structure and surface is processed etc. steel production carried out with process together with critically important process.Pickling
Pickle concentration used is usually 200g/L, constantly there is ferrous ion generation in acid cleaning process, and its concentration gradually increases
Add while acid concentration constantly reduces.In order to ensure that the quality of acid-washed product and effect need to discharge pickle liquor, change new
Pickle.The whole nation is annual at present will be about discharging up to million cubic metres of waste liquid, and it is just with the raising of steel yield and quality
And increase.The characteristics of pickle liquor is concentration height, and waste liquid amount is big, and temperature is up to 50-100 DEG C, and containing a considerable amount of residual
Spent acid, ferrous salt is rich in, separately containing a small amount of insoluble matter.Pickle liquor has the characteristics that concentration is high, concentration is high, temperature is high, own quilt
Various countries are managed as hazardous waste, and the U.S. is included in《Protection of resources and regeneration bill》, it is also included in by China《Country
Hazardous Waste List》.
The content of the invention
In order to solve the above-mentioned problems in the prior art, the present invention provides one kind and utilizes white clay and iron content by-product abraum salt
The method that acid prepares anhydrous calcium chloride, anhydrous calcium chloride cost is very low made from this method, and process equipment is simple, easily operated
Promote.Raw material additionally, due to this method is white clay and iron content by-product waste hydrochloric acid, can not only be turned waste into wealth, and is met to white clay
The problem of with iron content by-product waste hydrochloric acid mass disposal, there is economic, society and environmental benefit well.
The present invention adopts the following technical scheme that, a kind of side that anhydrous calcium chloride is prepared using white clay and iron content by-product waste hydrochloric acid
Method, comprise the following steps：
1) white clay and iron content by-product abraum salt acid reaction
White clay will be dried and waste hydrochloric acid containing iron is put into the reaction tank of agitating device, stop stirring after reacting 0.5-2h
Mix；
2) calcium chloride solution is made
Reservoir is introduced after reaction solution is clarified, regulation ph values are 8-9, and calcium chloride solution is produced after filtering；
3) anhydrous calcium chloride solid product is obtained
By the evaporation of the 3rd step resulting solution, crystallisation by cooling, and dried at 200-300 DEG C to constant weight.
In a preferred embodiment of the present invention, described white clay is that ammonia-soda process prepares the alkali discharged during soda ash
Slag, alkaline residue crushed the use of 20 mesh sieve, and alkaline residue particle diameter is less than 840 μm.
In a preferred embodiment of the present invention, the mass ratio of iron content by-product waste hydrochloric acid and white clay is 1-4.
In a preferred embodiment of the present invention, described iron content by-product waste hydrochloric acid is acid washing rolled steel waste liquid, mainly into
It is divided into hydrogen chloride and frerrous chloride, Chlorine in Solution ion concentration is 130-160g/L, and iron ion total concentration is 60-80g/L, is dissociated
Hydrochloric acid 50-70g/L.
In a preferred embodiment of the present invention, the conditioning agent of pH value is lime milk solution.
In a preferred embodiment of the present invention, the above method, which also includes subsequent detection anhydrous calcium chloride solid product, is
It is no to meet standard, wherein by national standard《GB/T 26520—2011》Relevant criterion detects to anhydrous calcium chloride solid.
Compared with prior art, present invention firstly provides prepare anhydrous chlorination as raw material using white clay and iron content by-product waste hydrochloric acid
Calcium, obtained anhydrous calcium chloride performance fully meet national standard, and preparation method cost is very low, and process equipment is simple, is easy to
The problem of operation is promoted, and can not only be turned waste into wealth, and satisfaction is to white clay and iron content by-product waste hydrochloric acid mass disposal, have very
Good economy, society and environmental benefit.
Embodiment
In order that the purpose of the present invention, technical scheme and beneficial effect are clearer, present invention specific examples below
Illustrate, but the present invention is limited to absolutely not these examples.
Embodiment 1：
White clay is crushed after drying 20 mesh sieve, it is 160g/L to take 150g white clays and 600g chlorions, and free hydrochloric acid is
70g/L, iron ion are 60g/L iron content by-product waste hydrochloric acid stirring reaction 1h in reaction tank, and reaction residual liquor is clarified, press filtration
After import reservoir, into reservoir be hydrogenated with calcium oxide solution adjust solution to pH=8, calcium chloride liquid, chlorination are obtained after filtering
Calcium liquid through evaporation, crystallisation by cooling, dry after obtain calcium chloride mass fraction be 91.3%, ferro element mass fraction be 0.0032%
Anhydrous calcium chloride 82.1g.The chemical reaction of the present embodiment is as follows：
CaCO3+2HCl→CaCl2+CO2↑+H2O,
FeCl2+Ca(OH)2→Fe(OH)2↓+CaCl2,
CaCl2 •nH2O→CaCl2+nH2O↑。
Embodiment 2：
After white clay crushed 20 mesh sieve, it is 140g/L, free hydrochloric acid 60g/L to take 150g white clays and 450g chlorions,
Iron ion is 50g/L iron content by-product waste hydrochloric acid stirring reaction 3h in reaction tank, and reaction residual liquor is clarified, is imported after press filtration
Reservoir, calcium oxide solution is hydrogenated with into reservoir and adjusts solution to ph=8.4, calcium chloride liquid, liquid calcium chloride are obtained after filtering
Body obtains the anhydrous chlorination that mass fraction is 95%, ferro element mass fraction is 0.00061% after evaporation, crystallisation by cooling, drying
Calcium 52.3g.The chemical equation of the present embodiment is such as the description to embodiment 1.
Embodiment 3：
After white clay crushed 20 mesh sieve, it is 130g/L, free hydrochloric acid 50g/L to take 150g white clays and 300g chlorions,
Iron ion is that 70g/L iron content by-product waste hydrochloric acid stirs anti-1h in reaction tank, and reaction residual liquor is clarified, storage is imported after press filtration
Liquid bath, calcium oxide solution is hydrogenated with into reservoir and adjusts solution to ph=8.8, calcium chloride liquid, calcium chloride liquid are obtained after filtering
The anhydrous chlorination that mass fraction is 95.6%, ferro element mass fraction is 0.00048% is obtained after evaporation, crystallisation by cooling, drying
Calcium 39.8g.The chemical equation of the present embodiment is such as the description to embodiment 1.
Press《GB/T 26520—2011》Industrial calcium chloride requirement, need to be to the outward appearance, calcium chloride content, alkali of calcium chloride product
Degree, total alkali metal chloride content, water-insoluble, iron, pH value, total magnesium, sulphates content are detected.Outside calcium chloride product
Sight, total alkali metal chloride content, water-insoluble, iron, pH value are according to national standard《GB/T 26520—2011》In method enter
Row detection, calcium chloride content, basicity, total magnesium are detected using the method for electrochemistry, and sulfate is then examined using ultraviolet specrophotometer
Survey.
The calcium chloride testing result of purity highest embodiment 3 is as follows：
Calcium chloride content is 95.6%, basicity 0.12%, and total alkali metal chloride is 3.45%, water-insoluble 0.16%,
Iron content is 0.00048%, pH value 8.2, and total content of magnesium is 0.45%, sulphates content 0.039%.
Although by referring to the preferred embodiments of the present invention, invention has been described, this area it is common
It will be appreciated by the skilled person that various changes can be made to it in the form and details, without departing from appended right
The spirit and scope of the present invention that claim is limited.
Claims (3)
- A kind of 1. method for preparing anhydrous calcium chloride using white clay and iron content by-product waste hydrochloric acid, it is characterised in that specific steps are such as Under：1) white clay and iron content by-product abraum salt acid reactionWhite clay will be dried and waste hydrochloric acid containing iron is put into the reaction tank of agitating device, stop stirring after reacting 0.5-2h；2) calcium chloride solution is madeReservoir is introduced after reaction mixture is clarified, regulation pH value is 8-9, and calcium chloride solution is produced after filtering；3) anhydrous calcium chloride solid product is obtainedBy the evaporation of the 3rd step resulting solution, crystallisation by cooling, and dried at 200-300 DEG C to constant weight；Described white clay is that ammonia-soda process prepares the alkaline residue discharged during soda ash；Described iron content by-product waste hydrochloric acid and the mass ratio of white clay are 1-4；Described iron content by-product waste hydrochloric acid is acid washing rolled steel waste liquid, and main component is hydrogen chloride and frerrous chloride, Chlorine in Solution from Sub- content is 130-160g/L, and iron ion total concentration is 60-80g/L, free hydrochloric acid 50-70g/L.
- 2. according to the method for claim 1, it is characterised in that described white clay is to be discharged during ammonia-soda process prepares soda ash Alkaline residue, alkaline residue crushed 20 mesh sieve use.
- 3. according to the method for claim 1, it is characterised in that the conditioning agent of pH value is lime milk solution.
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| CN107662934B (en) * | 2017-10-19 | 2018-05-01 | 黑龙江科技大学 | A kind of method that applicable industry waste prepares hydrated calcium silicate and magnetic hydrotalcite |
| CN108585012B (en) * | 2018-05-28 | 2023-09-15 | 福建鼎盛元环保科技有限公司 | Process and production line for producing calcium chloride and aluminum hydroxide by utilizing waste |
| CN114159963B (en) * | 2021-12-01 | 2023-05-16 | 山东海化集团有限公司 | Method for producing calcium chloride solution from waste residues generated in alkali preparation by ammonia-soda process |
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| CN1194898C (en) * | 2001-10-15 | 2005-03-30 | 广西大学 | Process for preparing both barium sulfate and calcium chloride from waste ardealite dregs |
| CN101045546A (en) * | 2007-04-28 | 2007-10-03 | 沈阳化工股份有限公司 | Production method of calcium chloride snow melting agent |
| CN104229854A (en) * | 2014-10-08 | 2014-12-24 | 攀枝花钢企欣宇化工有限公司 | Calcium chloride solution producing method |
| CN105624430A (en) * | 2016-02-04 | 2016-06-01 | 马守栋 | Method for extracting nickel and cobalt from nickel laterite ore through caustic sludge and waste pickling liquid |
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