CN102001687B - Method for preparing calcium chloride with co-produced sodium chloride and gypsum by using sodium carbonate distillation waste liquor - Google Patents
Method for preparing calcium chloride with co-produced sodium chloride and gypsum by using sodium carbonate distillation waste liquor Download PDFInfo
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- CN102001687B CN102001687B CN2010101689174A CN201010168917A CN102001687B CN 102001687 B CN102001687 B CN 102001687B CN 2010101689174 A CN2010101689174 A CN 2010101689174A CN 201010168917 A CN201010168917 A CN 201010168917A CN 102001687 B CN102001687 B CN 102001687B
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Abstract
The invention belongs to the technical field of treatment and utilization of chemical three-waste, in particular to a method for preparing calcium chloride with co-produced sodium chloride and gypsum by using sodium carbonate distillation waste liquor. The main technical scheme of the method comprises the following steps of: settling, distilling and re-distilling the sodium carbonate distillation waste liquor to obtain the sodium chloride and the calcium chloride; removing chlorine, purifying, synthesizing, washing, drying, grinding and packaging the deposits to obtain the gypsum. The invention can not only remove chemical pollution, but also can modify the distillation waste liquor into chemical products having a certain economic value; particularly, the method can clearly separate chlorine-containing compound and calcium-containing mixture from the resultant after reaction.
Description
Technical field
The invention belongs to the technical field of the inorganic chemical industry disposal of three wastes and comprehensive utilization, especially prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda.
Technical background
The ammonia still process of soda industry is an important operation unit in the solvay soda process, and this unitary disadvantage is exactly in the process of ammonia still process, to need to get rid of a large amount of evaporated waste ammonia liquids.Will cause no small pollution to physical environment if this waste liquid is handled bad random discharging, therefore, the evaporated waste ammonia liquid of handling and make good use of solvay soda process also is the important link of a step of soda industry.
Application number is that 200810129372.9 document discloses a kind of waste soda ash solution and calcium carbide waste slag of utilizing and removes SO
2Method.Utilize the CaCl in the waste soda ash solution
2With the SO in the flue gas
2Reaction generates white CaSO
3Deposition is emitted HCl, the very low hydrochloric acid of the water-soluble formation concentration of HCl; With the Ca in the calcium carbide waste slag (OH)
2In and HCl, generate CaCl
2And water, CaCl
2Recycle.That main consumption is the Ca (OH) in the calcium carbide waste slag in sweetening process
2If this locality does not have waste soda ash solution, can buy the Calcium dichloride dihydrate (CaCl that produces by waste soda ash solution
22HO), be mixed with CaCl
2Solution.This method removes SO when consuming waste soda ash solution
2, consume waste soda ash solution by sulfur removal technology, quantitatively very little, avoided problem of environmental pollution, but its economic benefit that turns waste into wealth is lower though above method has partly solved the stacking of alkaline residue; At present also not about prepare the report of the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda.
Summary of the invention
The invention provides a kind of not only with low cost, be easy to realize that and technology and production unit simply prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda.
In order to reach above-mentioned purpose, technical scheme of the present invention is:
Prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda, comprise physical treatment course and chemically treated process;
Said physical treatment course is:
Steps A, distillation waste liquid of calcined soda are concentrated in the suction slurry tank, sedimentation 2～4 hours;
Step B, get in the steps A clear liquid after the sedimentation and pump into to reduce pressure in the distiller one to steam with product pump and slip;
Step C, when moisture evaporation sodium-chlor is all separated out, through water cooler one cooling, carry out liquid-solid separation with suction filtration machine one then again, the solid after the separation obtains sodium chloride crystal through drying;
Step D, the liquid that solid-liquid separation among the step C is obtained continue in distiller two, to be distilled to calcium chloride dihydrate all separates out, after water cooler two cools off, liquid-solid separation obtains the calcium chloride product with suction filtration machine two suction filtrations; Settled throw out is further produced and is contained calcium compounds.
Said chemical treating process is:
Step e, the throw out after the sedimentation in the steps A is removed impurity through washing, calculate with lime carbonate with hydrochloric acid then, put into according to the mass ratio 1: 0.53～0.93 of pure substance and purify reaction in the cleaner, generate calcium chloride, carbonic acid gas and water;
Step F, with the purification resultant of reaction in the step e with suction filtration machine three suction filtrations, the calcium chloride solution behind the suction filtration is put into according to the mass ratio 1: 0.68～1.08 of pure substance with dilute sulphuric acid and is carried out building-up reactions in the synthesizer, generates two H 2 O calcium sulphates and hydrochloric acid;
Step G, with the building-up reactions resultant in the step F with suction filtration machine four suction filtrations, the white filter cake behind the suction filtration successively through washing and spin-drying machine, moisture eliminator, kibbler wash drying, pulverizing, drying, pack two H 2 O calcium sulphate finished products; Two H 2 O calcium sulphates are our said plaster stone just.
Wherein, among the said step B, decompression is steamed the temperature of slipping and is controlled at 90～100 degree.
Among the said step G, the building-up reactions resultant uses the liquid behind suction filtration machine four suction filtrations to be hydrochloric acid, and this hydrochloric acid returns in the cleaner among the step B through the recycle system, recycles.
The present invention utilizes distillation waste liquid of calcined soda to obtain sodium-chlor and calcium chloride through sedimentation, distillation, redistillation; Throw out through dechlorination, purification, synthetic, washing, dry, pulverize, be packaged to be plaster stone; The present invention not only can eliminate chemical pollution, and can slops be transformed into the Chemicals with certain economic value, especially can separate the chlorine-containing compound in the resultant of reaction back clearly and contain calcium compounds.The object of the invention is handled complicated problems with the simplest way exactly, not only saves fund but also handled evaporated waste ammonia liquid to reach, and also extracts valuable material simultaneously.The slops staple of solvay soda process is: staples such as calcium chloride, sodium-chlor, lime carbonate, quicklime, calcium sulfate, Marinco H.Other trace ingredientss also are no more than 3～5% and just are used as impurity and can have ignored.The treating method of saving most in the face of such waste liquid is exactly that liquid-solid separation is handled respectively again, comes not only to have practiced thrift fund but also can take out valuable thing compared with way in the past, and be the good method of killing two birds with one stone.
Reaction equation in the chemical treatment of the present invention is:
CaCO
3+2HCl＝＝＝＝CaCl
2+CO
2+H
2O
Ca(OH)
2+2HCl＝＝＝＝CaCl
2+H
2O
CaSO
4+2HCl＝＝＝＝CaCl
2+H
2SO
4
CaCl
2+H
2SO
4＝＝＝＝CaSO
4·2H
2O+2HCl
Description of drawings
Fig. 1 is the process flow diagram of physical treatment;
Wherein:
1---slurry tank, 2---product pump, 3---distiller one, 4---water cooler one, 5---sodium chloride crystal, 6---suction filtration machine one, 7---distiller two, 8---suction filtration machine two, 9---water cooler two, 10---calcium chloride products;
Fig. 2 is chemically treated process flow diagram;
Wherein:
11---cleaner, 12---suction filtration machine three, 13---synthesizer, 14---suction filtration machine four, 15---washing and spin-drying machine, 16---moisture eliminator, 17---kibbler, 18---the plaster stone finished product.
Concrete embodiment
Embodiment 1
Prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda, the preparation process is following:
Concentrate 1 li of suction slurry tank to distillation waste liquid of calcined soda 400kg, sedimentation is got its clear liquid clear liquid and is pumped into the steaming slide of reducing pressure in the distiller 1 with product pump 2 after 2 hours; Steaming slide temperature remains on 90 degree separates out moisture evaporation sodium-chlor, through water cooler one 4 coolings, carries out liquid-solid separation with suction filtration machine 1 then again, and the solid after the separation obtains 16.8kg sodium chloride crystal 5 through drying; The liquid that separation obtains continues in distiller 27, to be distilled to calcium chloride dihydrate all separates out, after water cooler 29 cools off, liquid-solid separation obtains 47.7kg calcium chloride product 10 with suction filtration machine 28 suction filtrations; Settled throw out is further produced and is contained calcium compounds.
Throw out in the above-mentioned slurry tank 1 after the sedimentation is removed impurity through washing; The 60kg that obtains contains calcium compounds (in lime carbonate); To contain calcium compounds and hydrochloric acid and put at 1: 0.53 in the cleaner 11 according to the mass ratio of pure substance and purify reaction, generate 48.35kg calcium chloride, carbonic acid gas and water; Purify resultant of reaction with suction filtration machine 3 12 suction filtrations, the calcium chloride solution behind the suction filtration is put into according to the mass ratio of pure substance with dilute sulphuric acid and is carried out building-up reactions in the synthesizer 13 at 1: 0.68, generates two H 2 O calcium sulphates and hydrochloric acid; With suction filtration machine 4 14 suction filtrations, the white filter cake behind the suction filtration successively through washing and spin-drying machine 15, moisture eliminator 16, kibbler 17 wash drying, pulverizing, drying, pack two H 2 O calcium sulphates (plaster stone) finished product 18 of 56.37kg; The clear filtrate hydrochloric acid dilute solution circulation that suction filtration obtains makes.
Prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda, the preparation process is following:
Concentrate distillation waste liquid of calcined soda 400kg in the suction slurry tank, sedimentation is got its clear liquid clear liquid and is pumped into the steaming slide of reducing pressure in the distiller one with product pump after 3 hours; Steaming slide temperature remains on 95 degree separates out moisture evaporation sodium-chlor, through water cooler one cooling, carries out liquid-solid separation with suction filtration machine one then again, and the solid after the separation obtains the 16.8kg sodium chloride crystal through drying; The liquid that separation obtains continues in distiller two, to be distilled to calcium chloride dihydrate all separates out, after water cooler two cools off, liquid-solid separation obtains 47.7kg calcium chloride product with suction filtration machine two suction filtrations; Settled throw out is further produced and is contained calcium compounds.
Throw out in the above-mentioned slurry tank after the sedimentation is removed impurity through washing; The 60kg that obtains contains calcium compounds (in lime carbonate); To contain calcium compounds and hydrochloric acid and put at 1: 0.73 according to the mass ratio of pure substance and purify reaction in the cleaner, generate 66.6kg calcium chloride, carbonic acid gas and water; Purify resultant of reaction with suction filtration machine three suction filtrations, the calcium chloride solution behind the suction filtration is put into according to the mass ratio of pure substance with dilute sulphuric acid and is carried out building-up reactions in the synthesizer at 1: 0.88, generates two H 2 O calcium sulphates and hydrochloric acid; With suction filtration machine four suction filtrations, the white filter cake behind the suction filtration successively through washing and spin-drying machine, moisture eliminator, kibbler wash drying, pulverizing, drying, pack two H 2 O calcium sulphates (plaster stone) finished product of 100.47kg; The clear filtrate hydrochloric acid dilute solution circulation that suction filtration obtains makes.
Prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda, the preparation process is following:
Concentrate distillation waste liquid of calcined soda 400kg in the suction slurry tank, sedimentation is got its clear liquid clear liquid and is pumped into the steaming slide of reducing pressure in the distiller one with product pump after 4 hours; Steaming slide temperature remains on 100 degree separates out moisture evaporation sodium-chlor, through water cooler one cooling, carries out liquid-solid separation with suction filtration machine one then again, and the solid after the separation obtains the 16.8kg sodium chloride crystal through drying; The liquid that separation obtains continues in distiller two, to be distilled to calcium chloride dihydrate all separates out, after water cooler two cools off, liquid-solid separation obtains 47.7kg calcium chloride product with suction filtration machine two suction filtrations; Settled throw out is further produced and is contained calcium compounds.
Throw out in the above-mentioned slurry tank after the sedimentation is removed impurity through washing; The 60kg that obtains contains calcium compounds (in lime carbonate); To contain calcium compounds and hydrochloric acid and put at 1: 0.93 according to the mass ratio of pure substance and purify reaction in the cleaner, generate 84.85kg calcium chloride, carbonic acid gas and water; Purify resultant of reaction with suction filtration machine three suction filtrations, the calcium chloride solution behind the suction filtration is put into according to the mass ratio of pure substance with dilute sulphuric acid and is carried out building-up reactions in the synthesizer at 1: 1.08, generates two H 2 O calcium sulphates and hydrochloric acid; With suction filtration machine four suction filtrations, the white filter cake behind the suction filtration successively through washing and spin-drying machine, moisture eliminator, kibbler wash drying, pulverizing, drying, pack two H 2 O calcium sulphates (plaster stone) finished product of 128.42kg; The clear filtrate hydrochloric acid dilute solution circulation that suction filtration obtains makes.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting practical range of the present invention, so all equivalences of being done with described characteristic of claim of the present invention and principle change or modify, all should be included within the claim scope of the present invention.
Claims (1)
1. prepare the method for calcium chloride co-producing sodium chloride and plaster stone with distillation waste liquid of calcined soda, it is characterized in that: comprise physical treatment course and chemically treated process;
Said physical treatment course is:
Steps A, distillation waste liquid of calcined soda are concentrated suction slurry tank (1) lining, sedimentation 2～4 hours;
Step B, get in the steps A clear liquid after the sedimentation and pump in the distiller one (3) with product pump (2) and carry out underpressure distillation;
Step C, when moisture evaporation sodium-chlor is all separated out, through water cooler one (4) cooling, use suction filtration machine one (6) to carry out liquid-solid separation then again, the solid after the separation obtains sodium chloride crystal (5) through drying;
Step D, the liquid that solid-liquid separation among the step C is obtained continue in distiller two (7), to be distilled to calcium chloride dihydrate all separates out, after water cooler two (9) cools off, liquid-solid separation obtains calcium chloride product (10) with suction filtration machine two (8) suction filtrations;
Said chemical treating process is:
Step e, the throw out after the sedimentation in the steps A is removed impurity through washing, calculate with lime carbonate with hydrochloric acid then, put in the cleaner (11) according to mass ratio 1:0.53～0.93 of pure substance and purify reaction, generate calcium chloride, carbonic acid gas and water;
Step F, with the purification resultant of reaction in the step e with suction filtration machine three (12) suction filtrations; Calcium chloride solution behind the suction filtration is put in the synthesizer (13) according to mass ratio 1:0.68～1.08 of pure substance with dilute sulphuric acid and is carried out building-up reactions, generates two H 2 O calcium sulphates and hydrochloric acid;
Step G, with the building-up reactions resultant in the step F with suction filtration machine four (14) suction filtrations, the white filter cake behind the suction filtration pass through successively washing and spin-drying machine (15), moisture eliminator (16), kibbler (17) wash drying, pulverizing, drying, pack plaster stone finished product (18);
Wherein, among the said step B, the temperature of underpressure distillation is controlled at 90～100 degree;
Among the said step G, the liquid of building-up reactions resultant after with suction filtration machine four (14) suction filtrations is hydrochloric acid, and this hydrochloric acid returns in the cleaner (11) in the step e through the recycle system, recycles.
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|---|---|---|---|
| CN2010101689174A CN102001687B (en) | 2010-04-30 | 2010-04-30 | Method for preparing calcium chloride with co-produced sodium chloride and gypsum by using sodium carbonate distillation waste liquor |
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| CN102515201B (en) * | 2011-12-27 | 2013-11-27 | 广东大众农业科技股份有限公司 | Method and device for recycling waste clear liquid produced in process for producing sodium carbonate by ammonia-soda process |
| CN104709933B (en) * | 2015-03-17 | 2017-01-25 | 青海大学 | Method for preparing high-purity calcium chloride by utilizing distilled ammonia waste liquid solar pond |
| CN111072054A (en) * | 2019-12-31 | 2020-04-28 | 安徽六国化工股份有限公司 | Preparation of high-purity gypsum powder and byproduct NH from phosphogypsum4Cl process |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297847A (en) * | 2000-12-06 | 2001-06-06 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1297847A (en) * | 2000-12-06 | 2001-06-06 | 化学工业部连云港设计研究院 | Comprehensive utilization method of waste ammonia sode liquid and sodium sulfate containing waste liquid |
Non-Patent Citations (2)
| Title |
|---|
| 孙歌东等.我厂蒸氨废液的综合利用.《河南化工》.1988,(第4期),45-46. * |
| 许海彬.用碱渣制取α型半水石膏的研究.《新型建筑材料》.1995,(第12期),26-27. * |
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