CN101823743A - Method for co-production of sodium carbonate and ammonium chloride in preparation of calcium carbonate by waste soda ash solution - Google Patents

Method for co-production of sodium carbonate and ammonium chloride in preparation of calcium carbonate by waste soda ash solution Download PDF

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Publication number
CN101823743A
CN101823743A CN 201010169004 CN201010169004A CN101823743A CN 101823743 A CN101823743 A CN 101823743A CN 201010169004 CN201010169004 CN 201010169004 CN 201010169004 A CN201010169004 A CN 201010169004A CN 101823743 A CN101823743 A CN 101823743A
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soda ash
ammonium chloride
filter cake
reaction
filtrate
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王嘉兴
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汪晋强
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Abstract

The invention belongs to the technical field of treatment and utilization of chemical 'three wastes', and particularly relates to a method for co-production of sodium carbonate and ammonium chloride in the preparation of calcium carbonate by waste soda ash solution, which mainly comprises the following steps that: waste ammonia solution and ammonium carbonate are placed in a corrosion-resistant reactor for reaction, and another chemical reaction is carried out simultaneously to generate sodium carbonate and ammonium chloride; the filter cake after filtration is washed, dehydrated, dried, crushed, weighed and packaged, thereby obtaining a calcium carbonate product; and the filtrate then reacts with the original residue filtrate to generate mixture of calcium carbonate and the like; filtration is carried then, the filter cake is washed, spun, dried, crushed, weighed and packaged, thereby obtaining a finished calcium carbonate product, and the filtrate is distilled under reduced pressure, thereby obtaining sodium chloride crystals and ammonium chloride crystals. The invention has the advantages of low production cost, high profit, large market demand and simple process and production equipment, and is a practical method for treatment and utilization. Moreover, the method not only can create considerable economic value, but also can eliminate chemical wastes and control the environmental pollution.

Description

A kind of method of making lime carbonate coproduction yellow soda ash and ammonium chloride with waste soda ash solution
Technical field
The invention belongs to the technical field of soda industry multipurpose use of three types of wastes, especially a kind of method of making lime carbonate coproduction yellow soda ash and ammonium chloride with waste soda ash solution.
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 to need to get rid of a large amount of evaporated waste ammonia liquids in the process of ammonia still process.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.
Chinese patent literature, application number are 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 3Precipitation 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.It is main in sweetening process that consume is Ca (OH) in the calcium carbide waste slag 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,, but consume waste soda ash solution by sulfur removal technology, quantitatively very little, intractable is fallen the waste liquid that soda industry produces.And waste soda ash solution also of no use is at present made the relevant report of the method for lime carbonate coproduction yellow soda ash and ammonium chloride.
Summary of the invention
The invention provides a kind of not only with low cost, be easy to realize, treatment capacity is big, and technology and production unit are simply made the method for lime carbonate coproduction yellow soda ash and ammonium chloride with waste soda ash solution.
To achieve the above object, technical scheme of the present invention is:
A kind of method with waste soda ash solution manufacturing lime carbonate coproduction yellow soda ash and ammonium chloride, manufacturing step is as follows:
Steps A, residue filtrate is dropped in the corrosion-resistant reactor with the ratio of volatile salt with mass ratio 1: 0.66~1.06 in calcium chloride, stir down that reaction generates lime carbonate and ammonium chloride, also another chemical reaction takes place simultaneously in the corrosion-resistant reactor and generate yellow soda ash and ammonium chloride with the ratio of mass ratio 1: 1.44~1.84;
Step B, resultant of reaction in the steps A is obtained filter cake and clear liquor with suction filter one suction filtration;
Step C, filter cake that suction filtration among the step B is obtained successively with centrigugal swing dryer one, moisture eliminator one, pulverizer one, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be the yellow soda ash product;
Step D, clear liquor that suction filtration among the step B is obtained in yellow soda ash again with original residue filtrate in calcium chloride, put in the reactor by mass ratio 1: 0.85~1.25 and to react the mixture that resultant of reaction and original ammonium chloride are formed; Resultant of reaction mainly is lime carbonate and sodium-chlor.
Step e, mixture among the step D is obtained filter cake and clear liquor with suction filter two suction filtrations;
Step F, filter cake that suction filtration in the step e is obtained successively with centrigugal swing dryer two, moisture eliminator two, pulverizer two, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be calcium carbonate product;
Step G, the filtrate that suction filtration in the step e is obtained successively obtain sodium-chlor and ammonia chloride crystal with the underpressure distillation of underpressure distillation device.
The present invention mainly is that the present invention mainly is the evaporated waste ammonia liquid that utilizes solvay soda process, and the main component in the evaporated waste ammonia liquid of solvay soda process is: main components such as calcium chloride, sodium-chlor, lime carbonate, calcium oxide, calcium sulfate, magnesium hydroxide.Other trace ingredientss also are no more than 3~5% and just are used as impurity and can have ignored.The present invention drops into the corrosion-resistant reactor reaction with evaporated waste ammonia liquid and volatile salt, another chemical reaction also takes place at the same time generate yellow soda ash and ammonium chloride; The filter cake of suction filtration through washing dehydration, drying, pulverize, checking the weight is packaged to be calcium carbonate product; Filtrate generates mixtures such as lime carbonate with the original residue filtrate reaction again; Suction filtration again, filter cake through washing dry, dry, pulverize, checking the weight is packaged to be the lime carbonate finished product, filtrate successively obtains sodium-chlor and ammonia chloride crystal through underpressure distillation; Not only production cost is cheap, profit is high in the present invention, the huge market demand, and technology and production unit are simple, and treatment capacity is big; Be a kind of relatively actual processing and utilize method, this method not only can create considerable economic value, but also has eliminated chemical sludge, administered environmental pollution.
Reaction principle of the present invention is:
CaCl 2+(NH 4) 2CO 3====CaCO 3+2NH 4C1
2NaCl+(NH 4) 2CO 3====Na 2CO 3+2NH 4Cl
Na 2CO 3+CaCl 2====CaCO 3+2NaCl
Description of drawings
Fig. 1 is a process flow sheet of the present invention;
Wherein:
1---corrosion-resistant reactor, 2---suction filter one, 3---centrigugal swing dryer one, 4---moisture eliminator one, 5---pulverizer one, 6---yellow soda ash product, 7---reactor, 8---suction filter two, 9---centrigugal swing dryer two, 10---moisture eliminator two, 11---pulverizer two, 12---calcium carbonate product, 13---underpressure distillation device, 14---sodium-chlor, 15---ammonia chloride crystal.
Concrete embodiment
Embodiment 1
A kind of method with waste soda ash solution manufacturing lime carbonate coproduction yellow soda ash and ammonium chloride, manufacturing step is as follows:
Steps A, residue filtrate is dropped into corrosion-resistant reactor 1 li with volatile salt with 1: 0.66 ratio of mass ratio in calcium chloride, stir reaction generation lime carbonate and ammonium chloride down, also another chemical reaction takes place simultaneously in the corrosion-resistant reactor and generate yellow soda ash and ammonium chloride with 1: 1.44 ratio of mass ratio;
Step B, resultant of reaction in the steps A is obtained filter cake and clear liquor with suction filter one 2 suction filtrations;
Step C, filter cake that suction filtration among the step B is obtained successively with centrigugal swing dryer 1, moisture eliminator 1, pulverizer 1, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be yellow soda ash product 6;
Step D, clear liquor that suction filtration among the step B is obtained in yellow soda ash again with original residue filtrate in calcium chloride, put into reactor at 1: 0.85 by mass ratio and react for 7 li, the mixture that resultant of reaction and original ammonium chloride are formed; Resultant of reaction mainly is lime carbonate and sodium-chlor.
Step e, mixture among the step D is obtained filter cake and clear liquor with suction filter 28 suction filtrations;
Step F, filter cake that suction filtration in the step e is obtained successively with centrigugal swing dryer 29, moisture eliminator 2 10, pulverizer 2 11, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be calcium carbonate product 12;
Step G, the filtrate that suction filtration in the step e is obtained successively obtain sodium-chlor 14 and ammonia chloride crystal 15 with 13 underpressure distillation of underpressure distillation device.
Embodiment 2
A kind of method with waste soda ash solution manufacturing lime carbonate coproduction yellow soda ash and ammonium chloride, manufacturing step is as follows:
Steps A, residue filtrate is dropped into corrosion-resistant reactor 1 li with volatile salt with 1: 0.86 ratio of mass ratio in calcium chloride, stir reaction generation lime carbonate and ammonium chloride down, also another chemical reaction takes place simultaneously in the corrosion-resistant reactor and generate yellow soda ash and ammonium chloride with 1: 1.64 ratio of mass ratio;
Step B, resultant of reaction in the steps A is obtained filter cake and clear liquor with suction filter one 2 suction filtrations;
Step C, filter cake that suction filtration among the step B is obtained successively with centrigugal swing dryer 1, moisture eliminator 1, pulverizer 1, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be yellow soda ash product 6;
Step D, clear liquor that suction filtration among the step B is obtained in yellow soda ash again with original residue filtrate in calcium chloride, put into reactor at 1: 1.05 by mass ratio and react for 7 li, the mixture that resultant of reaction and original ammonium chloride are formed; Resultant of reaction mainly is lime carbonate and sodium-chlor.
Step e, mixture among the step D is obtained filter cake and clear liquor with suction filter 28 suction filtrations;
Step F, filter cake that suction filtration in the step e is obtained successively with centrigugal swing dryer 29, moisture eliminator 2 10, pulverizer 2 11, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be calcium carbonate product 12;
Step G, the filtrate that suction filtration in the step e is obtained successively obtain sodium-chlor 14 and ammonia chloride crystal 15 with 13 underpressure distillation of underpressure distillation device.
Embodiment 3
A kind of method with waste soda ash solution manufacturing lime carbonate coproduction yellow soda ash and ammonium chloride, manufacturing step is as follows:
Steps A, residue filtrate is dropped into corrosion-resistant reactor 1 li with volatile salt with 1: 1.06 ratio of mass ratio in calcium chloride, stir reaction generation lime carbonate and ammonium chloride down, also another chemical reaction takes place simultaneously in the corrosion-resistant reactor and generate yellow soda ash and ammonium chloride with 1: 1.84 ratio of mass ratio;
Step B, resultant of reaction in the steps A is obtained filter cake and clear liquor with suction filter one 2 suction filtrations;
Step C, filter cake that suction filtration among the step B is obtained successively with centrigugal swing dryer 1, moisture eliminator 1, pulverizer 1, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be yellow soda ash product 6;
Step D, clear liquor that suction filtration among the step B is obtained in yellow soda ash again with original residue filtrate in calcium chloride, put into reactor at 1: 1.25 by mass ratio and react for 7 li, the mixture that resultant of reaction and original ammonium chloride are formed; Resultant of reaction mainly is lime carbonate and sodium-chlor.
Step e, mixture among the step D is obtained filter cake and clear liquor with suction filter 28 suction filtrations;
Step F, filter cake that suction filtration in the step e is obtained successively with centrigugal swing dryer 29, moisture eliminator 2 10, pulverizer 2 11, carry out centrifuge dripping, drying, pulverize, checking the weight is packaged to be calcium carbonate product 12;
Step G, the filtrate that suction filtration in the step e is obtained successively obtain sodium-chlor 14 and ammonia chloride crystal 15 with 13 underpressure distillation of underpressure distillation device.
The foregoing description is preferred embodiment of the present invention, is not to be used for limiting the scope of the present invention, so all equivalences of being done with described feature 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. make the method for lime carbonate coproduction yellow soda ash and ammonium chloride with waste soda ash solution for one kind, it is characterized in that: manufacturing step is as follows:
Steps A, residue filtrate is dropped into corrosion-resistant reactor (1) lining with volatile salt with the ratio of mass ratio 1: 0.66~1.06 in calcium chloride, stir down that reaction generates lime carbonate and ammonium chloride, also another chemical reaction take place simultaneously in the corrosion-resistant reactor and generate yellow soda ash and ammonium chloride with the ratio of mass ratio 1: 1.44~1.84:
Step B, resultant of reaction in the steps A is obtained filter cake and clear liquor with suction filter one (2) suction filtration;
Step C, the filter cake that suction filtration among the step B is obtained are used centrigugal swing dryer one (3), moisture eliminator one (4), pulverizer one (5) successively, carry out centrifuge dripping, drying, are pulverized, checking the weight is packaged to be yellow soda ash product (6);
Step D, clear liquor that suction filtration among the step B is obtained in yellow soda ash again with original residue filtrate in calcium chloride, put into reactor (7) lining by mass ratio 1: 0.85~1.25 and react, the mixture that resultant of reaction and original ammonium chloride are formed;
Step e, mixture among the step D is obtained filter cake and clear liquor with suction filter two (8) suction filtrations;
Step F, the filter cake that suction filtration in the step e is obtained are used centrigugal swing dryer two (9), moisture eliminator two (10), pulverizer two (11) successively, carry out centrifuge dripping, drying, are pulverized, checking the weight is packaged to be calcium carbonate product (12);
Step G, the filtrate that suction filtration in the step e is obtained successively obtain sodium-chlor (14) and ammonia chloride crystal (15) with underpressure distillation device (13) underpressure distillation.
CN 201010169004 2010-04-30 2010-04-30 Method for co-production of sodium carbonate and ammonium chloride in preparation of calcium carbonate by waste soda ash solution Pending CN101823743A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110589863A (en) * 2019-09-18 2019-12-20 西部矿业集团有限公司 Method for rapidly preparing high-purity micro-nano-scale porous metastable vaterite calcium carbonate from ammonia distillation waste liquid

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941860A (en) * 1956-07-10 1960-06-21 Diamond Alkali Co Method of producing finely divided caco3
CN1285312A (en) * 1999-08-22 2001-02-28 李怀然 novel process for preparing fodder grade calcium hydrophosphate and by-product calcium carbonate and ammonium chloride by hydrochloric acid method
WO2007061073A1 (en) * 2005-11-25 2007-05-31 New Lime Kenkyusha Co., Inc. Crossed-disk-, hamburger- or disk-shaped vaterite type calcium carbonate and process for producing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2941860A (en) * 1956-07-10 1960-06-21 Diamond Alkali Co Method of producing finely divided caco3
CN1285312A (en) * 1999-08-22 2001-02-28 李怀然 novel process for preparing fodder grade calcium hydrophosphate and by-product calcium carbonate and ammonium chloride by hydrochloric acid method
WO2007061073A1 (en) * 2005-11-25 2007-05-31 New Lime Kenkyusha Co., Inc. Crossed-disk-, hamburger- or disk-shaped vaterite type calcium carbonate and process for producing the same

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
《化工矿物与加工》 20071231 庄斌等 由氯化钙制备纳米碳酸钙研究 第26-28页 1 , 第2期 2 *
《化工科技》 20001231 李国庭等 氯化钙废液制备高纯碳酸钙副产工业氯化铵新工艺 第46-48页 1 第8卷, 第6期 2 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110589863A (en) * 2019-09-18 2019-12-20 西部矿业集团有限公司 Method for rapidly preparing high-purity micro-nano-scale porous metastable vaterite calcium carbonate from ammonia distillation waste liquid

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Application publication date: 20100908