CN101823746B - Method for producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and powdered carbon - Google Patents

Method for producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and powdered carbon Download PDF

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CN101823746B
CN101823746B CN2010101695673A CN201010169567A CN101823746B CN 101823746 B CN101823746 B CN 101823746B CN 2010101695673 A CN2010101695673 A CN 2010101695673A CN 201010169567 A CN201010169567 A CN 201010169567A CN 101823746 B CN101823746 B CN 101823746B
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carbon black
calcium carbonate
white carbon
chloride
sodium chloride
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CN101823746A (en
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王嘉兴
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汪晋强
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Abstract

The invention discloses a method for producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and powdered carbon, which comprises the following steps: using coproduction alkali waste liquid and carbide slag as raw materials; firstly, using ammonium chloride in the coproduction alkali waste liquid to react with calcium hydroxide in the carbide slag to produce carbon filter cake, calcium chloride and ammonium hydroxide; placing the calcium chloride and the ammonium hydroxide into a carbonizing tower, and introducing carbon dioxide gas for carrying out carbonizing reaction; and making the produced calcium carbonate precipitates and the ammonium chloride solution react with water glass to obtain the white carbon black and the sodium chloride. The method uses the industrial waste products of coproduction alkali waste liquid and the carbide slag to produce the calcium carbonate and white carbon black coproduction sodium chloride and powdered carbon,fully utilizes the active ingredients in the industrial waste products, reduces the production cost of industrial products, has simple production process and very low production cost, and belongs to an economic and effective method.

Description

A kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust
Technical field
The present invention relates to three industrial wastes comprehensive utilization and process field, particularly, relate to a kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, the used starting material of this method are waste associated alkali solution and carbide slag.
Background technology
Uniting system soda ash method (being called for short the connection alkaline process) is the main method of producing soda ash, is accompanied by the generation of soda ash, also produces a large amount of ammonium chloride exhausted liquids.Can be used for producing nitrogenous fertilizer behind the ammonium chloride exhausted liquid purifying.
Carbide slag is that the resistates that acetylene produced is produced in the calcium carbide hydrolysis, be the emulsion of solid content at 8%-10%, have another name called calcium carbide mud, its main chemical compositions is a calcium hydroxide, also contain the aqueous solution such as solid impurities such as Calucium Silicate powder, calcium aluminate, ferrosilicon and breeze and sulfurated lime, calcium hydroxide, acetylene, being a kind of strong basicity that is, being rich in abundant calcium resource, is that can to produce a series of needs such as lime carbonate, cement calcareous be the product of raw material to raw material with it.But because wherein impurities is more, water content is high, composition is complicated, undressed carbide slag can't directly utilize.On the other hand, flourish along with the calcium carbide industry, the quantity discharged of carbide slag also increases day by day, factory's discharging calcium carbide mud of producing 200,000 tons of PVC year reaches 3,600,000 tons/year, a large amount of carbide slags can't effectively utilize, directly pile up, cause the soil artificially to alkalize, ecotope is caused the pollution that is difficult to recover severe contamination farmland and underground water.
Preparation white carbon black (SiO 2) traditional method be the precipitator method: promptly use water glass (water glass) and strong acid, example hydrochloric acid and sulfuric acid, reaction generates the hydrated SiO 2 precipitation, is example with hydrochloric acid, its reactive chemistry equation is:
Na 2O·nSiO 2+2HCl+(n·m-1)H 2O→2NaCl+n(SiO 2·mH 2O)↓
Hydrated SiO 2 precipitates the white carbon black of treated system.This method is produced 1 ton of white carbon black will consume 4~4.5 tons of water glass and 1.5 tons of hydrochloric acid, and industrial chemicals consumption is big, and is uneconomical.
In order to overcome the defective of traditional method, people have also explored other and have prepared the method for white carbon black, as application number is that to disclose a kind of be the method that main raw material prepares white carbon black with silicofluoric acid, water glass for 200710055061.8 patent of invention, lower and the raw material of silicofluoric acid cost is easy to get in this method, thereby has reduced the production cost of white carbon black to a certain extent.Yet this method production technique is very loaded down with trivial details, has especially produced a large amount of by product Sodium Fluorides, and Sodium Fluoride can corrode skin, and stimulating mucosal has disoperation to neural system, thereby having relatively high expectations to production environment and equipment.
Application number is that 200810107069.9 patent of invention discloses happy a kind of method with producing nano-scale white carbon black with rice hull ash.This method with after the concentrating of the alkaline process Processing of Preparation water glass of rice hull ash, water glass solution again with sulfuric acid reaction, thereby make white carbon black.This method is not broken away from the defective for preparing white carbon black with traditional method.Thereby, also be a uneconomic method.
On the other hand, white carbon black mainly is used as natural rubber and elastomeric strengthening agent, toothpaste abrasives, also as coating and unsaturated polyester thickening material, and Coating Matting agent, thickening material, plastic film open agent etc.In recent years, along with the fast development of China's process of industrialization, dialogue sooty demand is growing, and this has also stimulated the production of white carbon black greatly, and the price of white carbon black also constantly raises at present, yet domestic output but can not satisfy the demand in market.
Thereby, ammonium chloride in the development and use waste associated alkali solution and the calcium hydroxide in the carbide slag, it will be a very cost-effective method that production simultaneously has the white carbon black of industrial value and lime carbonate.
Summary of the invention
In order to address the above problem, the invention provides a kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, the used starting material of this method are waste associated alkali solution and carbide slag.
Technical scheme of the present invention is: a kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, the used starting material of this method are waste associated alkali solution and carbide slag, comprise the steps:
A: convert ammonium chloride content in the waste associated alkali solution and the calcium hydroxide content in the carbide slag respectively;
B: is 1: 1.08~1.45 to drop in the corrosion-resistant reactors (1) carbide slag and waste associated alkali solution according to the pure substance mass ratio of calcium hydroxide and ammonium chloride, reacts, and obtains containing the mixed solution of calcium chloride and ammoniacal liquor;
C: through first suction filter pump (2) suction filtration, first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying filtrate with the mixed solution that contains calcium chloride and ammoniacal liquor of step B gained;
D: the clarifying filtrate of step C gained is dropped in the carbonating tower (4), with mass concentration is that 1~5% tensio-active agent carries out surface treatment, stir speed (S.S.) is 120~220r/min, then feeds carbon dioxide and carries out carburizing reagent, obtains containing the mixture of carbonic acid calcium deposit and ammonium chloride;
E: the mixture that contains carbonic acid calcium deposit and ammonium chloride of step D gained is centrifugal with second suction filter pump (6) and second whizzer (7), obtain calcium carbonate filter cake and the solution that contains ammonium chloride;
F: with the calcium carbonate filter cake of step e gained successively through washing whizzer (8) washing dehydration, first drying machine (9) drying, pulverizer (10) is pulverized, and is packaged to be calcium carbonate product (11);
G: is 1: 0.64~2.39 to drop in the reactors (17) contain chlorination ammonium solution and the water glass of step e gained according to ammonium chloride and water glass pure substance mass ratio, under the stirring that blows slowly, carry out two hydrolysis reaction, ammonium chloride is hydrolyzed to ammonia radical ion and chlorion in the aqueous solution, water glass is hydrolyzed to silicate ion in the aqueous solution, sodium ion and hydroxide ion, the hydrolysis of ammonia radical ion and silicate ion is mutually promoted, thereby generation ammonia, hydrogen ion and precipitation of silica, hydrogen ion and hydroxide ion directly are combined into water molecules, precipitation of silica is a white carbon black, ammonia effusion solution, chlorion and sodium ion are in conjunction with forming sodium-chlor;
H: the reaction product of step G gained is filtered through filter (18), obtain the solution of white carbon black crude product and sodium chloride-containing;
I: the white carbon black crude product of step H gained obtains white carbon black product (20) through second moisture eliminator (19) drying;
J: the solution of the sodium chloride-containing of step H gained is sent into to distill in the underpressure distillation device (21) and is obtained sodium-chlor product (22);
K: described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (12), removes the carbide slag that does not have complete reaction, obtains purified carbon filter cake through the 3rd suction filter pump (13) suction filtration;
L: described purified carbon filter cake through dehydration, dry in carbon dust loft drier (14), is crushed into carbon dust product (16) again in the carbon dust pulverizer (15).
With the carbonization terminal point of the described carburizing reagent of chlorination table (5) control, be the carbonization terminal point when reading is motionless to be zero when showing to go up.
The described carbon dioxide of step D is pure carbon dioxide gas or carbonic acid gas volume content greater than 20% mixed gas.
Described tensio-active agent is selected from emulsifiable concentrate, tween 80 and the mixture of the two.
Described ammonia returns the utilization of system alkali systemic circulation.
The chemical principle that aforesaid method relates to is:
2NH 4Cl+Ca(OH) 2====CaCl 2+2NH 4OH
CaCl 2+2NH 4OH+CO 2====CaCO 3+2NH 4Cl+H 2O
2NH 4Cl+Na 2O·nSiO 2======nSiO 2+2NaCl+2NH 3+H 2O
The method of production fine precipitated calcium carbonate of the present invention and white carbon black coproduction sodium chloride and carbon dust, utilize industrial waste product waste associated alkali solution and carbide slag to produce lime carbonate and white carbon black coproduction sodium chloride and carbon dust, made full use of the effective constituent in the industrial waste product, reduced the production cost of Industrial products, its production process is simple, production cost is extremely low, is a very cost-effective method.
Description of drawings
Fig. 1 has showed the processing step of the method for production fine precipitated calcium carbonate of the present invention and white carbon black coproduction sodium chloride and carbon dust, wherein:
(1)---corrosion-resistant reactor, (2)---first suction filter pump, (3)---first whizzer,
(4)---carbonating tower, (5)---chlorination table, (6)---second suction filter pump,
(7)---first whizzer, (8)---washing whizzer, (9)---first drying machine,
(10)---pulverizer, (11)---calcium carbonate product, (12)---carbon dust cleaner,
(13)---the 3rd suction filter pump, (14)---carbon dust loft drier, (15)---carbon dust pulverizer,
(16)---the carbon dust product, (17)---reactor, (18)---strainer,
(19)---second moisture eliminator, (20)---white carbon black product, (21)---underpressure distillation device,
(22)---the sodium-chlor product.
Embodiment
Be described further and illustrate below in conjunction with the method for specific embodiment production fine precipitated calcium carbonate of the present invention and white carbon black coproduction sodium chloride and carbon dust.
Embodiment one
A kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, ammonium chloride mass content in the conversion waste associated alkali solution and the calcium hydroxide mass content in the carbide slag earlier; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution ammonium chloride is to drop in corrosion-resistant reactor (1) at 1: 1.08 according to the pure substance mass ratio of calcium hydroxide and ammonium chloride, stirs, and reacts, and obtains containing the mixed solution of calcium chloride and ammoniacal liquor; Through first suction filter pump (2) suction filtration, first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying liquid with the mixed solution that contains calcium chloride and ammoniacal liquor of gained; The carbon filter cake of black is used to prepare carbon dust; Clarifying liquid drops in the carbonating tower (4), with mass concentration is that 1% tensio-active agent emulsifiable concentrate is handled, stir speed (S.S.) is 220r/min, then feed carbon dioxide and carry out carburizing reagent, with the carbonization terminal point of the described carburizing reagent of chlorination table (5) control, be the carbonization terminal point when reading is motionless to be zero when showing to go up; Carburizing reagent obtains containing carbonic acid calcium deposit and ammonium chloride mixt; It is centrifugal with second suction filter pump (6) filtration and second whizzer (7) to contain lime carbonate and ammonium chloride mixt, obtains calcium carbonate filter cake and the solution that contains ammonium chloride; The gained calcium carbonate filter cake is successively through washing whizzer (8) washing dehydration, drying machine (9) drying, and pulverizer (10) is pulverized, and is packaged to be the calcium carbonate product (11) that contains 504.67kg lime carbonate; Described chlorination ammonium solution and the water glass of containing is to drop in reactor (17) at 1: 2.39 according to ammonium chloride and water glass pure substance mass ratio, carries out two hydrolysis reaction under the stirring that blows slowly, and generates ammonia, white carbon black and sodium-chlor; Ammonia is overflowed, and returns the utilization of system alkali systemic circulation; With strainer (18) filtering reaction product, obtain white carbon black crude product and sodium chloride solution; Described white carbon black crude product obtains white carbon black product (20) through second moisture eliminator (19) drying; Described sodium chloride solution is sent into to distill in the underpressure distillation device (21) and is obtained sodium-chlor product (22).
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (12), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (13) suction filtration, obtains purified carbon dust; Described purified carbon dust through dehydration, dry in carbon dust loft drier (14), is crushed into carbon dust product (16) again in the carbon dust pulverizer (15).
Embodiment two
A kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, ammonium chloride mass content in the conversion waste associated alkali solution and the calcium hydroxide mass content in the carbide slag earlier; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution ammonium chloride is to drop in corrosion-resistant reactor (1) at 1: 1.45 according to the pure substance mass ratio of calcium hydroxide and ammonium chloride, stirs, and reacts, and obtains containing the mixed solution of calcium chloride and ammoniacal liquor; Through first suction filter pump (2) suction filtration, first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying liquid with the mixed solution that contains calcium chloride and ammoniacal liquor of gained; The carbon filter cake of black is used to prepare carbon dust; Clarifying liquid drops in the carbonating tower (4), with mass concentration is that 3% tensio-active agent is handled, stir speed (S.S.) is 180r/min, wherein containing mass concentration in the tensio-active agent and be 2% emulsifiable concentrate and mass concentration is 1% tween 80, the mixed gas that then feeds carbon dioxide containing gas 25% carries out carburizing reagent, with the carbonization terminal point of the described carburizing reagent of chlorination table (5) control, be the carbonization terminal point when reading is motionless to be zero when showing to go up; Carburizing reagent generates and contains carbonic acid calcium deposit and ammonium chloride mixt; It is centrifugal with second suction filter pump (6) and second whizzer (7) to contain lime carbonate and ammonium chloride mixt, obtains calcium carbonate filter cake and the solution that contains ammonium chloride; The gained calcium carbonate filter cake is successively through washing whizzer (8) washing dehydration, drying machine (9) drying, and pulverizer (10) is pulverized, and is packaged to be the calcium carbonate product (11) that contains 677.57kg lime carbonate; Described solution and the water glass that contains ammonium chloride is that 1: 0.64 input reactor (in (17), carries out two hydrolysis reaction, and generates ammonia, white carbon black and sodium-chlor under the stirring that blows slowly according to ammonium chloride and water glass pure substance mass ratio; Ammonia is overflowed, and returns the utilization of system alkali systemic circulation; With strainer (18) filtering reaction product, obtain the solution of white carbon black crude product and sodium chloride-containing; Described white carbon black crude product obtains white carbon black product (20) through second moisture eliminator (19) drying; The solution of described sodium chloride-containing is sent into to distill in the underpressure distillation device (21) and is obtained sodium-chlor product (22).
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (12), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (13) suction filtration, obtains purified carbon dust; Described purified carbon dust through dehydration, dry in carbon dust loft drier (14), is crushed into carbon dust product (16) again in the carbon dust pulverizer (15).
Embodiment three
A kind of method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, ammonium chloride mass content in the conversion waste associated alkali solution and the calcium hydroxide mass content in the carbide slag earlier; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution ammonium chloride is to drop in corrosion-resistant reactor (1) at 1: 1.32 according to the pure substance mass ratio of calcium hydroxide and ammonium chloride, stirs, and reacts, and obtains containing the mixed solution of calcium chloride and ammoniacal liquor; Through first suction filter pump (2) suction filtration, first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying liquid with the mixed solution that contains calcium chloride and ammoniacal liquor of gained; The carbon filter cake of black is used to prepare carbon dust; Clarifying liquid drops in the carbonating tower (4), with mass concentration is that 5% tensio-active agent tween 80 is handled, stir speed (S.S.) is 180r/min, then the mixed gas of carbon dioxide containing gas 40% carries out carburizing reagent, with the carbonization terminal point of the described carburizing reagent of chlorination table (5) control, be the carbonization terminal point when reading is motionless to be zero when showing to go up; Carburizing reagent obtains containing carbonic acid calcium deposit and ammonium chloride mixt; Precipitation of calcium carbonate and ammonium chloride mixt is centrifugal with second suction filter pump (6) filtration and second whizzer (7), obtain calcium carbonate filter cake and the solution that contains ammonium chloride; The gained calcium carbonate filter cake is successively through washing whizzer (8) washing dehydration, drying machine (9) drying, and pulverizer (10) is pulverized, and is packaged to be calcium carbonate product calciferous (11); Described solution and the water glass that contains ammonium chloride is that 1: 1.50 input reactor (in (17), carries out two hydrolysis reaction, and generates ammonia, white carbon black and sodium-chlor under the stirring that blows slowly according to ammonium chloride and water glass pure substance mass ratio; Ammonia is overflowed, and returns the utilization of system alkali systemic circulation; With strainer (18) filtering reaction product, obtain the solution of white carbon black crude product and sodium chloride-containing; Described white carbon black crude product obtains white carbon black product (20) through second moisture eliminator (19) drying; The solution of described sodium chloride-containing is sent into to distill in the underpressure distillation device (21) and is obtained sodium-chlor product (22).
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (12), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (13) suction filtration, obtains purified carbon dust; Described purified carbon dust through dehydration, dry in carbon dust loft drier (14), is crushed into carbon dust product (16) again in the carbon dust pulverizer (15).
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 (4)

1. method of producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and carbon dust, the used starting material of this method are waste associated alkali solution and carbide slag, it is characterized in that, comprise the steps:
A: convert ammonium chloride content in the waste associated alkali solution and the calcium hydroxide content in the carbide slag respectively;
B: is 1: 1.08~1.45 to drop in the corrosion-resistant reactors (1) carbide slag and waste associated alkali solution according to the pure substance mass ratio of calcium hydroxide and ammonium chloride, reacts, and obtains containing the mixed solution of calcium chloride and ammoniacal liquor;
C: through first suction filter pump (2) suction filtration, first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying filtrate with the mixed solution that contains calcium chloride and ammoniacal liquor of step B gained;
D: the clarifying filtrate of step C gained is dropped in the carbonating tower (4), with mass concentration is that 1~5% tensio-active agent carries out surface treatment, stir speed (S.S.) is 120~220r/min, then feeds carbon dioxide and carries out carburizing reagent, obtains containing the mixture of carbonic acid calcium deposit and ammonium chloride;
E: the mixture that contains carbonic acid calcium deposit and ammonium chloride of step D gained is centrifugal with second suction filter pump (6) and second whizzer (7), obtain calcium carbonate filter cake and the solution that contains ammonium chloride;
F: with the calcium carbonate filter cake of step e gained successively through washing whizzer (8) washing dehydration, first drying machine (9) drying, pulverizer (10) is pulverized, and is packaged to be calcium carbonate product (11);
G: is 1: 0.64~2.39 to drop in the reactors (17) contain chlorination ammonium solution and the water glass of step e gained according to ammonium chloride and water glass pure substance mass ratio, under the stirring that blows slowly, carry out two hydrolysis reaction, generate ammonia, precipitation of silica, water and sodium-chlor;
H: the reaction product of step G gained is filtered through filter (18), obtain the solution of white carbon black crude product and sodium chloride-containing;
I: the white carbon black crude product of step H gained obtains white carbon black product (20) through second moisture eliminator (19) drying;
J: the solution of the sodium chloride-containing of step H gained is sent into to distill in the underpressure distillation device (21) and is obtained sodium-chlor product (22);
K: described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (12), removes the carbide slag that does not have complete reaction, obtains purified carbon filter cake through the 3rd suction filter pump (13) suction filtration;
L: described purified carbon filter cake through dehydration, dry in carbon dust loft drier (14), is crushed into carbon dust product (16) again in the carbon dust pulverizer (15).
2. the method for production fine precipitated calcium carbonate as claimed in claim 1 and white carbon black coproduction sodium chloride and carbon dust is characterized in that, with the carbonization terminal point of the described carburizing reagent of chlorination table (5) control, is the carbonization terminal point when reading is motionless to be zero when showing to go up among the step D.
3. the method for production fine precipitated calcium carbonate as claimed in claim 1 and white carbon black coproduction sodium chloride and carbon dust is characterized in that described tensio-active agent is selected from tween 80.
4. the method for production fine precipitated calcium carbonate as claimed in claim 1 and white carbon black coproduction sodium chloride and carbon dust is characterized in that, described ammonia returns the utilization of system alkali systemic circulation.
CN2010101695673A 2010-04-30 2010-04-30 Method for producing fine precipitated calcium carbonate and white carbon black coproduction sodium chloride and powdered carbon Expired - Fee Related CN101823746B (en)

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CA3168752A1 (en) 2020-02-25 2021-09-08 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
CA3182421A1 (en) 2020-06-30 2022-01-06 Ryan J. Gilliam Methods and systems for forming vaterite from calcined limestone using electric kiln

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