CN102092757A - Method for producing fine lightweight calcium carbonate, ammonium chloride and carbon powder by using soda production waste liquor and carbide slag - Google Patents

Method for producing fine lightweight calcium carbonate, ammonium chloride and carbon powder by using soda production waste liquor and carbide slag Download PDF

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CN102092757A
CN102092757A CN 201010169164 CN201010169164A CN102092757A CN 102092757 A CN102092757 A CN 102092757A CN 201010169164 CN201010169164 CN 201010169164 CN 201010169164 A CN201010169164 A CN 201010169164A CN 102092757 A CN102092757 A CN 102092757A
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ammonium chloride
calcium carbonate
carbide slag
filter cake
carbon
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CN102092757B (en
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王嘉兴
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Rugao Yongxing Casing Co., Ltd.
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汪晋强
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Abstract

The invention discloses a method for producing fine lightweight calcium carbonate, ammonium chloride and carbon powder by using soda production waste liquor and carbide slag, which comprises the following steps of: putting the carbide slag and the soda production waste liquor into an anticorrosion reactor according to the pure substance mass ratio of calcium hydroxide to ammonium chloride of 1:1.08-1.45 for reaction to generate the mixed liquor of calcium chloride and ammonia water; performing suction filtration and centrifugation on the obtained mixed liquor to obtain a black carbon filter cake and clear liquid; introducing the clear liquid into a carbonizer, performing surface treatment by using a surfactant at the mass concentration of 1 to 5 percent, performing carbonization reaction on the liquid and a carbon dioxide gas to generate a mixture of calcium carbonate and ammonium chloride, and performing suction filtration and centrifugation on the mixture to obtain a calcium carbonate filter cake and solution of ammonium chloride; sequentially performing washing, dehydration, drying and crushing on the calcium carbonate filter cake to obtain the calcium carbonate product; and performing distillation under reduced pressure on the solution of ammonium chloride to obtain ammonium chloride crystal products.

Description

Method with waste associated alkali solution and carbide slag production fine precipitated calcium carbonate, ammonium chloride and carbon dust
Technical field
The present invention relates to three industrial wastes comprehensive utilization and process field, particularly, relate to the method for producing fine precipitated calcium carbonate, ammonium chloride and carbon dust with 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 the waste liquid that contains a large amount of ammonium chlorides.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.
For this reason, be necessary further to develop carbide slag, make effective constituent wherein transform the utilizable Industrial products in position.
Summary of the invention
For this reason, the invention provides a kind of method of producing fine precipitated calcium carbonate, ammonium chloride and carbon dust with waste associated alkali solution and carbide slag, industrial waste product ammonium chloride exhausted liquid and carbide slag have effectively been consumed, excavate the value of ammonium chloride exhausted liquid and carbide slag, and solved the problem of environmental pollution that causes because of the two.
Technical scheme of the present invention is: the method with waste associated alkali solution and carbide slag are produced fine precipitated calcium carbonate, ammonium chloride and carbon dust comprises the steps:
A: convert the mass content of the ammonium chloride in the waste associated alkali solution and the mass content of the calcium hydroxide 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: the mixed solution that will wrap the calcium chloride of step B gained and ammoniacal liquor is through first suction filter pump (2) suction filtration, and first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying filtrate;
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.) 120~220r/min, then, feed carbon dioxide and carry out carburizing reagent, obtain 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) filtration 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, drying machine (9) drying, pulverizer (10) is pulverized, and is packaged to be calcium carbonate product (11);
G: solution process underpressure distillation device (12) underpressure distillation that contains ammonium chloride with the step e gained obtains ammonia chloride crystal product (13);
H: the carbon filter cake and the excessive hydrochloric acid of the black of step C gained are reacted in carbon dust cleaner (14), remove the carbide slag that does not have complete reaction, obtain purified carbon filter cake through the 3rd suction filter pump (15) suction filtration;
I: with the purified carbon filter cake of step H gained again through dehydration, in carbon dust loft drier (16) drying, be crushed into carbon dust product (18) in the carbon dust pulverizer (17).
Among the step D,, be the carbonization terminal point when reading is motionless to be zero when showing to go up with the carbonization terminal point of chlorination table (5) control carburizing reagent.
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 reaction principle of producing the method for fine precipitated calcium carbonate, ammonium chloride and carbon dust with waste associated alkali solution and carbide slag is:
Its chemical equation is: 2NH 4Cl+Ca (OH) 2====CaCl 2+ 2NH 4OH
CaCl 2+2NH 4OH+CO 2===CaCO 3+2NH 4Cl+H 2O
Method of producing fine precipitated calcium carbonate, ammonium chloride and carbon dust of the present invention with waste associated alkali solution and carbide slag, industrial waste product ammonium chloride exhausted liquid and carbide slag have effectively been consumed, excavated the value of ammonium chloride exhausted liquid and carbide slag, and solved the problem of environmental pollution that causes because of the two, this method is simple to operate, the required equipment less investment is the method for a low-consumption high-efficiency.
Description of drawings
Fig. 1 has showed the processing step of using the method for waste associated alkali solution and carbide slag production fine precipitated calcium carbonate, ammonium chloride and carbon dust of the present invention, 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)---drying machine,
(10)---pulverizer, (11)---calcium carbonate product, (12)---underpressure distillation device,
(13)---the ammonia chloride crystal product, (14)---carbon dust cleaner, (15)---the 3rd suction filter pump,
(16)---carbon dust loft drier, (17)---carbon dust pulverizer, (18)---carbon dust product.
Embodiment
Below in conjunction with specific embodiment the method with waste associated alkali solution and carbide slag production fine precipitated calcium carbonate, ammonium chloride and carbon dust of the present invention is described further and illustrates.
Embodiment one
With the method that waste associated alkali solution and carbide slag are produced fine precipitated calcium carbonate, ammonium chloride and carbon dust, convert earlier ammonium chloride mass content in the waste associated alkali solution and the calcium hydroxide mass content in the carbide slag respectively; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution 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 filtrate with the mixed solution of the calcium chloride of gained and ammoniacal liquor; The carbon filter cake of black is used to prepare carbon dust; Clarifying filtrate is dropped in the carbonating tower (4), adding mass concentration is that 4% tensio-active agent emulsifiable concentrate is handled, stir speed (S.S.) is 200r/min, then feed pure carbon dioxide gas and carry out carburizing reagent, the Ventilation Rate of carbonic acid gas is 2 liters/minute, with the carbonization terminal point of chlorination table (5) control carburizing reagent, 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) 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 the calcium carbonate product (11) that contains 504.67kg lime carbonate; Described solution process underpressure distillation device (12) underpressure distillation that contains ammonium chloride obtains containing the ammonia chloride crystal product (13) of 540kg ammonium chloride.
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (14), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (15) suction filtration, obtains purified carbon filter cake; Described purified carbon dust through dehydration, dry in carbon dust loft drier (16), is crushed into carbon dust product (18) again in the carbon dust pulverizer (17).
Embodiment two
With the method that waste associated alkali solution and carbide slag are produced fine precipitated calcium carbonate, ammonium chloride and carbon dust, convert earlier ammonium chloride mass content in the waste associated alkali solution and the calcium hydroxide mass content in the carbide slag respectively; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution 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 filtrate 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 filtrate is dropped in the carbonating tower (4), with mass concentration is that 4% emulsifiable concentrate and mass concentration are 2% tween 80 processing, stir speed (S.S.) is 250r/min, the Ventilation Rate that the feeding carbon dioxide carries out the carburizing reagent carbonic acid gas is 4 liters/minute, with the carbonization terminal point of chlorination table (5) control carburizing reagent, be the carbonization terminal point when reading is motionless to be zero when showing to go up; The mixture that carburizing reagent obtains containing the carbonic acid calcium deposit and contains ammonium chloride; 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 ammonium chloride solution; 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 process underpressure distillation device (12) underpressure distillation that contains ammonium chloride obtains containing the ammonia chloride crystal product (13) of 725kg ammonium chloride.
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (14), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (15) suction filtration, obtains purified carbon filter cake; Described purified carbon filter cake through dehydration, dry in carbon dust loft drier (16), is crushed into carbon dust product (18) again in the carbon dust pulverizer (17).
Embodiment three
With the method that waste associated alkali solution and carbide slag are produced fine precipitated calcium carbonate, ammonium chloride and carbon dust, convert earlier ammonium chloride mass content in the waste associated alkali solution and the calcium hydroxide mass content in the carbide slag respectively; To contain the carbide slag of 500kg calcium hydroxide and waste associated alkali solution 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 filtrate 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 filtrate is dropped in the carbonating tower (4), with mass concentration is that 8% tensio-active agent tween 80 is handled, stir speed (S.S.) is 320r/min, feed carbon dioxide and carry out carburizing reagent, the Ventilation Rate of carbonic acid gas is 4 liters/minute, with the carbonization terminal point of chlorination table (5) control carburizing reagent, 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 carbonic acid calcium deposit 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 process underpressure distillation device (12) underpressure distillation that contains ammonium chloride obtains containing the ammonia chloride crystal product (13) of 725kg ammonium chloride.
Described carbon filter cake and excessive hydrochloric acid be excessive response in carbon dust cleaner (14), removes the carbide slag that does not have complete reaction, through the 3rd suction filter pump (15) suction filtration, obtains purified carbon filter cake; Described purified carbon filter cake through dehydration, dry in carbon dust loft drier (16), is crushed into carbon dust product (18) again in the carbon dust pulverizer (17).
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. the method for producing fine precipitated calcium carbonate, ammonium chloride and carbon dust with waste associated alkali solution and carbide slag is characterized in that, comprises the steps:
A: convert the mass content of the ammonium chloride in the waste associated alkali solution and the mass content of the calcium hydroxide 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: the mixed solution that contains calcium chloride and ammoniacal liquor that will wrap step B gained is through first suction filter pump (2) suction filtration, and first whizzer (3) is centrifugal, obtains black carbon filter cake and clarifying filtrate;
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.) 120~220r/min, then, feed carbon dioxide and carry out carburizing reagent, obtain 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) filtration 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, drying machine (9) drying, pulverizer (10) is pulverized, and is packaged to be calcium carbonate product (11);
G: solution process underpressure distillation device (12) underpressure distillation that contains ammonium chloride with the step e gained obtains ammonia chloride crystal product (13);
H: the carbon filter cake and the excessive hydrochloric acid of the black of step C gained are reacted in carbon dust cleaner (14), remove the carbide slag that does not have complete reaction, obtain purified carbon filter cake through the 3rd suction filter pump (15) suction filtration;
I: with the purified carbon filter cake of step H gained again through dehydration, in carbon dust loft drier (16) drying, be crushed into carbon dust product (18) in the carbon dust pulverizer (17).
2. method of producing fine precipitated calcium carbonate, ammonium chloride and carbon dust with waste associated alkali solution and carbide slag as claimed in claim 1 is characterized in that, among the step D, with the carbonization terminal point of the described carburizing reagent of chlorination table (5) control.
3. method of producing fine precipitated calcium carbonate, ammonium chloride and carbon dust as claimed in claim 1 with waste associated alkali solution and carbide slag, it is characterized in that the described carbon dioxide of step D is pure carbon dioxide gas or carbonic acid gas volume content greater than 20% mixed gas.
4. method of producing fine precipitated calcium carbonate, ammonium chloride and carbon dust with waste associated alkali solution and carbide slag as claimed in claim 1 is characterized in that described tensio-active agent is selected from emulsifiable concentrate, tween 80 and the mixture of the two.
CN 201010169164 2010-04-30 2010-04-30 Method for producing fine lightweight calcium carbonate, ammonium chloride and carbon powder by using soda production waste liquor and carbide slag Expired - Fee Related CN102092757B (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite

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* Cited by examiner, † Cited by third party
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US9902652B2 (en) 2014-04-23 2018-02-27 Calera Corporation Methods and systems for utilizing carbide lime or slag

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CN1796284A (en) * 2004-12-20 2006-07-05 王嘉兴 Method for fabricting Nano active calcium carbonate as well as carbon powder from carbide slag
CN101643229A (en) * 2009-06-08 2010-02-10 王嘉兴 Co-production method for making high-quality calcium hydroxide, industrial salt and carbon powder by acetylene sludge

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1796284A (en) * 2004-12-20 2006-07-05 王嘉兴 Method for fabricting Nano active calcium carbonate as well as carbon powder from carbide slag
CN101643229A (en) * 2009-06-08 2010-02-10 王嘉兴 Co-production method for making high-quality calcium hydroxide, industrial salt and carbon powder by acetylene sludge

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《无机盐工业》 20091031 彭展英等 联碱厂联产纳米碳酸钙的四联产绿色新工艺 第35-38页 1-4 第41卷, 第10期 2 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US11577965B2 (en) 2020-02-25 2023-02-14 Arelac, Inc. Methods and systems for treatment of lime to form vaterite
US11377363B2 (en) 2020-06-30 2022-07-05 Arelac, Inc. Methods and systems for forming vaterite from calcined limestone using electric kiln

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