CN102101690A - Process for preparing barium chloride and calcium chloride by utilizing chlor-alkali waste salt sludge - Google Patents
Process for preparing barium chloride and calcium chloride by utilizing chlor-alkali waste salt sludge Download PDFInfo
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- CN102101690A CN102101690A CN2011100049921A CN201110004992A CN102101690A CN 102101690 A CN102101690 A CN 102101690A CN 2011100049921 A CN2011100049921 A CN 2011100049921A CN 201110004992 A CN201110004992 A CN 201110004992A CN 102101690 A CN102101690 A CN 102101690A
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- bariumchloride
- calcium chloride
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Abstract
The invention relates to a process for preparing barium chloride and calcium chloride by utilizing chlor-alkali waste salt sludge. In the process, barium chloride is prepared from waste salt sludge, wherein the main component (barium sulfate) of the salt sludge, raw coal, a fluxing agent and the barium sulfate are further calcined at the high temperature of 600-1000 DEG C so as to generate barium chloride and CaS melts. The process has the advantages of solving the problems that the production process of a barium sulfate method is complicated, barium sulfate raw materials are expensive, the product cost is high, and the application range of the product is limited, and also solving the problem of restricted continuous production caused by gradual reduction of witherite raw materials in a witherite method.
Description
Technical field
The invention belongs to the chlor-alkali production technology field, relate to the application of chlor-alkali abandoned salty mud, specifically a kind of technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride.
Background technology
China is the big country of Production of Barium Chloride and use, also be to produce one of bariumchloride country early in the world, China's barium salt produce on output, qualitatively, the technical international most advanced level that all reaches, oneself becomes genuine barium salt big producing country.The method of producing bariumchloride in China has two kinds, a kind of is the barium sulphide method, this method is to be that raw material carries out replacement(metathesis)reaction with hydrochloric acid and barium sulphide, generates barium chloride solution, then barium chloride solution is filtered, filtrate is through acidifying, desulfurization, in and sedimentation, the gained clear liquid through the evaporation, the crystallization oven dry makes the industrial chlorinating titanate product; Another kind method is the witherite method, this method be to be that raw material carries out acidolysis reaction with witherite and hydrochloric acid, then acidolysis solution is squeezed into operations such as settling bowl precipitates, filters, concentrates, crystallization, drying and is made the industrial chlorinating titanate product.The eighties in 20th century is in the past because witherite mineral's resource is less and acidization bariumchloride technology is not mature enough, so the production technique of Production of Barium Chloride enterprise is mainly based on the barium sulphide method, but barium sulphide method complex manufacturing, raw material ratio is expensive, the hydrogen sulfide of attached product also must absorb system Sodium sulfhydrate or other products with liquid caustic soda, products production cost height is restricted the range of application of product.Owing to the continuous innovation and the introduction of technology, the inorganic salt technology of China has obtained the speed development after the eighties, and therefore the heavy method manufacture of poison bariumchloride has become bariumchloride development inexorable trend.Each manufacturing enterprise studies and transforms the Production of Barium Chloride technology in succession and improve processing condition in order to impel enterprise development, has studied successfully with witherite (natural B aCO in the mid-80
3) being the less energy-consumption in source, barium ore deposit, low-cost witherite method bariumchloride technology makes the bariumchloride product obtain developing by leaps and bounds.There is family more than 200 in the enterprise of domestic production bariumchloride at present.Its production level and technical equipment are ripe, do not see relevant report as yet but fully utilize salt slurry production bariumchloride technical matters.
At present, whole nation caustic soda industry development is swift and violent, be example only with safe chemical industry in the Xinjiang, produce 370000 tons in caustic soda per year, and the salt slurry waste bulk deposition of refined brine output in the caustic soda preparation process is produced 100000 tons of caustic soda per year according to the data introduction and can be discharged 7 over thousands of tons of salt slurries, but nearly 2.8 ten thousand tons of safe chemical industry salt discharge in every year mud therefore, cause serious environmental to pollute and the wasting of resources like this, therefore the recycling to salt slurry has become caustic soda industry problem demanding prompt solution.
Summary of the invention
In order to address the above problem, the invention provides a kind of technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride, prepare bariumchloride by the depleted salt slurry, both solved abandoned salty mud to the pollution of environment and the waste of resource, bariumchloride of Sheng Chaning and calcium chloride product also have very high value simultaneously.
Technical scheme of the present invention is:
A kind of technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride, carry out according to following steps:
(1) salt slurry oven dry:
By banded extruder, extrusion molding utilizes the high-temperature flue tail gas institute waste heat of kiln to dry 300～500 ℃ of exhaust temperatures through the track type dryer then with salt slurry;
(2) batching:
Oven dry salt slurry and raw coal and fusing assistant, calcium chloride is pulverized and is mixed by proportioning, and blending ratio is as follows by weight:
Salt slurry: calcium chloride: raw coal: fusing assistant=80～120: 40～80: 6～10: 1～5,
Described salt slurry main component is a barium sulfate, and described fusing assistant is CaO, and described raw coal chemical ingredients is C;
(3) high-temperature calcination:
With hot conditions next step calcining generation bariumchloride and the CaS melt at 600～1000 ℃ of the batching in the step (2), the reactive chemistry equation is as follows:
BaSO
4+4C+?CaCl
2=?CaS+4CO+?BaCl
2?；
(4) bariumchloride is produced:
Above-mentioned melt passes through to pulverize, leaching, the soluble in water and insoluble CaS melt of bariumchloride solid-liquid separation, and liquid is produced bariumchloride after desulfurization, tailings is treated aftertreatment;
(5) tailings is handled:
Above-mentioned tailings master is contained CaS, fusing assistant CaO, add hcl acidifying, produce hydrogen sulfide and make Sodium sulfhydrate through the liquid caustic soda absorption, solution is transferred alkali with lime, filtered liquid system Calcium dichloride dihydrate, residual residue master contains cinder, sandstone and a small amount of lime mud, can be used as brickmaking, and the chemical equation of reaction is as follows:
CaS+2HCl=CaCl
2+H
2S
CaO+2HCl=?CaCL
2+H
2O
H
2S+NaOH=NaHS+H
2O
The best mixed weight ratio of described step (2) is salt slurry: calcium chloride: raw coal: fusing assistant=100: 60: 8: 3.
Beneficial effect of the present invention is:
Technology of the present invention is abandoned salty mud and calcium chloride, raw coal and catalyst mix batching, in High Temperature Furnaces Heating Apparatus, control 600～1000 ℃ of reactions, one-step calcination generates the bariumchloride melt, and impurity calcium iron when leaching can not change solution over to, so quality is good easy to control during the formulations prepared from solutions bariumchloride.
Both solved barium sulphide method complex manufacturing, the barium sulphide raw material ratio is expensive, and the difficult problem that product cost is high is restricted the range of application of product, has solved again that the witherite starting material reduce gradually in the witherite method, a restriction quantity-produced difficult problem.
The used material of technology of the present invention is the waste salt slurry of refined brine output in the caustic soda preparation process, produce bariumchloride by production, and bariumchloride loops back the raw material that caustic soda enterprise produces caustic soda, table salt, forms closed cycle economy, forms sustainable cyclic production.
Technic index parameter and production cost comparison sheet:
Its this technology of direct production cost is than the low 300-400 unit/T of conventional method as seen from the above table, and as seen its profit margin is big and the market competitiveness is strong.
Description of drawings
Fig. 1 is a process flow sheet of the present invention.
Embodiment
Below the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein only is used for description and interpretation the present invention, and be not used in qualification the present invention.
Embodiment 1
As shown in Figure 1, a kind of technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride, carry out according to following steps:
One, materials proportioning:
Salt slurry (butt) 1000kg
Calcium chloride (68%) 600kg
Coal dust 80kg
Auxiliary agent 30kg
Two, operation
1, salt slurry is passed through banded extruder, extrusion molding utilizes the high-temperature flue tail gas institute waste heat of kiln to dry 300～500 ℃ of exhaust temperatures through the track type dryer then.
2, with salt slurry, calcium chloride, coal dust, auxiliary agent by the metering of the consumption in the prescription () after, with ball mill melt is milled to 200 purpose powders, in the dry powder blend device, fully mixed 40 minutes.
3, the powder that mixes is added the rotation roasting in kilns 2 hours that is preheated to 800 ℃ in advance, generate bariumchloride and CaS melt, emit and be cooled to normal temperature, the reactive chemistry equation is as follows:
BaSO
4+4C+?CaCl
2=?CaS+4CO+?BaCl
2
4, with ball mill the CaS melt is milled to fineness 240 orders.
5, the heat that in the leaching pond, adds 3000kg80 ℃. water adds then and is milled to 240 purpose melt powder, and the part by weight of water and powder is 1:0.4, stirring and dissolving 2-3 hour, squeezes into the settling tank sedimentation;
The above-mentioned 200 purpose powders that are milled to pass through leaching, the soluble in water and insoluble CaS melt of bariumchloride solid-liquid separation, and liquid is produced bariumchloride after desulfurization, tailings is treated aftertreatment;
With settling bowl at the middle and upper levels clear liquid directly put into bariumchloride mother liquor storage pool, lower floor's sedimentation slag filters with plate-and-frame filter press, filtrate is put into the mother liquor pond, feeds flushing with clean water then, washes to BaCl
2Content reaches below 1%, and washing fluid is put into the leaching pond preheating next time of usefulness again, and filter residue enters in the acidolysis enamel reaction still, treats that next procedure handles.
6, mother liquor is made BaCl through concentrated, crystallization, dehydration
2
7, the 200 purpose powder tailings masters that are milled in the aforesaid reaction vessel are contained CaS and fusing assistant CaO, add 30% hydrochloric acid 1500kg and stirred acidification reaction 1 hour, the generation hydrogen sulfide is introduced to absorb in another enamel that fills 40% liquid sodium hydroxide reaction absorption still by gas diversion tube on the still and is made the liquid sulfur sodium hydride in the reaction, solution is transferred PH to 7.5～8 with lime, filtered liquid system Calcium dichloride dihydrate, residual residue master contains cinder, sandstone and a small amount of lime mud, can be used as brickmaking.
8, with plate-and-frame filter press the mixed solution in the acidolysis still is filtered, filtrate is put into calcium water concentrating pan, makes CaCl through concentrating
22H
2O uses the flushing with clean water filter residue then, puts into calcium water storage pool to the washing fluid degree Beaume at 2 following washing fluids, and filter residue send brick field brickmaking, and the chemical equation of reaction is as follows:
CaS+2HCl=CaCl
2+H
2S
CaO+2HCl=?CaCL
2+H
2O
H
2S+NaOH=NaHS+H
2O
Embodiment 2
One, materials proportioning:
Salt slurry (butt) 800kg
Calcium chloride (68%) 400kg
Coal dust 60kg
Auxiliary agent 10kg
Two, operation steps is identical with embodiment 1.
Embodiment 3
One, materials proportioning:
Salt slurry (butt) 1200kg
Calcium chloride (68%) 800kg
Coal dust 100kg
Auxiliary agent 50kg
Two, operation steps is identical with embodiment 1.
It should be noted that at last: the above only is the preferred embodiments of the present invention, be not limited to the present invention, although the present invention is had been described in detail with reference to previous embodiment, for a person skilled in the art, it still can be made amendment to the technical scheme that aforementioned each embodiment put down in writing, and perhaps part technical characterictic wherein is equal to replacement.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (2)
1. a technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride is characterized in that, carries out according to following steps:
(1) salt slurry oven dry:
With the salt slurry extrusion molding, dry 300～500 ℃ of bake out temperatures then;
(2) batching:
Oven dry salt slurry and raw coal and fusing assistant, calcium chloride is pulverized and is mixed by proportioning, and blending ratio is as follows by weight:
Salt slurry: calcium chloride: raw coal: fusing assistant=80～120: 40～80: 6～10: 1～5
Described salt slurry main component is a barium sulfate, and described fusing assistant is CaO;
(3) high-temperature calcination:
With hot conditions next step calcining generation bariumchloride and the CaS melt of the batching in the step (2) at 600～1000 ℃;
(4) bariumchloride is produced:
Above-mentioned melt passes through to pulverize, leaching, the soluble in water and insoluble CaS melt of bariumchloride solid-liquid separation, and liquid is produced bariumchloride after desulfurization, tailings is treated aftertreatment;
(5) tailings is handled:
Above-mentioned tailings master is contained CaS, fusing assistant CaO, add hcl acidifying, produce hydrogen sulfide and make Sodium sulfhydrate through the liquid caustic soda absorption, solution is transferred alkali with lime, filtered liquid system Calcium dichloride dihydrate, residual residue master contains cinder, sandstone and a small amount of lime mud, can be used as brickmaking.
2. a kind of technology of utilizing the chlor-alkali abandoned salty mud to prepare bariumchloride and calcium chloride according to claim 1, its feature is salt slurry in the mixed weight ratio of described step (2): calcium chloride: raw coal: fusing assistant=100: 60: 8: 3.
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|---|---|---|---|
| CN201110004992.1A CN102101690B (en) | 2011-01-12 | 2011-01-12 | Process for preparing barium chloride and calcium chloride by utilizing chlor-alkali waste salt sludge |
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|---|---|---|---|
| CN201110004992.1A CN102101690B (en) | 2011-01-12 | 2011-01-12 | Process for preparing barium chloride and calcium chloride by utilizing chlor-alkali waste salt sludge |
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| CN102101690A true CN102101690A (en) | 2011-06-22 |
| CN102101690B CN102101690B (en) | 2014-04-02 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113800549A (en) * | 2020-06-17 | 2021-12-17 | 南风化工集团股份有限公司 | Method for extracting barium chloride from precipitated barium sulfate waste residue |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342612A (en) * | 2001-10-15 | 2002-04-03 | 广西大学 | Process for preparing both barium sulfate and calcium chloride from waste ardealite dregs |
| CA2764755A1 (en) * | 2009-06-25 | 2010-12-29 | Ditommaso, Anthony | Method of making pure salt from frac-water/wastewater |
-
2011
- 2011-01-12 CN CN201110004992.1A patent/CN102101690B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1342612A (en) * | 2001-10-15 | 2002-04-03 | 广西大学 | Process for preparing both barium sulfate and calcium chloride from waste ardealite dregs |
| CA2764755A1 (en) * | 2009-06-25 | 2010-12-29 | Ditommaso, Anthony | Method of making pure salt from frac-water/wastewater |
Non-Patent Citations (3)
| Title |
|---|
| 吴祖万等: "氯化钙法生产氯化钡", 《浙江化工》, no. 5, 31 December 1959 (1959-12-31), pages 31 - 37 * |
| 王晓军等: "重晶石高温催化转型生产沉淀硫酸钡方法研究报告", 《无机盐工业》, no. 4, 31 December 1991 (1991-12-31), pages 22 - 24 * |
| 田洪鹏等: "应用FactSage预测CaO助熔剂对模拟灰熔融特性的影响", 《上海市化学化工学会2008年度学术年会论文集》, 31 December 2008 (2008-12-31), pages 43 - 44 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113800549A (en) * | 2020-06-17 | 2021-12-17 | 南风化工集团股份有限公司 | Method for extracting barium chloride from precipitated barium sulfate waste residue |
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