CN1205307A - Integrate prodn. method for barium chloride and magnesium carbonate - Google Patents
Integrate prodn. method for barium chloride and magnesium carbonate Download PDFInfo
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- CN1205307A CN1205307A CN 98112917 CN98112917A CN1205307A CN 1205307 A CN1205307 A CN 1205307A CN 98112917 CN98112917 CN 98112917 CN 98112917 A CN98112917 A CN 98112917A CN 1205307 A CN1205307 A CN 1205307A
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Abstract
A process for join production of barium chloride and magnesium carbonate includes replacement reaction of magnesium chloride with CO2 ammonia gas to obtain magnesium carbonate and ammonium chloride, reaction of ammonium chloride on witherite or barytocalcite to generate barium chloride, ammonia gas, CO2 and water, and introduction of ammonia gas and CO2 into magnesium chloride solution to obtain magnesium carbonate. It features no waste gas or water discharge as ammonia is reused.
Description
The invention relates to a joint production method of barium chloride and magnesium carbonate.
The magnesium carbonate can be produced by mineral or bittern. The method using minerals as raw materials comprises a dolomite carbonization method, a magnesite carbonization method and an asbestos tailing (serpentine) carbonization method; the brine is taken as a raw material and comprises the following components: brine soda process, brine carbonization process, and brine ammonium carbonate process. In addition, the double decomposition method using saturated ammonium bicarbonate and magnesium sulfate solution as raw materials is also provided.
The barium chloride is produced by using barite, witherite and baryte as raw materials. Among the various methods for preparing barium chloride from barite, the hydrochloric acid method and the calcium chloride method are most widely used industrially. But all can not leave the process of high-temperature calcination. The method mainly adopts hydrochloric acid decomposition method by using witherite and barnaconite as raw materials.
The chemical reaction formula of the method is generally as follows:
namely:
in the last decade, witherite and barite ores in the region of Chuanshan are developed and utilized, and nearly sixty thousand tons of ores are mined every year and sold all over the country as main raw materials for producing barium salt. However, the production process mostly adopts hydrochloric acid for decomposition, so that the production cost is high. In particular, the market of the caustic soda is not in good sight in recent years, the price of the hydrochloric acid is increased, and the production cost of the barium salt is increased increasingly. Manufacturers strive to purchase high-grade ore (the content of the selected ore is more than 70%) to alleviate the contradiction of cost increase. Therefore, the mine is disorderly mined, the ore with the barium carbonate content lower than 65 percent is discarded, and a large amount of resources are wasted and damaged.
The invention aims to recycle ammonia gas and provide a combined production method of barium chloride and magnesium carbonate, which has no emission of waste gas and waste water and has no pollution to the environment.
The technical scheme for realizing the aim of the invention is as follows, and the principle is that ammonia is used in magnesium chloride, witherite or barnacite (main component BaCO)3) Non-metal ions are transmitted in an indirect circulation mode to prepare barium chloride and magnesium carbonate.
Namely, magnesium chloride is subjected to double decomposition reaction with carbon dioxide and ammonia gas to produce magnesium carbonate and ammonium chloride. The ammonium chloride reacts with witherite or bartholite (the main component of which is barium carbonate) to generate barium chloride, ammonia gas, carbon dioxide and water. And (3) directly introducing ammonia gas and carbon dioxide into the magnesium chloride solution, reacting to prepare magnesium carbonate, and obtaining the ammonium chloride solution for returning use. In the whole reaction process, only one kind of assistant, namely ammonia, is continuously circulated between magnesium chloride and witherite or barnolite ore to respectively transmit chloride ions and carbon dioxide ions, and according to the process method, two kinds of raw materials (magnesium chloride and barium carbonate or minerals) are consumed to obtain two kinds of products, namely barium chloride and magnesium carbonate.
The chemical reaction formula is as follows:
namely:
barium carbonate reacts with ammonium chloride to produce barium chloride, carbon dioxide, ammonia and water.
The present invention uses magnesium chloride, witherite or bartholite (also suitable for industrial barium carbonate) as raw material and ammonia gas as adjuvant, and circularly transfers chloride ion and carbon dioxide ion between two raw materials to produce magnesium carbonate and barium chloride. The positive effects are as follows:
1. the barium chloride produced by the present invention is a low iron, sulfur free product (see table 1). The quality test shows that the product has the percentage content of iron (Fe) of 0.001 and no sulfur. Fills the blank required in high technology, especially in the field of electronic industry. Solves the problem of overhigh sulfur content which is not fundamentally solved in the barium salt production process for a long time.
2. The invention uses ammonia gas as an auxiliary agent for recycling. The only raw materials consumed are magnesium chloride and mineral powder. Namely, two products-barium chloride and magnesium carbonate can be produced only by consuming two raw materials, which greatly reduces the production cost (see tables 3 and 4) and improves the economic benefit (see table 5). From the examination of the trial production period cost and the benefit of the inorganic chemical plant in the county, the production cost of barium chloride is 1066 yuan/T. The production cost of the magnesium carbonate is 1027.40 yuan/T. For example, 1500T barium chloride and 1000T magnesium carbonate are produced annually. The enterprise sales profit can reach 235 ten thousand yuan.
3. The process is carried out in a totally-enclosed manner, and ammonia gas is recycled. No waste gas and waste water discharge, and no pollution to the environment.
4. The invention uses the discarded low-grade witherite or baryta stone as raw material. Solves the problems of high cost and inconvenient transportation and storage of hydrochloric acid in the traditional process of preparing barium chloride by using hydrochloric acid to detoxify barite or barnaconite. Opens up a new way for developing and utilizing the low-grade witherite or bartonite in China to manufacture barium salt, and protects national mineral resources.
The present invention is further illustrated by the following examples.
The present invention uses magnesium chloride, witherite or bartholite (also suitable for industrial barium carbonate) as raw material and ammonia gas as adjuvant, and circularly transfers chloride ion and carbon dioxide ion between two raw materials to produce magnesium carbonate and barium chloride. The specific production steps are as follows:
1. the low-grade witherite or bartolite is ground into 200-mesh 250-mesh powder, preferably 250-mesh powder, by grinding after being baked at the low temperature of 650-800 ℃.
2. And adding the saturated solution of ammonium carbonate subjected to impurity removal treatment and the refined magnesium chloride solution into a reactor with a stirrer in a metering manner while stirring. The ammonium carbonate and magnesium chloride are subjected to double decomposition reaction.
3. The magnesium carbonate precipitate is aged, filtered, washed and separated from the ammonium chloride solution to obtain the magnesium carbonate with the moisture content of 50-85 percent.
4. And drying the washed magnesium carbonate to obtain a finished product.
5. And (3) testing the ammonium chloride solution obtained by filtering in the step (3), adding the mineral powder obtained in the step (1) according to the required amount, and reacting in a heating reaction kettle. The amount of ammonium chloride is 1.2 times of the theoretical value of the chemical reaction for complete reaction of the ore powder. The temperature in the reaction kettle is controlled to be 98-100 ℃, and the optimal temperature is 100 ℃. The reaction time is generally 3 hours.
6. And 5, allowing the ammonia gas and the carbon dioxide gas generated in the reaction in the step 5 to enter a magnesium chloride solution pool through an exhaust pipe to continuously participate in the reaction. I.e. back to the loop in step 2.
7. And (5) precipitating and filtering the barium chloride solution obtained in the step (5) and removing solid impurities to obtain a barium chloride clear solution.
8. And (4) feeding the filtered barium chloride clear solution into a crystallization tank, adding a calcium chloride auxiliary agent, and naturally crystallizing.
9. And (3) feeding the crystallized mother liquor into an evaporator for concentration, wherein the auxiliary agent in the step 8) can be recycled.
10. And dehydrating, washing and drying the crystallized barium chloride crystals in a centrifugal machine to obtain a finished barium chloride product.
According to the process researched by the invention, the inorganic chemical plant is tested in Shanxi county in the period from 2 months to 5 months in 1998, the product quality in the test process is shown in tables 1 and 2, the economic benefit is shown in tables 3, 4 and 5, and the indexes reach the expected targets.
TABLE 1 barium chloride product quality test results
Index name specification index test result
GB1617-89 (first-class) barium chloride (BaCl)2·2H2Content of O)%>= 98.098.6 calcium (Ca)% = 0.0900.08 sodium (Na)% (% = -sulfide (S)% (%)<= 0.008-iron (Fe) content%<= 0.0030.001 water-insoluble content%<= 0.100.09
TABLE 2 magnesium carbonate product quality test results item name specification index test results
GB1612-88 hydrochloric acid insoluble content%<= 0.20.18 calcium oxide content%<= 1.00.35 magnesium oxide content%>= 38.038.8 ignition loss% is greater than 5253 Chloride (CL) content%<= 0.30.28 iron (Fe) content%<= 0.080.03 manganese (Mn) content<= -sulfate content<= 0.3-
TABLE 3 magnesium carbonate cost accounting TABLE (1000T annual output) project unit cost annual total cost
(Yuan) (Wanyuan) 1, magnesium chloride T2.5240600602, auxiliary agent T0.1545067.56.753, coal T0.523011511.54, packaging strip 401.4565.65, water T20.510.16, electric power 2012027, production wage 120128, manufacturing cost 47.94.79 (depreciation) (23.5) (2.35) 9, manufacturing cost 1027.4102.7410, management cost 1201211, financial cost 30312, sales cost 727.213, sales cost 1249.4124.94
TABLE 4 barium chloride cost accounting Table (annual 1500T) project Unit cost Total annual cost (Yuan) (yuan) (Wanyuan) 1. mineral powder T1.836064897.22. coal T123023034.53. packaging Bar 201.4284.24. Water T50.52.50.3755. Electricity degree 301304.56. production payroll 8080127. manufacturing cost 47.97.185 (depreciation) (23.5) (3.525) 8. manufacturing cost 1066.4159.969. management cost 60910. sales cost 40611. financial cost 304.512. sales cost 1196.4179.46
TABLE 5 sales profits and related index comparison sheet
Unit: ten thousand yuan
Project barium chloride 1500T/H magnesium carbonate 1000T/H total 1, salesincome 2703606302, Total cost 179.46124.94304.43, tax 22.9544.8270.77 () deduction tax (23.87) (14.6) (38.47) 4, sales profit 67.59187.24254.835, income tax 22.3161.7984.16, Net profit 45.28125.4170.737, Net profit margin 16.77% 34.85% 27.1%
Claims (1)
1. A combined production method of barium chloride and magnesium carbonate is characterized in that magnesium chloride, witherite or bartonite are used as raw materials, ammonia gas is used as an auxiliary agent, chloride ions and carbon dioxide ions are circularly transferred between the two raw materials to produce the magnesium carbonate and the barium chloride, and the production method is characterized by comprising the following production steps:
1) low-grade witherite or bartolite is ground into 200-mesh 250-mesh powder by grinding after being baked at the low temperature of 650-800 ℃,
2) adding the saturated solution of ammonium carbonate and refined magnesium chloride solution into a reactor with stirring while stirring, carrying out double decomposition reaction on ammonium carbonate and magnesium chloride,
3) the magnesium carbonate precipitation is aged, filtered, washed and separated from the ammonium chloride solution to obtain magnesium carbonate with the moisture content of 50-85 percent,
4) drying the washed magnesium carbonate to obtain a finished product,
5) testing the ammonium chloride solution obtained by filtering in the step 3, adding the ammonium chloride solution into the mineral powder obtained in the step 1 according to the required amount, reacting the mineral powder in a heating reaction kettle, wherein the amount of the ammonium chloride is 1-1.4 times of the theoretical value of the chemical reaction of complete reaction of the mineralpowder, controlling the temperature in the reaction kettle at 98-100 ℃, and the reaction time is 2-4 hours,
6) the ammonia gas and the carbon dioxide gas generated in the step 5 enter the magnesium chloride solution pool through the exhaust pipe to continue to participate in the reaction, namely, the reaction returns to the step 2 for circulation,
7) precipitating and filtering the barium chloride solution obtained in the step 5 and removing solid impurities to obtain a barium chloride clear solution,
8) feeding the clear barium chloride solution obtained after filtration into a crystallization tank, adding a calcium chloride auxiliary agent, naturally crystallizing,
9) feeding the crystallized mother liquor into an evaporator for concentration,
10) and dehydrating, washing and drying the crystallized barium chloride crystals in a centrifugal machine to obtain the finished barium chloride product.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 98112917 CN1205307A (en) | 1998-07-13 | 1998-07-13 | Integrate prodn. method for barium chloride and magnesium carbonate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 98112917 CN1205307A (en) | 1998-07-13 | 1998-07-13 | Integrate prodn. method for barium chloride and magnesium carbonate |
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| CN 98112917 Pending CN1205307A (en) | 1998-07-13 | 1998-07-13 | Integrate prodn. method for barium chloride and magnesium carbonate |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| CN105347368A (en) * | 2015-12-14 | 2016-02-24 | 苏州市泽镁新材料科技有限公司 | Preparing method of high purity magnesium carbonate |
| CN105347369A (en) * | 2015-12-14 | 2016-02-24 | 苏州市泽镁新材料科技有限公司 | Preparation method of high-purity magnesium carbonate |
-
1998
- 1998-07-13 CN CN 98112917 patent/CN1205307A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008028343A1 (en) | 2006-08-31 | 2008-03-13 | China Petroleum & Chemical Corporation | A process for catalytic converting hydrocarbons |
| WO2008034299A1 (en) | 2006-08-31 | 2008-03-27 | China Petroleum & Chemical Corporation | A catalyst for converting hydrocarbons |
| CN105347368A (en) * | 2015-12-14 | 2016-02-24 | 苏州市泽镁新材料科技有限公司 | Preparing method of high purity magnesium carbonate |
| CN105347369A (en) * | 2015-12-14 | 2016-02-24 | 苏州市泽镁新材料科技有限公司 | Preparation method of high-purity magnesium carbonate |
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