CN1310131A - Preparation of barium nitrate - Google Patents
Preparation of barium nitrate Download PDFInfo
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- CN1310131A CN1310131A CN 01103924 CN01103924A CN1310131A CN 1310131 A CN1310131 A CN 1310131A CN 01103924 CN01103924 CN 01103924 CN 01103924 A CN01103924 A CN 01103924A CN 1310131 A CN1310131 A CN 1310131A
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Abstract
The present invention utilizes witherite in preparation of barium nitrate directly, nitrate and barium carbonate in witherite are made to produce double decomposition and the resultant is further treated through cooling crystallization, bleaching, filtering and eliminating impurity to obtain barium nitrate product. The product may be further purified through recrystallization to obtain 99.5% over purity barium nitrate product.
Description
The present invention relates to a method for directly preparing barium nitrate by using witherite.
The existing barium nitrate production method is all made of industrial BaCO3、BaS、BaCl2… …, and the like, and the method comprises three methods: 1. a nitric acid method: the method is to prepare barium nitrate by reacting industrial barium nitrate or barium sulfide with nitric acid, and the reaction formula is as follows:
or:
the method has serious environmental pollution problem, such as CO2And H2The S is discharged with a large amount of nitrogen oxides and H2S, a highly toxic product, is extremely harmful to human bodies and the environment, and is shown in figure 1.
Meanwhile, the method is eliminated because the raw materials are expensive, so that the production cost of barium nitrate is high and the market competitiveness does not exist. 2. The nitrate method mainly refers to a production method for preparing barium nitrate by using barium chloride and nitrate, and mainly comprises the following reaction formula:
although the method solves the problem of environmental pollution caused by toxic waste gas, the used raw materials are more expensive, the recovery value of byproducts is not high, the production cost is higher, the method does not have the basis of general industrial production, and the method is eliminated industrially, as shown in figure 2. 3. The double decomposition method, which is an improvement of the first two methods, aims to select some cheap raw materials to produce barium nitrate, such as calcium nitrate instead of potassium nitrate and sodium nitrate, and adopts the following reaction formula, and the process flow is shown in figure 3.
The above method has never been carried out with industrial products (BaCO)3、BaCl2Etc.) to produce barium nitrate, the production cost is high.
The invention aims to solve the problems of the manufacturing method for preparing the barium nitrate.
The invention adopts the method for directly producing barium nitrate by using the witherite ore powder with extremely large reserve in China, wherein the witherite contains CaCO besides barium carbonate3、MgCO3、SrCO3、Fe2O3、SiO2、Al2O3And various gangue natural ores, the processing of the ores by the three methods is not feasible because the processes do not have the impurity removal function.
The method can effectively remove the gangue in the witherite, ensure the product quality and reduce the production cost.
The invention can make full use of useful elements, has no pollution to environment (except that nontoxic slag is discharged), can recycle the washing water and the mother liquor, and can obtain byproducts, thereby achieving the purpose of reducing cost.
The present invention relates to a method for preparing barium nitrate by using double decomposition method, and the double decomposition agent can be NH4NO3、Ca(NO3)2、NaNO3、、KNO3But ammonium nitrate is generally employed.
The invention is carried out according to the following reaction principle:
as can be seen from the reaction kinetics and thermodynamic principles, the two reactions are completed in the direction indicated by the arrow due to the evolution of ammonium carbonate, but sufficient ammonium nitrate (calcium) and sufficient heat of reaction (since the reaction is endothermic) must be ensured. This indicates to the process the direction in which care should be taken in choosing the reaction conditions.
The present invention prepares barium nitrate through double decomposition reaction of witherite powder and ammonium nitrate, and through dissolving, double decomposition, cooling crystallization, rinsing, filtering to eliminate dregs, re-crystallization, washing with water for reuse and recovering side product ammonium carbonate, other products may be produced.
The raw material witherite adopted by the invention is not limited by the grade of the ore, and certainly, BaCO in the ore3The higher the content, the lower the impurity content, the better.
Firstly, dissolving ammonium nitrate in a reaction kettle, and heating an ammonium nitrate solution to 100-160 ℃ under continuous stirring. The adding amount of ammonium nitrate is 2-6: 1 of the molar ratio of the BaCO3 content in the mineral powder. The ammonium nitrate used is commercially available industrial or agricultural ammonium nitrate, and the concentration of the ammonium nitrate used in the double decomposition reaction is 50 to 90%.
The witherite ore powder with the fineness of 80-250 meshes is slowly added into a reaction kettle, and can be dry powder, paste or slurry, but cannot be added at one time. The witherite is crushed to more than 80 meshes, preferably about 150 meshes, so that the fineness is too fine, the energy consumption is high, and the reaction speed can be increased; too coarse results in slow reaction rate, low metathesis rate and increased energy consumption.
The addition mode of the witherite ore powder can only be slowly and continuously added so as to prevent the damage caused by the pot. The witherite ore powder can be added as dry powder, or can be added in a paste or slurry state by being mixed with liquid (water or dilute ammonium nitrate), and when the reaction is violent, defoaming measures (physical, chemical defoaming or both) can be properly adopted to ensure that the reaction is normally carried out.
The reaction time is related to the adding mode of the witherite ore powder and the defoaming effect, generally 1-3 hours are needed, or the witherite ore powder is reacted for 0.1-1 hour after being added, and barium nitrate is more and more along with the increase of the reaction amount, so that crystals are separated out after supersaturation is achieved. The temperature in the reaction kettle is 110-160 ℃, the liquid-solid ratio is kept at 0.5-1: 1, the molar ratio of ammonium nitrate to barium carbonate is 2-6: 1 and cannot be lower than 2, and the reaction is carried out for 0.1-1 hour after the completion of the feeding of the witherite ore powder.
And further cooling and crystallizing the slurry after the double decomposition reaction to ensure that barium nitrate appears in a large-particle crystal form as much as possible, so that the barium nitrate in the solution is reduced, and the cooling temperature is generally controlled to be 5-50 ℃.
A special device for controlling large-particle slag to enter the rinsing tower is arranged above the rinsing tower, the temperature of rinsing liquid is as low as possible and is 4-40 ℃, the flow rate of washing water is 0.01-10 m/s, the washing water is preferably dilute solution containing ammonium nitrate but does not contain impurities such as calcium, magnesium and the like, and a flocculating agent can be added after the slag is removed.
And rinsing the slurry by using dilute ammonium nitrate, and separating impurities (solid and liquid) to obtain pure barium nitrate crystals. And further filtering the rinsing liquid with the slurry to remove solid residues, washing the residues, and concentratingthe recovered solution containing ammonium nitrate, barium nitrate, calcium nitrate and the like and the filtrate and then returning the solution to a double decomposition process or directly returning the solution to a pulping tank to be mixed with mineral powder for recycling.
The barium nitrate crystal can be refined and recrystallized repeatedly, the dissolving temperature is 50-110 ℃, and the cooling temperature is 5-50 ℃.
In order to further improve the quality of the barium nitrate product, the barium nitrate crystal obtained after rinsing can be subjected to one or more times of recrystallization treatment, and the mother liquor can be recycled, so that the quality of the barium nitrate can be greatly improved.
The liquid for dissolving the barium nitrate crystals can be pure water or dilute ammonium nitrate liquid, or dilute ammonium nitrate solution obtained after barium carbonate is precipitated by a conversion method, the dissolving temperature is 50-100 ℃, and the cooling crystallization temperature is 5-40 ℃.
The condensation temperature of the ammonium carbonate recovered by the condenser is generally controlled to be 10-60 ℃. During the double decomposition reaction, a great amount of water vapor and ammonium carbonate are escaped and condensed and recovered, so that the product can be used for preparing barium carbonate by a conversion method, or can be recovered as a byproduct of ammonium bicarbonate by carbonization, and can also be used for other products.
The invention can be a process route for independently processing barium nitrate, and can also be combined with a process for preparing barium carbonate by a conversion method, as shown in figure 4.
FIG. 1 is a flow chart of anitric acid method
FIG. 2 is a process flow diagram of the nitrate method
FIG. 3 is a process flow diagram of the double decomposition method
FIG. 4 is a flow chart of a process for preparing barium nitrate from witherite
Examples
1000 g of 60% witherite ore powder containing barium carbonate with the fineness of 200 meshes is weighed and mixed with 500ml of dilute ammonium nitrate solution containing 25% of ammonium nitrate and 10% of calcium nitrate to prepare paste for later use. Weighing 800 g of ammonium nitrate, adding 500 g of water into a 2L reactor, heating while stirring, slowly adding the mineral powder paste when the temperature reaches 120 ℃, controlling the reaction temperature to be about 130 ℃ generally, and adding a large amount of (NH) immediately after the mineral powder is added4)2CO3And the steam escapes, and is recovered by a condenser, the temperature of cold water is 20 ℃, and the yield is 95%. Stopping the reaction after 30 min after the addition of the paste, cooling the reaction product to 20 deg.C to precipitate a large amount of crystals, placing the crystallized slurry in a rinsing tower, and diluting with cold (20 deg.C) dilute nitreRinsing with ammonium solution to remove mineral powder residue and Ca (NO)3)2The nitrate solution was rinsed out together and further filtered, and dried to obtain 770 g of barium nitrate crystals having a purity of 98.5% with a yield of 92%. And (4) flocculating and precipitating the rinsed residues and solution, filtering and washing the residues, discarding the residues, and returning the filtrate for use.
The obtained barium nitrate is crystallized. Adding 700 g of the mother liquor into a diluted ammonium nitrate solution at 100 ℃ and 2800 g, immediately removing water insoluble substances after dissolution, cooling and crystallizing at the crystallization temperature of 20 ℃, filtering, washing and drying to obtain 500 g of a product with the barium nitrate purity of 99.5%, wherein the mother liquor is recycled, the yield of primary crystallization is 74%, but the yield is gradually improved along with the increase of the cycle number.
Claims (1)
1. A process for preparing barium nitrate includes such steps as double decomposition reaction between witherite powder and ammonium nitrate to obtain barium nitrate, dissolving, double decomposition, cooling crystallization, rinsing, filtering to remove dregs, recrystallization, cyclic use of washing water and recovery of ammonium carbonate as by-product; dissolving ammonium nitrate in a reaction kettle, heating the solution to 100-160 ℃, and slowly adding the witherite ore powder with the fineness of 80-250 meshes into the reaction kettle, wherein the witherite ore powder can be dry powder, paste or slurry, but cannot be added at one time; the temperature in the reaction kettle is 110-160 ℃, the liquid-solid ratio is kept at 0.5-1: 1, the molar ratio of ammonium nitrate to barium carbonate is 2-6: 1 and cannot be lower than 2, and the reaction is carried out for 0.1-1 hour after the feeding of the witherite powder is finished; a special device for controlling large-particle materials to enter the rinsing tower is arranged above the rinsing tower, the temperature of rinsing liquid is as low as possible and is 4-40 ℃, the flow rate of washing water is 0.01-10 m/s, the washing water is preferably dilute solution containing ammonium nitrate but does not contain impurities such as calcium, magnesium and the like, a flocculating agent can be added after slag is removed, and the washing water is recycled; refining barium nitrate crystals, namely repeatedly recrystallizing for many times, wherein the dissolving temperature is 50-110 ℃, and the cooling temperature is 5-50 ℃; the condensation temperature of the ammonium carbonate recovered by the condenser is generally controlled to be 10-60 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 01103924 CN1310131A (en) | 2001-02-14 | 2001-02-14 | Preparation of barium nitrate |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 01103924 CN1310131A (en) | 2001-02-14 | 2001-02-14 | Preparation of barium nitrate |
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| CN1310131A true CN1310131A (en) | 2001-08-29 |
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| CN 01103924 Pending CN1310131A (en) | 2001-02-14 | 2001-02-14 | Preparation of barium nitrate |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583489A (en) * | 2012-03-30 | 2012-07-18 | 贵州红星发展股份有限公司 | Low-strontium and high-purity nitrate barium and preparation method thereof |
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2001
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583489A (en) * | 2012-03-30 | 2012-07-18 | 贵州红星发展股份有限公司 | Low-strontium and high-purity nitrate barium and preparation method thereof |
| CN102583489B (en) * | 2012-03-30 | 2014-02-26 | 贵州红星发展股份有限公司 | Low-strontium and high-purity nitrate barium and preparation method thereof |
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