CN1721044A - Fluorine-containing waste gas utilization method in phosphorus fertilizer production - Google Patents
Fluorine-containing waste gas utilization method in phosphorus fertilizer production Download PDFInfo
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Abstract
The present invention relates to utility method for fluoric gases in phosphoric acid manufacture. Bring directly the ammonium fluoride and / or ammonia in system to obtain solution with (NH4)2SiF6 25-37%; use ammonia to ammoniate the solution and prepare deposition of silicon dioxide (white carbon black) with specific surface area of 100-180m2/g and NHF solution with concentration of 30-45%; use the two solutions to react, filter, wash and obtain filter cake; based on it, prepare cryolite and aluminun fluoride with high quality and low cost.
Description
Technical Field
The invention relates to a production method for comprehensively utilizing fluorine-containing waste gas in phosphate fertilizer production, belongs to the field of inorganic chemical industry, and particularly relates to a production method for producing cryolite, aluminum fluoride, byproduct white carbon black and the like by utilizing the fluorine-containing waste gas in phosphate fertilizer production.
Background
As is known, phosphate ore contains a certain amount of fluorine and silicon compounds, when the phosphate ore is processed to prepare common superphosphate, extract phosphoric acid, heavy calcium and the like, a part of fluorine in the phosphate ore reacts with silicon and escapes in the forms of silicon tetrafluoride and hydrogen fluoride, and in order to eliminate the influence of the fluorine-containing waste gas on the environment, fluosilicic acid is obtained by water absorption and then is further processed and utilized.
At present, most of phosphate fertilizer manufacturers in China further process fluosilicic acid into a sodium fluosilicate product, which is a product with low value and small market capacity, and the secondary pollution treatment amount is large in the processing process. In order to change the situation, five sets of complete production devices for preparing aluminum fluoride by taking fluosilicic acid as a raw material in different countries and different methods are introduced in sequence from 80 s in China, but the production is not ideal due to a plurality of reasons. Some manufacturers, such as Jiangxi Guixi fertilizer factories which introduce 6000 tons/year Aluminum fluoride from the French Alumium Pechiney company direct method (called AP method), have produced sodium fluosilicate.
In foreign countries, there are many production methods for producing aluminum fluoride using fluorosilicic acid as a raw material, and the so-called ammonia process and direct process are typical. The ammonia process, such as the TVA process of America, uses fluosilicic acid, ammonia water, aluminum hydroxide and aluminum sulfate as raw materials, tail gas is washed by ammonia water, silicon dioxide is precipitated and separated when fluosilicic acid is ammoniated, and filtrate, namely ammonium fluoride solution and H2SO4And Al2(SO4)3Reacting, and using the residue of Al (OH)3The process can use fluosilicic acid raw material with higher phosphorus content; direct method, such as French AP method, uses fluosilicic acid and aluminium hydroxide as raw materials, directly heats to react and precipitate silicon dioxide, removes silicon by belt filter, directly heats to crystallize without seed crystal, dries and calcines in two sections, has requirement for phosphorus content of fluosilicic acid, and aluminium hydroxide can be fed by dry method or wet method. There are also many methods for producing cryolite by using fluosilicic acid as raw material, such as direct synthesis method, which prepares the solution of sodium fluoride and aluminum fluoride by using fluosilicic acid respectively, then directly synthesizes cryolite; the intermediate product method of fluosilicic acid-ammonium fluoride, react with aqueous ammonia with fluosilicic acid, make ammonium fluoride solution after separating silicon dioxide, then react with aluminum sulfate and sodium sulfate, produce cryolite and by-product ammonium sulfate; the intermediate product process of fluorosilicic acid-sodium fluorosilicate is to prepare sodium fluorosilicate from fluorosilicic acid, react with ammonia water to separate silica to obtain solution of sodium fluoride and ammonium fluoride, and then react with aluminum sulfate and sodium chloride to prepare cryolite or react with sodium aluminate to prepare cryolite.
Since the above method cannot compete with the traditional production method using fluorite as raw material in terms of product quality and economy, the fluorine chemical products including aluminum fluoride, cryolite and the like except sodium fluorosilicate are still mainly produced using fluorite as raw material. However, the storage amount of fluorite is limited and exhausted, in view of the importance of fluorite resource, the nation determines fluorite as strategic resource and limits export, the fluorine in phosphorite is the only fluorine resource which can replace fluorite, the fluorine is mainly in the fluorine-containing waste gas and is a very cheap fluorine resource, and the fluorite chemical product taking fluorite as the raw material is difficult to counter and compete withthe fluorite chemical product as long as an economic and effective recycling method is provided.
Disclosure of Invention
The invention aims to provide a novel method for producing cryolite, aluminum fluoride and byproduct white carbon black by using fluorine-containing waste gas in phosphate fertilizer production as a raw material, which is economical and effective.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps and characteristics:
1. preparation of ammonium fluoride solution and by-product white carbon black
Fluorine-containing waste gas in phosphate fertilizer production is used as raw materials, wherein the most representative of the raw materials is fluorine-containing waste gas mainly containing silicon tetrafluoride in calcium superphosphate production and fluorine-containing waste gas mainly containing silicon tetrafluoride and hydrogen fluoride which escapes during phosphoric acid extraction concentration, ammonium fluoride and/or ammonia are used for absorption, the absorption is continuously or in batches, the temperature of absorption liquid is controlled to be 50-95 ℃, and the obtained ammonium fluosilicate solution contains 25-37% (NH)4)2SiF6(ii) a Ammoniating an ammonium fluosilicate solution by using ammonia, controlling the temperature to be 40-80 ℃, adopting a batch or continuous two-stage ammoniation method, controlling the pH value of a first-stage liquid phase to be 7.2-7.5 and controlling the pH value of a second-stage liquid phase to be more than 8, wherein the ammonium fluosilicate solution can be an unsaturated, saturated or solution in which solid ammonium fluosilicate is suspended, ageing is carried out for more than 1 hour after ammoniation, and then filtering, countercurrent washing and drying are carried out to prepare the ammonium fluosilicate solution with the specific surface area of 100-180 m2A precipitated silica product per gram; and separating the silicon dioxide to obtain an ammonium fluoride solution with the concentration of 30-45%.
The fluorine-containing waste gas in the step is most typically fluorine-containing waste gas mainly containing silicon tetrafluoride in the production of calcium superphosphate and waste gas mainly containing silicon tetrafluoride and hydrogen fluoride which are escaped during the concentration of extracted phosphoric acid, and for the former, the fluorine-containing waste gas is absorbed by an ammonium fluoride solution, and the reaction formula is as follows:
the latter is absorbed by ammonia, and the reaction formula is:
in view of HF and SiF escaping in the gas phase during the concentration of phosphoric acid4The molecular ratio of (A) is not strictly in accordance with the 2: 1 relationship in the reaction formula, and when the molecular ratio is less than 2: 1, there is an excess of SiF in the gas phase4There should be a certain amount of NH in the absorption liquid4F to ensure (NH)4)2SiF6And (4) generating.
The ammonification reaction formula of the ammonium fluosilicate is as follows:
in order to obtain precipitated silica suitable for rubber reinforcement and the like, ammoniation operation is carried out by adopting a method of continuously or batch two-stage pH value control, ammonia and ammonium fluosilicate solution are simultaneously added in the first stage, the pH value is controlled to be 7.2-7.5, and ammonia is continuously introduced after the ammonium fluosilicate solution is added, namely the so-called second stageStep, continuously introducing ammonia until the pH value of the solution reaches more than 8, simultaneously controlling the temperature to be preferably 50-70 ℃, and increasing the loss of ammonia when the temperature exceeds 70 ℃; aging the ammoniated slurry for at least 1 hour, filtering, and adopting a countercurrent washing mode to recover the ammonium fluoride solution in the filter cake to the maximum extent with the minimum amount of washing water; the filter cake is dried to obtain the precipitated silica-white carbon black product, and the specific surface area of the precipitated silica-white carbon black product can reach 100-180 m2(ii)/g; the washing liquid and part of the filtrate are prepared into the required ammonium fluoride solution concentration for returning to the fluorine absorption system for application. In order to obtain the ammonium fluosilicate concentration and the ammonium fluoride concentration which are as high as possible, the ammonia used in the system is liquid ammonia or gas ammonia containing water vapor. Or ammoniation with ammonia, but this will drastically reduce the concentration of the ammonium fluoride solution obtained. Or ammonifying the ammonium fluosilicate to a pH value of more than 8 in one step to obtain 30-45% NH4The solution F, but the silicon dioxide filter cake can only be used as a raw material for preparing water glass, the economy is far lower than that of a white carbon black product, and the solution F cannot be the first choice of the method.
Or 8-25% H obtained by absorbing fluorine-containing waste gas with water2SiF6The fluosilicic acid is used for preparing the ammonium fluoride solution and by-producing the white carbon black according to the ammonium fluosilicate ammonification method, or the fluosilicic acid is used for preparing the ammonium fluoride solution by ammonifying the pH value to be more than 8, although the technology is feasible, the economy is necessarily influenced to a certain extent due to low concentration, and the method also cannot be the first choice of the method.
The reaction formula of the fluosilicic acid ammoniation is as follows:
2. preparation of aluminium fluoride solution
The concentration of fluosilicic acid is 8-25% H2SiF6Decomposing aluminum-containing mineral raw materials such as bauxite or kaolin or industrial aluminum hydroxide to obtain an aluminum fluoride solution, wherein the reaction formula is as follows:
the using amount of the fluosilicic acid is 90-110% of the theoretical amount, the reaction temperature is 70-105 ℃, and after the reaction is finished, the aluminum fluoride solution can be separated from the residue after being filtered and washed.
3. Synthesis of ammonium fluoroaluminate
The ammonium fluosilicate can be conveniently prepared by the synthetic reaction of the prepared ammonium fluoride and aluminum fluoride solution, and the reaction formula is as follows:
the synthesis of the ammonium fluoroaluminate is carried out by adopting a continuous or batch method under the conditions that the ammonium fluoride dosage is 85-115% of the theoretical amount and the temperature is between room temperature and 70 ℃, and soluble and insoluble impurities in the ammonium fluoroaluminate are removed by adopting a conventional method for separation, filtration and washing.
The ammonium fluoroaluminate can also be prepared by adopting other raw materials, or solid or solution of aluminum sulfate, or solid or solution of aluminum fluoride and ammonium fluoride solution through reaction, wherein the reaction formula is as follows:
the ammonium sulfate or chloride in solution form is seen in the reaction formula, and the recovery and utilization of the ammonium sulfate or chloride are very troublesome, so the aluminum sulfate or chloride should not be the first choice of the method of the invention.
4. Preparation of cryolite
Reacting the filter cake of the ammonium fluoroaluminate with a saturated or nearly saturated sodium fluoride solution or a sodium sulfate solution to obtain cryolite (sodium fluoroaluminate), wherein the reaction formula is as follows:
the reaction can be carried out continuously or in batch, in order to ensure that the ammonium fluoroaluminate can be fully reacted, the reaction is carried out under the condition that the using amount of sodium chloride or sodium sulfate is 100-140% of the theoretical amount and the temperature is 50-95 ℃, and then the filtered and washed cryolite filter cake is dried to obtain the cryolite product. The ammonium chloride or ammonium sulfate solution can be directly sold as fertilizer or sold after concentration and crystallization.
5. Preparation of aluminium fluoride
Drying and calcining the ammonium fluoroaluminate filter cake at 500-700 ℃, wherein the calcining time is less than 2 hours, and the aluminum fluoride product can be obtained, and the reaction formula is as follows:
absorbing ammonium fluoride gas escaping from calcination by water to obtain NH with the concentration of ammonium fluoride being more than 40%4The solution F can be recycled, i.e. returned to the step<3>After synthesizing ammonium fluoroaluminate, drying and calcining to prepare the aluminum fluoride.
Drawings
FIG. 1 is a schematic view of the process of the present invention
Detailed Description
Example 1
The concentration is 20% NH4The F solution is introduced into a formation chamber waste gas absorption system which produces 10 ten thousand tons of common calcium per year for absorption to obtain the solution with the concentration of 34 percent (NH)4)2SiF6Adding the solution and liquid ammonia into an ammoniation device at the same time, controlling the pH value of the ammoniation device to be 7.2-7.5, introducing the liquid ammonia into the ammoniation device, controlling the final pH value of an ammoniation reaction to be more than 8, controlling the temperature to be 50-70 ℃, aging the obtained slurry for 1 hour, filtering, washing with clear water in a counter-current manner until the eluate is nearly neutral, drying the filter cake at 110 ℃ to obtain the product with the specific surface area of 110m2Precipitated silica (white carbon) product/g and NH concentration of 40.6%4F, ammonium fluoride solution; in another reactor, 15% H was added2SiF6After the fluosilicic acid is preheated to 75 ℃, theoretical amount of bauxite is added, the reaction is carried out for 25 minutes at the temperature of 95 ℃, then the filtration and the washing are carried out, and the AlF with the concentration of 12.9 percent is obtained after the filtration and the washing are combined3Aluminum fluoride solution ofAnd (4) liquid. Mixing ammonium fluoride solution and aluminum fluoride solution, reacting at 40 deg.C to obtain ammonium fluoroaluminate crystal, filtering, washing to obtain ammonium fluoroaluminate filter cake, adding sodium chloride solution containing 25% NaCl and 110% of the theoretical amount of the filter cake, reacting at 85 deg.C to obtain cryolite crystal, filtering, washing, and drying to obtain cryolite product with ammonium chloride concentration of 20.7% NH4Cl, cryolite product quality is given in Table 1.
TABLE 1 cryolite national Standard and product quality for the Process of the invention
Note: the product of the invention is orthocryolite which is a cone cryolite product in the current national standard, so indexes of F, Al and Na are slightly different, and the orthocryolite belongs to the development direction of cryolite products.
Example 2
The ammonium fluoroaluminate filter cake in example 1 is dried at 110 ℃ and then calcined at 550 ℃ for 1.5 hours to obtain an aluminum fluoride product, and gas generated by calcination is absorbed to obtain the aluminum fluoride productTo a concentration of 42.6% NH4The ammonium fluoride solution of F is returned to the example 1 to react with the aluminum fluoride solution, so as to prepare ammonium fluoroaluminate and reuse the ammonium fluoroaluminate for producing aluminum fluoride. The product quality is shown in Table 2.
TABLE 2. national standard for aluminum fluoride and quality of product by the process of the invention
Claims (4)
1. The method for utilizing the fluorine-containing waste gas in the production of the phosphate fertilizer comprises the following production steps and technical characteristics:
<1>preparing ammonium fluoride solution and by-producing white carbon black: fluorine-containing waste gas in phosphate fertilizer production is used as raw materials, wherein the fluorine-containing waste gas mainly containing silicon tetrafluoride in calcium superphosphate production and the fluorine-containing waste gas mainly containing silicon tetrafluoride and hydrogen fluoride escaping during phosphoric acid extraction concentration are used as raw materials, ammonium fluoride and/or ammonia are used for absorption, the absorption is continuously or in batches, the temperature of absorption liquid is controlled to be 50-95 ℃, and the obtained ammonium fluosilicate solution contains 25-37% (NH)4)2SiF6(ii) a Ammoniating an ammonium fluosilicate solution by using ammonia, controlling the temperature to be 40-80 ℃, adopting a batch or continuous two-stage ammoniation method, controlling the pH value of a first-stage liquid phase to be 7.2-7.5 and controlling the pH value of a second-stage liquid phase to be more than 8, wherein the ammonium fluosilicate solution can be an unsaturated, saturated or solution in which solid ammonium fluosilicate is suspended, ageing is carried out for more than 1 hour after ammoniation, and then filtering, countercurrent washing and drying are carried out to prepare the ammonium fluosilicate solution with the specific surface area of 100-180 m2A/g precipitated silica product, and separating the silica to obtain NH with the concentration of 30-45%4F, ammonium fluoride solution; or 8-25% H obtained by absorbing fluorine-containing waste gas with water2SiF6The ammonium fluosilicate is prepared into ammonium fluoride solution and byproduct white carbon black according to the ammonification method of the ammonium fluosilicate, or the ammonium fluosilicate or the fluosilicic acid is ammonified to the PH value of more than 8 in one step to prepare the ammonium fluoride solution;
<2>preparation of aluminum fluoride solution: the concentration of fluosilicic acid is 8-25% H2SiF6Decomposing aluminum-containing mineral raw materials such as bauxite or kaolin or industrial aluminum hydroxide, wherein the using amount of fluosilicic acid is 90-110% of the theoretical amount, the reaction temperature is 70-105 ℃, and after the reaction is finished, filtering and washing are carried out, so as to obtain an aluminum fluoride solution;
<3>Synthesis of ammonium fluoroaluminate: reacting the prepared ammonium fluoride and aluminum fluoride solution by a continuous or batch method under the conditions that the ammonium fluoride dosage is 85-115% of the theoretical amount and the temperature is between room temperature and 70 ℃, and then separating, filtering and washing to obtain a filter cake of ammonium fluoroaluminate; or reacting solid or solution of aluminum sulfate or solid or solution of aluminum chloride with ammonium fluoride solution to prepare ammonium fluoroaluminate filter cake under the conditions;
<4>preparation of cryolite: reacting an ammonium fluoroaluminate filter cake with a saturated or nearly saturated sodium chloride solution or sodium sulfate solution in a continuous or batch method at 50-95 ℃ under the condition that the amount of sodium chloride or sodium sulfate is 100-140% of the theoretical amount, and then filtering, washing and drying to obtain a cryolite product;
<5>preparation of aluminum fluoride: drying the ammonium fluoroaluminate filter cake, and calcining at 500-700 ℃, wherein the calcining time is less than 2 hours, so that an aluminum fluoride product is obtained; calcining the escaped gas, and absorbing to obtain NH with the concentration of ammonium fluoride being more than 40%4And F, solution.
2. The method for utilizing waste gas containing fluorine in phosphate fertilizer production according to claim 1, wherein the ammonia in step<1>is liquid ammonia, gaseous ammonia or vapor-containing gaseous ammonia or aqueous ammonia.
3. The method for utilizing waste gas containing fluorine in phosphate fertilizer production according to claim 1, wherein the ammonium fluoride solution for absorption in step<1>is prepared from a washing solution obtained by filtering and washing silica and a part of the filtrate.
4. The method for utilizing waste gas containing fluorine in phosphate fertilizer production according to claim 1, wherein the step of utilizing waste gas containing fluorine is performed<5>The concentration of the ammonium fluoride obtained by absorption is more than 40% NH4The solution F can be recycled, i.e. returned to the step<3>After synthesizing ammonium fluoroaluminate, drying and calcining to prepare the aluminum fluoride.
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