CN113735352A - Combined treatment method for hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid - Google Patents
Combined treatment method for hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid Download PDFInfo
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Abstract
The invention relates to a combined treatment method of hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid, which comprises the following steps: (1) adding the hydrofluoric acid-containing nitric acid waste liquid into a urea solution with the concentration of 55% and stirring to form a mixture of a crystal combined solution A; (2) cooling, filtering to obtain urea nitrate crystals and a solution A, washing, and merging filtrate into the solution A to form a new solution A; (3) adding a solution of a calcium-containing substance, stirring, and adjusting the pH value to 7 to form a mixture of solution B and calcium fluoride; (4) filtering to obtain secondary calcium fluoride and a solution B, washing, and merging filtrate into the solution B to form a new solution B; (5) carrying out vacuum evaporation; (6) adding the new solution B and the hydrofluoric acid waste liquid into a reaction kettle at the same time and stirring to form a mixture of calcium fluoride and the solution C; (7) filtering to obtain calcium fluoride and solution C, washing the calcium fluoride, and merging the filtrate into the solution C. The method can realize recycling, is simple to operate and has low risk coefficient.
Description
Technical Field
The invention belongs to the technical field of hazardous waste treatment and recycling of electronic industrial enterprises, and particularly relates to a process method for harmlessly treating waste acid generated in industrial manufacturing processes of semiconductors, liquid crystal panels, solar cells and the like and recycling the value of the waste acid.
Background
In the production of semiconductor, liquid crystal panel, solar cell and other industries, hydrofluoric acid and nitric acid are used to etch silicon and silicon compounds in the production process, and a large amount of mixed waste acid containing fluorine and nitric acid is generated. One is concentrated hydrofluoric acid containing partial nitric acid, fluorine concentration is about 10mol/L, and nitric acid concentration is 0.5-2 mol/L. The other is concentrated nitric acid containing partial hydrofluoric acid, wherein the fluorine concentration is 0.5-2mol/L, and the nitric acid concentration is different from 10% to 60%. The concentration of hydrofluoric acid and nitric acid contained in the two waste acids is not low, and the two waste acids contain silicon, boron and other impurities. The major hazards in such waste streams are acids, fluoride ions and total nitrogen. Concentrated hydrofluoric acid and nitric acid are known to be highly hazardous and this spent acid cannot be directly utilized to other routes.
With the rapid development of the domestic electronic industry in recent years, the amount of the waste acid generated in the industry is increased, a short-flow low-cost comprehensive treatment process scheme of waste hydrofluoric acid and waste nitric acid is researched, the valuable components are recovered, the environmental protection is facilitated, the development of the national electronic industry can be assisted, and the economic and social benefits are great.
Therefore, at present, the treatment of the waste nitric acid and hydrofluoric acid liquid is a hot point of enterprise research, and many research works are carried out in various countries. Generally, chemical neutralization, rectification, membrane separation, and the like are used. The rectification method can recover some valuable substances, but the process is complicated and the equipment is more. The membrane separation method has the problems of dilute acid concentration and incomplete separation. The chemical neutralization method has the advantages of low energy consumption, short flow, easy selection of equipment and materials and low cost, but the reported methods are all used for independently treating one acid.
For waste nitric acid in the electronic industry, a process for preparing calcium nitrate by neutralizing calcium hydroxide is reported, and the process is simple and easy to industrialize. But only solves the problem of recycling waste nitric acid; and because the daily treatment liquid amount of the waste nitric acid in a single plant area is very small, the equipment is unsaturated in operation, and the treatment is not economical. The product obtained by the neutralization method of hydrofluoric acid waste liquid is difficult to filter and has insufficient purity of about 70 percent, the recovery rate of valuable elements is low, and the problem of recovering the neutralized liquid nitrate can not be solved.
Chinese invention patent CN102892928A reports a method for obtaining or recovering nitric and hydrofluoric acid from solutions of stainless steel pickling plants and/or from solutions of metal salts containing acids, preferably fluorides of iron, chromium, nickel, into a spray dryer with a 350 ℃ hot air carrying mixed acids, the gas at about 140 ℃ discharged from the spray dryer mainly containing nitric acid, followed by washing with water in an absorption tower. The dried flowable metal salt, mainly fluoride, is discharged at the bottom of the spray dryer and subsequently calcined in a calcination reactor at 700 c, the gaseous acid produced here mainly comprising hydrofluoric acid, which is recovered in an absorption column with water washing. The method effectively realizes the separation of hydrofluoric acid and nitric acid, but has the disadvantages of complex process, high temperature, high requirement on equipment and difficult industrial application.
The Chinese invention patent CN109761225A reports a method for recycling fluorine-containing nitric acid waste liquid. The process comprises the steps of firstly combining a substance containing aluminum elements with fluorine in waste liquid to generate aluminum fluoride, then reacting the sodium-containing substance with the aluminum fluoride under certain conditions to generate cryolite and a salt-containing solution, continuously supplementing sulfuric acid to the salt-containing solution under reduced pressure concentration to obtain nitric acid and a sodium bisulfate solution, cooling and centrifuging the sodium bisulfate solution to obtain sodium bisulfate crystals, dissolving and neutralizing the crystals to obtain a sodium sulfate solution, and freezing, centrifuging and drying the sodium sulfate solution to obtain anhydrous sodium sulfate crystals. The used raw materials are simple in type and simple in operation; a novel industrial process for converting sodium nitrate to sodium sulfate is provided; the product with high economic value can be obtained without using hydrofluoric acid and fluorine-containing substances with higher danger coefficients, and the synthesized cryolite and sodium sulfate products have higher purity and higher nitric acid conversion rate. However, the process flow is too long, the equipment investment is large, and the process is not suitable for the characteristics of small waste liquid amount and multiple types in the electronic industry. And the cryolite has high solubility and incomplete fluorine recovery, and is not suitable for the environmental protection requirement of similar waste liquid treatment.
Chinese invention patents CN106430267A and CN107720795A disclose cryolite synthesis methods, both of which adopt the addition of aluminum salt and sodium salt into fluorine-containing waste liquid to ensure that the ratio of sodium to aluminum to fluorine is about 3:1:6, and the scheme is theoretically feasible, but when three substances exist in a system in a large amount, the solubility of cryolite is higher, the residual fluorine is still subjected to subsequent treatment, and the solution has high impurities and cannot obtain qualified cryolite products.
The Chinese patent CN105948083A discloses that a magnesium-containing compound is used as a precipitator for defluorination, and the method is not widely used in industry mainly because magnesium fluoride precipitate generated after reaction needs to react with sulfuric acid at high temperature to generate hydrofluoric acid, the required equipment material requirements are severe, the operation risk factors are more, and the method is not as mature as calcium fluoride precipitate in subsequent industrial utilization.
Chinese patent CN1583716A discloses a method for preparing inactive nitric acid powder, which can solidify nitric acid into solid acid, and mix with CM-911 solid corrosion inhibitor, and is used as acidification de-plugging material in oil field production. The method can be used for recovering the valuable nitrogen element in the waste acid liquid, but the reaction recovery rate is only about 75 percent, the residual waste acid cannot be discharged, and the environmental protection requirement cannot be met.
In view of the above problems in the prior art, it is necessary to design a method for recovering fluorine and nitric acid from hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid, respectively.
Disclosure of Invention
In order to realize the recycling of nitrogen resources and fluorine resources and synthesize an industrial product with higher purity and stable property; but also meets the process requirements of simple operation and low risk coefficient; and simultaneously meets the environmental protection requirement of no three-waste discharge. The invention provides a combined treatment method of hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid, which can simultaneously produce urea nitrate and high-quality calcium fluoride (more than or equal to 90%) as intermediates of industrial nitrogenous fertilizer products, wherein residual nitrogen and fluorine are recycled in a system without discharge, and the recovery rate of the urea nitrate can reach about 95%; the production water is recycled.
In order to achieve the above purpose, the invention provides the following technical scheme:
a combined treatment method for hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid is characterized by comprising the following steps:
(1) adding the hydrofluoric acid-containing nitric acid waste liquid into a urea solution with the concentration of 55%, and stirring to form a mixture of a crystal combined solution A;
(2) cooling the mixture of the crystal combined solution A, filtering to obtain urea nitrate crystals and a solution A, washing the urea nitrate crystals, and combining the filtrate into the solution A to form a new solution A;
(3) adding a solution of a calcium-containing substance into the new solution A, stirring, and adjusting the pH value to 7 to form a mixture of a solution B and calcium fluoride;
(4) filtering the mixture of the solution B and the calcium fluoride to obtain secondary calcium fluoride and a solution B, washing the secondary calcium fluoride, and merging filtrate into the solution B to form a new solution B;
(5) concentrating the new solution B by vacuum evaporation;
(6) adding the new solution B and hydrofluoric acid waste liquid after vacuum evaporation into a reaction kettle at the same time and stirring to form a mixture of calcium fluoride and the solution C;
(7) and filtering the mixture of the calcium fluoride and the solution C to obtain the calcium fluoride and the solution C, washing the calcium fluoride, and merging the filtrate into the solution C.
Further, in the step (1), the urea is used in such an amount that the molar ratio of urea to nitric acid is 1-2; the reaction temperature was room temperature and the reaction time was 0.5h with stirring.
Further, in the step (2), the cooling is coil pipe refrigerant cooling, and the cooling temperature is between room temperature and-20 ℃; the filtration is centrifugal filtration by adopting a water washing type centrifuge.
Still further, in the step (3), the calcium-containing substance is one or more of calcium hydroxide, calcium oxide and calcium carbonate, and the amount of the calcium-containing substance is such that the molar ratio of calcium to nitric acid is 1-1.1; the reaction temperature is 60-100 ℃, and the stirring reaction time is 1-3 h.
And wherein, in the step (4), the filtration is a filter pressing by a water washing type filter press.
Further, in the step (5), the concentrated specific gravity of the new solution B is 1.4-1.7 g/mL.
Further, in the step (6), the new solution B is heated to 80-100 ℃, and the new solution B and the hydrofluoric acid waste liquid are added into the reaction kettle at equal speed.
Finally, in the step (7), the solution C is a hydrofluoric nitric acid mixture.
The combined treatment method of the hydrofluoric acid waste liquid containing the hydrogen nitrate and the nitric acid waste liquid containing the hydrogen fluoride fully considers the recovery of the mixed nitric acid and a small amount of fluorine in the nitric acid waste liquid and the recovery of the fluorine and the small amount of nitric acid in the concentrated hydrofluoric acid waste liquid, has overall consideration, utilizes the displacement reaction, effectively realizes the recovery and utilization of fluorine and nitrogen resources, and can simultaneously obtain high-quality calcium fluoride (not less than 90%) products and nitrogen fertilizer intermediate urea nitrate. Meanwhile, the nitrogen resource and the fluorine resource are recycled, and residual nitrogen and fluorine are recycled in the system without discharge; the production water is recycled.
Moreover, the method has the advantages of simple process, short flow and low cost; the required process equipment is easy to operate, the two waste liquids are treated in a matching way, the equipment utilization rate is improved, the industrial waste acid treatment cost is reduced, and the universality and the economy are realized. .
Detailed Description
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the present invention.
The invention relates to a short-flow low-cost comprehensive treatment method for waste hydrofluoric acid and waste nitric acid, which can recover the valuable components of the waste hydrofluoric acid and the waste nitric acid, is not only beneficial to environmental protection, but also can assist the development of the national electronic industry, and has great economic and social benefits.
The combined treatment method of the hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid comprises the following steps:
firstly, adding the hydrofluoric acid-containing nitric acid waste liquid into a urea solution with the concentration of 55%, and stirring to form a mixture of crystal combined solution A.
Wherein the dosage of the urea is such that the molar ratio of the urea to the nitric acid is 1-2. The reaction temperature was room temperature and the reaction time was 0.5h with stirring.
And secondly, cooling the mixture of the crystal combined solution A, filtering to obtain urea nitrate crystals and a solution A, washing the urea nitrate crystals, and combining the filtrate into the solution A to form a new solution A.
In the invention, the cooling is coil pipe refrigerant cooling, and the cooling temperature is between room temperature and minus 20 ℃. The filtration is centrifugal filtration by adopting a water washing type centrifuge.
And thirdly, adding a solution of a calcium-containing substance into the new solution A, stirring, and adjusting the pH value to 7 to form a mixture of the solution B and calcium fluoride.
The calcium-containing substance is one or more of calcium hydroxide, calcium oxide and calcium carbonate, and the dosage of the calcium-containing substance is such that the molar ratio of calcium to nitric acid is 1-1.1; the reaction temperature is 60-100 ℃, and the stirring reaction time is 1-3 h.
And fourthly, filtering the mixture of the solution B and the calcium fluoride to obtain secondary calcium fluoride and a solution B, washing the secondary calcium fluoride, and merging filtrate into the solution B to form a new solution B.
Wherein, the filtration is carried out by adopting a water washing type filter press.
And fifthly, carrying out vacuum evaporation on the new solution B so as to concentrate the new solution B.
Wherein the concentrated specific gravity of the new solution B is 1.4-1.7 g/mL.
And sixthly, simultaneously adding the new solution B and the hydrofluoric acid waste liquid after vacuum evaporation into the reaction kettle and stirring to form a mixture of calcium fluoride and the solution C.
Wherein, the new solution B needs to be heated to 80-100 ℃, and the new solution B and the hydrofluoric acid waste liquid are added into the reaction kettle at equal speed.
And seventhly, filtering the mixture of the calcium fluoride and the solution C to obtain the calcium fluoride and the solution C, washing the calcium fluoride, and merging the filtrate into the solution C.
Wherein the solution C is a hydrofluoric nitrate acid mixture.
Meanwhile, in the present invention, the hydrofluoric acid-containing nitric acid waste liquid which is one of the steps of the solution C may be treated again by adding a urea solution having a concentration of 55%, and the cycle is performed.
The present invention is described in detail below with reference to a specific example.
880g of urea is weighed and added into 900mL of water, 1000mL of fluorine-containing nitric acid waste liquid (with the fluorine content of 8g/L and the nitric acid content of 900g/L) of a production line of an electronic manufacturer is added after heating, stirring and dissolving, cooling and stirring are carried out for 0.5h, centrifugal filtration is carried out, 1700g of urea nitrate is obtained, 900mL of water is used for washing crystals, and the washing water is recycled to prepare the urea; 1240ml of filtrate.
220ml of prepared 32 percent lime slurry liquid is added into the filtrate, stirred and adjusted to stabilize the pH value of the solution to 7, thus obtaining 860ml of calcium nitrate solution and 387g of secondary calcium fluoride mixture. 500mL of water was washed with the precipitate and the filtrate was evaporated to a Baume of about 1.58 g/mL. And taking 1000mL of calcium nitrate hot solution, taking 1000mL of hydrofluoric acid waste liquid, simultaneously adding the hydrofluoric acid waste liquid into a reaction tank which is placed in a seed crystal in advance at the same flow rate, stirring for 0.5h, filtering, returning 1000mL of filtrate to react with the urea solution, and obtaining urea nitrate. Washing the first-stage calcium fluoride with 1000ml of water to obtain a first-stage calcium fluoride solid and 1000ml of a filter washing solution, and returning the washing solution to the urea nitrate precipitation solution to react with the calcium hydroxide slurry. After the first-level calcium fluoride is dried, 240g of first-level calcium fluoride solid with the content of more than 90 percent and the granularity concentrated on 1-20 microns is obtained. The nitrate nitrogen (calculated by N) content of the urea nitrate is more than 33 percent; the water content is more than 10 percent, and the product can be sold as an intermediate of a nitrogen fertilizer.
The combined treatment method of the hydrofluoric acid waste liquid containing the hydrogen nitrate and the nitric acid waste liquid containing the hydrogen fluoride fully considers the recovery of the mixed nitric acid and a small amount of fluorine in the nitric acid waste liquid and the recovery of the fluorine and the small amount of nitric acid in the concentrated hydrofluoric acid waste liquid, has overall consideration, utilizes the displacement reaction, effectively realizes the recovery and utilization of fluorine and nitrogen resources, and can simultaneously obtain high-quality calcium fluoride (not less than 90%) products and nitrogen fertilizer intermediate urea nitrate. Meanwhile, the nitrogen resource and the fluorine resource are recycled, and residual nitrogen and fluorine are recycled in the system without discharge; the production water is recycled.
Moreover, the method has the advantages of simple process, short flow and low cost; the required process equipment is easy to operate, the two waste liquids are treated in a matching way, the equipment utilization rate is improved, the industrial waste acid treatment cost is reduced, and the universality and the economy are realized. .
The above examples of the present invention are merely examples for clearly illustrating the present invention and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (8)
1. A combined treatment method for hydrofluoric acid waste liquid containing nitric acid and hydrofluoric acid waste liquid containing nitric acid is characterized by comprising the following steps:
(1) adding the hydrofluoric acid-containing nitric acid waste liquid into a urea solution with the concentration of 55%, and stirring to form a mixture of a crystal combined solution A;
(2) cooling the mixture of the crystal combined solution A, filtering to obtain urea nitrate crystals and a solution A, washing the urea nitrate crystals, and combining the filtrate into the solution A to form a new solution A;
(3) adding a solution of a calcium-containing substance into the new solution A, stirring, and adjusting the pH value to 7 to form a mixture of a solution B and calcium fluoride;
(4) filtering the mixture of the solution B and the calcium fluoride to obtain secondary calcium fluoride and a solution B, washing the secondary calcium fluoride, and merging filtrate into the solution B to form a new solution B;
(5) concentrating the new solution B by vacuum evaporation;
(6) adding the new solution B and hydrofluoric acid waste liquid after vacuum evaporation into a reaction kettle at the same time and stirring to form a mixture of calcium fluoride and the solution C;
(7) and filtering the mixture of the calcium fluoride and the solution C to obtain the calcium fluoride and the solution C, washing the calcium fluoride, and merging the filtrate into the solution C.
2. The combined treatment method of the nitric-hydrofluoric acid-containing waste liquid and the hydrofluoric-nitric acid-containing waste liquid according to claim 1, wherein in the step (1), the urea is used in such an amount that the molar ratio of the urea to the nitric acid is 1-2; the reaction temperature was room temperature and the reaction time was 0.5h with stirring.
3. The joint treatment method of the hydrofluoric acid and nitric acid containing nitric acid waste liquid according to claim 2, wherein in the step (2), the cooling is coil cooling, and the cooling temperature is between room temperature and-20 ℃; the filtration is centrifugal filtration by adopting a water washing type centrifuge.
4. The combined treatment method of the hydrofluoric acid and hydrofluoric acid-containing nitric acid waste liquid according to claim 3, wherein in the step (3), the calcium-containing substance is one or more of calcium hydroxide, calcium oxide, and calcium carbonate, and the amount of the calcium-containing substance is such that the molar ratio of calcium to nitric acid is 1 to 1.1; the reaction temperature is 60-100 ℃, and the stirring reaction time is 1-3 h.
5. The combined treatment method of the hydrofluoric acid and nitric acid containing nitric acid waste liquid containing nitric acid according to claim 4, wherein in the step (4), the filtration is filter pressing using a water washing type filter press.
6. The combined treatment method of the nitric-hydrofluoric acid-containing waste liquid and the hydrofluoric acid-containing nitric acid-containing waste liquid according to claim 5, wherein in the step (5), the concentrated specific gravity of the new solution B is 1.4-1.7 g/mL.
7. The method for combined treatment of waste liquid containing nitric acid, hydrofluoric acid and nitric acid, according to claim 6, wherein in the step (6), the new solution B is heated to 80-100 ℃ and added to the reaction vessel at the same rate as the hydrofluoric acid waste liquid.
8. The combined treatment method of the hydrofluoric acid and nitric acid-containing waste liquid containing nitric acid and nitric acid according to claim 7, wherein in the step (7), the solution C is a hydrofluoric acid and nitric acid mixture.
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CN110902883A (en) * | 2019-12-05 | 2020-03-24 | 中广核环境科技(深圳)有限责任公司 | Recycling method of fluorine-containing wastewater |
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CN116692874A (en) * | 2023-07-13 | 2023-09-05 | 河南省氟基新材料科技有限公司 | Semiconductor waste acid recycling method |
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