CN112574069B - Resource utilization method of waste phosphoric acid in microelectronic industry - Google Patents
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- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
- C07C273/02—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of urea, its salts, complexes or addition compounds
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Abstract
The invention discloses a resource utilization method of waste phosphoric acid in the microelectronic industry, and relates to a method for preparing industrial-grade urea phosphate by resource utilization of electronic-grade waste phosphoric acid in liquid crystal panels, semiconductor wafers and integrated circuit enterprises. Comprises the following steps: (1) waste phosphoric acid and urea are synthesized by heating reaction; (2) statically adsorbing the urea phosphate preparation solution by using activated carbon, cation exchange resin and anion exchange resin; (3) negative pressure evaporation, concentration, cooling, crystallization and separation of the deionized urea phosphate solution; (4) adding water for primary crystallization, heating, redissolving, cooling and recrystallizing; (5) drying the recrystallized crystal by low-temperature hot air. Compared with the prior degradation use of electronic grade waste phosphoric acid, the method can obtain a high-purity urea phosphate product, has higher industrial value and has wide market application prospect. The whole treatment process is simple to operate, the reagent is cheap to input, and the byproduct waste meets the requirements of a common biochemical wastewater station, so that the method is the optimal choice for resource utilization of the electronic grade waste phosphoric acid.
Description
Technical Field
The invention relates to the technical field of water treatment, in particular to a resource utilization method of waste phosphoric acid in the microelectronic industry, and more particularly relates to a method for producing a urea phosphate product from the waste phosphoric acid in semiconductor or panel cleaning and etching in the microelectronic industry.
Background
Electronic grade phosphoric acid is a key raw material for semiconductor wafer production, integrated circuit etching and panel production in the microelectronic industry, the market value of phosphoric acid with the minimum purity requirement is not lower than 2 times of the price of industrial grade phosphoric acid, and the content of total weight metal ions in the phosphoric acid is not higher than 1 ppm. Before 2014, Chinese electronic grade phosphoric acid is basically and completely imported, Chinese self-produced electronic grade phosphoric acid is still not higher than 10 ten thousand tons by 2018, the technology is basically oriented to the panel and semiconductor manufacturing industry, and the IC grade phosphoric acid for chips of large-scale integrated circuits still needs to be imported.
Phosphoric acid which is put into the electronic industry is mainly applied to the aspects of panel etching, semiconductor manufacturing and cleaning and integrated circuit etching, and the using environment of the phosphoric acid is basically in a clean factory building; in general, only reagent mixing pollution and etched object pollution exist in domestic use, wherein the reagent mainly comprises acetic acid, nitric acid and high-purity water, and the etched object mainly comprises various heavy metals, Al and Si. The waste phosphoric acid removed from the production lines is still in a clear and transparent state basically, but various heavy metal ions and blending reagents in the waste phosphoric acid are removed in the subsequent resource utilization process, so that the purity of the product can be ensured, and the market value of the product can be guaranteed.
At the present stage, the waste phosphoric acid produced by electronic enterprises is generally used by downstream enterprises to produce insoluble salt or soluble salt in a simple neutralization mode, so that harmless treatment or simple resource utilization is realized, for example, slaked lime is added into the waste phosphoric acid to prepare phosphogypsum, or liquid alkali is used for neutralizing and preparing inorganic phosphate such as sodium phosphate and the like. Because of the inherent characteristics of the products, the prior art cannot be grafted with a heavy metal ion removal process, cannot take out an electronic reagent added in the heavy metal ion removal process, and most waste acid used for etching contains nitric acid with low concentration, so that a large amount of yellow smoke is emitted in the neutralization process, and the risk of the disposal process is very high.
Urea is a simple organic matter with the lowest molecular weight, is a main raw material for providing animal/plant non-protein nitrogen, is combined with phosphoric acid according to the molar ratio of 1:1 to form molecular compound urea phosphate, has low dissociation degree of anions and cations in aqueous solution, can select strong acid cation exchange resin and strong base anion exchange resin, and can quickly and conveniently remove various metal ion pollutants brought by the etching and cleaning processes of the front-end electronic industry. Meanwhile, most of divalent and trivalent inorganic salts of phosphoric acid are insoluble in water, and urea phosphate solution with extremely high purity can be obtained through simple physical adsorption filtration.
Urea phosphate is a molecular double salt, hardly ionizing any anions and cations in aqueous solution; the urea phosphate solution can be subjected to evaporation concentration to obtain primary wet crystals, and the high-purity urea phosphate product meeting the national standard can be obtained by heating up tap water, re-dissolving, cooling, crystallizing and drying by low-temperature hot air. The fraction formed in the evaporation process is dilute acetic acid clear liquid, and the discharged water can directly reach the standard by a biochemical treatment system in a wastewater station after the pH is adjusted; the mother liquor obtained by the two centrifugal separation processes can be returned to the front-end urea phosphate solution for synthesis, and the phosphorus resource is continuously recycled. The urea phosphate can be used as a plant fertilizer or an animal non-protein nitrogen feed additive; is a main additive component of a fire extinguishing agent in the plastic industry and can be used as a synthetic material of ammonium polyphosphate; is also an excellent metal cleaner. The urea phosphate prepared by adopting the waste phosphoric acid in the electronic industry has wide application and low yield compared with inorganic phosphate, can improve the market value of phosphorus in the waste phosphoric acid, and increases the profit margin of resource disposal enterprises.
Disclosure of Invention
In view of this, the embodiments of the present disclosure provide a resource utilization method for waste phosphoric acid in the microelectronics industry, which at least partially solves the problems in the prior art.
The invention provides a resource utilization method of waste phosphoric acid in the microelectronic industry, which comprises the following steps:
s1, mixing waste phosphoric acid and a urea aqueous solution, heating, reacting at a constant temperature for 1-2 hours, adding water to adjust the density, and ensuring that the waste phosphoric acid is not crystallized after being cooled at room temperature;
s2, enabling the reaction solution to sequentially pass through activated carbon, a strong-acid cation exchange resin packed column and a strong-base anion exchange resin packed column;
s3, collecting the solution after ion exchange, evaporating and concentrating to improve the density, and treating the fraction obtained by evaporation into a clear solution containing acetic acid in a biochemical system; cooling the concentrated solution to naturally crystallize, and centrifugally separating to obtain primary wet crystals and a crystallization mother solution; the crystallization mother liquor is returned to the step S1;
s4, adding water into the primary wet crystals to heat and redissolve, cooling again, adding seed crystals, cooling the solution to room temperature, and performing centrifugal separation to obtain secondary crystals and recrystallization mother liquor; the crystallization mother liquor is returned to the step S1;
and S5, drying the secondary crystallization by adopting low-temperature hot air to obtain an industrial grade urea phosphate product.
As a further protection of the invention, the temperature rise and constant temperature reaction temperature in the step S1 is 60-80 ℃, and water is added after the reactionAdjusting to a density of not more than 1.25g/cm3(ii) a Total P in the mixed solution: the ratio of the total N content is 1 (1.5-2.5).
As a further protection of the invention, the activated carbon in the step S2 is coconut shell activated carbon, and the iodine adsorption value is not lower than 800 ppm; the strong acid cation exchange resin is D001 macroporous hydrogen type cation exchange resin or 001X7 strong acid styrene type cation exchange resin; the strong-base anion exchange resin is D201 macroporous strong-base styryl hydroxyl type anion exchange resin or 201X7 strong-base styryl anion exchange resin.
As a further protection of the present invention, the evaporative concentration density endpoint in the step S3 is not less than 1.48g/cm3And the temperature of the whole evaporation process is not higher than 95 ℃.
As a further protection of the invention, in the step S4, the mass ratio of the wet crystals to the water in the primary wet crystal water-adding temperature-rising re-dissolution is (2-4): 1, the temperature of the seed crystal is 50-60 ℃, and the addition amount of the seed crystal is 10 wt% of the weight of the added water.
As a further protection of the invention, the seed crystal is urea phosphate crystal.
As a further protection of the invention, the low-temperature hot air drying in the step S5 is drying by a vibrating fluidized bed, and the temperature of the drying air is 50-85 ℃.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present disclosure, the drawings needed to be used in the embodiments will be briefly described below, and it is apparent that the drawings in the following description are only some embodiments of the present disclosure, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The embodiments of the present disclosure are described in detail below with reference to the accompanying drawings.
The embodiments of the present disclosure are described below with specific examples, and other advantages and effects of the present disclosure will be readily apparent to those skilled in the art from the disclosure in the specification. It is to be understood that the described embodiments are merely illustrative of some, and not restrictive, of the embodiments of the disclosure. The disclosure may be embodied or carried out in various other specific embodiments, and various modifications and changes may be made in the details within the description without departing from the spirit of the disclosure. It is to be noted that the features in the following embodiments and examples may be combined with each other without conflict. All other embodiments, which can be derived by a person skilled in the art from the embodiments disclosed herein without making any creative effort, shall fall within the protection scope of the present disclosure.
It is noted that various aspects of the embodiments are described below within the scope of the appended claims. It should be apparent that the aspects described herein may be embodied in a wide variety of forms and that any specific structure and/or function described herein is merely illustrative. Based on the disclosure, one skilled in the art should appreciate that one aspect described herein may be implemented independently of any other aspects and that two or more of these aspects may be combined in various ways. For example, an apparatus may be implemented and/or a method practiced using any number of the aspects set forth herein. Additionally, such an apparatus may be implemented and/or such a method may be practiced using other structure and/or functionality in addition to one or more of the aspects set forth herein.
It should be noted that the drawings provided in the following embodiments are only for illustrating the basic idea of the present disclosure, and the drawings only show the components related to the present disclosure rather than the number, shape and size of the components in actual implementation, and the type, amount and ratio of the components in actual implementation may be changed arbitrarily, and the layout of the components may be more complicated.
In addition, in the following description, specific details are provided to facilitate a thorough understanding of the examples. However, it will be understood by those skilled in the art that the aspects may be practiced without these specific details.
A plurality of execution requirements of the invention are directed at the waste phosphoric acid in the electronic industry, in particular to the waste phosphoric acid discharged from a production line mixing nitric acid, acetic acid and etching or cleaning pollutants, and the invention provides a recycling comprehensive utilization process with strong adaptability, simple treatment process, cheap application reagents and high product value.
In order to realize the above purpose, the invention provides a resource utilization process of waste phosphoric acid in the microelectronic industry, which comprises the following steps:
step 1, performing component assay on waste phosphoric acid to be treated, wherein the total P: preparing sufficient urea according to the ratio of the total N substances to 1 (1.5-2.5); adding water into urea to properly dissolve the urea in a reactor to form a concentrated solution, and adding waste phosphoric acid to be treated into the urea solution; heating the solution to 60-80 ℃, keeping the temperature for 1-2 h, adding water to cool the solution and simultaneously ensuring that the density is not more than 1.25g/cm3；
Step 2, enabling the urea phosphate preparation solution after the reaction and the temperature reduction to sequentially pass through an activated carbon packed column, a hydrogen ion type strong acid sulfonic acid group strong acid resin packed column and a hydroxyl type strong base styrene-based resin packed column in a fixed bed adsorption column mode, wherein the adsorption process control solution is free of crystallization separation in the resin packed column and the ascending linear velocity is not more than 3 cm/s;
preferably, the activated carbon filled column recommends selecting coconut shell activated carbon as the filler;
optionally, the hydrogen ion type strong acid sulfonic acid group strong acid resin packed column can be selected from 001X7 strong acid styrene cation exchange resin, or can be selected from D001 macroporous strong acid styrene cation exchange resin;
optionally, the hydroxyl strongly basic styrene-based resin packed column can be selected from 201X7 strongly basic styrene-based anion exchange resin, and can also be selected from D201 macroporous strongly basic styrene-based anion exchange resin;
step 3, the deionized urea phosphate solution obtained by adsorption is evaporated and concentrated by negative pressureThe whole evaporation process is controlled to concentrate the adsorption solution to the density of not less than 1.48g/cm under the condition that the temperature is not higher than 95 DEG C3(ii) a Slowly cooling to naturally crystallize; obtaining a crystallization mother liquor and primary wet crystals of urea phosphate by adopting a centrifugal separation mode; the negative pressure fraction produced in the step is clear liquid containing acetic acid, does not contain any pollution factor, and meets the biochemical treatment requirement of a general wastewater station;
preferably, the negative pressure evaporation concentration method is recommended to be a single-effect or double-effect forced circulation evaporation process;
step 4, adding tap water according to the mass ratio of (2-4) to 1 to the primary wet crystals of the urea phosphate, heating to 70 ℃ for full dissolution, then slowly cooling to 50-60 ℃, and adding seed crystal urea phosphate crystals according to 10% of the primary wet crystal amount to promote the growth of crystals in the cooling process; separating the fully cooled urea phosphate crystal liquid by using a centrifugal machine to obtain a recrystallization mother liquid and wet crystals of a urea phosphate product, and returning the recrystallization mother liquid to the front end to prepare a urea solution;
preferably, the recrystallization suspension centrifugal separation mode is an intermittent manual discharging lining bag type centrifugal device, such as a top discharging type flat plate centrifuge;
and 5, drying the recrystallized urea phosphate wet crystal by adopting a low-temperature hot air drying mode to remove water, wherein the drying temperature is not higher than 85 ℃ until the water content is not more than 0.5%.
The preferable low-temperature hot air drying mode is the hot air drying of a vibrating fluidized bed.
Embodiment 1 resource utilization method of waste phosphoric acid in microelectronic industry
The method comprises the following steps:
s1, mixing waste phosphoric acid with a urea aqueous solution, wherein the total P: the ratio of the total N substances is 1:1.5, after the temperature is raised and the reaction is carried out for 1 hour at the constant temperature of 60 ℃, water is added to adjust the density to be 1.05g/cm3Ensuring that the crystal is not crystallized after cooling at room temperature;
s2, enabling the reaction solution to sequentially pass through activated carbon, a strong-acid cation exchange resin packed column and a strong-base anion exchange resin packed column;
s3, collecting the solution after ion exchange, evaporating and concentrating, wherein the temperature in the whole evaporation process is not higher than 95 ℃, and increasingDensity 1.52g/cm3The fraction obtained by evaporation is clear liquid containing acetic acid, and the clear liquid enters a biochemical system for treatment; cooling the concentrated solution to naturally crystallize, and centrifugally separating to obtain primary wet crystals and a crystallization mother solution; the crystallization mother liquor is returned to the step S1;
s4, adding water into the primary wet crystals, heating to redissolve, wherein the mass ratio of the wet crystals to the water is 2:1, cooling, adding urea phosphate crystal seeds, cooling to 50 ℃, adding 10 wt% of the urea phosphate crystal seeds, cooling the solution to room temperature, and performing centrifugal separation to obtain secondary crystallization and recrystallization mother liquor; the crystallization mother liquor is returned to the step S1;
s5, drying the secondary crystallization by adopting a vibrating fluidized bed, wherein the drying air temperature is 50 ℃, and obtaining an industrial grade urea phosphate product, wherein the detection indexes are as follows:
| serial number | Name (R) | Standard of merit | Test products | Determination |
| 1 | Phosphorus pentoxide | ≥44 | 45.51 | Is superior to the standard requirement |
| 2 | Total nitrogen | ≥17 | 17.15 | Is superior to the standard requirement |
| 3 | Water insoluble substance | ≤0.1 | Not detected out | Conform to |
| 4 | Dry weight reduction | ≤0.5 | 0.38 | Conform to |
| 5 | Fluoride (F) | ≤0.05 | 0.008 | Conform to |
| 6 | As | ≤0.01 | Not detected out | Conform to |
| 7 | Heavy metals (in Pb) | ≤0.03 | 0.012 | Conform to |
| 8 | pH (10g/L in water) | 1.6～2.4 | 1.67 | Conform to |
Embodiment 2 resource utilization method of waste phosphoric acid in microelectronic industry
The method comprises the following steps:
s1, mixing waste phosphoric acid with a urea aqueous solution, wherein the total P: the ratio of the total N substances is 1:2.5, the temperature is raised and the reaction is carried out for 2 hours at the constant temperature of 80 ℃, and then water is added to adjust the density to be 1.12g/cm3Ensuring that the crystal is not crystallized after cooling at room temperature;
s2, enabling the reaction solution to sequentially pass through activated carbon, a strong-acid cation exchange resin packed column and a strong-base anion exchange resin packed column;
s3, collecting the solution after ion exchange, evaporating and concentrating, wherein the temperature in the whole evaporation process is not higher than 95 ℃, and the density is increased by 1.50g/cm3The fraction obtained by evaporation is clear liquid containing acetic acid, and the clear liquid enters a biochemical system for treatment; cooling the concentrated solution to naturally crystallize, and centrifugally separating to obtain primary wet crystals and a crystallization mother solution; the crystallization mother liquor is returned to the step S1;
s4, adding water into the primary wet crystals, heating to redissolve, wherein the mass ratio of the wet crystals to the water is 4:1, cooling, adding urea phosphate crystal seeds, cooling to 60 ℃, adding 10 wt% of the urea phosphate crystal seeds, cooling the solution to room temperature, and performing centrifugal separation to obtain secondary crystallization and recrystallization mother liquor; the crystallization mother liquor is returned to the step S1;
s5, drying the secondary crystallization by adopting a vibrating fluidized bed, wherein the temperature of drying air is 85 ℃, and obtaining an industrial grade urea phosphate product, wherein the detection indexes are as follows:
| serial number | Name (R) | Standard of merit | Test products | Determination |
| 1 | Phosphorus pentoxide | ≥44 | 44.51 | Is superior to the standard requirement |
| 2 | Total nitrogen | ≥17 | 17.65 | Is superior to the standard requirement |
| 3 | Water insoluble substance | ≤0.1 | Not detected out | Conform to |
| 4 | Dry weight reduction | ≤0.5 | 0.42 | Conform to |
| 5 | Fluoride (F) | ≤0.05 | Not detected out | Conform to |
| 6 | As | ≤0.01 | Not detected out | Conform to |
| 7 | Heavy metals (in Pb) | ≤0.03 | 0.016 | Conform to |
| 8 | pH (10g/L in water) | 1.6～2.4 | 1.74 | Conform to |
Embodiment 3 resource utilization method of waste phosphoric acid in microelectronic industry
The method comprises the following steps:
s1, mixing waste phosphoric acid with a urea aqueous solution, wherein the total P: the ratio of the total N substances is 1:2.1, the temperature is raised and the reaction is carried out for 1h at the constant temperature of 70 ℃, and then water is added to adjust the density to be 1.20g/cm3Ensuring that the crystal is not crystallized after cooling at room temperature;
s2, enabling the reaction solution to sequentially pass through activated carbon, a strong-acid cation exchange resin packed column and a strong-base anion exchange resin packed column;
s3, collecting the solution after ion exchange, evaporating and concentrating, wherein the temperature in the whole evaporation process is not higher than 95 ℃, and the density is increased by 1.49g/cm3The fraction obtained by evaporation is clear liquid containing acetic acid, and the clear liquid enters a biochemical system for treatment; cooling the concentrated solution to naturally crystallize, and centrifugally separating to obtain primary wet crystals and a crystallization mother solution; the crystallization mother liquor is returned to the step S1;
s4, adding water into the primary wet crystals, heating to redissolve, wherein the mass ratio of the wet crystals to the water is 3:1, cooling, adding urea phosphate crystal seeds, cooling to 55 ℃, adding 10 wt% of the urea phosphate crystal seeds, cooling the solution to room temperature, and performing centrifugal separation to obtain secondary crystallization and recrystallization mother liquor; the crystallization mother liquor is returned to the step S1;
s5, drying the secondary crystallization by adopting a vibrating fluidized bed, wherein the temperature of drying air is 65 ℃, and obtaining an industrial grade urea phosphate product, wherein the detection indexes are as follows:
| serial number | Name (R) | Standard of merit | Test products | Determination |
| 1 | Phosphorus pentoxide | ≥44 | 45.32 | Is superior to the standard requirement |
| 2 | Total nitrogen | ≥17 | 18.13 | Is superior to the standard requirement |
| 3 | Water insoluble substance | ≤0.1 | Not detected out | Conform to |
| 4 | Dry weight reduction | ≤0.5 | 0.48 | Conform to |
| 5 | Fluoride (F) | ≤0.05 | Not detected out | Conform to |
| 6 | As | ≤0.01 | Not detected out | Conform to |
| 7 | Heavy metals (in Pb) | ≤0.03 | 0.022 | Conform to |
| 8 | pH (10g/L in water) | 1.6～2.4 | 1.9 | Conform to |
The above description is only for the specific embodiments of the present disclosure, but the scope of the present disclosure is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present disclosure should be covered within the scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.
Claims (7)
1. A resource utilization method of waste phosphoric acid in the microelectronic industry is characterized by comprising the following steps:
s1, mixing waste phosphoric acid and a urea aqueous solution, heating, reacting at a constant temperature for 1-2 hours, and adding water to adjust the density to be not more than 1.25g/cm3Ensuring that the crystal is not crystallized after cooling at room temperature;
s2, enabling the reaction solution to sequentially pass through activated carbon, a strong-acid cation exchange resin packed column and a strong-base anion exchange resin packed column;
s3, collecting the solution after ion exchange, evaporating and concentrating to improve the density, and treating the fraction obtained by evaporation into a clear solution containing acetic acid in a biochemical system; cooling the concentrated solution to naturally crystallize, and centrifugally separating to obtain primary wet crystals and a crystallization mother solution; the crystallization mother liquor is returned to the step S1;
s4, adding water into the primary wet crystals to heat and redissolve, cooling again, adding seed crystals, cooling the solution to room temperature, and performing centrifugal separation to obtain secondary crystals and recrystallization mother liquor; the crystallization mother liquor is returned to the step S1;
and S5, drying the secondary crystallization by adopting low-temperature hot air to obtain an industrial grade urea phosphate product.
2. The resource utilization method of waste phosphoric acid in the microelectronic industry according to claim 1, characterized in that, in the step S1, the temperature rise constant temperature reaction temperature is 60-80 ℃, the total P: the ratio of the total N content is 1 (1.5-2.5).
3. The resource utilization method of waste phosphoric acid in the microelectronic industry as claimed in claim 1, wherein in step S2, the activated carbon is coconut shell activated carbon, and the iodine adsorption value is not less than 800 ppm; the strong acid cation exchange resin is D001 macroporous hydrogen type cation exchange resin or 001X7 strong acid styrene type cation exchange resin; the strong-base anion exchange resin is D201 macroporous strong-base styryl hydroxyl type anion exchange resin or 201X7 strong-base styryl anion exchange resin.
4. The method for recycling waste phosphoric acid in the microelectronic industry as claimed in claim 1, wherein the concentration density end point of evaporation in step S3 is not less than 1.48g/cm3And the temperature of the whole evaporation process is not higher than 95 ℃.
5. The resource utilization method of waste phosphoric acid in the microelectronic industry as claimed in claim 1, wherein in step S4, the mass ratio of wet crystal to water in the primary wet crystal water heating re-dissolution is (2-4): 1, the temperature of seed crystal addition is 50-60 ℃, and the seed crystal addition amount is 10 wt% of the weight of added water.
6. The method as claimed in claim 5, wherein the seed crystal is urea phosphate crystal.
7. The resource utilization method of waste phosphoric acid in the microelectronic industry as claimed in claim 1, wherein the low-temperature hot air drying in step S5 is a vibrated fluidized bed drying, and the drying air temperature is 50-85 ℃.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1440056A (en) * | 1921-06-28 | 1922-12-26 | Clarkson Fuller | Method of making urea phosphate |
| US4461913A (en) * | 1981-11-24 | 1984-07-24 | Tennessee Valley Authority | Production of urea phosphate |
| CN105314612A (en) * | 2014-07-18 | 2016-02-10 | Oci有限公司 | Method for removing metal ions from phosphoric acid solution |
| CN107056388A (en) * | 2017-05-27 | 2017-08-18 | 深圳市深投环保科技有限公司 | The preparation method of chemical polishing waste phosphoric acid processing method and fertilizer |
| CN107162935A (en) * | 2017-05-27 | 2017-09-15 | 深圳市深投环保科技有限公司 | The recovery method of phosphorus-containing compound in useless chemical polishing agent |
| CN107188861A (en) * | 2017-05-27 | 2017-09-22 | 深圳市深投环保科技有限公司 | Recycle the method that phosphorous acid waste liquid prepares melamine polyphosphate |
-
2020
- 2020-12-04 CN CN202011408374.9A patent/CN112574069B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US1440056A (en) * | 1921-06-28 | 1922-12-26 | Clarkson Fuller | Method of making urea phosphate |
| US4461913A (en) * | 1981-11-24 | 1984-07-24 | Tennessee Valley Authority | Production of urea phosphate |
| CN105314612A (en) * | 2014-07-18 | 2016-02-10 | Oci有限公司 | Method for removing metal ions from phosphoric acid solution |
| CN107056388A (en) * | 2017-05-27 | 2017-08-18 | 深圳市深投环保科技有限公司 | The preparation method of chemical polishing waste phosphoric acid processing method and fertilizer |
| CN107162935A (en) * | 2017-05-27 | 2017-09-15 | 深圳市深投环保科技有限公司 | The recovery method of phosphorus-containing compound in useless chemical polishing agent |
| CN107188861A (en) * | 2017-05-27 | 2017-09-22 | 深圳市深投环保科技有限公司 | Recycle the method that phosphorous acid waste liquid prepares melamine polyphosphate |
Non-Patent Citations (2)
| Title |
|---|
| 化学蚀刻废磷酸制备饲料级磷酸脲的研究;周兆安等;《无机盐工业》;20181031;第50卷(第10期);第66-69页 * |
| 湿法磷酸制备工业级磷酸脲的工艺研究;柳潇;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20190815;B016-107 * |
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