CN107162935B - The recovery method of phosphorus-containing compound in useless chemical polishing agent - Google Patents
The recovery method of phosphorus-containing compound in useless chemical polishing agent Download PDFInfo
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- CN107162935B CN107162935B CN201710392425.5A CN201710392425A CN107162935B CN 107162935 B CN107162935 B CN 107162935B CN 201710392425 A CN201710392425 A CN 201710392425A CN 107162935 B CN107162935 B CN 107162935B
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- chemical polishing
- polishing agent
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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
- C07C273/14—Separation; Purification; Stabilisation; Use of additives
- C07C273/16—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B15/00—Organic phosphatic fertilisers
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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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- Organic Chemistry (AREA)
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Abstract
The present invention provides a kind of recovery method of phosphorus-containing compound in useless chemical polishing agent, includes the following steps: to extract acetic acid and nitric acid in useless chemical polishing agent；Useless chemical polishing agent extracted is concentrated；Urea will be added in useless chemical polishing agent after concentration, is crystallized after fully reacting, isolated PHOSPHORIC ACID TECH.GRADE urea and crystalline mother solution；Precipitating reagent will be added in crystalline mother solution, sediment separate out is purified mother liquor；By the purification mother liquor concentrations, Crystallization Separation obtains feed grade urea phosphate and secondary crystallization mother liquor.Method recovery product purity is high provided by the present invention, it is high-quality, industrial circle can not only be reached and use rank, moreover it is possible to be used as the additive of feed or the raw material of high concentration N-P compound fertilizer.The production process of this method is simple, easily operated, and easy control of reaction conditions is at low cost, high to the rate of recovery of phosphorus, and large-scale production easy to accomplish has obviously economic benefit and environmental benefit.
Description
Technical field
The present invention relates to a kind of recovery methods of phosphorus-containing compound in useless chemical polishing agent.
Background technique
The etch in the polishing solution for matching reasonable corrosive agent, oxidant, additive composition of metal material or product, warp
After series reaction occurs, surface becomes clean bright, referred to as chemical polishing.Most of chemical polishing of aluminium and aluminium alloy uses
Phosphoric acid based sols carry out, the solution based on the phosphoric acid of 70% (mass percent).The most commonly used is phosphoric acid, sulfuric acid, nitric acid or
Acetic acid mixed liquor, the high solution of phosphorus acid content can make the surface after mechanically polishing reach comparable high bright with electropolishing
Degree is used for fine aluminium, Al-Mg-Zn and Al-Cu-Mg alloy of the zinc content not higher than 8%, copper content not higher than 4%.
A large amount of waste liquid is generated during the polishing process, and mainly containing phosphoric acid, acetic acid, heavy metal ion of higher concentration etc. has
Harmful chemical substance has very strong corrosivity, belongs to the HW34 class of " National Hazard waste register ".Before this, this is generally handled
The method of kind chemical polishing agent is that lime is added to neutralize, waste landfills.The method can generate a large amount of phosphorus containing sludges, increase landfill at
This, or even environmental pollution can be caused.
Currently, the comprehensive utilization for such waste phosphoric acid has some related patents and document report, such as patent CN
101456547 B realize purification and the fertilizer grade phosphorus of heavy metal ion by step-by-step precipitation method as neutralizer using milk of lime
The preparation of the product of sour hydrogen calcium generates contain a large amount of aluminium salt in the calcium monohydrogen phosphate come in this way, and phosphoric acid hydrogen
The market outlet of calcium is bad, and added value of product is lower.Patent 201610795470.0 proposes a kind of aluminium polishing waste phosphoric acid liquid resource
Change recovery method, the fluorine-containing solution of addition and sodium salt is used to be precipitated in the form of ice crystal except aluminium, then is raw with calcium salt three-step precipitation method
It produces calcium monohydrogen phosphate and general calcium, phosphoric acid is fully used, but precipitation and separation is complicated, added value of product is low.
Summary of the invention
For the defects in the prior art, the object of the present invention is to provide one kind being capable of the useless chemical polishing of high-efficiency environment friendly processing
The recovery method of agent.
The present invention provides a kind of recovery method of phosphorus-containing compound in useless chemical polishing agent, includes the following steps:
Acetic acid and nitric acid in useless chemical polishing agent is extracted using extractant, the extractant includes tributyl phosphate, phosphorus
At least one of sour three monooctyl esters；
Useless chemical polishing agent extracted is concentrated；
Urea will be added in useless chemical polishing agent after concentration, is crystallized after fully reacting, isolated PHOSPHORIC ACID TECH.GRADE urea
And crystalline mother solution；
Sulfide precipitation agent will be added in crystalline mother solution, sediment separate out is purified mother liquor, the sulfide precipitation agent
Including at least one of hydrogen sulfide, ammonium sulfide or vulcanized sodium；
By the purification mother liquor concentrations, Crystallization Separation obtains feed grade urea phosphate and secondary crystallization mother liquor.
Method provided by the present invention mainly recycles phosphorus-containing compound in useless chemical polishing agent in the form of urea phosphate,
Purity is high, it is high-quality, industrial circle can not only be reached and use rank, moreover it is possible to which the additive or high concentration N-P as feed are multiple
The raw material in Hefei uses.Its product purpose is extensive, and added value is high.
This method finally only generates a small amount of sludge simultaneously, reduces landfill expense.And production process is simple, is easy to
Operation, easy control of reaction conditions is at low cost, high to the rate of recovery of phosphorus, and large-scale production easy to accomplish has obviously
Economic benefit and environmental benefit.
Specific embodiment
The solution of the present invention is explained in detail below with reference to reference attached drawing, it will be understood to those of skill in the art that under
Face example for explaining only the invention, and is not considered as limiting the invention.
One aspect of the present invention provides a kind of recovery method of phosphorus-containing compound in useless chemical polishing agent, includes the following steps:
Extract acetic acid and nitric acid in useless chemical polishing agent；
Useless chemical polishing agent extracted is concentrated；
Urea will be added in useless chemical polishing agent after concentration, is crystallized after reaction, isolated PHOSPHORIC ACID TECH.GRADE urea and knot
Brilliant mother liquor；
Precipitating reagent will be added in crystalline mother solution, sediment separate out is purified mother liquor；
By the purification mother liquor concentrations, Crystallization Separation obtains feed grade urea phosphate and secondary crystallization mother liquor.
According to a particular embodiment of the invention, in the useless chemical polishing agent of the extraction and separation in acetic acid and nitric acid, using extraction
Agent is taken to be extracted, the extractant includes at least one of tributyl phosphate, trioctyl phosphate, and diluent includes kerosene etc..
According to a particular embodiment of the invention, the mode of the extraction uses two-stage extraction or two-stage or more to extract.
According to a particular embodiment of the invention, the additional amount of the urea is phosphorus in the useless chemical polishing agent after the concentration
0.9~1.1 times of the amount of acid substance, the mass percentage of the urea are 98% or more.
According to a particular embodiment of the invention, the temperature of the useless chemical polishing agent after the concentration and urea reaction be 30~
80 DEG C, 30~120min of mixing time, by the way of crystallisation by cooling, the temperature of the crystallisation by cooling is less than the crystallization after reaction
Equal to 30 DEG C.
According to a particular embodiment of the invention, it is crystallized after the useless chemical polishing agent and urea reaction after the concentration, into one
Step includes centrifugal filtration, is washed, dry, obtains PHOSPHORIC ACID TECH.GRADE urea and crystalline mother solution.The centrifugal filtration, washing, dry
Method well known to those skilled in the art can be used in method.
According to a particular embodiment of the invention, the precipitating reagent is sulfide, and the mass percentage of the sulfide is
98% or more.The amount that precipitating reagent is added is that precipitating is no longer generated into crystalline mother solution i.e. only.Precipitating reagent is added in the present invention can
Remove the partly or completely foreign ions such as Cu, Pb, As.
According to a particular embodiment of the invention, the sulfide include hydrogen sulfide, ammonium sulfide or vulcanized sodium at least it
One.
According to a particular embodiment of the invention, by the mode of the purification mother liquor concentrations using vacuum concentration, the vacuum
Thickening temperature is 60~80 DEG C, and vacuum degree is more than or equal to 0.06Mpa.
According to a particular embodiment of the invention, the institute by the way of crystallisation by cooling will be crystallized after the purification mother liquor concentrations
Stating crystallisation by cooling also needs addition urea phosphate crystal seed, and additive amount is 0.5~5g/L.
According to a particular embodiment of the invention, it will be separated by filtration after crystallization further includes crystallization after the purification mother liquor concentrations,
It is dry, obtain feed grade urea phosphate and secondary crystallization mother liquor.Described to be separated by filtration, those skilled in the art can be used in dry method
Method known to member.
According to a particular embodiment of the invention, by the useless chemical polishing agent extracted be concentrated into density be 1.4~
1.6g/mL, and by the purification mother liquor concentrations to phosphorus content be 14~15.5%.
It is useless that useless chemical polishing agent of the present invention can be regarded as phosphoric acid commonly used in this field-acetic acid system chemical polishing agent
Liquid.Preferably, in the useless chemical polishing agent total phosphorus content be 122~200g/L, acetic acid 0.7~5%, nitric acid 0.1~
0.3%.The content of useless chemical polishing agent other compositions of the present invention is is not limited in the present invention.
Embodiment 1
Phosphoric acid-acetic acid system is taken to give up chemical polishing agent 1000mL, relative density 1.21, wherein total phosphorus content is 122g/
L, acetic acid 0.7%, nitric acid 0.1%, aluminium content 0.9g/L, Fe content 6mg/L, Cu content 5mg/L, Zn content 4mg/L, Pb content
0.05mg/L。
(1) extractant is used as using 15% tributyl phosphate and 85% kerosene first, compared to O/A=1/2, two under room temperature
Grade extraction and separation remove the acetic acid and nitric acid in useless chemical polishing agent, and the loss late of phosphorus is 6%；
(2) then raffinate is concentrated by evaporation to density is 1.50g/mL；
(3) reactor is poured into after cooling, then is slowly added to 253g agricultural grade (98%) urea (urea and phosphoric acid while stirring
Molar ratio be 1.1:1), at 80 DEG C, stir 30min, reaction synthesis urea phosphate；
(4) it is cooled to 25 DEG C of crystallization 2h, centrifugal filtration after complete reaction, 50 DEG C of drying obtain 447.3g urea phosphate, produce
Product meet technical grade primary standard；
(5) ammonium sulfide of 98% metering is added by total metals for mother liquor, and purification mother liquor is obtained by filtration in precipitation reaction；
(6) previous step end gained filtrate is sent into cold boiler, keeps temperature 60 C, vacuum degree 0.09Mpa, concentration
It is 14.0% to being concentrated into phosphorous, cools down and 0.5g/L urea phosphate crystal seed is added and stir and be cooled to 30 DEG C of crystallization 1h, filtering point
From to get 96.7g urea phosphate, product meets feed grade standard for 50 DEG C of drying.
Two-step crystallization there are urea phosphate product 544.0g, and the direct yield of phosphoric acid reaches 86.7%, and remaining a small amount of mother liquor makees fertilizer
Material is used.
Embodiment 2
Phosphoric acid-acetic acid system is taken to give up chemical polishing agent 500mL, relative density 1.35, wherein total phosphorus content is 200.5g/
L, acetic acid 5%, nitric acid 0.3%, aluminium content 3.9g/L, Fe content 10mg/L, Cu content 7mg/L, Zn content 15mg/L, Pb content
0.1mg/L。
(1) extractant is used as using 50% trioctyl phosphate and 50% tri-n-octyl amine (TOA) first, compares O/A=1/
4, three-level extraction and separation remove the acetic acid and nitric acid in useless chemical polishing agent under room temperature, and the loss late of phosphorus is 6%；
(2) then raffinate is concentrated by evaporation to density is 1.60g/mL；
(3) reactor is poured into after cooling, then is slowly added to 167.1g agricultural grade (98%) urea (urea and phosphorus while stirring
The molar ratio of acid is 0.9:1), at 30 DEG C, stir 120min, reaction synthesis urea phosphate；
(4) it is cooled to 25 DEG C of crystallization 2h, centrifugal filtration after complete reaction, 50 DEG C of drying obtain 368.6g urea phosphate, produce
Product meet technical grade primary standard；
(5) ammonium sulfide of 100% metering is added by total metals for mother liquor, and purification mother liquor is obtained by filtration in precipitation reaction；
(6) previous step end gained filtrate is sent into cold boiler, is kept for 80 DEG C of temperature, vacuum degree 0.06Mpa, concentration
It is 15.5% to being concentrated into phosphorous, 5g/L urea phosphate crystal seed is added and stirs and be cooled to 30 DEG C of crystallization 1h, is separated by filtration, 50 DEG C of bakings
It does to get 50.7g urea phosphate, product meets feed grade standard.
Two-step crystallization there are urea phosphate product 419.3g, and the direct yield of phosphoric acid reaches 84.1%, and remaining a small amount of mother liquor makees fertilizer
Material is used.
The above-described embodiments are merely illustrative of preferred embodiments of the present invention, not to model of the invention
It encloses and is defined, without departing from the spirit of the design of the present invention, this field ordinary engineering and technical personnel is to the technology of the present invention
The various changes and improvements that scheme is made, should fall within the scope of protection determined by the claims of the present invention.
Claims (7)
1. the recovery method of phosphorus-containing compound, includes the following steps: in a kind of useless chemical polishing agent
Acetic acid and nitric acid in useless chemical polishing agent is extracted using extractant, the extractant includes tributyl phosphate, tricresyl phosphate
At least one of monooctyl ester；
Useless chemical polishing agent extracted is concentrated；
Urea will be added in useless chemical polishing agent after concentration, is crystallized after fully reacting, isolated PHOSPHORIC ACID TECH.GRADE urea and knot
Brilliant mother liquor；
Sulfide precipitation agent will be added in crystalline mother solution, sediment separate out is purified mother liquor, and the sulfide precipitation agent includes
At least one of hydrogen sulfide, ammonium sulfide or vulcanized sodium；
By the purification mother liquor concentrations, Crystallization Separation obtains feed grade urea phosphate and secondary crystallization mother liquor.
2. recovery method according to claim 1, which is characterized in that the additional amount of the urea is useless after the concentration
0.9~1.1 times of the amount of phosphoric acid substance in chemical polishing agent.
3. recovery method according to claim 1, which is characterized in that the useless chemical polishing agent and urea after the concentration are anti-
The temperature answered is 30~80 DEG C, 30~120min of mixing time.
4. recovery method according to claim 1, which is characterized in that the useless chemical polishing agent and urea after the concentration are anti-
It should crystallize by the way of crystallisation by cooling afterwards, the temperature of the crystallisation by cooling is less than or equal to 30 DEG C.
5. recovery method according to claim 1, which is characterized in that the mode of the purification mother liquor concentrations is used vacuum
Concentration, the temperature concentrated in vacuo are 60~80 DEG C, and vacuum degree is more than or equal to 0.06Mpa.
6. recovery method according to claim 1, which is characterized in that by crystallization after the purification mother liquor concentrations using cooling
The mode of crystallization, the crystallisation by cooling also need addition urea phosphate crystal seed, and additive amount is 0.5~5g/L.
7. recovery method according to claim 1, which is characterized in that the useless chemical polishing agent extracted to be concentrated into
Density be 1.4~1.6g/mL, and by the purification mother liquor concentrations to phosphorus content be 14~15.5%.
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| CN201710392425.5A CN107162935B (en) | 2017-05-27 | 2017-05-27 | The recovery method of phosphorus-containing compound in useless chemical polishing agent |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112574069B (en) * | 2020-12-04 | 2021-12-28 | 上海天汉环境资源有限公司 | Resource utilization method of waste phosphoric acid in microelectronic industry |
| CN112827466B (en) * | 2020-12-31 | 2023-01-17 | 深圳市环保科技集团有限公司 | Preparation method and application of aluminum type adsorbent |
| CN115304514B (en) * | 2022-08-17 | 2023-11-14 | 新中天环保股份有限公司 | Process for preparing urea phosphate by recycling waste phosphoric acid in photoelectric industry |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456547A (en) * | 2008-12-19 | 2009-06-17 | 深圳市危险废物处理站有限公司 | Comprehensive utilization method of chemical polishing waste phosphoric acid |
| CN105088246A (en) * | 2015-08-13 | 2015-11-25 | 合肥鑫艺达抛光机械有限公司 | Environment-friendly stainless steel chemical polishing agent |
| CN106349116A (en) * | 2016-08-25 | 2017-01-25 | 湖北三宁化工股份有限公司 | Method for continuously producing feed-grade urea phosphate from wet-method purified phosphoric acid strip liquor or washing residual liquid |
| CN106430267A (en) * | 2016-08-31 | 2017-02-22 | 池州西恩新材料科技有限公司 | Resource recycling method for aluminum polishing phosphoric acid waste liquid |
-
2017
- 2017-05-27 CN CN201710392425.5A patent/CN107162935B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101456547A (en) * | 2008-12-19 | 2009-06-17 | 深圳市危险废物处理站有限公司 | Comprehensive utilization method of chemical polishing waste phosphoric acid |
| CN105088246A (en) * | 2015-08-13 | 2015-11-25 | 合肥鑫艺达抛光机械有限公司 | Environment-friendly stainless steel chemical polishing agent |
| CN106349116A (en) * | 2016-08-25 | 2017-01-25 | 湖北三宁化工股份有限公司 | Method for continuously producing feed-grade urea phosphate from wet-method purified phosphoric acid strip liquor or washing residual liquid |
| CN106430267A (en) * | 2016-08-31 | 2017-02-22 | 池州西恩新材料科技有限公司 | Resource recycling method for aluminum polishing phosphoric acid waste liquid |
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