CN110040695A - Utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution - Google Patents
Utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution Download PDFInfo
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- CN110040695A CN110040695A CN201910344086.2A CN201910344086A CN110040695A CN 110040695 A CN110040695 A CN 110040695A CN 201910344086 A CN201910344086 A CN 201910344086A CN 110040695 A CN110040695 A CN 110040695A
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- Prior art keywords
- sulfuric acid
- acid solution
- zinc phosphate
- waste sulfuric
- trbasic zinc
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/88—Concentration of sulfuric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
- Electrolytic Production Of Metals (AREA)
Abstract
The invention belongs to waste acid liquor processing technology fields, and in particular to utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution.The technical problem to be solved by the present invention is to the method higher costs of existing processing waste sulfuric acid solution.The invention discloses the methods using trbasic zinc phosphate processing waste sulfuric acid solution, include the following steps: trbasic zinc phosphate and waste sulfuric acid solution is separated in same closed container at normal temperature, until the mass concentration of sulfuric acid is 50~55% in waste sulfuric acid solution, sulfuric acid solution and aqueous zinc phosphate after being handled.The concentration that waste sulfuric acid solution is improved using the method for the present invention efficiently utilizes useless raw material, and alleviates pressure caused by environment, and reduce costs.
Description
Technical field
The invention belongs to waste acid liquor processing technology fields, and in particular to utilize the side of trbasic zinc phosphate processing waste sulfuric acid solution
Method.
Background technique
Titanium dioxide is a kind of excellent white pigment, is widely used in paint, coating, papermaking, plastics and electric welding at present
The industries such as item.
Currently, the technique of production titanium dioxide mainly has sulfuric acid process and chloridising, two kinds of techniques are simultaneously deposited, and production capacity and yield
It is very huge.However, both production technologies all have certain environmental pressure.It is raw for Production By Sulfuric Acid Process technique
Green vitriol (FeSO during production by a large amount of hydrolysis spent acid is generated and containing seven crystallizations water4·7H2O).When with ilmenite concentrate
(main component is metatitanic acid iron FeTiO3, wherein the content of titanium dioxide is 45-50 weight %) and when being raw material, generally produce 1
3.5~4 ton of seven inkstone of output is generated 7~8 tons of hydrolysis spent acid for containing 20% sulfuric acid by ton titanium dioxide.
There is processing difficulty in view of a large amount of green vitriols in European countries, therefore turn to chloridising production to avoid.This
Outside, high titanium slag is used to carry out Production By Sulfuric Acid Process for raw material, though the problem of can avoid green vitriol, the utilization of hydrolysis Waste Sulfuric Acid is still
In the presence of.
Due to too big using the waste sulfuric acid solution quantum of output of method for producing gtitanium dioxide with sulphuric acid by-product, and contain a certain amount of sulphur
It is sour ferrous, so that this waste sulfuric acid solution can not be utilized in other fields using dilute sulfuric acid.Currently, generalling use lime
The method that stone carries out neutralizing generation calcium sulfate handles this waste sulfuric acid solution.However, obtained calcium sulfate does not utilize
It is worth and can only store up, not only utilize raw material well, but also biggish pressure can be caused to environment.
The prior art, which also first passes through evaporation, makes the concentration of waste sulfuric acid solution be increased to 30%~40%, isolates sulfuric acid Asia
Iron, further evaporation makes the concentration of waste sulfuric acid solution be increased to 50% or more, returns to acidolysis operation, uses for continuous acidolysis,
To be fully exploited.But corrosivity is extremely strong at high temperature for sulfuric acid solution, it is desirable that it is worth higher graphite material, meanwhile,
It is concentrated by evaporation the steam boiler for needing large capacity, so that the equipment investment of this method is high.
Summary of the invention
The technical problem to be solved by the present invention is to the method for existing processing waste sulfuric acid solution is at high cost.
Trbasic zinc phosphate processing waste sulfuric acid solution is utilized the technical solution used to solve the technical problems of the present invention is that providing
Method.Include the following steps: trbasic zinc phosphate and waste sulfuric acid solution is separated in same closed container at normal temperature, until useless
The mass concentration of sulfuric acid is 50~55% in sulfuric acid solution, sulfuric acid solution and aqueous zinc phosphate after being handled.
Wherein, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, every 100 weight of waste sulfuric acid solution
Part, use 642~1289 parts by weight of trbasic zinc phosphate.
Further, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, every 100 weight of waste sulfuric acid solution
Part is measured, 1284~1289 parts by weight of trbasic zinc phosphate are used.
Further, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, the time of the placement is half cycle
~1 week.
Wherein, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, the waste sulfuric acid solution is by sulfuric acid process
Prepare the by-product of titanium dioxide generation.
Further, sulfuric acid and ferrous sulfate are contained in the waste sulfuric acid solution, using the total weight of waste sulfuric acid solution as base
Standard, the concentration of sulfuric acid is not higher than 20% in the waste sulfuric acid solution.
Further, the concentration of sulfuric acid is 17~20% in the waste sulfuric acid solution, and the concentration of ferrous sulfate is 2~3%.
Wherein, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, the aqueous zinc phosphate is 100~105
DEG C it is dried to obtain trbasic zinc phosphate, trbasic zinc phosphate continues to use processing waste sulfuric acid solution.
Further, the aqueous zinc phosphate includes a water trbasic zinc phosphate and phosphate dihydrate zinc.
Wherein, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, sulfuric acid solution is for molten after the processing
Ilmenite concentrate is solved to prepare titanium dioxide.
Wherein, in the above-mentioned method using trbasic zinc phosphate processing waste sulfuric acid solution, when gained aqueous zinc phosphate is not up to inhaled
It is when water saturation state, aqueous zinc phosphate and new waste sulfuric acid solution is separated in same closed container, until all turning
Become phosphate dihydrate zinc, takes out phosphate dihydrate zinc and be dried, be recycled；Remaining waste sulfuric acid solution continues in closed container
It is placed with the trbasic zinc phosphate not absorbed water, until sulfuric acid concentration reaches 50% or more, the hydrolysis procedure for returning to sulfate process titanium dioxide is used.
The beneficial effects of the present invention are:
The method of the present invention completely avoids the use of boiler and evaporator, avoids the use of expensive resistant material,
To reduce fixed investment, and operation carries out under conditions of room temperature, significantly improves operating condition in this way, but also
The economy of Waste Sulfuric Acid concentration is improved.Waste acid treatment method provided by the invention not only efficiently utilizes Producing Titanium Dioxide institute
The scrap feed material of generation, but also can reduce the pressure caused by environment, improves operating environment, before great industrial application
Scape.
Specific embodiment
Waste sulfuric acid solution is handled using existing method, cannot not only efficiently use raw material, but also environment can be given
Cause biggish pressure.Although using positive evaporating concentrating method, can by waste sulfuric acid solution return acidolysis carry out using,
It is that sulfuric acid solution corrosivity is high during high temperature evaporation, it is desirable that evaporation equipment has high corrosion resistance, and evaporation is set
Standby price general charged is higher, causes the processing cost of waste sulfuric acid solution to improve, also, the service life of evaporation equipment is shorter.Therefore,
After study, can handle to obtain using the equipment that technical solution of the present invention does not need valuableness can return to acidolysis use to inventor
Sulfuric acid solution.
Specifically, the present invention provides the methods using trbasic zinc phosphate processing waste sulfuric acid solution.Include the following steps: phosphoric acid
Zinc and waste sulfuric acid solution are separated in same closed container at normal temperature, up to the mass concentration of sulfuric acid in waste sulfuric acid solution
It is 50~55%, sulfuric acid solution and aqueous zinc phosphate after being handled.
The concentration of sulfuric acid is 17~20% in the waste sulfuric acid solution that the present invention uses, and the concentration of ferrous sulfate is 2~3%.
In the present invention, every 100 parts by weight of the waste sulfuric acid solution used, use 642~1289 parts by weight of trbasic zinc phosphate.Phosphoric acid
The dosage of zinc and the time of concentration are to be mutually related, and the dosage of trbasic zinc phosphate is more, then concentration time is short, and the dosage of trbasic zinc phosphate is few,
Then concentration time is long, in order to make concentration time reduce one times, every 100 parts by weight of waste sulfuric acid solution, can be used trbasic zinc phosphate 1284~
1289 parts by weight.
In the past to the processing of Waste Sulfuric Acid, it is exactly to be stored up in lime with generation calcium sulfate, due to having spent acid, pollutes ring
Border.As environmental protection policy is increasingly stringent, handled using being concentrated by evaporation, and the corrosivity of sulfuric acid at relatively high temperatures is extremely strong, one
As will using graphite plate, pipe, add steam boiler etc., invest high maintenance costs it is also larger.Therefore, the economy of the method for the present invention
Clearly.
The solution of the present invention is explained below in conjunction with embodiment.It will be understood to those of skill in the art that following
Embodiment is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Particular technique or item are not specified in embodiment
Part, it described technology or conditions or is carried out according to the literature in the art according to product description.Agents useful for same or instrument
Production firm person is not specified in device, and being can be with conventional products that are commercially available.
The present invention will further be elaborated by specific embodiment below.
In the present invention, concentration is mass percent.
Embodiment 1
The sulfuric acid for being 20% containing concentration by 100g, the waste sulfuric acid solution and 642g trbasic zinc phosphate of 2~3% ferrous sulfate are normal
The separated sulfuric acid solution and phosphate dihydrate zinc for obtaining concentration after 1 week in same closed container and being 50% under temperature, by 50%
Sulfuric acid solution the step of returning to method for producing gtitanium dioxide with sulphuric acid in use, phosphate dihydrate zinc is dried at 100~105 DEG C de-
Except the crystallization water, continue on for handling waste sulfuric acid solution.
Embodiment 2
The sulfuric acid for being 20% containing concentration by 100g, the waste sulfuric acid solution and 1284g trbasic zinc phosphate of 2~3% ferrous sulfate exist
The separated sulfuric acid solution and a water trbasic zinc phosphate for obtaining concentration after 3.5 days in closed container and being 50% under room temperature, by 50%
Sulfuric acid solution the step of returning to method for producing gtitanium dioxide with sulphuric acid in use, a water trbasic zinc phosphate is dried at 100~105 DEG C de-
Except the crystallization water, continue on for handling waste sulfuric acid solution.
Embodiment 3
In order to improve the utilization rate of trbasic zinc phosphate, the mode of operation of " adverse current " can be used.
The sulfuric acid that the water trbasic zinc phosphate and 100g that embodiment 2 is obtained are 20% containing concentration, 2~3% ferrous sulfate
Waste sulfuric acid solution is separated in same closed container at normal temperature, and the sulfuric acid solution and two that concentration is 50% is obtained after 1 week
Phosphate dihydrate zinc is dried the removing crystallization water at 100~105 DEG C, obtains trbasic zinc phosphate by water trbasic zinc phosphate, and it is useless to continue on for processing
Sulfuric acid solution.
The sulfuric acid solution that concentration is 50% continues and trbasic zinc phosphate is separated in closed container at normal temperature, after half cycle
It is used in the step of sulfuric acid solution for being 55% to concentration, return method for producing gtitanium dioxide with sulphuric acid.
Solid phase trbasic zinc phosphate still has the space of water suction, its continuation is allowed separately to put in closed container with new waste sulfuric acid solution
It sets, until phosphoric acid zincification is phosphate dihydrate zinc, phosphate dihydrate zinc is obtained into phosphoric acid in 100~105 DEG C of dry removing crystallizations water
Zinc continues on for handling waste sulfuric acid solution.Waste sulfuric acid solution is continued to act on new trbasic zinc phosphate, until sulfuric acid concentration reaches
55% stops.
Claims (7)
1. utilizing the method for trbasic zinc phosphate processing waste sulfuric acid solution, characterized by the following steps: by trbasic zinc phosphate and Waste Sulfuric Acid
Solution is separated in same closed container at normal temperature, until waste sulfuric acid solution in sulfuric acid mass concentration be 50~
55%, sulfuric acid solution and aqueous zinc phosphate after being handled.
2. the method according to claim 1 using trbasic zinc phosphate processing waste sulfuric acid solution, it is characterised in that: the Waste Sulfuric Acid
Every 100 parts by weight of solution, use 642~1289 parts by weight of trbasic zinc phosphate.
3. the method according to claim 2 using trbasic zinc phosphate processing waste sulfuric acid solution, it is characterised in that: the Waste Sulfuric Acid
Every 100 parts by weight of solution, use 1284~1289 parts by weight of trbasic zinc phosphate.
4. the method according to claim 1 using trbasic zinc phosphate processing waste sulfuric acid solution, it is characterised in that: the Waste Sulfuric Acid
Solution is the by-product generated by method for producing gtitanium dioxide with sulphuric acid.
5. the method according to claim 1 using trbasic zinc phosphate processing waste sulfuric acid solution, it is characterised in that: the aqueous phosphorus
Sour zinc is dried to obtain trbasic zinc phosphate at 100~105 DEG C, and trbasic zinc phosphate continues to use processing waste sulfuric acid solution.
6. described in any item methods using trbasic zinc phosphate processing waste sulfuric acid solution according to claim 1~5, it is characterised in that:
Sulfuric acid solution is for dissolving ilmenite concentrate to prepare titanium dioxide after the processing.
7. the method according to claim 1 using trbasic zinc phosphate processing waste sulfuric acid solution, it is characterised in that: when gained is aqueous
It is when trbasic zinc phosphate is not up to water suction saturation state, aqueous zinc phosphate and new waste sulfuric acid solution is separated in same closed container
In, until being completely reformed into phosphate dihydrate zinc, takes out phosphate dihydrate zinc and be dried, be recycled；It is remaining in closed container
Waste sulfuric acid solution continues to place with the trbasic zinc phosphate not absorbed water, until sulfuric acid concentration reaches 50% or more, returns to sulfate process titanium dioxide
Hydrolysis procedure uses.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910344086.2A CN110040695A (en) | 2019-04-24 | 2019-04-24 | Utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution |
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| CN201910344086.2A CN110040695A (en) | 2019-04-24 | 2019-04-24 | Utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution |
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| CN110040695A true CN110040695A (en) | 2019-07-23 |
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| CN201910344086.2A Withdrawn CN110040695A (en) | 2019-04-24 | 2019-04-24 | Utilize the method for trbasic zinc phosphate processing waste sulfuric acid solution |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910594A (en) * | 2012-11-06 | 2013-02-06 | 黄正源 | Method for concentrating waste sulfuric acid by utilizing waste heat of titanium dioxide calcinator |
-
2019
- 2019-04-24 CN CN201910344086.2A patent/CN110040695A/en not_active Withdrawn
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102910594A (en) * | 2012-11-06 | 2013-02-06 | 黄正源 | Method for concentrating waste sulfuric acid by utilizing waste heat of titanium dioxide calcinator |
Non-Patent Citations (2)
| Title |
|---|
| 韩长日等: "《精细无机化学品制造技术》", 30 August 2008 * |
| 黄玉缓等: "《精细化工配方常用原料手册》", 31 March 1998 * |
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Application publication date: 20190723 |
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