CN110040693A - Utilize the method for calcium monohydrogen phosphate processing waste sulfuric acid solution - Google Patents
Utilize the method for calcium monohydrogen phosphate processing waste sulfuric acid solution Download PDFInfo
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- CN110040693A CN110040693A CN201910334689.4A CN201910334689A CN110040693A CN 110040693 A CN110040693 A CN 110040693A CN 201910334689 A CN201910334689 A CN 201910334689A CN 110040693 A CN110040693 A CN 110040693A
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- Prior art keywords
- sulfuric acid
- acid solution
- calcium monohydrogen
- monohydrogen phosphate
- waste sulfuric
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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
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention belongs to waste acid liquor processing technology fields, and in particular to utilize the method for calcium monohydrogen 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 calcium monohydrogen phosphate processing waste sulfuric acid solution, include the following steps: calcium monohydrogen 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 water-bearing phosphate hydrogen calcium 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 calcium monohydrogen 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.
Waste sulfuric acid solution is handled using calcium monohydrogen phosphate the technical solution used to solve the technical problems of the present invention is that providing
Method.Include the following steps: by calcium monohydrogen phosphate and waste sulfuric acid solution it is separated in same closed container at normal temperature, directly
Into waste sulfuric acid solution, the mass concentration of sulfuric acid is 50~55%, sulfuric acid solution and water-bearing phosphate hydrogen calcium after being handled.
Wherein, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, every 100 weight of waste sulfuric acid solution
Part, use 227~459 parts by weight of calcium monohydrogen phosphate.
Further, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, the waste sulfuric acid solution every 100
Parts by weight use 454~459 parts by weight of calcium monohydrogen phosphate.
Further, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, the time of the placement is half
Week~1 week.
Wherein, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, the waste sulfuric acid solution is by sulfuric acid
Method prepares 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 calcium monohydrogen phosphate processing waste sulfuric acid solution, the water-bearing phosphate hydrogen calcium 115~
120 DEG C are dried to obtain calcium monohydrogen phosphate, and calcium monohydrogen phosphate continues to use processing waste sulfuric acid solution.
Further, the water-bearing phosphate hydrogen calcium includes a water calcium monohydrogen phosphate and dicalcium phosphate dihydrate.
Wherein, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, sulfuric acid solution is used for after the processing
Ilmenite concentrate is dissolved to prepare titanium dioxide.
Wherein, in the above-mentioned method using calcium monohydrogen phosphate processing waste sulfuric acid solution, when gained water-bearing phosphate hydrogen calcium does not reach
To water suction saturation state when, by water-bearing phosphate hydrogen calcium and new waste sulfuric acid solution it is separated in same closed container, until
It is completely reformed into dicalcium phosphate dihydrate, dicalcium phosphate dihydrate is taken out and is dried, be recycled；Remaining sulfur waste in closed container
Acid solution continues to place with the calcium monohydrogen phosphate not absorbed water, until sulfuric acid concentration reaches 50% or more, returns to the acid of sulfate process titanium dioxide
Process is solved to use.
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 calcium monohydrogen phosphate processing waste sulfuric acid solution.Include the following steps: phosphorus
Sour hydrogen calcium and waste sulfuric acid solution are separated in same closed container at normal temperature, up to the quality of sulfuric acid in waste sulfuric acid solution
Concentration is 50~55%, sulfuric acid solution and water-bearing phosphate hydrogen calcium 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 227~459 parts by weight of calcium monohydrogen phosphate.Phosphorus
The dosage of sour hydrogen calcium and the time of concentration are to be mutually related, and the dosage of calcium monohydrogen phosphate is more, then concentration time is short, calcium monohydrogen phosphate
Dosage is few, then concentration time is long, and in order to make concentration time reduce one times, phosphoric acid hydrogen is can be used in every 100 parts by weight of waste sulfuric acid solution
4~459 parts by weight of Ca45.
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 227g calcium monohydrogen phosphate of 2~3% ferrous sulfate exist
The separated sulfuric acid solution and dicalcium phosphate dihydrate for obtaining concentration after 1 week in same closed container and being 50% under room temperature, will
50% sulfuric acid solution returns to be used in the step of method for producing gtitanium dioxide with sulphuric acid, and dicalcium phosphate dihydrate is carried out at 115~120 DEG C
The dry removing crystallization water, continues 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 454g calcium monohydrogen phosphate of 2~3% ferrous sulfate exist
The separated sulfuric acid solution and a water calcium monohydrogen phosphate for obtaining concentration after 3.5 days in closed container and being 50% under room temperature, will
50% sulfuric acid solution returns to be used in the step of method for producing gtitanium dioxide with sulphuric acid, and a water calcium monohydrogen phosphate is carried out at 115~120 DEG C
The dry removing crystallization water, continues on for handling waste sulfuric acid solution.
Embodiment 3
In order to improve the utilization rate of calcium monohydrogen phosphate, the mode of operation of " adverse current " can be used.
The sulfuric acid that the water calcium monohydrogen phosphate and 100g that embodiment 2 is obtained are 20% containing concentration, 2~3% ferrous sulfate
Waste sulfuric acid solution it is separated in same closed container at normal temperature, obtained after 1 week concentration be 50% sulfuric acid solution and
Dicalcium phosphate dihydrate is dried the removing crystallization water at 115~120 DEG C, obtains calcium monohydrogen phosphate, continue to use by dicalcium phosphate dihydrate
In processing waste sulfuric acid solution.
The sulfuric acid solution that concentration is 50% continues and calcium monohydrogen phosphate is separated in closed container at normal temperature, after half cycle
It is used in the step of obtaining the sulfuric acid solution that concentration is 55%, returning to method for producing gtitanium dioxide with sulphuric acid.
Solid phase calcium monohydrogen 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 calcium monohydrogen phosphate saturation is dicalcium phosphate dihydrate, dicalcium phosphate dihydrate is obtained in 115~120 DEG C of dry removing crystallizations water
Continue on for handling waste sulfuric acid solution to calcium monohydrogen phosphate.Waste sulfuric acid solution is continued to act on new calcium monohydrogen phosphate, until sulfuric acid
Concentration reaches 55% and stops.
Claims (7)
1. utilizing the method for calcium monohydrogen phosphate processing waste sulfuric acid solution, characterized by the following steps: by calcium monohydrogen phosphate and give up
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 water-bearing phosphate hydrogen calcium after being handled.
2. the method according to claim 1 using calcium monohydrogen phosphate processing waste sulfuric acid solution, it is characterised in that: the sulfur waste
Every 100 parts by weight of acid solution, use 227~459 parts by weight of calcium monohydrogen phosphate.
3. the method according to claim 2 using calcium monohydrogen phosphate processing waste sulfuric acid solution, it is characterised in that: the sulfur waste
Every 100 parts by weight of acid solution, use 454~459 parts by weight of calcium monohydrogen phosphate.
4. the method according to claim 1 using calcium monohydrogen phosphate processing waste sulfuric acid solution, it is characterised in that: the sulfur waste
Acid solution is the by-product generated by method for producing gtitanium dioxide with sulphuric acid.
5. the method according to claim 1 using calcium monohydrogen phosphate processing waste sulfuric acid solution, it is characterised in that: described aqueous
Calcium monohydrogen phosphate is dried to obtain calcium monohydrogen phosphate at 115~120 DEG C, and calcium monohydrogen phosphate continues to use processing waste sulfuric acid solution.
6. described in any item methods using calcium monohydrogen phosphate processing waste sulfuric acid solution, feature exist according to claim 1~5
In: sulfuric acid solution is for dissolving ilmenite concentrate to prepare titanium dioxide after the processing.
7. the method according to claim 1 using calcium monohydrogen phosphate processing waste sulfuric acid solution, it is characterised in that: when gained contains
It is when water calcium monohydrogen phosphate is not up to water suction saturation state, water-bearing phosphate hydrogen calcium is separated in same close with new waste sulfuric acid solution
It closes in container, until being completely reformed into dicalcium phosphate dihydrate, takes out dicalcium phosphate dihydrate and be dried, be recycled；Closed appearance
Remaining waste sulfuric acid solution continues to place with the calcium monohydrogen phosphate not absorbed water in device, until sulfuric acid concentration reaches 50% or more, returns
The hydrolysis procedure of sulfate process titanium dioxide uses.
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| CN201910334689.4A CN110040693A (en) | 2019-04-24 | 2019-04-24 | Utilize the method for calcium monohydrogen phosphate processing waste sulfuric acid solution |
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086039A (en) * | 2010-12-28 | 2011-06-08 | 漯河市兴茂钛业有限公司 | Method for preparing ammonium sulfate and Fe3O4 from titanium dioxide production waste acid solution |
| CN102491285A (en) * | 2011-12-05 | 2012-06-13 | 韩扶军 | Waste sulphuric acid concentrating and recycling equipment |
| 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 |
| CN108793093A (en) * | 2017-12-06 | 2018-11-13 | 绍兴文理学院 | A kind of technique that dilute/Waste Sulfuric Acid prepares the regeneration concentrated sulfuric acid |
| CN108840373A (en) * | 2018-09-05 | 2018-11-20 | 襄阳龙蟒钛业有限公司 | A kind of method that titanium pigment waste acid recycles |
| WO2019035319A1 (en) * | 2017-08-16 | 2019-02-21 | 住友金属鉱山株式会社 | Leaching treatment method, and wet smelting method of nickel oxide ore |
-
2019
- 2019-04-24 CN CN201910334689.4A patent/CN110040693A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102086039A (en) * | 2010-12-28 | 2011-06-08 | 漯河市兴茂钛业有限公司 | Method for preparing ammonium sulfate and Fe3O4 from titanium dioxide production waste acid solution |
| CN102491285A (en) * | 2011-12-05 | 2012-06-13 | 韩扶军 | Waste sulphuric acid concentrating and recycling equipment |
| 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 |
| WO2019035319A1 (en) * | 2017-08-16 | 2019-02-21 | 住友金属鉱山株式会社 | Leaching treatment method, and wet smelting method of nickel oxide ore |
| CN108793093A (en) * | 2017-12-06 | 2018-11-13 | 绍兴文理学院 | A kind of technique that dilute/Waste Sulfuric Acid prepares the regeneration concentrated sulfuric acid |
| CN108840373A (en) * | 2018-09-05 | 2018-11-20 | 襄阳龙蟒钛业有限公司 | A kind of method that titanium pigment waste acid recycles |
Non-Patent Citations (1)
| Title |
|---|
| 辽宁省石油化学工业厅编: "《辽宁化工产品大全》", 31 December 1994 * |
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Application publication date: 20190723 |