CN110040696A - Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process - Google Patents
Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process Download PDFInfo
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- CN110040696A CN110040696A CN201910354750.1A CN201910354750A CN110040696A CN 110040696 A CN110040696 A CN 110040696A CN 201910354750 A CN201910354750 A CN 201910354750A CN 110040696 A CN110040696 A CN 110040696A
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- manganese chloride
- acid
- sulfuric acid
- titanium dioxide
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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
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0532—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing sulfate-containing salts
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- Organic Chemistry (AREA)
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- Inorganic Compounds Of Heavy Metals (AREA)
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Abstract
The method that the present invention relates to the use of manganese chloride processing titanium dioxide waste acid by sulfuric acid process, belongs to the waste acid treatment field of Chemical Manufacture.The present invention provides the processing methods of titanium dioxide waste acid by sulfuric acid process, this method comprises the following steps: a, will not inhale water saturated manganese chloride and the spent acid is placed in same closed container, two kinds of materials are separated, until sulfuric acid concentration reaches 50 weight % or more in spent acid, two kinds of materials are taken out；B, the manganese chloride of taking-up is dried, is recycled；The hydrolysis procedure that processed spent acid returns to sulfate process titanium dioxide uses；The concentration of sulfuric acid is C, 0 weight of < C≤20 % in the spent acid.Waste acid treatment method provided by the invention not only efficiently utilizes scrap feed material caused by Producing Titanium Dioxide, but also can reduce the pressure caused by environment, improves operating environment, great prospects for commercial application.
Description
Technical field
The method that the present invention relates to the use of manganese chloride processing titanium dioxide waste acid by sulfuric acid process belongs to the waste acid treatment neck of Chemical Manufacture
Domain.
Background technique
Titanium dioxide is a kind of excellent white pigment, is widely used in paint, coating, papermaking, plastics and welding rod etc.
Industry.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 are equal
It is very huge.However, both production technologies all have certain environmental pressure.For Production By Sulfuric Acid Process technique, production
A large amount of hydrolysis spent acid and the green vitriol (FeSO containing seven crystallizations water can be generated in the process4·7H2O).When (main with ilmenite concentrate
Wanting ingredient is metatitanic acid iron FeTiO3, wherein the content of titanium dioxide is 45-50 weight %) and when being raw material, generally produce 1 ton of titanium
Seven inkstone of output 3.5-4 ton is generated 7~8 tons of hydrolysis spent acid for containing 20% sulfuric acid by white powder.
European countries' problem difficult in view of the processing of a large amount of green vitriols, therefore turn to chloridising production.In addition, using high titanium
The problem of slag is that raw material carries out Production By Sulfuric Acid Process, also can avoid green vitriol.However, the processing of hydrolysis Waste Sulfuric Acid and Utilizing question are still
It could not be well solved.
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, typically only by
Following two method is handled reluctantly, but there is apparent defect:
Using the method in lime stone with generation calcium sulfate.The calcium sulfate that this method obtains does not have utility value and can only
Stockpiling does not utilize raw material well not only, but also can cause biggish pressure to environment.
More positive processing mode is to first pass through the preliminary concentration for being concentrated by evaporation raising sulfuric acid to 30%~40%
When, isolate ferrous sulfate；Further evaporation and concentration becomes 50% or more sulfuric acid, acidolysis operation is returned to, for continuous acidolysis
It uses, to completely be utilized.Currently, domestic large size titanium white enterprise all uses this method mostly.But sulfuric acid is molten
The corrosivity of liquid at high temperature is extremely strong, it is desirable that is worth higher graphite material, while being concentrated by evaporation the steam boiler for needing large capacity
Furnace, so that the equipment investment of this method is high, and energy consumption and operating cost are also high.Come from the application effect of each producer
It sees, the processing cost that the sulfuric acid concentration in spent acid doubles is about 1000 yuan/t, and the cost of gelled acid per ton is even than fresh
(500~800 yuan/t98%H of sulfuric acid2SO4) also want it is expensive very much, cause the middle-size and small-size sulfuric acid method titanium pigment factory of most domestic dare not
It makes inquiries, is all made of lime neutralisation.Moreover, the problem that the graphite heater in the presence of evaporating concentration process blocks does not have also so far
It can be completely resolved.
Summary of the invention
The present invention is directed at least solve one of the technical problems existing in the prior art.For this purpose, it is an object of the invention to
Method using manganese chloride processing titanium dioxide waste acid by sulfuric acid process is provided.
The present invention provides the processing methods of titanium dioxide waste acid by sulfuric acid process, include the following steps:
A, water saturated manganese chloride will not be inhaled and the spent acid is placed in same closed container, and two kinds of materials are separately put
It sets, until sulfuric acid concentration reaches 50 weight % or more in spent acid, two kinds of materials is taken out；
B, the manganese chloride of taking-up is dried, is recycled；Processed spent acid returns to the acidolysis work of sulfate process titanium dioxide
Sequence uses；
The concentration of sulfuric acid is C, 0 weight of < C≤20 % in the spent acid.
Further, water saturated manganese chloride is not inhaled described in step a and is selected from anhydrous Manganese chloride, three water manganese chlorides or its mixing
Object.
Further, not inhaling water saturated manganese chloride described in step a is anhydrous Manganese chloride, anhydrous Manganese chloride and the spent acid
Weight ratio >=105:100.
Preferably, weight ratio >=140:100 of anhydrous Manganese chloride and the spent acid.
Wherein, the amount of the anhydrous Manganese chloride is increased, can exponentially shortens action time in this way.
Preferably, the weight ratio of anhydrous Manganese chloride and the spent acid is (105~140): 100.
Preferably, the weight ratio of anhydrous Manganese chloride and the spent acid is (105~110): 100 or (140~145): 100.
Further, placement described in step a meets at least one of following:
Water saturated manganese chloride and the spent acid will not be inhaled in room temperature；
Standing time is 3.5~7 days.
Further, step a is until sulfuric acid concentration reaches 50~55 weight % in spent acid.
Further, the manganese chloride of taking-up is dried step b in 200~250 DEG C.
Further, the concentration of sulfuric acid is 17~20 weight % in the titanium dioxide waste acid by sulfuric acid process.
Preferably, the concentration of sulfuric acid is 20 weight % in the titanium dioxide waste acid by sulfuric acid process.
Further, also contain ferrous sulfate in the titanium dioxide waste acid by sulfuric acid process.
Preferably, the concentration of ferrous sulfate is 2~3 weight %.
Further, when the manganese chloride that step a takes out not up to absorbs water saturation state, the alternative of step b are as follows:
B1, the manganese chloride of taking-up and new spent acid are placed in same closed container, two kinds of materials are separated, until all transformations
For tetrahydrate manganese chloride, takes out tetrahydrate manganese chloride and be dried, be recycled；In b2, closed container remaining spent acid continue with not
It inhales water saturated manganese chloride to place, until sulfuric acid concentration reaches 50 weight % or more, the hydrolysis procedure for returning to sulfate process titanium dioxide makes
With.
By above-mentioned countercurrent treatment, the utilization rate of manganese chloride can be improved.
Further, the processing method meets at least one of following:
The tetrahydrate manganese chloride of taking-up is dried step b1 in 200~250 DEG C；
Step b2 is until sulfuric acid concentration reaches 50~55 weight %.
Titanium dioxide waste acid by sulfuric acid process of the present invention refers to the waste sulfuric acid solution using method for producing gtitanium dioxide with sulphuric acid by-product.
Wherein, it will not inhale that water saturated manganese chloride is separated in same closed container with the spent acid, and the two cannot
Directly contact.
The present invention provides can carry out having for economy to using the waste sulfuric acid solution of method for producing gtitanium dioxide with sulphuric acid by-product
The method for imitating processing.This method completely avoids the use of boiler and evaporator, avoids the use of expensive resistant material,
To reduce fixed investment, and operate it is at normal temperature or slightly hot under conditions of carry out, significantly improve work in this way
Condition, but also the economy of Waste Sulfuric Acid concentration is improved.Waste acid treatment method provided by the invention not only effectively utilizes
Scrap feed material caused by Producing Titanium Dioxide, but also can reduce the pressure caused by environment, improve operating environment, it is great
Prospects for commercial application.
Specific embodiment
The present invention provides the processing methods of titanium dioxide waste acid by sulfuric acid process, and this method comprises the following steps: a, will not absorb water it is full
The manganese chloride of sum and the spent acid are placed in same closed container, and two kinds of materials are separated, until sulfuric acid concentration in spent acid
Reach 50 weight % or more, two kinds of materials are taken out；B, the manganese chloride of taking-up is dried, is recycled；It is processed useless
The hydrolysis procedure that acid returns to sulfate process titanium dioxide uses；The concentration of sulfuric acid is C, 0 weight of < C≤20 % in the spent acid.
In the past to the processing of titanium white waste 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.
Embodiment 1 handles titanium dioxide waste acid by sulfuric acid process using the method for the present invention
100 grams of titanium dioxide waste acid by sulfuric acid process are taken, wherein the ferrous sulfate of sulfuric acid and 2~3 weight % containing 20 weight %.With
105 grams of anhydrous Manganese chloride (MnCl2) be placed in same closed container at normal temperature, two kinds of materials are separated, cannot mix.
Two kinds of materials are taken out after 7 days.Solid is tetrahydrate manganese chloride (MnCl2·4H2O), removing crystallization is dried at 200~250 DEG C
Water becomes anhydrous Manganese chloride and returns to use.Liquid is the sulfuric acid of 50~55% weight, returns to acidolysis and uses for continuous acidolysis.
Embodiment 2 handles titanium dioxide waste acid by sulfuric acid process using the method for the present invention
100 grams of titanium dioxide waste acid by sulfuric acid process are taken, wherein the ferrous sulfate of sulfuric acid and 2~3 weight % containing 20 weight %.With
140 grams of anhydrous Manganese chloride (MnCl2) be placed in same closed container at normal temperature, two kinds of materials are separated, cannot mix.
Two kinds of materials are taken out after 4.7 days.Solid is three water manganese chloride (MnCl2·3H2O), removing crystallization is dried at 200~250 DEG C
Water becomes anhydrous Manganese chloride and returns to use.Liquid is the sulfuric acid of 50~55 weight %, returns to acidolysis and uses for continuous acidolysis.
Time needed for the present embodiment only has 2/3rds of embodiment 1.
Embodiment 3 handles titanium dioxide waste acid by sulfuric acid process using the method for the present invention
In order to improve the utilization rate of anhydrous Manganese chloride, the mode of operation of following " adverse currents " can be used.
The first step, takes used anhydrous Manganese chloride (having turned into three water manganese chlorides) in example 2, continue with it is new
100 grams of titanium dioxide waste acid by sulfuric acid process (the wherein ferrous sulfate of the sulfuric acid containing 20 weight % and 2~3 weight %) are placed at normal temperature
In same closed container, two kinds of materials are separated, cannot mix.Two kinds of materials are taken out after 3.5 days.Solid is tetrahydrate manganese chloride
(MnCl2·4H2O), the removing crystallization water is dried at 200~250 DEG C, becomes anhydrous Manganese chloride and returns to use.Liquid is about 25
The sulfuric acid of weight %.
Second step places liquid (sulfuric acid of 25 weight %) continuation and the new anhydrous Manganese chloride of taking-up at normal temperature
In same closed container, two kinds of materials are separated, cannot mix.Two kinds of materials are taken out after 3.5 days.Liquid is about 50~55
The sulfuric acid of weight % returns to acidolysis and uses for continuous acidolysis.And solid-phase chlorination manganese still has the space of water suction, continues and new sulfur waste
Acid effect, until it is saturated and becomes tetrahydrate manganese chloride (MnCl2·4H2O).Removing knot is dried at 200~250 DEG C for solid phase
Brilliant water becomes anhydrous Manganese chloride and returns to use.And liquid phase continues to act on new anhydrous Manganese chloride, until its concentration reach 50~
Until 55 weight %.
It should be noted that particular features, structures, materials, or characteristics described in this specification can any one or
It can be combined in any suitable manner in multiple embodiments.In addition, without conflicting with each other, those skilled in the art can incite somebody to action
The feature of difference embodiment described in this specification and different embodiments is combined.
Claims (10)
1. the processing method of titanium dioxide waste acid by sulfuric acid process, it is characterized in that: including the following steps:
A, water saturated manganese chloride will not be inhaled and the spent acid is placed in same closed container, and two kinds of materials are separated, directly
Into spent acid, sulfuric acid concentration reaches 50 weight % or more, and two kinds of materials are taken out；
B, the manganese chloride of taking-up is dried, is recycled；The hydrolysis procedure that processed spent acid returns to sulfate process titanium dioxide makes
With；
The concentration of sulfuric acid is C, 0 weight of < C≤20 % in the spent acid.
2. processing method as described in claim 1, it is characterized in that: not inhaling water saturated manganese chloride described in step a selected from anhydrous
Or mixtures thereof manganese chloride, three water manganese chlorides.
3. processing method as described in claim 1, it is characterized in that: not inhaling water saturated manganese chloride described in step a is anhydrous chlorine
Change manganese, weight ratio >=105:100 of anhydrous Manganese chloride and the spent acid；Preferably, the weight of anhydrous Manganese chloride and the spent acid
Than >=140:100；Preferably, the weight ratio of anhydrous Manganese chloride and the spent acid is (105~140): 100；Preferably, anhydrous chlorine
The weight ratio for changing manganese and the spent acid is (105~110): 100 or (140~145): 100.
4. processing method as described in claim 1, it is characterized in that: at least one of below placement satisfaction described in step a:
Water saturated manganese chloride and the spent acid will not be inhaled in room temperature；
Standing time is 3.5~7 days.
5. processing method as described in claim 1, it is characterized in that: step a is until sulfuric acid concentration reaches 50~55 weights in spent acid
Measure %.
6. processing method as described in claim 1, it is characterized in that: step b carries out the manganese chloride of taking-up in 200~250 DEG C
It is dry.
7. the processing method as described in claim 1~6 any one, it is characterized in that: sulfuric acid in the titanium dioxide waste acid by sulfuric acid process
Concentration be 17~20 weight %；Preferably, the concentration of sulfuric acid is 20 weight % in the titanium dioxide waste acid by sulfuric acid process.
8. the processing method as described in claim 1~7 any one, it is characterized in that: also containing in the titanium dioxide waste acid by sulfuric acid process
There is ferrous sulfate；Preferably, the concentration of ferrous sulfate is 2~3 weight %.
9. the processing method as described in claim 1~8 any one, it is characterized in that: when the step a manganese chloride taken out is not up to
When the saturation state that absorbs water, the alternative of step b are as follows: the manganese chloride of taking-up and new spent acid b1, are placed in same closed appearance
In device, two kinds of materials are separated, until being completely reformed into tetrahydrate manganese chloride, take out tetrahydrate manganese chloride and are dried, circulation makes
With；Remaining spent acid continues and does not inhale water saturated manganese chloride placement in b2, closed container, until sulfuric acid concentration reaches 50 weights
% or more is measured, the hydrolysis procedure for returning to sulfate process titanium dioxide uses.
10. processing method as claimed in claim 9, it is characterized in that: meeting at least one of following:
The tetrahydrate manganese chloride of taking-up is dried step b1 in 200~250 DEG C；
Step b2 is until sulfuric acid concentration reaches 50~55 weight %.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201910354750.1A CN110040696A (en) | 2019-04-29 | 2019-04-29 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
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| CN201910354750.1A CN110040696A (en) | 2019-04-29 | 2019-04-29 | Utilize the method for manganese chloride processing titanium dioxide waste acid by sulfuric acid process |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10346339A1 (en) * | 2003-10-06 | 2005-05-04 | Kerr Mcgee Pigments Gmbh | Process for working up metal chloride residues |
| 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 |
| CN103723765A (en) * | 2014-01-20 | 2014-04-16 | 韶关学院 | Method for preparing titanium dioxide through sulfuric acid method |
| CN106745887A (en) * | 2016-12-20 | 2017-05-31 | 攀枝花市精研科技有限公司 | Industrial waste acid removal of impurities recovery process |
-
2019
- 2019-04-29 CN CN201910354750.1A patent/CN110040696A/en not_active Withdrawn
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10346339A1 (en) * | 2003-10-06 | 2005-05-04 | Kerr Mcgee Pigments Gmbh | Process for working up metal chloride residues |
| WO2005040436A1 (en) * | 2003-10-06 | 2005-05-06 | Tronox Pigments Gmbh | Method for processing heavy metal chloride residues |
| 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 |
| CN103723765A (en) * | 2014-01-20 | 2014-04-16 | 韶关学院 | Method for preparing titanium dioxide through sulfuric acid method |
| CN106745887A (en) * | 2016-12-20 | 2017-05-31 | 攀枝花市精研科技有限公司 | Industrial waste acid removal of impurities recovery process |
Non-Patent Citations (1)
| Title |
|---|
| 郁明谏 等: "《人工土绿化栽培技术》", 30 April 1999, 上海科学技术文献出版社 * |
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Application publication date: 20190723 |