CN106938839B - Utilize the method for concentrating waste acid production phosphoric acid by wet process - Google Patents
Utilize the method for concentrating waste acid production phosphoric acid by wet process Download PDFInfo
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- CN106938839B CN106938839B CN201710014812.5A CN201710014812A CN106938839B CN 106938839 B CN106938839 B CN 106938839B CN 201710014812 A CN201710014812 A CN 201710014812A CN 106938839 B CN106938839 B CN 106938839B
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- phosphoric 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
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
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Abstract
The present invention relates to a kind of production technologies of phosphoric acid by wet process, specifically disclose a kind of method using concentrating waste acid production phosphoric acid by wet process, include the following steps: that A, phosphorus ore raw ore carry out crushing ore grinding；B, ore pulp, sulfur trioxide reagent and concentrating waste acid are mixed and carries out extraction reaction；C, extracted by filtration slurry obtains phosphoric acid by wet process.The present invention has the advantages that realizing the usage amount for further increasing concentrating waste acid on the basis of original production phosphoric acid by wet process using concentrating waste acid, having found new approach for the recycling of titanium white waste acid, there are good environment benefits and economic gains.
Description
Technical field
The present invention relates to a kind of production method of phosphoric acid by wet process, especially a kind of utilize to generate in sulfuric acid method titanium pigment production
By-product production phosphoric acid by wet process method.
Background technique
It using the every production 1t titanium dioxide of sulfuric acid process, needs to consume the sulfuric acid of 4t or more, while generating 4.5~6t H2SO4Matter
Measure the spent acid that concentration is 20%~25%, referred to as titanium white waste acid also has 25%(mass percent in titanium white waste acid) sulphur that controls
Sour ferrous, the method for being recycled titanium white waste acid at present mainly has neutralisation, concentration method.
Neutralisation is to carry out neutralization reaction with lime stone, lime or carbide slag etc. and titanium white waste acid, and producing can be used as
The gypsum etc. of construction material.Neutralization method needs to consume a large amount of lime, carbide slag etc., recycles the cost of titanium white waste acid
Height, about 1200 yuan/ton, and neutralization reaction can generate a large amount of waste.
Concentration method is that titanium white waste acid is concentrated, and improves the concentration of titanium white waste acid, reaches the standard that can be recycled.It should
Method does not need to consume a large amount of lime, carbide slag etc. compared to neutralisation, does not need to discharge a large amount of wastes yet.Common practice
It is to mix titanium white waste acid with the concentrated sulfuric acid, obtains the gelled acid of mass concentration about 55%, due in concentration process in titanium white waste acid
The solubility of major impurity ferrous sulfate reduced with the raising of sulfuric acid concentration, therefore filtering and concentrating acid can remove major part
Ferrous sulfate, we term it concentrating waste acids for the sulfuric acid obtained after filtering.
Phosphoric acid is a kind of ternary acid, strong acid in category, and industrial process can be divided into two major classes, and one kind is thermal method production,
System is produced by element phosphorus oxidation, and sour matter is preferable, is chiefly used in manufacturing phosphate product or food-grade phosphate；Another kind of is that wet process is raw
It produces, is that phosphoric acid is made with sour decomposing phosphate rock, sour matter is poor, usually to produce fertilizer or purified rear manufacture phosphate.
" phosphoric acid by wet process " typically refers to sulfuric acid process phosphoric acid by wet process, i.e., the phosphoric acid produced with sulfuric acid decomposition phosphorus ore.Sulfuric acid
The characteristics of method is that the product phosphoric acid after ore decomposition is liquid phase, and byproduct calcium sulfate is the solid phase of solubility very little.Point of the two
From being simple solid-liquor separation, there is the unrivaled superiority of other processes.Therefore, Production By Sulfuric Acid Process phosphoric acid process exists
Leading position is in Wet-process Phosphoric Acid Production.
Typical Wet-process Phosphoric Acid Production method is by mass fraction P2O5The phosphorus ore of the precomminution of % > 27.0% uses ball mill
It is crushed to obtain ore pulp, extraction tank then is added in ore pulp and 98 acid and carries out extraction reaction, the extraction slurry for reacting end is straight
It connects and phosphoric acid by wet process is obtained by filtration.Exemplary production method is as follows:
(1) phosphorus ore raw ore is added in ball mill after precrushing and crushes ore grinding, obtain ore pulp；
(2) extraction tank reaction is added in ore pulp and 98 acid together, obtains extraction slurry；
(3) extracted by filtration slurry obtains phosphoric acid by wet process.
Our company combines sulphur phosphorus titanium circular economy, mixed acid is configured to using concentrating waste acid and 98 acid, to substitute traditional work
98 acid in skill carry out extraction with ore pulp and react, to achieve the purpose that save 98 sour dosages and recycle concentrating waste acid.And
This scheme is disclosed in the patent document of Publication No. CN1376635A.The program is that the raising of titanium white waste acid concentration is utilized
During the solubility of wherein impurity ferrous sulfate accordingly reduce, thus be directly separated by solid-liquid separation can separating most sulfuric acid it is sub-
Iron tramp, obtained concentrating and impurity removing spent acid is that is, heretofore described concentrating waste acid.
In the actual moving process of the scheme of the patent concentrating waste acid of mass concentration 55% and 98 acid application percentages about
For 1.5:1.And since the waste acid quantity generated in production process of titanium pigment is very big, if the application percentage can be improved, increase
The usage amount of concentrating waste acid will largely solve recycling and the problem of environmental pollution of titanium white waste acid, while can be further
The production cost for reducing phosphoric acid by wet process, is one and is related to resource reclaim, the important subject of environmental protection and economic benefit.
Summary of the invention
For the use ratio for increasing concentrating waste acid in wet method phosphoric acid manufacture process, thickened waste is utilized the present invention provides a kind of
The method of acid production phosphoric acid by wet process.
The technical scheme adopted by the invention is that: using the method for concentrating waste acid production phosphoric acid by wet process, include the following steps:
A, phosphorus ore raw ore carries out crushing ore grinding, obtains ore pulp；
B, ore pulp is added in extraction reactor, at the same be added sulfur trioxide reagent and concentrating waste acid extract it is anti-
It answers, obtains extraction slurry；
C, extracted by filtration slurry obtains phosphoric acid by wet process and filter residue.
Inventor has found in process of production, when the mixed proportion of concentrating waste acid and 98 acid reaches a certain level, followed by
The continuous usage amount for increasing concentrating waste acid will cause extraction tank temperature relatively low, and the temperature of extraction tank is directly related to phosphorus ore extraction
Rate.Phosphorus ore extraction yield is improved with temperature and is continuously improved, but due to extraction tank ontology material and mixing plant material, Yi Jiwei
Improve the strainability for generating ardealite in extraction process, usually controls extraction tank reaction temperature at 83~88 DEG C, therefore
Temperature reduces the reduction that will lead to extraction yield, thus constrains the usage amount of concentrating waste acid in the technique.
For this problem, 98 acid in the prior art is substituted using sulfur trioxide reagent substitution or part in the present invention.
The sulfur trioxide reagent refers to: can be dissolved in water using the sulfur trioxide in sulfur trioxide reagent and generate sulfuric acid and release
A kind of reagent containing sulfur trioxide of this characteristic of amount of heat.The present invention utilizes this characteristic of the reagent, extracts improving
Also the temperature of extraction tank can be improved in slot while sulfuric acid concentration, so that needing to be added more concentrating waste acids in reaction process
Reaction temperature is maintained into reasonable level, thus achievees the purpose that increase concentrating waste acid additive amount.
The sulfur trioxide reagent can be liquid or solid-state sulfur trioxide, and pure sulfur trioxide is dissolved in water energy and releases more
Heat, and the concentration of concentrating waste acid in extraction tank can be increased to a certain extent, further increase the maximum addition of concentrating waste acid
Amount.
The sulfur trioxide reagent can also be oleum, and oleum is the sulfuric acid solution of sulfur trioxide, when its with
Wherein sulfur trioxide is dissolved in water generation sulfuric acid and releases amount of heat when concentrating waste acid mixes, so that it is dense to play raising concentrating waste acid
Degree and exothermic effect.
As a further improvement of the present invention, filter residue is obtained in water-washing step C, obtains washing slag and washing lotion.Due to filter residue
In there are part phosphoric acid, directly stacking can cause environmental pollution, can be by washing removal wherein phosphoric acid, obtained main component
It can closed circulation recycling for the washing lotion of phosphoric acid,diluted.
More preferably, filters pressing is carried out to the ore pulp that step A is obtained and obtains filter cake, then filter cake is beaten with washing lotion and is starched
Material, then add slurry into extraction reactor and carry out extraction with sulfur trioxide reagent and concentrating waste acid mixing and react.Contain in ore pulp
There is a large amount of moisture, removing these moisture by filters pressing can further improve the usage amount of concentrating waste acid.The filter obtained after filters pressing
Cake can be added washing lotion and is beaten, and on the one hand play the role of recycling phosphoric acid,diluted ingredient in washing lotion；On the one hand washing lotion is able to
It is recycled in system inner sealing, meets requirement of the country to phosphorous chemical industry closed circulation；On the other hand mashing is so that slurry is evenly dispersed,
The progress of more conducively subsequent extraction reaction.
As a further improvement of the present invention, the solid content of slurry is greater than 50% after mashing.Higher solid content can reduce into
The moisture for entering extraction tank increases the reuse amount of spent acid.
As a further improvement of the present invention, in step A phosphorus ore raw ore ore grinding fineness are as follows: 100 mesh percent of pass are greater than
80%.Improving grinding fineness can be improved extraction reaction rate and phosphorus ore extraction yield.
As a further improvement of the present invention, the mass concentration of concentrating waste acid used in step B is 55%.
The beneficial effects of the present invention are: realization further mentions on the basis of original production phosphoric acid by wet process using concentrating waste acid
The usage amount of highly enriched spent acid has found new approach for the recycling of titanium white waste acid.By means of the present invention, ton wet process
Phosphoric acid is (with P2O5Meter) it can be mostly using about 2 tons of concentrating waste acid, mating 1,000,000 tons according to 200,000 tons of titanium dioxides of mass concentration 55%
Phosphate meter can use about 1,000,000 tons of concentrating waste acid of mass concentration 55%, about 150,000 tons of hundred spent acid of folding of folding meter recycling more every year.
Relative to the scheme for using neutralisation recycling titanium white waste acid, it can reduce and neutralize about 120,000 tons of lime consumption (expense about 50,000,000),
Waste acid recovery value about 60,000,000, two total about 1.1 hundred million, while the stockpiling of neutralized reaction product titanium gypsum can be largely reduced, have
Huge environment benefits and economic gains.
Specific embodiment
Below with reference to embodiment, the present invention is further described.
Illustrate: the degree of substance refers both to mass percent without illustrating in following embodiment and comparative example.
Embodiment one:
After phosphorus ore raw ore passes through precrushing, adds water to be crushed to 100 mesh percent of pass using ball mill and be greater than 80%, qualified mine
Slurry uses phosphoric acid filtration system washing lotion to be beaten to solid content as 50% by plate and frame filter press filtering, filter cake；Gained slurry is straight
Connect addition extraction tank, while the concentrating waste acid of mass concentration 55% be added, liquid sulphur trioxide, maintain extraction tank slurry temperature be
85 DEG C, the mass ratio that concentrating waste acid and liquid sulphur trioxide are measured at a temperature of this is 4:1.Sufficiently after reaction, the extraction that will obtain
Slurry directly filters, and obtains phosphoric acid by wet process and filter residue, and the washing lotion return system after being rinsed to filter residue is beaten for filter cake.
In the present solution, phosphorus ore extraction yield is 96%, P in gained phosphoric acid by wet process2O5=250g/l, sulfate radical content is (with SO3Meter)
=28g/l.Ton phosphoric acid by wet process is (with ton P2O5Meter) consumption 3.0 tons of concentrating waste acid of mass concentration 55%, consumption of sulfur trioxide (folding meter
98% sulfuric acid) 0.65 ton.
Embodiment two:
After phosphorus ore raw ore passes through precrushing, adds water to be crushed to 100 mesh percent of pass using ball mill and be greater than 80%, qualified mine
Slurry uses phosphoric acid filtration system washing lotion to be beaten to solid content as 50% by plate and frame filter press filtering, filter cake；Gained slurry is straight
Addition extraction tank is connect, while the concentrating waste acid of mass concentration 55% is added, oleum, sulfuric acid concentration is in the oleum
104.5%(is with sulphur acid meter), sulfur trioxide concentration is the free sulfur trioxide of 20%(), maintaining extraction tank slurry temperature is 85 DEG C, this
At a temperature of to measure the mass ratio of concentrating waste acid and oleum be 3.5:1.Sufficiently after reaction, the direct mistake of extraction slurry that will obtain
Filter, obtains phosphoric acid by wet process and filter residue, and the washing lotion return system after being rinsed to filter residue is beaten for filter cake.
In the present solution, phosphorus ore extraction yield is 96%, P in gained phosphoric acid by wet process2O5=250g/l, sulfate radical content is (with SO3Meter)
=28g/l.Ton phosphoric acid by wet process is (with ton P2O5Meter) consumption 2.8 tons of concentrating waste acid of mass concentration 55%, consumption oleum (folding meter
98% sulfuric acid) 0.75 ton.
Comparative example three:
After phosphorus ore raw ore passes through precrushing, adds water to be crushed to 100 mesh percent of pass using ball mill and be greater than 80%, qualified mine
Slurry is directly added into extraction tank, while the concentrating waste acid of mass concentration 55% is added, and 98 acid, maintaining extraction tank slurry temperature is 85 DEG C,
The mass ratio that concentrating waste acid and 98 acid are measured at a temperature of this is 1.6:1.Sufficiently after reaction, the direct mistake of extraction slurry that will obtain
Filter, obtains phosphoric acid by wet process and filter residue, filter residue is directly stacked.
In the present solution, phosphorus ore extraction yield is 96%, P in gained phosphoric acid by wet process2O5=250g/l, sulfate radical content is (with SO3Meter)
=28g/l.Ton phosphoric acid by wet process is (with ton P2O5Meter) consumption 1.5 tons of concentrating waste acid of mass concentration 55%, 98 1.65 tons of acid of consumption.
Comparative example four:
After phosphorus ore raw ore passes through precrushing, adds water to be crushed to 100 mesh percent of pass using ball mill and be greater than 80%, qualified mine
Slurry uses phosphoric acid filtration system washing lotion to be beaten to solid content as 50% by plate and frame filter press filtering, filter cake；Gained slurry is straight
Addition extraction tank is connect, while the concentrating waste acid of mass concentration 55% is added, 98 acid, maintaining extraction tank slurry temperature is 85 DEG C, this temperature
The mass ratio that concentrating waste acid and 98 acid are measured under degree is 2:1.Sufficiently after reaction, obtained extraction slurry is directly filtered, is obtained
Phosphoric acid by wet process and filter residue, the washing lotion return system after being rinsed to filter residue are beaten for filter cake.
In the present solution, phosphorus ore extraction yield is 96%, P in gained phosphoric acid by wet process2O5=250g/l, sulfate radical content is (with SO3Meter)
=28g/l.Ton phosphoric acid by wet process is (with ton P2O5Meter) consumption 2.2 tons of concentrating waste acid of mass concentration 55%, 98 1.1 tons of acid of consumption.
Claims (8)
1. being included the following steps: using the method for concentrating waste acid production phosphoric acid by wet process
A, phosphorus ore raw ore carries out crushing ore grinding, obtains ore pulp；
B, ore pulp is added in extraction reactor, while sulfur trioxide reagent is added and concentrating waste acid carries out extraction reaction, obtained
To extraction slurry；
C, extracted by filtration slurry obtains phosphoric acid by wet process and filter residue.
2. the method according to claim 1 using concentrating waste acid production phosphoric acid by wet process, it is characterised in that: three oxidation
Sulphur reagent is liquid or solid-state sulfur trioxide.
3. the method according to claim 1 using concentrating waste acid production phosphoric acid by wet process, it is characterised in that: three oxidation
Sulphur reagent is oleum.
4. special using the method for concentrating waste acid production phosphoric acid by wet process described in any claim according to claim 1~3
Sign is further comprising the steps of: obtaining filter residue in water-washing step C, obtains washing slag and washing lotion.
5. the method according to claim 4 using concentrating waste acid production phosphoric acid by wet process, it is characterised in that further include following
Step: carrying out filters pressing to the ore pulp that step A is obtained and obtain filter cake, is then beaten to obtain slurry to filter cake with washing lotion, then will slurry
Material is added in extraction reactor to carry out extraction and reacts with sulfur trioxide reagent and concentrating waste acid mixing.
6. the method according to claim 5 using concentrating waste acid production phosphoric acid by wet process, it is characterised in that: the slurry
The mass fraction of solid content is greater than 50%.
7. special using the method for concentrating waste acid production phosphoric acid by wet process described in any claim according to claim 1~3
Sign is: the fineness of phosphorus ore raw ore ore grinding in step A are as follows: 100 mesh percent of pass are greater than 80%.
8. special using the method for concentrating waste acid production phosphoric acid by wet process described in any claim according to claim 1~3
Sign is: the mass concentration of concentrating waste acid used in step B is 55%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376635A (en) * | 2002-05-09 | 2002-10-30 | 四川龙蟒集团有限责任公司 | Process for preparing phosphoric acid from waste sulfuric acid as by-product of titanium oxide powder by wet method |
| CN101591011A (en) * | 2009-07-06 | 2009-12-02 | 马健 | Processing spent acid is the method for calcium hydrophosphate fertilizer |
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- 2017-01-10 CN CN201710014812.5A patent/CN106938839B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1376635A (en) * | 2002-05-09 | 2002-10-30 | 四川龙蟒集团有限责任公司 | Process for preparing phosphoric acid from waste sulfuric acid as by-product of titanium oxide powder by wet method |
| CN101591011A (en) * | 2009-07-06 | 2009-12-02 | 马健 | Processing spent acid is the method for calcium hydrophosphate fertilizer |
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Effective date of registration: 20230811 Address after: No. 1 to No. 3, Chengguan Bianhe Road, Nanzhang County, Xiangyang City, Hubei Province, 441500 Patentee after: Nanzhang longmang phosphorus products Co.,Ltd. Address before: 618200 Xinshi Industrial Development Zone (Zone A), Mianzhu City, Sichuan Province Patentee before: SICHUAN LOMON PHOSPHOROUS CHEMISTRY Co.,Ltd. |