CN103359700A - Method for saving acid and reducing ammonium in ammonium phosphate production - Google Patents
Method for saving acid and reducing ammonium in ammonium phosphate production Download PDFInfo
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- CN103359700A CN103359700A CN2013102955690A CN201310295569A CN103359700A CN 103359700 A CN103359700 A CN 103359700A CN 2013102955690 A CN2013102955690 A CN 2013102955690A CN 201310295569 A CN201310295569 A CN 201310295569A CN 103359700 A CN103359700 A CN 103359700A
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- phosphoric acid
- acid
- ore pulp
- pipeline
- desulfurizer
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Abstract
The invention discloses a method for saving acid and reducing ammonium in ammonium phosphate production. The method comprises the following two steps of: (A) preparing phosphoric acid by a sulfuric acid method; (B) removing sulfate radicals. The method is characterized in that the step (B) of removing sulfate radicals comprises the following steps of: mixing and reacting a reaction raw material of phosphoric ore pulp in the step (A) with a reaction product of phosphoric acid, reacting sulfate ions and calcium ions to form a calcium sulfate precipitate, removing the sulfate ions contained in phosphoric acid, separating solid phase phosphoric ore pulp and calcium sulfate from phosphoric acid through sludge settlement to obtain sulfate-free phosphoric acid, introducing the obtained phosphoric acid to an ammonium phosphate production process to participate in ammonium phosphate production, and introducing the sludge formed by settlement into the step (A) for recycling. According to the method for saving acid and reducing ammonium in the ammonium phosphate production, the sulfate ions in phosphoric acid are effectively removed, the phosphoric acid participates in an ammonium phosphate reaction, the liquid ammonia consumption is reduced, the quality of ammonium phosphate is improved, meanwhile, the phosphoric ore pulp obtained by settlement is recycled, the consumption amount of sulfuric acid for phosphoric acid preparation is reduced, the yield of phosphoric acid is improved, and resources are saved.
Description
Technical field
The invention belongs to the production of phosphate fertilizer technical field, specifically, relate to the acid of a kind of phosphorus ammonium production joint and fall the ammonia method.
Background technology
China's phosphor resource occupies the second place of the world.But national phosphorus ore average grade only 16.95%, P
20
5Grade only has 11.08 hundred million tons greater than 30% rich ore, because the high-quality phosphate rock resource is day by day rare, can not satisfy one of 20 mineral of national economic development demand after Ministry of Land and Resources classified phosphorus ore as 2010 in 2000, high-quality phosphate rock resource deficiency will seriously restrict the development of China's phosphate fertilizer industry.Under this condition, how producing high-concentration phosphate compound fertilizers in the face of the raw material of high impurity phosphorus ore has become our difficult problem in the urgent need to address.
Because the fast development of domestic phosphate ﹠ compound fertilizer industry, larger breach appears in the demand of phosphorus ore, and except the part dependence on import, most of enterprise has in the face of utilizing the reality of mid low grade phosphate rock.Along with China's Rock Phosphate (72Min BPL) rich ore reduces, my company faces the predicament that the higher-grade Rock Phosphate (72Min BPL) is difficult to purchase day by day in recent years.The low grade ore foreign matter content is relatively higher, and is very large on the quality product impact, makes company's total nutrient of product monoammonium phosphate not reach 58%.For guaranteeing the product nutrient, " the high SO of high temperature is adopted in extraction in ammonium phosphate production process
3" replace that former " high temperature hangs down SO
3" technique, in the finished product phosphoric acid that generates, will bring excessive SO into like this
4 2-, for follow-up neutralization increases the ammonia consumption, and in extraction process, increase the consumption of sulfuric acid.The present invention utilizes desulfurizer in phosphoric acid and before to remove SO excessive in the phosphoric acid
4 2-, and sweetening agent returned extraction tank, reach the purpose of resource circulation utilization.
The prior art shortcoming: phosphoric acid is pure not, wherein contains excessive SO
4 2-, and excessive SO
4 2-In phosphorus ammonium production process, be easy to the liquefied ammonia reaction and generate (NH
4)
2SO
4Brought impurity into, made product pure not.
Summary of the invention
For solving above technical problem, the object of the present invention is to provide the phosphorus ammonium production joint acid of a kind of consumption that can remove sulfate ion in the phosphoric acid, reduce sulfuric acid in the phosphoric acid production, raising phosphoric acid output, the consumption that reduces liquefied ammonia in the phosphoric acid production and raising phosphorus ammonium quality to fall the ammonia method.
The object of the present invention is achieved like this: the ammonia method falls in the acid of a kind of phosphorus ammonium production joint, comprises that (A) sulfuric acid process prepares phosphoric acid; (B) remove two steps of sulfate radical, its key is that described step (B) removal sulfate radical is: the reaction raw materials phosphate ore pulp in the step (A) and reaction product phosphoric acid are carried out hybrid reaction, and sulfate ion and calcium binding form CaSO
4.2H
2The O precipitation, thus remove the sulfate ion that contains in the phosphoric acid, then by the sludge sedimentation, with solid phase phosphate ore pulp, CaSO
4.2H
2O separates with phosphoric acid, obtains the not phosphoric acid of sulphate-containing ion, and gained phosphoric acid is passed in the ammonium phosphate production process, participates in the production of phosphorus ammonium; The sludge that sedimentation forms then passes in the step (A) and carries out recycle; The reaction that occurs after described reaction raw materials phosphate ore pulp and reaction product phosphoric acid mix is:
Ca
5F(PO
4)
3+SO
4 2-+10H
2O=5CaSO
4.2H
2O↓+PO
4 3-+F
-。
Above-mentioned steps (A) sulfuric acid process prepares phosphoric acid and is: be that 98% the vitriol oil and the phosphate ore pulp that is stored in the ore pulp storage tank join fully reaction in the extraction tank with excessive volume fraction, then filter by strainer, filtered liquid passes into gas-liquid separator, separates at last the phosphoric acid that obtains containing sulfate ion; The reaction that occurs in the described extraction tank is:
Ca
5F(PO
4)
3+5H
2SO
4+10H
2O=5CaSO
4.2H
2O↓+3H
3PO
4+HF。
Above-mentioned steps (B) is removed sulfate radical and realized by desulfurization sedimentation purification system: described desulfurization sedimentation purification system comprises desulfurizer, doctor solution transferpump and the subsider of connecting successively by pipeline, the feeding mouth of described desulfurizer is communicated with discharge port and the described ore pulp storage tank discharge port of described gas-liquid separator respectively by pipeline, and the phosphoric acid outlet of described subsider also is communicated with the described phosphoric acid storage tank of phosphoric acid storage tank by pipeline access phosphorus ammonium production system.
Adopt said structure, contain excessive SO in the phosphoric acid for preparing by finished product phosphoric acid preparation system
4 2-, the calcium ion that contains in the ore pulp in desulfurizer can be with SO
4 2-Reaction precipitation, sedimentation is carried out in being deposited in of forming in the subsider, solid-liquid separation, make phosphoric acid purification, the phosphoric acid that obtains by this system enters ammonium phosphate production process, participates in the production of phosphorus ammonium, can be not again excessive sulfate ion and liquefied ammonia react, reduce the consumption of liquefied ammonia in the phosphorus ammonium production process, avoided bringing into of impurity, improved the quality that the phosphorus ammonium is produced.
Pipeline between above-mentioned gas-liquid separator and the desulfurizer is provided with the phosphoric acid control valve, pipeline between described ore pulp storage tank and the desulfurizer is provided with the ore pulp control valve, pipeline between described desulfurizer and the described doctor solution transferpump is provided with the doctor solution control valve, be provided with agitator in the described desulfurizer, this desulfurizer outer wall is fixed with liquidometer.
Adopt said structure, SO in phosphoric acid
4 2-Open the phosphoric acid control valve when excessive, open simultaneously the ore pulp control valve, phosphoric acid and ore pulp passed in the desulfurizer react, open the doctor solution control valve, doctor solution passed into carry out solid-liquid separation in the subsider, and the agitator in the desulfurizer can mix ore pulp and phosphoric acid, and by the liquid level in the liquidometer observation desulfurizer, conveniently the doctor solution control valve is controlled.。
Be provided with in the above-mentioned subsider and scrape filter, the sewage draining exit of this subsider is communicated with described extraction tank by pipeline, and this pipeline is provided with and is provided with successively residual sea water pump control valve and subsider residual sea water pump.
Adopt said structure, water and calcium sulfate that the ore pulp that sewage draining exit is got rid of and reaction obtain are passed into extraction tank and reuse, simultaneously owing to contain sulfate ion in the ore pulp, therefore reduce the add-on of sulfuric acid in the phosphoric acid preparation process, improved the output of phosphoric acid, saved resource.
Beneficial effect:
The ammonia method falls in the acid of a kind of phosphorus ammonium of the present invention production joint, method is easy, can effectively process the phosphoric acid that enters the reaction of phosphorus ammonium, remove the sulfate ion in the phosphoric acid, reduce liquefied ammonia consumption, improve the quality that the phosphorus ammonium is produced, the phosphate ore pulp that contains sulfate ion that simultaneously recycle sedimentation obtains, reduce the consumption of sulfuric acid in the phosphoric acid preparation, improved the output of phosphoric acid, saved resource.
Description of drawings
Fig. 1 is process flow sheet of the present invention;
Fig. 2 is the syndeton synoptic diagram of ore pulp storage tank 1 among the present invention, extraction tank 2, strainer 3, gas-liquid separator 4 and desulfurization sedimentation purification system.
Embodiment
The invention will be further described below in conjunction with drawings and Examples:
Embodiment:
As depicted in figs. 1 and 2: the ammonia method falls in the acid of a kind of phosphorus ammonium production joint, prepares phosphoric acid by (A) sulfuric acid process; (B) removing two steps of sulfate radical forms:
(A) sulfuric acid process prepares phosphoric acid and is: be that 98% the vitriol oil and the phosphate ore pulp that is stored in ore pulp storage tank 1 join fully reaction in the extraction tank 2 with excessive volume fraction, then filter by strainer 3, filtered liquid passes into gas-liquid separator 4, separates at last the phosphoric acid that obtains containing sulfate ion; The reaction that occurs in the described extraction tank is:
Ca
5F(PO
4)
3+5H
2SO
4+10H
2O=5CaSO
4.2H
2O↓+3H
3PO
4+HF。
(B) removing sulfate radical is: the reaction raw materials phosphate ore pulp in the step (A) and reaction product phosphoric acid are carried out hybrid reaction, and sulfate ion and calcium binding form CaSO
4.2H
2The O precipitation, thus remove the sulfate ion that contains in the phosphoric acid, then by the sludge sedimentation, with solid phase phosphate ore pulp, CaSO
4.2H
2O separates with phosphoric acid, obtains the not phosphoric acid of sulphate-containing ion, and gained phosphoric acid is passed in the ammonium phosphate production process, participates in the production of phosphorus ammonium; The sludge that sedimentation forms then passes in the step (B) and carries out recycle; The reaction that occurs after described reaction raw materials phosphate ore pulp and reaction product phosphoric acid mix is:
Ca
5F(PO
4)
3+SO
4 2-+10H
2O=5CaSO
4.2H
2O↓+PO
4 3-+F
-。
Described step (B) is removed sulfate radical and realized by desulfurization sedimentation purification system: described desulfurization sedimentation purification system comprises the desulfurizer 5 of connecting successively by pipeline, doctor solution transferpump 6 and subsider 7, the feeding mouth of described desulfurizer 5 is communicated with discharge port and described ore pulp storage tank 1 discharge port of described gas-liquid separator 4 respectively by pipeline, the phosphoric acid outlet of described subsider 7 also is communicated with phosphoric acid storage tank 11, be provided with in the described subsider 7 and scrape filter 7a, the sewage draining exit of this subsider 7 is communicated with described extraction tank 2 by pipeline 7b, and this pipeline 7b is provided with and is provided with successively residual sea water pump control valve 7c and subsider residual sea water pump 7d; Pipeline between described gas-liquid separator 4 and the desulfurizer 5 is provided with phosphoric acid control valve 8, pipeline between described ore pulp storage tank 1 and the desulfurizer 5 is provided with ore pulp control valve 9, pipeline between described desulfurizer 5 and the described doctor solution transferpump 6 is provided with doctor solution control valve 10, be provided with agitator 5a in the described desulfurizer 5, these desulfurizer 5 outer walls are fixed with liquidometer 5b; Described phosphoric acid storage tank 11 is by pipeline access phosphorus ammonium production system.
Contained SO in phosphoric acid
4 2-When excessive, then open phosphoric acid control valve 8 and ore pulp control valve 9, phosphoric acid and ore pulp passed into carry out mix and blend in the desulfurizer 5, open doctor solution control valve 10 after the reaction, by doctor solution transferpump 6 doctor solution is pumped into and to carry out sedimentation in the subsider 7, the liquid that obtains is phosphoric acid, and it is passed into phosphoric acid storage tank 11, and the sludge that obtains is after opening residual sea water pump control valve 7c, and 7d pumps into recycle in the extraction tank 2 with it by the subsider residual sea water pump.
Claims (5)
1. the ammonia method falls in phosphorus ammonium production joint acid, comprises that (A) sulfuric acid process prepares phosphoric acid; (B) remove two steps of sulfate radical, it is characterized in that described step (B) removal sulfate radical is: the reaction raw materials phosphate ore pulp in the step (A) and reaction product phosphoric acid are carried out hybrid reaction, and sulfate ion and calcium binding form CaSO
4.2H
2The O precipitation, thus remove the sulfate ion that contains in the phosphoric acid, then by the sludge sedimentation, with solid phase phosphate ore pulp, CaSO
4.2H
2O separates with phosphoric acid, obtains the not phosphoric acid of sulphate-containing ion, and gained phosphoric acid is passed in the ammonium phosphate production process, participates in the production of phosphorus ammonium; The sludge that sedimentation forms then passes in the step (A) and carries out recycle; The reaction that occurs after described reaction raw materials phosphate ore pulp and reaction product phosphoric acid mix is:
Ca
5F(PO
4)
3+SO
4 2-+10H
2O=5CaSO
4.2H
2O↓+PO
4 3-+F
-。
2. the ammonia method falls in the acid of described a kind of phosphorus ammonium production joint according to claim 1, it is characterized in that described step (A) sulfuric acid process prepares phosphoric acid and is: be that 98% the vitriol oil and the phosphate ore pulp that is stored in ore pulp storage tank (1) join fully reaction in the extraction tank (2) with excessive volume fraction, then filter by strainer (3), filtered liquid passes into gas-liquid separator (4), separates at last the phosphoric acid that obtains containing sulfate ion; The reaction that occurs in the described extraction tank is:
Ca
5F(PO
4)
3+5H
2SO
4+10H
2O=5CaSO
4.2H
2O↓+3H
3PO
4+HF。
3. the ammonia method falls in the acid of described a kind of phosphorus ammonium production joint according to claim 1, it is characterized in that: described step (B) is removed sulfate radical and realized by desulfurization sedimentation purification system: described desulfurization sedimentation purification system comprises the desulfurizer (5) of connecting successively by pipeline, doctor solution transferpump (6) and subsider (7), the feeding mouth of described desulfurizer (5) is communicated with discharge port and described ore pulp storage tank (1) discharge port of described gas-liquid separator (4) respectively by pipeline, and the phosphoric acid outlet of described subsider (7) also is communicated with the described phosphoric acid storage tank of phosphoric acid storage tank (11) (11) by pipeline access phosphorus ammonium production system.
4. the ammonia method falls in the acid of described a kind of phosphorus ammonium production joint according to claim 3, it is characterized in that: the pipeline between described gas-liquid separator (4) and the desulfurizer (5) is provided with phosphoric acid control valve (8), pipeline between described ore pulp storage tank (1) and the desulfurizer (5) is provided with ore pulp control valve (9), pipeline between described desulfurizer (5) and the described doctor solution transferpump (6) is provided with doctor solution control valve (10), be provided with agitator (5a) in the described desulfurizer (5), this desulfurizer (5) outer wall is fixed with liquidometer (5b).
5. the ammonia method falls in the acid of described a kind of phosphorus ammonium production joint according to claim 4, it is characterized in that: be provided with in the described subsider (7) and scrape filter (7a), the sewage draining exit of this subsider (7) is communicated with described extraction tank (2) by pipeline (7b), and this pipeline (7b) is provided with and is provided with successively residual sea water pump control valve (7c) and subsider residual sea water pump (7d).
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103754850A (en) * | 2014-01-07 | 2014-04-30 | 瓮福(集团)有限责任公司 | Method for reducing content of sulfate radicals in dihydrate dilute phosphoric acid |
CN103787291A (en) * | 2013-12-27 | 2014-05-14 | 安徽六国化工股份有限公司 | Method for removing sulfate ions from diluted phosphoric acid |
CN104495771A (en) * | 2014-12-25 | 2015-04-08 | 瓮福(集团)有限责任公司 | Desulfuration method for diluted phosphoric acid |
CN106365137A (en) * | 2016-11-28 | 2017-02-01 | 贵阳开磷化肥有限公司 | High-water solubility diammonium phosphate production device and production method |
Citations (3)
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CN1460635A (en) * | 2003-06-17 | 2003-12-10 | 东华工程科技股份有限公司 | Method for producing phosphoric acid by using 93%-98% concentrated sulfuric acid to extract phosphate rock and its equipment |
CN1683239A (en) * | 2004-04-16 | 2005-10-19 | 四川承源化工有限公司 | Method for producing phosphoric acid with low and medium grade phosphorous mine ore |
CN102431981A (en) * | 2011-09-01 | 2012-05-02 | 贵州开磷(集团)有限责任公司 | Method for reducing SO3 concentration in diluted phosphoric acid |
-
2013
- 2013-07-15 CN CN2013102955690A patent/CN103359700A/en active Pending
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1460635A (en) * | 2003-06-17 | 2003-12-10 | 东华工程科技股份有限公司 | Method for producing phosphoric acid by using 93%-98% concentrated sulfuric acid to extract phosphate rock and its equipment |
CN1683239A (en) * | 2004-04-16 | 2005-10-19 | 四川承源化工有限公司 | Method for producing phosphoric acid with low and medium grade phosphorous mine ore |
CN102431981A (en) * | 2011-09-01 | 2012-05-02 | 贵州开磷(集团)有限责任公司 | Method for reducing SO3 concentration in diluted phosphoric acid |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103787291A (en) * | 2013-12-27 | 2014-05-14 | 安徽六国化工股份有限公司 | Method for removing sulfate ions from diluted phosphoric acid |
CN103754850A (en) * | 2014-01-07 | 2014-04-30 | 瓮福(集团)有限责任公司 | Method for reducing content of sulfate radicals in dihydrate dilute phosphoric acid |
CN103754850B (en) * | 2014-01-07 | 2016-01-06 | 瓮福(集团)有限责任公司 | The method of sulfate radical content in a kind of reduction by two water law dilute phosphoric acids |
CN104495771A (en) * | 2014-12-25 | 2015-04-08 | 瓮福(集团)有限责任公司 | Desulfuration method for diluted phosphoric acid |
CN106365137A (en) * | 2016-11-28 | 2017-02-01 | 贵阳开磷化肥有限公司 | High-water solubility diammonium phosphate production device and production method |
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Application publication date: 20131023 |