CN106380231A - Method for producing calcium superphosphate with phosphate rock tailings and phosphoric acid sludge - Google Patents
Method for producing calcium superphosphate with phosphate rock tailings and phosphoric acid sludge Download PDFInfo
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- CN106380231A CN106380231A CN201610762330.3A CN201610762330A CN106380231A CN 106380231 A CN106380231 A CN 106380231A CN 201610762330 A CN201610762330 A CN 201610762330A CN 106380231 A CN106380231 A CN 106380231A
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- phosphoric acid
- phosphate rock
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05B—PHOSPHATIC FERTILISERS
- C05B1/00—Superphosphates, i.e. fertilisers produced by reacting rock or bone phosphates with sulfuric or phosphoric acid in such amounts and concentrations as to yield solid products directly
- C05B1/02—Superphosphates
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F17/00—Preparation of fertilisers characterised by biological or biochemical treatment steps, e.g. composting or fermentation
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/40—Bio-organic fraction processing; Production of fertilisers from the organic fraction of waste or refuse
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Abstract
The invention discloses a method for producing common calcium superphosphate by using phosphate rock tailings, phosphoric acid sludge and ground phosphate rock as raw materials. The method is characterized by fully mixing 1 t of phosphate rock tailings with the P2O5 effective content being 8-8.5% and the solid content being 12-15%, 0.3-0.8 t of phosphoric acid sludge with the P2O5 effective content being 45.0-46.0% and the solid content being 12-15%, and 0.2 t of ground phosphate rock with the P2O5 effective content being 25.0-26.0%, adding 0.4 t of concentrated H2SO4, and carrying out a reaction in a stirring state for 1 h; and adding 0.03-0.08 t of quicklime for neutralizing free acid and transferring the obtained product in a compost depot for curing for 5-7 days to make a qualified common calcium superphosphate phosphate fertilizer product with the P2O5 effective content no less than 14%. The method provides a new way for integrated application of phosphate rock tailings and phosphoric acid sludge. Through addition of quicklime for neutralizing redundant acid, the use ratio of phosphorus is increased at a certain degree.
Description
Technical field
The invention belongs to phosphate fertilizer preparing technical field is and in particular to a kind of preparation method of calcium superphosphate.
Background technology
At present world's phosphor resource is day by day exhausted, in China, low-grade phosphate ore in the majority, with respect to high-grade phosphorus ore, right
In, low-grade phosphate ore carry out process extract phosphorus concentrate when, substantial amounts of tailings can be produced, be commonly called as mine tailing, these mine tailings belong to industry
Mining industry solid waste in solid waste.According to relevant data display, the comprehensive utilization ratio of China's phosphorite tailings is only 7% left side
The right side, substantial amounts of mine tailing can only be stacked for a long time, if things go on like this, it will cause serious pollution to air and periphery water and soil, and lead to
Land deterioration vegetation deterioration even directly threatens the existence of people and animals.And can produce when using Phosphate Rock acid and contain in a large number
The phosphoric acid slag acid of the impurity such as ardealite, these slag acid belong to industrial liquid garbage.Most of phosphoric acid production enterprises all can be by slag
Acid returns process units, and the membership of entering of a large amount of solid slag affects phosphoric acid quality.Therefore, phosphorite tailings and phosphoric acid how are strengthened
The comprehensive utilization of slag acid, the available scope of extension phosphate rock resource, it has also become the deficient task of top priority of phosphor resource.
Traditional normal superphosphate production method is with phosphorus ore and sulphuric acid as raw material, is produced by two step chemical reactions
P2O5Product more than 12% for the effective ingredient, the production cycle of this production method is usually 12-15 days.And with phosphorite tailings and phosphorus
Acid sludge acid is raw material production normal superphosphate, due in, the P of low-grade phosphate ore mine tailing2O5Effective ingredient in 5%-8%, compared with phosphorus ore
Low, therefore lead to the normal superphosphate product P going out with it for raw material production2O5Effective ingredient is unable to reach GB20413-2006
Requirement, need add adjuvant improve P2O5The content of effective ingredient.And substantial amounts of phosphoric acid slag can be produced in production process of phosphoric acid
Acid produces qualified product it is generally the case that some return production system is understood in these slag acid together with raw material again, its
He part then naturally clarification after by supernatant return system, the precipitation with a large amount of phosphorus is then discharged into slag field heap with ardealite
Put etc. pending.
Content of the invention
The technical problem to be solved is to discard, for a large amount of phosphor resource of phosphatic fertilizer company, problem of shelving to provide one kind effectively
Using approach.
Technical problem for solving the present invention adopts the following technical scheme that：
A kind of utilization phosphorite tailings and the method for phosphoric acid slag acid production calcium superphosphate, are carried out in the steps below：
（1）Carry out material proportion by weight
P in phosphorite tailings 1t, wherein phosphorite tailings2O5Effective ingredient is measured as 8%-8.5% so that mine tailing is dried, and solid content is 12%-
15%；
The H of mass concentration >=93%2SO40.4t；
P in phosphoric acid slag acid 0.3t-0.8t, the wherein acid of phosphoric acid slag2O5Effective ingredient is 45.0%-46.0%, and solid content is 12%-
15%；
P in ground phosphate rock 0.2t, wherein ground phosphate rock2O5Effective ingredient is 25.0%-26.0%；
Calcium oxide content is 85% quick lime 0.03t-0.08t；
（2）According to step（1）Described in material proportion, will phosphorite tailings, the acid of phosphoric acid slag and ground phosphate rock put into mixed in reactor
Close uniformly；
（3）By dense H2SO4It is homogeneously added in mixed material in 10-15 minute under conditions of stirring, 0.8-1 is little for reaction
When after add quick lime, after material pH value be less than 7 when reaction end make material be down to room temperature after, stop stirring；
（4）Above-mentioned compound is proceeded to compost storehouse and carries out ripening, the time is 5-7 days, obtains P2O5Effective ingredient is more than 14%
Normal superphosphate product.
Described step（4）Compound is made to become P by turning during middle ripening2O5Effective ingredient is more than 14% common mistake
Phosphoric acid calcium product.
Described step（1）In carry out material proportion phosphorite tailings by weight：The acid of phosphoric acid slag：Ground phosphate rock：Mass concentration is 98%
H2SO4：Quick lime is 1:0.3:0.2:0.4:0.03.
The reaction mechanism of the inventive method is as follows：
Phosphorite tailings decompose：
React for exothermic reaction, reaction mass temperature can be increased to more than 100 DEG C quickly.
In traditional normal superphosphate reaction, after the exothermic reaction of only phosphorus ore and sulphuric acid first stage completes, produce
Raw phosphoric acid just can carry out, with remaining phosphorus ore, the reaction that second stage generates one-lime phosphate.And in the methods of the invention, in tail
While ore deposit and sulfuric acid reaction, phosphoric acid directly can carry out reaction and generate one-lime phosphate with mine tailing：
Because phosphoric acid is longer with the duration of the reaction of mine tailing, after stirring stops in the reactor, also can react in compost storehouse
A period of time is it is simply that follow-up maturing process.
Then should be neutralized with alkaline material if there are unnecessary free acid in general calcium after ripening：
The present invention utilizes phosphorite tailings to prepare P for raw material by the operation such as mix and blend, ripening with the acid of phosphoric acid slag2O5Effective ingredient
Qualified normal superphosphate product for more than 14%.On the one hand the acid of phosphoric acid slag passed through to increase H+Improve the decomposition of phosphorite tailings
Rate, on the other hand improves by the P in phosphoric acid calcium product2O5Effective ingredient.Table 1 is general calcium national standard (GB20143-
2006) index of calcium superphosphate, in 14%-18%, water-soluble phosphorus content exists the calcium superphosphate available phosphorus content of present invention preparation
12.4%-16.5%, water-soluble phosphoruses proportion accounts for more than the 80% of available phosphorus content, meets general calcium national standard (GB20143-2006)
Index, also comply with the New Set that water-soluble phosphorus proportion at present accounts for more than the 70% of available phosphorus content simultaneously.The present invention entirely reacted
Journey is simple, and reaction condition is gentle it is easy to operation, the phosphorite tailings that can produce in substantial amounts of consumption company ore-dressing technique and phosphoric acid work
The slag acid producing in skill, improves the utilization rate to phosphor resource, saves production cost, improve Business Economic Benefit.
Table 1 general calcium national standard (GB20143-2006)
Specific embodiment
With reference to embodiment, the present invention is described in further details.
Embodiment 1
A kind of utilization phosphorite tailings and the method for phosphoric acid slag acid production calcium superphosphate, are carried out in the steps below：
（1）Raw material mixes：Take solid content to be 15%, P2O5Effective ingredient measures phosphorite tailings 1t, P for 8% so that mine tailing is dried2O5
Effective ingredient 45.0% phosphoric acid slag acid 0.4t, P2O5Effective ingredient is 25.0% ground phosphate rock 0.2t, fully mixed in the reactor
Close；
（2）With sulfuric acid reaction：The dense H that 0.4t mass concentration is 93%2SO4Under conditions of stirring in 10 minutes equably
It is added in mixed material, reaction added quick lime 0.03t after 1 hour, reaction end when material pH value is less than 7 makes material drop
To room temperature, stop stirring；
（3）The preparation of normal superphosphate：Material is proceeded to compost storehouse, ripening 5 days, it can be made by turning during this ripening
Become P2O5Effective ingredient increases, normal superphosphate product P manufactured in the present embodiment2O5Effective ingredient is 15.15%.
Embodiment 2
A kind of utilization phosphorite tailings and the method for phosphoric acid slag acid production calcium superphosphate, are carried out in the steps below：
（1）Raw material mixes：Take solid content to be 12%, P2O5Effective ingredient measures phosphorite tailings 1t for 8.5% so that mine tailing is dried,
P2O5Effective ingredient 45.0% phosphoric acid slag acid 0.5t, P2O5Effective ingredient is 25.0% ground phosphate rock 0.2t, fills in the reactor
Divide mixing；
（2）With sulfuric acid reaction：The dense H that 0.4t mass concentration is 93%2SO4Under conditions of stirring in 15 minutes equably
It is added in mixed material, reaction added quick lime 0.05t after 0.8 hour, reaction end when material pH value is less than 7 makes material
After being down to room temperature, stop stirring；
（3）The fertile preparation of normal superphosphate：Complete according to step (3) in embodiment 1, common peroxophosphoric acid manufactured in the present embodiment
Calcium product P2O5Effective ingredient is 16.67%.
Embodiment 3
A kind of utilization phosphorite tailings and the method for phosphoric acid slag acid production calcium superphosphate, are carried out in the steps below：
（1）Raw material mixes：Take solid content to be 13%, P2O5Effective ingredient measures phosphorite tailings 1t for 8.3% so that mine tailing is dried,
P2O5Effective ingredient 46.0% phosphoric acid slag acid 0.3t, P2O5Effective ingredient is 26.0% ground phosphate rock 0.2t, fills in the reactor
Divide mixing；
（2）With sulfuric acid reaction：The dense H that 0.4t mass concentration is 98%2SO4Under conditions of stirring in 15 minutes equably
It is added in mixed material, reaction added quick lime 0.03t after 0.8 hour, reaction end when material pH value is less than 7 makes material
After being down to room temperature, stop stirring；
（3）The fertile preparation of normal superphosphate：Material is proceeded to compost storehouse, ripening 7 days, can be made by turning during this ripening
It becomes P2O5Effective ingredient increases, normal superphosphate product P manufactured in the present embodiment2O5Effective ingredient is 17.90%.
Embodiment 4
A kind of utilization phosphorite tailings and the method for phosphoric acid slag acid production calcium superphosphate, are carried out in the steps below：
（1）Raw material mixes：Take solid content to be 13%, P2O5Effective ingredient measures phosphorite tailings 1t for 8.3% so that mine tailing is dried,
P2O5Effective ingredient 46.0% phosphoric acid slag acid 0.8t, P2O5Effective ingredient is 26.0% ground phosphate rock 0.2t, fills in the reactor
Divide mixing；
（2）With sulfuric acid reaction：The dense H that 0.4t mass concentration is 96%2SO4Under conditions of stirring in 12 minutes equably
It is added in mixed material, reaction added quick lime 0.08t after 0.8 hour, reaction end when material pH value is less than 7 makes material
After being down to room temperature, stop stirring；
（3）The fertile preparation of normal superphosphate：Material is proceeded to compost storehouse, ripening 7 days, can be made by turning during this ripening
It becomes P2O5Effective ingredient increases, normal superphosphate product P manufactured in the present embodiment2O5Effective ingredient is 17.15%.
Claims (3)
1. a kind of utilization phosphorite tailings and phosphoric acid slag acid produce calcium superphosphate method it is characterised in that：Carry out in the steps below：
（1）Carry out material proportion by weight
P in phosphorite tailings 1t, wherein phosphorite tailings2O5Effective ingredient is measured as 8%-8.5% so that mine tailing is dried, and solid content is 12%-
15%；
The H of mass concentration >=93%2SO40.4t；
P in phosphoric acid slag acid 0.3t-0.8t, the wherein acid of phosphoric acid slag2O5Effective ingredient is 45.0%-46.0%, and solid content is 12%-15%；
P in ground phosphate rock 0.2t, wherein ground phosphate rock2O5Effective ingredient is 25.0%-26.0%；
Calcium oxide content is 85% quick lime 0.03t-0.08t；
（2）According to step（1）Described in material proportion, will phosphorite tailings, the acid of phosphoric acid slag and ground phosphate rock put into mixed in reactor
Close uniformly；
（3）By H2SO4It is homogeneously added in mixed material in 10-15 minute under conditions of stirring, react 0.8-1 hour
Add quick lime afterwards, after reaction end makes material be down to room temperature when material pH value is less than 7, stop stirring；
（4）Above-mentioned compound is proceeded to compost storehouse and carries out ripening, the time is 5-7 days, obtains P2O5Effective ingredient is more than 14%
Normal superphosphate product.
2. the method for a kind of utilization phosphorite tailings according to claim 1 and phosphoric acid slag acid production calcium superphosphate, its feature
It is：Described step（4）Compound is made to become P by turning during middle ripening2O5Effective ingredient is more than 14% common phosphorus excessively
Sour calcium product.
3. the method for a kind of utilization phosphorite tailings according to claim 1 and 2 and phosphoric acid slag acid production calcium superphosphate, it is special
Levy and be：Described step（1）In by weight 1:0.3:0.2:0.4:0.03 carries out material phosphorite tailings：The acid of phosphoric acid slag：Phosphorus ore
Powder：Mass concentration is 98% H2SO4：The proportioning of quick lime.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610762330.3A CN106380231A (en) | 2016-08-30 | 2016-08-30 | Method for producing calcium superphosphate with phosphate rock tailings and phosphoric acid sludge |
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| CN201610762330.3A CN106380231A (en) | 2016-08-30 | 2016-08-30 | Method for producing calcium superphosphate with phosphate rock tailings and phosphoric acid sludge |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456007A (en) * | 2018-04-02 | 2018-08-28 | 金正大生态工程集团股份有限公司 | A kind of calcium polyphosphate magnesium fertilizer and preparation method thereof prepared as raw material using phosphoric acid and phosphorus tailing |
| CN108530175A (en) * | 2018-05-28 | 2018-09-14 | 郑州大学 | A kind of granular compound fertilizer and its production method using the production of phosphoric acid slag acid |
| CN110483125A (en) * | 2019-08-02 | 2019-11-22 | 史丹利化肥当阳有限公司 | Utilize the method for waste phosphoric acid production S-based compound fertilizer raw material |
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| CN1206701A (en) * | 1998-04-27 | 1999-02-03 | 威远县磷钙饲料厂 | Process for producing calcium superphosphate from defluorinated slag |
| CN101367672A (en) * | 2008-09-26 | 2009-02-18 | 瓮福（集团）有限责任公司 | Manufacturing method of high concentration enrich superphosphate phosphorus fertilizer |
| CN102992275A (en) * | 2012-11-15 | 2013-03-27 | 宜都兴发化工有限公司 | Production method for producing calcium superphosphate by using phosphoric acid sludge |
| CN104446673A (en) * | 2014-12-05 | 2015-03-25 | 甘肃瓮福化工有限责任公司 | Method for producing calcium superphosphate by using phosphate rock tailings |
-
2016
- 2016-08-30 CN CN201610762330.3A patent/CN106380231A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1206701A (en) * | 1998-04-27 | 1999-02-03 | 威远县磷钙饲料厂 | Process for producing calcium superphosphate from defluorinated slag |
| CN101367672A (en) * | 2008-09-26 | 2009-02-18 | 瓮福（集团）有限责任公司 | Manufacturing method of high concentration enrich superphosphate phosphorus fertilizer |
| CN102992275A (en) * | 2012-11-15 | 2013-03-27 | 宜都兴发化工有限公司 | Production method for producing calcium superphosphate by using phosphoric acid sludge |
| CN104446673A (en) * | 2014-12-05 | 2015-03-25 | 甘肃瓮福化工有限责任公司 | Method for producing calcium superphosphate by using phosphate rock tailings |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108456007A (en) * | 2018-04-02 | 2018-08-28 | 金正大生态工程集团股份有限公司 | A kind of calcium polyphosphate magnesium fertilizer and preparation method thereof prepared as raw material using phosphoric acid and phosphorus tailing |
| CN108456007B (en) * | 2018-04-02 | 2021-05-25 | 金正大生态工程集团股份有限公司 | Calcium-magnesium polyphosphate fertilizer prepared by taking phosphoric acid and phosphate tailings as raw materials and preparation method thereof |
| US11787748B2 (en) | 2018-04-02 | 2023-10-17 | Kingenta Ecological Engineering Group Co., Ltd. | Polyphosphoric acid calcium magnesium fertilizer, polyphosphoric acid calcium magnesium fertilizer prepared by using phosphoric acid and phosphorus tailings as raw material and preparation method therefor |
| CN108530175A (en) * | 2018-05-28 | 2018-09-14 | 郑州大学 | A kind of granular compound fertilizer and its production method using the production of phosphoric acid slag acid |
| CN110483125A (en) * | 2019-08-02 | 2019-11-22 | 史丹利化肥当阳有限公司 | Utilize the method for waste phosphoric acid production S-based compound fertilizer raw material |
| CN110483125B (en) * | 2019-08-02 | 2022-03-04 | 史丹利化肥当阳有限公司 | Method for producing raw material for sulfur-based compound fertilizer by using waste phosphoric acid |
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Application publication date: 20170208 |
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