CN103073344B - Production method for high-concentration defluorinate nitronitrogen phosphorus and potassium compound fertilizer - Google Patents
Production method for high-concentration defluorinate nitronitrogen phosphorus and potassium compound fertilizer Download PDFInfo
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- CN103073344B CN103073344B CN201310024190.6A CN201310024190A CN103073344B CN 103073344 B CN103073344 B CN 103073344B CN 201310024190 A CN201310024190 A CN 201310024190A CN 103073344 B CN103073344 B CN 103073344B
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Abstract
The invention discloses a production method for high-concentration defluorinate nitro nitrogen phosphorus and potassium compound fertilizer, which is based on the conventional process route of nitric acid phosphatic manure production, an acid-insoluble substance deep desorbing procedure is added in an acid-insoluble substance precipitation separation procedure so as to radically separate the acid-insoluble substance; a mother liquor defluorinating procedure is added between calcium nitrate filtration and mother liquor neutralization, by adding potassium nitrate into mother liquor, fluosilicic acid ions in mother liquor is reacted with potassium ion to generate potassium fluorosilicate product, after defluorinating reaction, potassium fluorosilicate is separated from slurry through filtering and separating, and ammonia neutralization, evaporation, pelletization, drying and cooling treatment are performed on defluorinated mother liquor by adding potassium nitrate and ammonium nitrate, namely, high-concentration nitro nitrogen phosphorus and potassium compound fertilizer is obtained. In the invention, mid low grade phosphate rock is used for preparing compound fertilizer, namely fluorine resource is recycled, and by-product potassium fluorosilicate is obtained, pollutions to the environment are reduced, the obtained product has an excellent performance, chlorine is not contained, the application range is broad, the probability of caking is low, and the market competitiveness is strong.
Description
Technical field
The invention belongs to chemical production technical field, be specifically related to a kind of production method of defluorinate high density nitro azophoska compound fertilizer.
Background technology
At present, nitro-compound fertilizer on market, is generally to take ammonium nitrate as nitrogenous source, by adding the compound fertilizer raw materials such as phosphorus, potassium, the N producing, P, K high-concentration compound fertilizer material.With decomposing phosphorite by using nitric acid, cold method deliming explained hereafter nitro phosphor complex, operational path is advanced, and fertilizer variety is good, and agricultural effect is obvious, in national economy, plays an important role.
From current fertilizer selling price situation, the price of nitrophosphate fertilizer unit nutrient is minimum in various composite fertilizers, has very strong competitive edge, develops the production of nitro multi-component composite fertilizer on Nitro Phosphate Unit basis, is necessary and with the obvious advantage.But the situation facing is at present that phosphate rock resource is in short supply, grade constantly declines, Chinese P
2o
5>=30% abundant ore source only can use 2014 (Zhang Weifeng, Marvin's is strange, Zhang Fusuo etc., natural resources journal, 2005,20 (3): 378-386; Lu Rukun, soil, 2004,36 (1): 1-4).Along with the continuous minimizing of high-quality phosphorus ore reserves, no matter be domestic or external, phosphorus compound fertilizer enterprise all will be faced with the predicament of using low-grade phosphate ore to produce, is particularly engaged in the enterprise that high concentration nitric-phosphate fertilizer is produced.On the other hand, along with improving constantly of the whole knowledge in rural area, scientific and technological level, the composite fertilizer of multiple nutrient structure and soil testing and fertilizer recommendation are more and more subject to friend's peasant concern, providing comprehensive, collaborative N, P, the K composite fertilizer absorbing of crop nutrition content to become the inexorable trend of modern chemical fertilizer development, is also one of responsibility of fertilizer enterprises.And along with the raising of environmental requirement and people's consciousness, the pollution problem of bringing fluorine in fertilizer system with phosphorus ore into needs to solve.
The technical process of Phosphate Fertilizer Nitrate with Frozen Method be phosphorus ore add nitric acid carry out acid non-soluble substance precipitate and separate, nitrocalcite freezing and crystallizing from acid hydrolysis solution in acidolysis, acid hydrolysis solution separated out, nitrocalcite filters, filter to isolate from nitrocalcite mother liquor carry out ammonia neutralization, and slip evaporation, then granulation, dry, the cooling nitrophosphate fertilizer product that obtains, wherein the fluorochemical in phosphorus ore 80% is transferred in mother liquor, finally enters nitrophosphate fertilizer product.Nitrophosphate fertilizer product total nutrient is greater than 38%, wherein containing P
2o
5~ 12.5%, N ~ 25%, other nutrient ~ 2%.The original design raw material phosphorus ore grade that requires of this technique is higher, and phosphorus ore quality index must meet P
2o
5>=31%, MgO≤1.0%, AI≤10%.But reality is that grade and the quality of phosphorus ore declining year by year, enterprise must be faced with use mid low grade phosphate rock.If produced with mid low grade phosphate rock tissue, must be on existing apparatus basis, development of new operational path, eliminates fluoride pollution problem, could solve low-grade phosphate ore and produce the technical barrier of high concentration nitric-phosphate fertilizer, nitro azophoska compound fertilizer, also could adapt to the market structure of China's phosphate rock resource.
China's chemical fertilizer nutrient structure be take nitrogen as main, lacks the few potassium phenomenon of phosphorus also more serious, and according to detection, in China's fertilizer, the average demand of N, P, K is with N:P
2o
5: K
2o=1:0.6:0.35 (Chinese patent CN1182085C) is best, and in fact the growth demand of crop still be take nitrogenous fertilizer as main.N:P in nitrophosphate fertilizer product
2o
5ratio is 1:0.5, approaches the best N∶P ratio of demand, by add all good saltpetre of consistency, suitability to system, realizes when nitro azophoska compound fertilizer is produced and eliminates fluoride pollution and reclaim fluorine resource.Therefore the Technology that, develops mid low grade phosphate rock stone production high density defluorinate nitro azophoska compound fertilizer on existing Nitro Phosphate Unit basis has strategic importance.
Summary of the invention
The object of the invention is intended to overcome the deficiency of existing production high density nitro azophoska compound fertilizer processing method, provide a kind of technique simple, reduce pollute, by the production method of mid low grade phosphate rock production defluorinate high density nitro azophoska compound fertilizer, with mid low grade phosphate rock, produce the production method that total nutrient is greater than 40% nitro azophoska compound fertilizer.
For achieving the above object, the present invention adopts following solution: a kind of production method of defluorinate high density nitro azophoska compound fertilizer, it is the operational path based on existing production nitrophosphate fertilizer, comprise following step successively: phosphorus ore adds nitric acid solution, acid non-soluble substance precipitate and separate, nitrocalcite freezing and crystallizing, nitrocalcite filtration, mother liquor neutralization, evaporation, granulation and dry, it is characterized in that: in acid non-soluble substance precipitate and separate step, increased acid non-soluble substance deep removal process, between nitrocalcite filtration and two steps of mother liquor neutralization, increased mother liquor defluorinate step.
The production method of above-mentioned a kind of defluorinate high density nitro azophoska compound fertilizer, is characterized in that: described acid non-soluble substance deep removal process is:
1) precipitate and separate process: acid hydrolysis solution is precipitated, filtered, make the acid non-soluble substance in acid hydrolysis solution carry out preliminary separation;
2) acid non-soluble substance deep removal process: to initial gross separation the acid hydrolysis solution of acid non-soluble substance add flocculation agent, flocculation sediment 0.5-1 hour, then carries out filtration treatment, the acid hydrolysis solution that has removed acid non-soluble substance is sent to nitrocalcite freezing and crystallizing.
The production method of above-mentioned a kind of defluorinate high density nitro azophoska compound fertilizer, is characterized in that: described mother liquor defluorinate step comprises following process:
1) defluorinate process: add saltpetre to mother liquor, make silicofluoric acid ion and potassium ion reaction in mother liquor generate potassium silicofluoride crystallization, process reaction condition is 10-50 ℃ of temperature of reaction, 0.5-1 hour reaction times, the add-on of saltpetre is pressed the silicofluoric acid content in mother liquor and is determined, and the mol ratio of saltpetre and silicofluoric acid is: 2-4;
2) solid-liquid separation process: the slip after defluorination reaction is separated by filtration out solid phase prod potassium silicofluoride, filtrate is defluorinate mother liquor, is sent in next step and operation.
The production method of above-mentioned a kind of defluorinate high density nitro azophoska compound fertilizer, it is characterized in that: the requirement according to fertilizer product to N-P-K content, at mother liquor N-process, add saltpetre and ammonium nitrate to adjust the nitrogen phosphoris and potassium fertilizer ratio of fertilizer product, the addition of saltpetre is 0.2-0.4 with phosphorus ore quality ratio, and the addition of ammonium nitrate is 0.12-0.20 with phosphorus ore quality ratio.
The production method of above-mentioned a kind of defluorinate high density nitro azophoska compound fertilizer, is characterized in that: in order to adjust the potassium content in fertilizer product, the saltpetre adding also can add at granulation process.
The production method of above-mentioned a kind of defluorinate high density nitro azophoska compound fertilizer, is characterized in that: at phosphorus ore, add in nitric acid solution process, described phosphorus ore is mid low grade phosphate rock, wherein P
2o
521%-30wt%, MgO≤2.0wt%, Fe
2(Al
2o)
3≤ 3.5wt %, F≤3.0wt%, AI≤20wt%.
Design of the present invention is mainly on Phosphate Fertilizer Nitrate with Frozen Method technical process basis, at phosphorus ore, add on the basis of nitric acid solution, acid non-soluble substance precipitate and separate, nitrocalcite freezing and crystallizing, nitrocalcite filtration, mother liquor neutralization, evaporation, granulation, the operation such as dry, cooling, in acid non-soluble substance precipitate and separate step, increased acid non-soluble substance deep removal process, by adding flocculation agent to acid hydrolysis solution, acid non-soluble substance has further been removed; For the fluoride pollution of eliminating in fertilizer reclaims fluorine resource, between nitrocalcite filtration and two steps of mother liquor neutralization, increased mother liquor defluorinate step, according to the silicofluoric acid in saltpetre and mother liquor, generate the method for potassium silicofluoride crystallization, from mother liquor, isolate fluorine resource; By add saltpetre nutrient in N-process or granulation process, produce required nitro azophoska compound fertilizer.
The process that the present invention realizes mid low grade phosphate rock production nitrophosphate fertilizer is: phosphorus ore and nitric acid join acidolysis groove and carries out phosphorus ore acid hydrolysis, then from acid hydrolysis solution, precipitate and isolate after acid non-soluble substance, again acid hydrolysis solution is added to the deep removal that flocculation agent carries out acid non-soluble substance, the acid hydrolysis solution of thoroughly separated acid non-soluble substance carries out freezing and crystallizing makes nitrocalcite crystallization from acid hydrolysis solution, carry out afterwards nitrocalcite filtration, nitrocalcite is filtered to the mother liquid obtained saltpetre defluorinate (SiF that adds
6 2-+ 2K
+=K
2siF
6↓), the mother liquor after defluorinate carries out ammonia neutralization, afterwards in and slip through evaporation, granulation, be drying to obtain the nitro azophoska compound fertilizer product that total nutrient is greater than 40%, the required saltpetre nutrient of nitrogen-phosphorus-potassium compound fertilizer adds at N-process or granulation process.
Tool of the present invention has the following advantages:
(1) nitro azophoska compound fertilizer of available mid low grade phosphate rock production high density;
(2) increase acid non-soluble substance deep removal, mother liquor defluorinate operation method is simple, relatively independent, have a style of one's own, be easy to realize technological transformation on former Phosphate Fertilizer Nitrate with Frozen Method device;
(3) beneficial effect that defluorinate process arranges: recycled fluorine resource on the one hand, obtained byproduct potassium silicofluoride, reduced on the other hand the pollution of fluorine to environment;
(4) on former Phosphate Fertilizer Nitrate with Frozen Method production equipment, by adding saltpetre at N-process or granulation process, convenient, to have realized simply, neatly nitrogen-phosphorus-potassium compound fertilizer production, the consistency that is embodied in saltpetre and nitrophosphate fertilizer technological process is good, and in nitro-compound fertilizer, the ratio of nitrogen phosphorus potassium is adjustable as required;
(5) products obtained therefrom good physical and chemical, not chloride, applied widely, shape is particulate state prevented from caking, has the very strong market competitiveness.
Utilize mid low grade phosphate rock to produce the inexorable trend that nitrogen-phosphorus-potassium compound fertilizer is China's development nitrophosphate fertilizer, and the ripe of development low-grade phosphate ore production high-quality nitrogen-phosphorus-potassium compound fertilizer, the enforcement of high density defluorinate nitro azophoska compound fertilizer production method of the present invention can be the long term growth of nitrophosphate fertilizer industry and lays a good foundation.
Accompanying drawing explanation
The process flow diagram of the embodiment of Fig. 1, high density defluorinate nitro azophoska compound fertilizer of the present invention.
In above-mentioned figure:
1-phosphorus ore 2-nitric acid, 3-acidolysis reaction, 4-precipitate and separate 5-acid non-soluble substance
6-acid non-soluble substance deep removal, 7-flocculation agent, 8-solid-liquid separation, 9-acid non-soluble substance
10-freezing and crystallizing, 11-nitre calcium filters 12-nitrocalcite 13-mother liquor
14-mother liquor defluorinate, 15-saltpetre, 16-solid-liquid separation, 17-potassium silicofluoride
The neutralization of 18-saltpetre, 19-ammonium nitrate, 20-ammonia, 21-mother liquor
22-slip evaporation, 23-slurry granulation, 24-dry materials, 25-material is cooling
26-nitro azophoska compound fertilizer
Embodiment
Below in conjunction with embodiment and accompanying drawing thereof, the specific embodiment of the present invention is described in detail, but they are not limitation of the invention.
Technical process explanation of the present invention:
The present embodiment is on the basis of the known Phosphate Fertilizer Nitrate with Frozen Method technological process of production, in acid non-soluble substance precipitate and separate step, increased acid non-soluble substance deep removal process 6, between nitrocalcite filtration and two steps of mother liquor neutralization, increased mother liquor defluorinate 14 operations, Fig. 1 is shown in its technical process.Nitric acid 2 and phosphorus ore 1 are added to and in acidolysis groove, carry out acidolysis reaction 3 by stoichiometry, acid non-soluble substance 5 in acid hydrolysis solution carries out initial gross separation through precipitate and separate 4, acid hydrolysis solution after separation enters in acid non-soluble substance deep removal operation 6, by adding flocculation agent 7, acid non-soluble substance 9 is carried out to deep removal through solid-liquid separation 8, then by thorough separation the acid hydrolysis solution of acid non-soluble substance send into freezing and crystallizing 10, through freezing and crystallizing nitrocalcite 12, separate out and enter nitrocalcite filtration 11 from acid hydrolysis solution and carry out solid-liquid separation, gained liquid is mother liquor 13; Will be through mother liquor defluorinate 14 operations before mother liquor 13 use ammonia 20 neutralizations, the mother liquor 13 that filters 11 from nitrocalcite is delivered in mother liquor defluorinate groove, by adding saltpetre 15, carry out mother liquor defluorinate, make the silicofluoric acid ion in mother liquor 13 react generation potassium silicofluoride crystallization 17 with potassium ion; According to the technique of Phosphate Fertilizer Nitrate with Frozen Method, at N-process, add ammonia 20 and ammonium nitrate 19 to neutralize, in order to obtain nitrogen-phosphorus-potassium compound fertilizer 26 products, at N-process, also to add the saltpetre 18 of calculated amount, then successively through evaporating 22, granulation 23, dry 24, cooling 25 makes defluorinate nitro azophoska compound fertilizer 26.
In order to obtain nitrogen-phosphorus-potassium compound fertilizer 26 products, the saltpetre 18 of the calculated amount that the present embodiment is required also can be added into granulating working procedure 23.
embodiment mono-
The quality index of the phosphorus ore 1 of the present embodiment: P
2o
527%, CaO 42%, AI 18%, F 2.9%, MgO 2%, Fe
2(Al
2o)
3total 3%, other impurity; The concentration of nitric acid 2 is 58%.
Nitric acid 2 and phosphorus ore 1 are added to and in acidolysis groove, carry out acidolysis reaction 3 by stoichiometry 1.2:1, acid non-soluble substance 5 in acid hydrolysis solution carries out initial gross separation through precipitate and separate 4, acid hydrolysis solution after separation enters in acid non-soluble substance deep removal operation 6, by adding flocculation agent 7, carry out acid non-soluble substance deep removal 6, flocculation sediment 0.5-1 hour by solid-liquid filtration separation 8 by acid non-soluble substance 9 deep removals, the acid hydrolysis solution of thoroughly separated acid non-soluble substance is sent into freezing and crystallizing 10, through freezing and crystallizing nitrocalcite 12, from acid hydrolysis solution, separate out and enter nitrocalcite filtration 11 and carry out solid-liquid separation, gained liquid is mother liquor 13, another feature of the present embodiment is that mother liquor 13 use ammonia 20 neutralizations before will be through mother liquor defluorinate 14 operations, the mother liquor 13 that filters 11 from nitrocalcite is delivered in mother liquor defluorinate groove, by adding saltpetre 15, carry out mother liquor defluorinate, make the silicofluoric acid ion in mother liquor 13 react generation potassium silicofluoride crystallization 17 with potassium ion, process reaction condition is 10-50 ℃ of temperature of reaction, in 0.5-1 hour reaction times, the add-on of saltpetre 15 according to the mol ratio of saltpetre and silicofluoric acid is: KNO
3/ H
2siF
6=2-4, according to the technique of Phosphate Fertilizer Nitrate with Frozen Method, add ammonia 20 and ammonium nitrate 19 to neutralize in the mother liquor after degree of depth defluorinate, the addition of ammonia is 0.10-15 with phosphorus ore quality ratio, the addition of ammonium nitrate is 0.12-0.20 with phosphorus ore quality ratio, in order to obtain nitrogen-phosphorus-potassium compound fertilizer 26 products, at N-process, also to add the saltpetre 18 of calculated amount, the addition of saltpetre is 0.2-0.4 with phosphorus ore quality ratio, then successively through evaporating 22, granulation 23, dry 24, cooling 25 makes nitro azophoska compound fertilizer 26.
In order to obtain nitrogen-phosphorus-potassium compound fertilizer 26 products, the saltpetre 18 of the calculated amount that the present embodiment is required also can be added into granulating working procedure.
Total nutrient concentration>=40% of the present embodiment gained nitrogen-phosphorus-potassium compound fertilizer 26 products, wherein containing P
2o
512.3%, N 22%, K
2o 7%, other nutrients 2%, other nutrients refer to trace element as calcium, magnesium, sulphur, aluminium, iron, manganese etc.
embodiment bis-
The quality index of the phosphorus ore 1 of the present embodiment is different from embodiment's mono-, and quality index is: P
2o
522%, CaO 45%, AI 18.7%, F 2.5%, MgO 2.0%, Fe
2(Al
2o)
3total 3.2%, other impurity; The concentration of nitric acid 2 is 58%.
Other processes are identical with the production process of embodiment mono-defluorinate high density nitro azophoska compound fertilizer.
Total nutrient concentration>=40% of the present embodiment gained nitrogen-phosphorus-potassium compound fertilizer 26 products, wherein containing P
2o
511%, N 20%, K
2o 7%, other nutrients 2.0%.
Claims (4)
1. the production method of a defluorinate high density nitro azophoska compound fertilizer, it is the operational path based on existing Phosphate Fertilizer Production, comprise following step successively: phosphorus ore adds nitric acid solution, acid non-soluble substance precipitate and separate, nitrocalcite freezing and crystallizing, nitrocalcite filtration, mother liquor neutralization, evaporation, granulation, dry and cooling, it is characterized in that: in acid non-soluble substance precipitate and separate step, increased acid non-soluble substance deep removal step, between nitrocalcite filtration and two steps of mother liquor neutralization, increased mother liquor defluorinate step; At mother liquor N-process, add saltpetre and ammonium nitrate to adjust the nitrogen phosphoris and potassium fertilizer ratio of fertilizer product, the addition of saltpetre with phosphorus ore quality than being 0.2-0.4, the addition of ammonium nitrate with phosphorus ore quality than being 0.12-0.20; The saltpetre adding also can add at granulation process.
2. the production method of a kind of defluorinate high density nitro azophoska compound fertilizer according to claim 1, is characterized in that: described acid non-soluble substance deep removal step comprises following process:
1) precipitate and separate process: acid hydrolysis solution is precipitated, filtered, make the acid non-soluble substance in acid hydrolysis solution carry out preliminary separation;
2) acid non-soluble substance deep removal process: to initial gross separation the acid hydrolysis solution of acid non-soluble substance add flocculation agent, flocculation sediment 0.5-1 hour, then carries out filtration treatment, the acid hydrolysis solution that has removed acid non-soluble substance is sent to nitrocalcite freezing and crystallizing.
3. the production method of a kind of defluorinate high density nitro azophoska compound fertilizer according to claim 1, is characterized in that: described mother liquor defluorinate step comprises following process:
1) defluorinate process: add saltpetre to mother liquor, make silicofluoric acid ion and potassium ion reaction in mother liquor generate potassium silicofluoride crystallization, process reaction condition is temperature of reaction 10-50 ℃, reaction times 0.5-1 hour, the add-on of saltpetre is pressed the silicofluoric acid content in mother liquor and is determined, and the mol ratio of saltpetre and silicofluoric acid is: 2-4;
2) solid-liquid separation process: the slip after defluorination reaction is separated by filtration out solid phase prod potassium silicofluoride, filtrate is defluorinate mother liquor, is sent in next step and operation.
4. the production method of a kind of defluorinate high density nitro azophoska compound fertilizer according to claim 1, is characterized in that: at phosphorus ore, add in nitric acid solution process, described phosphorus ore is mid low grade phosphate rock, wherein P
2o
521%-30wt%, MgO≤2.0wt%, Fe
2(Al
2o)
3≤ 3.5wt %, F≤3.0wt%, AI≤20wt%.
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| CN103524150B (en) * | 2013-09-27 | 2015-04-15 | 深圳市芭田生态工程股份有限公司 | Method and device for producing granular nitric phosphateby decomposing phosphate ore through nitric acid |
| CN104108968B (en) * | 2014-07-04 | 2017-10-03 | 贵州芭田生态工程有限公司 | A kind of granulation process of nitrophosphate fertilizer |
| CN104211485B (en) * | 2014-09-17 | 2017-07-14 | 中化化肥有限公司 | The method for producing crystalloid potassium dihydrogen phosphate and potassium nitrate a great number of elements Water soluble fertilizer |
| CN104387156B (en) * | 2014-10-25 | 2016-09-07 | 贵州芭田生态工程有限公司 | A kind of improvement technique producing spheric granules nitrogen-phosphorus-potassium compound fertilizer based on Nitro Phosphate Unit |
| CN105175029A (en) * | 2015-09-11 | 2015-12-23 | 云南云天化股份有限公司 | Method for preparing phosphor (potassium) nitrate fertilizer by wet process phosphate sludge acid |
| CN105272441B (en) * | 2015-09-23 | 2018-11-13 | 四川泸天化股份有限公司 | The technique for producing liquid composite fertilizer using decomposing phosphorite by using nitric acid combination sylvite deliming |
| CN106187327A (en) * | 2016-07-12 | 2016-12-07 | 贵州芭田生态工程有限公司 | Mid low grade phosphate rock prepares method and the compound fertilizer product of high contents of calcium and magnesium compound fertilizer |
| CN106380232A (en) * | 2016-08-19 | 2017-02-08 | 贵州芭田生态工程有限公司 | A nitrogen-phosphorous composite fertilizer and a preparing method thereof |
| CN107954749B (en) * | 2016-10-18 | 2021-03-30 | 贵州芭田生态工程有限公司 | Polyphosphate-containing nitrogen-phosphorus compound fertilizer and preparation method thereof |
| CN106518222B (en) * | 2016-11-03 | 2019-09-06 | 太原理工大学 | A kind of viscosity reducing process of Phosphate Fertilizer Nitrate with Frozen Method neutralize slip |
| CN106565282A (en) * | 2016-11-03 | 2017-04-19 | 贵州芭田生态工程有限公司 | Production method of high-concentration water-soluble nitrophosphate fertilizer |
| CN106517293B (en) * | 2016-11-14 | 2018-03-13 | 重庆华强生态肥业有限公司 | A kind of method of industrial calcium product coproduction chemical synthesis fertilizer |
| CN112758937B (en) * | 2021-01-14 | 2023-08-01 | 襄阳泽东化工集团有限公司 | Method for preparing potassium fluosilicate and NPK compound fertilizer from associated phosphate-potassium ore |
| CN113184855A (en) * | 2021-04-21 | 2021-07-30 | 武汉工程大学 | Resource comprehensive utilization method of phosphogypsum and potassium feldspar |
| CN113173584A (en) * | 2021-04-21 | 2021-07-27 | 武汉工程大学 | Resource comprehensive utilization method of phosphorus tailings and potassium feldspar |
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| CN101486595B (en) * | 2009-02-25 | 2011-03-30 | 天脊煤化工集团股份有限公司 | Technological process for producing high concentration nitric-phosphate fertilizer |
| CN101717290B (en) * | 2009-11-02 | 2012-06-27 | 山东红日阿康化工股份有限公司 | Method for producing defluorinated sulfenyl nitrogen-phosphorus-potassium compound fertilizer |
| CN102233201A (en) * | 2010-04-23 | 2011-11-09 | 北京化工大学 | Chemical flocculation precipitation separation of polyacrylamide on acid-insoluble residues in production of nitrophosphate fertilizer |
| CN102580362B (en) * | 2011-01-14 | 2014-05-28 | 北京化工大学 | Process flow for separating acid-insoluble substances in nitric phosphate production by chemical flocculence method |
| CN102126740B (en) * | 2011-01-20 | 2012-08-15 | 山东金正大生态工程股份有限公司 | Method for producing byproduct gypsum of niter-sulfur-based compound fertilizer by decomposing phosphorite with nitric acid |
| CN102126737A (en) * | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | Method for producing nitrate-and-sulfur-based compound fertilizer and co-producing gypsum by utilizing potassium hydrogen sulfate |
| CN102351591B (en) * | 2011-07-18 | 2013-04-10 | 贵州省化工研究院 | Method for highly water-soluble nitrophosphate fertilizer production through decomposition of rare earth-containing phosphate rock by nitric acid and for rare earth recovery |
| CN102351590B (en) * | 2011-07-18 | 2013-07-24 | 贵州省化工研究院 | Method for producing high-water solubility nitrophosphate fertilizer by phosphorite nitrolysis and calcium nitrate freezing |
| CN102503591B (en) * | 2011-10-20 | 2014-05-14 | 太原理工大学 | Method for preventing scars of refrigerating coil of calcium nitrate crystallizer for nitrophosphate fertilizer |
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