CN104477866A - Method for preparation of sodium dihydrogen phosphate and co-production of fennel-dedicated composite fertilizer - Google Patents
Method for preparation of sodium dihydrogen phosphate and co-production of fennel-dedicated composite fertilizer Download PDFInfo
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- CN104477866A CN104477866A CN201410479098.3A CN201410479098A CN104477866A CN 104477866 A CN104477866 A CN 104477866A CN 201410479098 A CN201410479098 A CN 201410479098A CN 104477866 A CN104477866 A CN 104477866A
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Abstract
The invention discloses a method for preparation of sodium dihydrogen phosphate and co-production of a fennel-dedicated composite fertilizer. The method comprises the following three steps: preparation of an intermediate by a reaction; preparation of sodium dihydrogen phosphate; and preparation of the fennel-dedicated composite fertilizer. By the above method, purity of the prepared sodium dihydrogen phosphate is high, and there is no discharge of exhaust gas, wastewater or waste residue. The method has a certain environmental protection value. In addition, residual mother liquor generated during the production process can be made into the fennel-dedicated composite fertilizer through subsequent processing. Therefore, resources are fully utilized, and costs are reduced.
Description
Technical field
The present invention relates to technical field of fertilizer, be specifically related to a kind of method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special.
Background technology
Large and small fennel is all conventional condiment, is the product that must use when carbonado fricassee, making marinated food.Because they except foul smell in meat, can make it again to add perfume (or spice), therefore say " fennel ".Star anise and aniseed, formal name used at school is " star anise ".The kind of sweet fennel is seasonings in fact, and its cauline leaf part also has fragrance, is often used to the fillings making steamed stuffed bun, dumpling and other food.Main component contained by them is all olium anisi, energy stimulating gastrointestinal neural blood vessel, and promoting digestion liquid is secreted, and increases gastrointestinal peristalsis, gets rid of the gas accumulated, so there is effect of stomach invigorating, promoting the circulation of qi; Sometimes gastrointestinal peristalsis can reduce again after excitement, thus contributes to alleviating spasm, easing the pain.Fennel is long for breeding time, and fertilizer requirement is large, happiness phosphorus potash fertilizer, and common fertilizer is after arable land applies, and a part is rising, dissipation and outflowing with water, and a part is fixed by soil and soil microorganisms and utilized, and only has a part wherein just absorbed by crops and utilize.Show after deliberation: the utilization ratio of urea, carbon ammonium is 20% one 46%, phosphate fertilizer (two ammoniums, an ammonium, coarse whiting) is 10% one 25%, potash fertilizer 45% one 60%.As can be seen here, common fertilizer utilization ratio is very low.For this reason, the present inventor is for the feature of fennel and a kind of method preparing fennel special fertilizer of the fertile characteristic research of happiness, need in a growth cycle of fennel to absorb more nutritive substance, being not only nitrogen that common fertilizer provides, phosphorus, potassium, as lacked other nutrients, just can not growing by normal growth, plant slight of stature, ear uneven, pollination rate is low, has a strong impact on output.The present invention is the synthesis containing multiple nutrient, not the chemical fertilizer that nutrient is single, it is also rich in the required element of the crops such as sodium, calcium, boron except the macronutrient such as nitrogenous, phosphorus, potassium, serving the effect regulating soil balanced nutrients, is a kind of new and effective no-pollution full nutrition chelating dedicated fertilizer.This special fertilizer be grow normally according to fennel, cultivation feature, irrigate habit, prepared by the nutritive element of needs.Add various nutrient elements, protection fennel is healthy, and fertility is more lasting, and effective regulating plant body defensive ability/resistance ability, alleviates disease, improves output.Greatly improve crop quality, improve the immunizing power of fennel self, can well prevent fennel regular incidence.
SODIUM PHOSPHATE, MONOBASIC is the raw material manufacturing Sodium hexametaphosphate 99 and trisodium phosphate, be mainly used in process hides, process feedwater, as quality improver and baking powder processed, and in foodstuffs industry, fermentation industry, make buffer reagent and saleratus raw material, be also used as fodder additives, washing composition and dye auxiliary agent etc.
As the publication number patent document that is CN101475463A discloses a kind of method of calcium formiate and peroxophosphoric acid reaction co-producing high-purity formic acid and SODIUM PHOSPHATE, MONOBASIC, the method adopts carbon monoxide to enter reaction three tower, potassium hydroxide enters reaction one tower, countercurrent reaction is carried out with the carbon monoxide carrying out autoreaction two tower, reaction solution overflow is to reaction two towers, with the carbon monoxide gas countercurrent reaction carrying out autoreaction three tower, reaction solution enters reaction three tower, countercurrent reaction is carried out with carbon monoxide, reaction solution enters batch can by reacting three towers spillings, make calcium formiate and prepare liquid, this calcium formiate prepares liquid, enter reactor, drip formic acid, pass into hydrogen sulfide, filter residue is separated through filter I, filtrate enters continuous crystallizer, crystal solution enters strainer II, finished product calcium formiate made by calcium formiate drying device after filtration, peroxophosphoric acid, formic acid and calcium formiate are input into into horizontal double-screw reactor, generate formic acid and monocalcium phosphate, enter the underpressure distillation of formic acid distillation still, monocalcium phosphate metering receiving tank transported to by monocalcium phosphate, formic acid enters formic acid receiving tank, although the formic acid purity that the method is prepared is high, but due to complicated process of preparation, equipment requirements is high, and the SODIUM PHOSPHATE, MONOBASIC product generated is unstable, cause production cost too high.
The present inventor by preparation SODIUM PHOSPHATE, MONOBASIC technology and the research repeatedly of document and experiment, propose a kind of can prepare high-purity phosphoric acid sodium dihydrogen while the method for coproduction fennel composite fertilizer special, make use of resource fully, reduce cost.
Summary of the invention
Prepare SODIUM PHOSPHATE, MONOBASIC complex process for solving in conventional art, equipment requirements is high, SODIUM PHOSPHATE, MONOBASIC product unstable, production cost is too high problem, the invention provides that a kind of environmental pollution is low, equipment requirements is low, production cost is low and effectively simplify the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special of production technique.
The present invention is achieved by the following technical programs:
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
Intermediate is prepared in a, reaction: use urea and phosphoric acid in molar ratio 1.3:1.6-2.1 mix, and temperature is risen to 121-126 DEG C, and stirring velocity is 60-65r/min stirring reaction 2.4h, is separated and obtains intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, control pH value is 3.4-4.1, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 86-94min, mother liquor is placed in cooling crystallizer decrease temperature crystalline, monitoring analysis is carried out to mother liquor simultaneously, when nitrogen content is 15.4-15.9%, phosphorus pentoxide content is 7.4-7.9%, when sodium content is 4.4-4.9%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add the element needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Being separated the intermediate obtained in described step a is Ureaphil.
In described step a, the reaction of urea and phosphoric acid is that urea solid and phosphoric acid solution react.
In described step a, the concentration of phosphoric acid is 68-73%.
In described step b, the reaction of intermediate and sodium hydroxide is that the sodium hydroxide solution obtained after intermediate solid and sodium hydroxide dissolve reacts.
In described step b, the cooling temperature of crystallisation by cooling is 18-23 DEG C.
Element in described step c needed for fennel is potassium, calcium, boron.
In described step c, fennel composite fertilizer special is chemical combination state Chemical Mixed Fertilizer, containing following N P and K chemical combination state structural formula in its composition:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
Beneficial effect of the present invention is: adopt phosphoric acid and urea reaction to prepare intermediate, re-use intermediate and sodium hydroxide to react and prepare SODIUM PHOSPHATE, MONOBASIC, the SODIUM PHOSPHATE, MONOBASIC product that this method is prepared stablizes and purity is higher, and the nutritive element added in mother liquor again needed for fennel, the special composite fertilizer of fennel just can be prepared by post-production process, make use of resource fully, reduce cost.
Embodiment
Below in conjunction with embodiment, technical scheme of the present invention is further described, but described in claimed scope is not limited to.
Reaction principle illustrates:
Urea and phosphatase reaction generate Ureaphil, and Ureaphil can form the ion double salt that a kind of positive and negative charge attracts mutually under containing phosphoric acid and hot environment, and under the environment that exists at phosphoric acid of Ureaphil ion double salt, H wherein
2nCONH
3 +ion and phosphoric acid close, form the intermediate-ion of C → O coordinate bond, be CO
5pN
2h
8 +ion, and then make in Ureaphil intermediate containing a large amount of H
2pO
4 -and CO
5pN
2h
8 +ion, when adding appropriate sodium ion, dihydrogen phosphate and sodium ion form biphosphate sodium crystal and are precipitated, and then add potassium ion and CO
5pN
2h
8 +ionic reaction, and displace part NH4+, make in solution containing CO
5pNH
4k
+double salt ion, by element adjustment, final drying filtrate can obtain composite fertilizer.Concrete reaction equation is as follows:
Reaction equation one:
H
2PO
3+CO(NH
2)
2—CO(NH
2)
2·H
3PO
4
Reaction equation two:
CO(NH
2)
2·H
3PO
4—H
2NCONH
3 ++H2PO
4 -
Reaction equation three:
H
2PO
4 -+Na
+—NaH
2PO
4
Reaction equation four:
Reaction equation five:
Below in conjunction with embodiment, the present invention is further elaborated:
Embodiment 1
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 68% phosphoric acid in molar ratio 1.3:1.6 mix, temperature is risen to 121 DEG C, stirring velocity is 60r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 3.4, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 86min, mother liquor being placed in cooling crystallizer control temperature is 18 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.4%, phosphorus pentoxide content is 7.4%, when sodium content is 4.4%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Embodiment 2
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 69% phosphoric acid in molar ratio 1.3:1.7 mix, temperature is risen to 122 DEG C, stirring velocity is 61r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 3.5, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 87min, mother liquor being placed in cooling crystallizer control temperature is 19 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.5%, phosphorus pentoxide content is 7.5%, when sodium content is 4.5%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Embodiment 3
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 70% phosphoric acid in molar ratio 1.3:1.8 mix, temperature is risen to 123 DEG C, stirring velocity is 62r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 3.6, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 88min, mother liquor being placed in cooling crystallizer control temperature is 20 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.6%, phosphorus pentoxide content is 7.6%, when sodium content is 4.6%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Embodiment 4
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 68-73% phosphoric acid in molar ratio 1.3:1.9 mix, temperature is risen to 124 DEG C, stirring velocity is 63r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 3.7, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 89min, mother liquor being placed in cooling crystallizer control temperature is 21 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.7%, phosphorus pentoxide content is 7.7%, when sodium content is 4.7%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Embodiment 5
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 71% phosphoric acid in molar ratio 1.3:1.9 mix, temperature is risen to 125 DEG C, stirring velocity is 64r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 3.8, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 91min, mother liquor being placed in cooling crystallizer control temperature is 22 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.8%, phosphorus pentoxide content is 7.8%, when sodium content is 4.8%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Embodiment 6
Prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, the method comprises the following steps:
A, reaction prepare intermediate: with urea and concentration be 72% phosphoric acid in molar ratio 1.3:2.1 mix, temperature is risen to 126 DEG C, stirring velocity is 65r/min stirring reaction 2.4h, separation obtain intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, controlling pH value is 4.1, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 94min, mother liquor being placed in cooling crystallizer control temperature is 23 DEG C of decrease temperature crystallines, carries out monitoring analysis to mother liquor simultaneously, when nitrogen content is 15.9%, phosphorus pentoxide content is 7.9%, when sodium content is 4.9%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add potassium, calcium, the boron needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
Below in conjunction with specific experiment example, product of the present invention and technique effect are further described.
Experimental example 1
The embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, in the fennel composite fertilizer special prepared detect according to GB1887-2002 standard, its result is as shown in table 1:
The detection of content of element of table 1 fennel composite fertilizer special of the present invention
| Test item | Criterion of acceptability | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | Embodiment 6 |
| N P and K | 30％ | 30.8％ | 31％ | 31.2％ | 31.4％ | 31.6％ | 31.8％ |
| Nitrogen | 15％ | 15.4％ | 15.5％ | 15.6％ | 15.7％ | 15.8％ | 15.9％ |
| Phosphorus | 7％ | 7.4％ | 7.5％ | 7.6％ | 7.7％ | 7.8％ | 7.9％ |
| Potassium | 8％ | 8％ | 8％ | 8％ | 8％ | 8％ | 8％ |
| Water content | ≤10％ | 4％ | 4％ | 4％ | 4％ | 4％ | 4％ |
By learning in table 1 that the constituent content of fennel composite fertilizer special prepared by the present invention not only reaches criterion of acceptability, and be much better than criterion of acceptability, illustrate that this composite fertilizer can meet the nutritive element demand of fennel, technique effect has progress significantly.
Experimental example 2
The embodiment of the present invention 1, embodiment 2, embodiment 3, embodiment 4, embodiment 5, embodiment 6, in the SODIUM PHOSPHATE, MONOBASIC product prepared detect by the detection method of GB25564-2010.
Table 2 SODIUM PHOSPHATE, MONOBASIC product purity of the present invention detects
As can be seen from Table 2, the SODIUM PHOSPHATE, MONOBASIC that technical scheme of the present invention is produced not only reaches criterion of acceptability, and the purity of product is also higher, illustrates that present method is prepared SODIUM PHOSPHATE, MONOBASIC product and had significant progress.
Claims (8)
1. prepare a method for SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special, it is characterized in that, the method comprises the following steps:
Intermediate is prepared in a, reaction: use urea and phosphoric acid in molar ratio 1.3:1.6-2.1 mix, and temperature is risen to 121-126 DEG C, and stirring velocity is 60-65r/min stirring reaction 2.4h, is separated and obtains intermediate;
B, preparation SODIUM PHOSPHATE, MONOBASIC: by intermediate and sodium hydroxide hybrid reaction, control pH value is 3.4-4.1, the mother liquor containing nitrogen, phosphorus, sodium is obtained after reaction 86-94min, mother liquor is placed in cooling crystallizer decrease temperature crystalline, monitoring analysis is carried out to mother liquor simultaneously, when nitrogen content is 15.4-15.9%, phosphorus pentoxide content is 7.4-7.9%, when sodium content is 4.4-4.9%, stop crystallization and filter, namely the filter cake obtained is SODIUM PHOSPHATE, MONOBASIC;
C, prepare fennel composite fertilizer special: in the filtrate obtained, add the element needed for fennel, and take the heat-up rate of 4 DEG C/min filtrate to be warming up to 28 DEG C to carry out drying, after dry 40min, when water content is 4%, obtain fennel composite fertilizer special finished product.
2. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: being separated the intermediate obtained in described step a is Ureaphil.
3. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: in described step a, the reaction of urea and phosphoric acid is that urea solid and phosphoric acid solution react.
4. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: in described step a, the concentration of phosphoric acid is 68-73%.
5. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: in described step b, the reaction of intermediate and sodium hydroxide is that the sodium hydroxide solution obtained after intermediate solid and sodium hydroxide dissolve reacts.
6. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: in described step b, the cooling temperature of crystallisation by cooling is 18-23 DEG C.
7. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: the element in described step c needed for fennel is potassium, calcium, boron.
8. the method preparing SODIUM PHOSPHATE, MONOBASIC coproduction fennel composite fertilizer special according to claim 1, is characterized in that: in described step c, fennel composite fertilizer special is chemical combination state Chemical Mixed Fertilizer, containing following N P and K chemical combination state structural formula in its composition:
wherein, the dotted line between carbon atom and Sauerstoffatom represents to there is coordinate bond between C atom and O atom.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| WO2000055104A1 (en) * | 1999-03-18 | 2000-09-21 | Oms Investments, Inc. | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| CN103787293A (en) * | 2014-01-24 | 2014-05-14 | 贵阳中化开磷化肥有限公司 | Method for preparing sodium dihydrogen phosphate by utilizing phosphoric acid by wet process |
-
2014
- 2014-09-19 CN CN201410479098.3A patent/CN104477866B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1060648A (en) * | 1990-10-08 | 1992-04-29 | 邢新华 | Polybasic fertilizer |
| WO2000055104A1 (en) * | 1999-03-18 | 2000-09-21 | Oms Investments, Inc. | Processes for preparing granular composite fertilizer compositions and products produced thereby |
| CN1583681A (en) * | 2004-05-24 | 2005-02-23 | 陈天骏 | Agricultural composite manure and preparing method thereof |
| CN103787293A (en) * | 2014-01-24 | 2014-05-14 | 贵阳中化开磷化肥有限公司 | Method for preparing sodium dihydrogen phosphate by utilizing phosphoric acid by wet process |
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Effective date of registration: 20170210 Address after: 550000 Huaxi District, Guizhou, Guiyang Applicant after: Guizhou University Applicant after: Phosphorylcholine group limited-liability company is opened in Guizhou Applicant after: Guizhou Ke Xinhua smelting company limited Address before: 550000 Huaxi District, Guizhou, Guiyang Applicant before: Guizhou University Applicant before: Zhonghuakai Phosphorous Chemical Fertilizer Co., Ltd., Guiyang Applicant before: Guizhou Ke Xinhua smelting company limited |
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