CN1049403C - Improved method for producing feed grade calcium hydrophosphate - Google Patents
Improved method for producing feed grade calcium hydrophosphate Download PDFInfo
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- CN1049403C CN1049403C CN97106487A CN97106487A CN1049403C CN 1049403 C CN1049403 C CN 1049403C CN 97106487 A CN97106487 A CN 97106487A CN 97106487 A CN97106487 A CN 97106487A CN 1049403 C CN1049403 C CN 1049403C
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- phosphoric acid
- section
- wet process
- thick slurry
- molten
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- 239000011575 calcium Substances 0.000 title claims abstract description 28
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title abstract description 9
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 112
- 238000000034 method Methods 0.000 claims abstract description 60
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 56
- 238000000746 purification Methods 0.000 claims abstract description 19
- 230000008569 process Effects 0.000 claims description 52
- 238000006386 neutralization reaction Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 28
- 238000005516 engineering process Methods 0.000 claims description 21
- 239000012535 impurity Substances 0.000 claims description 19
- 239000000920 calcium hydroxide Substances 0.000 claims description 16
- 235000011116 calcium hydroxide Nutrition 0.000 claims description 16
- 238000001556 precipitation Methods 0.000 claims description 15
- 238000005352 clarification Methods 0.000 claims description 12
- 238000002203 pretreatment Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 1
- 238000005755 formation reaction Methods 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 29
- 239000011574 phosphorus Substances 0.000 abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 29
- 239000003337 fertilizer Substances 0.000 abstract description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 19
- 239000007788 liquid Substances 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000002994 raw material Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000012065 filter cake Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 230000003472 neutralizing effect Effects 0.000 description 6
- 239000013049 sediment Substances 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 3
- 235000011941 Tilia x europaea Nutrition 0.000 description 3
- 239000004571 lime Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 229910004261 CaF 2 Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000009313 farming Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000006115 defluorination reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 235000019700 dicalcium phosphate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000012066 reaction slurry Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Fodder In General (AREA)
- Removal Of Specific Substances (AREA)
- Fertilizers (AREA)
Abstract
The invention discloses an improved method for producing feed calcium hydrophosphate, which has the core that wet-process phosphoric acid, particularly medium-low quality wet-process phosphoric acid, is purified by a combined purification process to meet the requirement of producing high-quality feed grade calcium hydrophosphate, the feed-fertilizer ratio reaches about 9, and the technical improvement requirement of the existing phosphorus feed industry is met.
Description
The present invention relates to the phosphoric acid by wet process is the method for raw material production calcium hydrophosphate fodder.
The crowd knows known, produces calcium hydrophosphate fodder take phosphoric acid by wet process as raw material, and present industrial two sections neutralisations of milk of lime that generally adopt, the main purpose of one section neutralization are to purify, and particularly defluorination makes one section clear liquid reach P
2O
5The requirement of/F 〉=300.Because the source difference of raw material phosphoric acid by wet process, reach with milk of lime neutralization and to purify when requiring, one section neutral terminal point PH need be controlled between 2.8～3.5, this moment, correspondingly the phosphorus in one section filter cake using of as fertilizer sources will account for the 30-45% of total phosphorus in the phosphoric acid by wet process, i.e. " fodder/ fertilizer ratio " lower (1.2～2.3), this is for being the factory of target product with the feed grade product, this kind technology is extremely uneconomical, particularly along with the dilution day by day of raw-material continuous rise in price and phosphorus ore grade, this operational path has been difficult to take into account the requirement of economy and steady quality two aspects, the development that has jeopardized the phosphorus fodder industry.For this reason, branch of industry wishes relevant scientific worker, proceed from the reality, take in the phosphoric acid by wet process of low-grade phosphorus ore gained as raw material, do not changing or seldom changing under the prerequisite of full-scale plant, the production technology of existing factory is transformed.Promote the development of phosphorus feed industry.
Purpose of the present invention is the shortcoming that overcomes prior art, and in conjunction with the phosphorus ore grade reality of dilution day by day, developed a kind of improving one's methods of calcium hydrophosphate fodder of producing, can make the phosphorus about 90% in the phosphoric acid by wet process be used to produce calcium hydrophosphate fodder (being that fodder/ fertilizer ratio reaches about 9), satisfy branch of industry old technological transformation requirement.
Design of the present invention is such:
The inventor finds: at present industrial used take phosphoric acid by wet process as raw material, the technology that adopts two sections neutralisations of milk of lime to produce calcium hydrophosphate fodder, the reason that its fodder/ fertilizer ratio is littler is mainly due to (namely require the P in the phosphoric acid for purifying phosphoric acid in " one section neutralization "
2O
5/ F 〉=300) have to so that " " 30～45% phosphorus is made cost in loss, the key that therefore will improve fodder/ fertilizer ratio is to improve in one section and technology, namely must solve " loss " of as far as possible managing to reduce phosphorus in the wet phosphoric acid purifying process under the prerequisite that satisfies the wet phosphoric acid purifying requirement.
The contriver imagines employing by " pre-treatment removal of impurities, one section neutralization purification, clarification and thick slurry return molten " three combination purification techniques (abbreviation combination purification technique) that technological process constitutes, transform " the one section neutralization " purification process in the existing industry, by combination purification technique of the present invention, can make in the phosphoric acid by wet process about 90% phosphorus enter two sections neutralizations and be used to produce the high-quality feed calcium hydrophosphate, thereby improve fodder/ fertilizer ratio widely.
The present invention also is achieved in that
The present invention has not only solved the purifying problem of phosphoric acid by wet process, and has solved the problem of high fodder/ fertilizer ratio by combination purification technique, and specific implementation process is summarized as follows:
(1), 80% impurity is removed, and guarantee phosphorus " loss " less than 10% in the phosphoric acid by wet process by " pre-treatment removal of impurities " technology;
(2) by " one section neutralization purifies " technology, can make wet process phosphoric further purification to the requirement of producing the high-quality feed calcium hydrophosphate, even phosphoric acid by wet process reaches P
2O
5The purification requirement of/F 〉=300;
(3) by " clarification is returned molten with thick slurry " technology, obtain the calcium hydrophosphate fodder of pure phosphoric acid clear liquid (not carrying fluorine-containing solid sediment secretly) pump to two section neutralization chamber production high-quality, the thick slurry of defecator bottom then pump to the preliminary treatment deblending slot, dissolve with the raw material phosphoric acid by wet process, can all reclaim the phosphorus (this is the core place that thick slurry returns molten technology) in the thick slurry;
Operate again and again according to the step of (1)-(3) then, batch operation of implementing phosphoric acid by wet process purifies.
Phosphoric acid after the purification can utilize in two sections of the prior art and technology easily, produces fine calcium hydrophosphate fodder product.
In a word, by adopting combination purification technique of the present invention, the high-quality of not only having implemented phosphoric acid by wet process purifies, and guaranteeing that phosphoric acid by wet process reaches under the prerequisite that purifies requirement, can make phosphorus contained in the phosphoric acid by wet process be used to produce the high-quality feed calcium monophosphate product more than 90%, guarantee that promptly fodder/ fertilizer ratio reaches more than 9.
Point out in passing: " clarification is returned molten with thick slurry " technology, can also return molten technology generations with " press filtration and filter cake " replaces, but the latter must establish a settler again, to guarantee to obtain purified phosphoric acid clear liquid (not carrying fluorine-containing solid sediment secretly), a spot of thick slurry in settler bottom then pumps in the pressure filter and filters once more.
Detailed content of the present invention such as following:
The present invention mainly comprises four technological processs, wherein first three technology is core content of the present invention, they have constituted the purification process of phosphoric acid by wet process, the 4th technology is milk of lime neutralisation productive target product high-quality feed calcium hydrophosphate, it is the indispensable content of production technique, but it belongs to prior art (in the abbreviation and technology, down with), and particular content is described below:
(1) pre-treatment impurity removal process
In pretreatment tank: at first will return molten " thick slurry " again dissolving in phosphoric acid by wet process, can all reclaim phosphorus contained in the thick slurry, regulate the PH=2.2 of pretreatment tank～2.5 with milk of lime then, under this PH condition:
1. the existing 70-85% of the fluorine in the phosphoric acid by wet process is with CaF
2Form be removed;
2. impurity such as iron, aluminium is existing is removed with phosphatic form more than 80%;
3. the phosphoric acid with calcium " combination " not yet forms precipitation, still stays aqueous phase (namely under the PH=2.2-2.5 condition, calcium ion not yet forms the calcium monohydrogen phosphate precipitation)
In a word, by the pH value of regulation and control pretreatment tank, make the loss of pretreatment stage phosphorus reduce to minimum, general less than 10%.
In (2) one sections and process for purifying
In one section neutralization chamber, with the further purification and impurity removal of milk of lime, the PH=2.8 of regulation and control neutralization chamber～3.3 can be with the fluorine in the phosphoric acid by wet process, further with CaF in one section neutralization chamber for the phosphoric acid by wet process of having removed 80% left and right sides impurity through preliminary treatment
2Form be removed, reach P
2O
5The purification requirement of/F 〉=300.The impurity such as other iron, aluminium are also further eliminated with phosphatic form, are attended by simultaneously more CaHPO
4Precipitation.
(3) clarification is returned molten technology with thick slurry
The system that one section neutralization is purified gained places clarifier, leaves standstill clarification 24-72hr, and upper clear supernate pumps in two sections neutralization chambers, and the thick slurry of bottom then returns to pretreatment tank, again dissolving.
By (1), (2), (3) as seen, dissolved (being that thick slurry returns molten technology), therefore do not had the loss of phosphorus in (2), (3) because the present invention returns one section resultant throw out of neutralization in the pretreatment tank and by phosphoric acid by wet process with the form of thick slurry.
(4) produce the calcium hydrophosphate fodder product in and technology (in the abbreviation and technology)
In two sections neutralization chambers, inject the upper clear supernate from technology (3) clarifier, regulate the PH=6.2 of two sections neutralization chambers～6.8 with lime slurry neutralization then, under the condition of this PH, the whole phosphorus in the system are with CaH-PO
4The form Precipitation obtains the said calcium hydrophosphate fodder product of the present invention (because two sections neutralization production calcium hydrophosphate fodders are present industrial routine techniques, so will not give unnecessary details) through separation.
Further illustrate content of the present invention below in conjunction with accompanying drawing.
Accompanying drawing is for producing the process schematic representation of high-quality feed calcium hydrophosphate
Wherein: 1---pretreatment tank
2---one section neutralizing well
3---settler
4---two sections neutralizing wells
5---filter-pressing device
In pretreatment tank 1:
At first will under agitation dissolve with phosphoric acid by wet process from the thick slurry of clarifier 3 bottoms, regulate the in advance PH=2.2 of place's groove～2.5 with milk of lime then, the fluorine 70-85% in the phosphoric acid by wet process is with CaF at this moment2Shape Formula is removed the impurity such as (precipitation), 80% iron, aluminium and is removed (precipitation) with phosphatic form, removes after filtration Go the clear liquid behind the sediment to pump in one section neutralization chamber.
In one section neutralization chamber 2:
Pump into the clear liquid from pre-place groove, with the PH=2.8 of one section neutralization chamber of milk of lime regulation and control～3.3, under the condition of this PH:
(1) in the phosphoric acid by wet process fluorine further with CaF2Form be removed, and reach P2O
5/ F 〉=300 clean Change requirement.
(2) impurity such as iron, aluminium is then further eliminated with phosphatic form.
(3) be attended by more CaHPO4Precipitation can play the carrier band sedimentation and remove other sedimentary effect.
In clarifier 3:
Pump into the system of a neutralization chamber gained, leave standstill clarification 24-72 hour, upper clear supernate pumps in two sections In groove 4, the thick stock pump in bottom returns to the pretreatment tank 1 molten.
In two sections neutralization chambers 4:
Will be from the upper clear supernate of clarifier 3, the PH=6.2～6.8. that regulates two sections neutralization chambers with milk of lime is under the condition of this PH, and the phosphorus in the purifying phosphoric acid is all with CaHPO4The form precipitation, then with the system pump extremely In the filter-pressing device.
In filter-pressing device 5
In filter-pressing device 5, from the system of two sections neutralization chambers 4, through press filtration, the filter cake of acquisition is drying again Get product after the post processings such as screening.
In sum as seen: by the said combination purification technique of the present invention, not only with phosphoric acid by wet process, particularly in inferior wet phosphoric acid purifying to P2O
5The requirement of/F 〉=300, and with in the phosphoric acid by wet process more than 90% Phosphorus (except the preliminary treatment impurity removal process has the phosphorus loss of less than 10%, not having the loss of phosphorus in all the other technologies) For the production of the high-quality feed calcium hydrophosphate, namely fodder/ fertilizer ratio reaches more than 9, thereby has satisfied existing phosphorus feed industry The technological transformation requirement.
Produce further simple and clear content of the present invention of example below in conjunction with one:
The phosphoric acid by wet process that makes with clear level ground phosphorus ore is a raw material, handle according to technical process of the present invention, as control pre-treatment terminal point PH=2.5, in one section and terminal point PH=3.3, in two sections and terminal point PH=6.6～6.8 o'clock, after five cyclical operations (thick slurry or filter cake return molten processing), system reaches stable state (equilibrium state).Its result is described below:
(1) in pretreatment tank
Drop into earlier the phosphoric acid by wet process 1m that is made by clear level ground phosphorus ore
3(wherein contain P
2O
5185g/L, F 15.3g/L, Fe
2O
38.7g/L, Al
2O
310.4g/L, Ca 10.2g/L), pump into again from the molten thick slurry 0.4m of returning of bottom of clarifier
3(wherein contain P
2O
582.2g/L, F 5.98g/L, Fe
2O
33.0g/L, Al
2O
33.75g/L), make solid material contained in thick slurry stirring and dissolving (consisting of the solution of homogeneous) under phosphatizing, regulate pretreatment tank terminal point PH=2.5 with milk of lime then, the fluorine in the solution existing 83.4% is with CaF at this moment
2Form remove (precipitation), impurity such as iron, aluminium existing 81.6% are removed (precipitation) with phosphatic form, by removing by filter sediment (filter cake), acquisition preliminary treatment clear liquid (abbreviation clear liquid) 2.1m
3(wherein contain P
2O
595.7g/L, F 1.38g/L, Fe
2O
30.81g/L, Al
2O
31.0g/L) enter in one section neutralization chamber, do the fertile utilization of farming after the filter cake drying.
(2) in one section neutralizing well
Clear liquid 2.1m with the pretreatment process gained
3With the terminal point PH=3.3 of one section neutralization chamber of lime slurry neutralization regulation and control, at this moment, fluorine residual in the clear liquid is further with CaF
2Form be removed (precipitation), the impurity such as iron, aluminium are further eliminated (precipitation) with phos-phate forms, and mix with more CaHPO is arranged
4Precipitation contains this then solid system and pumps in the clarifier.
(3) in settler
From containing of one section neutralization chamber of solid system, in clarifier, to leave standstill clarification and (be advisable to clarify 48 hours) more than 24 hours, top can obtain clear liquid (being purifying phosphoric acid) 2.24m
3(it consists of: P
2O
575g/L, F0.23g/L, P
2O
5=326) pump into two sections neutralization chambers and produce the calcium hydrophosphate fodder product, the thick slurry 0.4m of bottom
3Then delivering to pretreatment tank returns molten.By (2), (3) as seen, there is not the loss of phosphorus in the two-step.
(4) in two sections neutralizing wells
Will be from clear liquid (the being purifying phosphoric acid) 2.24m on clarifier top
3, further regulate the terminal point PH=6.6 of two sections neutralization chambers～6.8 with milk of lime, the phosphorus in this moment purifying phosphoric acid is all with CaHPO
4Form precipitation, after filtration, washing, dry, pulverize, screening, (its ratio of components is: P to obtain 400kg calcium hydrophosphate fodder product
2O
541%wt, Ca 23.8%wt, F 0.126%wt).
According to above-mentioned production instance operation, P in the product
2O
5With respect to the total P in the phosphoric acid by wet process
2O
5, its yield reaches 90.8%.
The phosphoric acid by wet process that makes with the Kaiyang phosphorus ore is a raw material, handles control pre-treatment terminal point PH=2.2 according to technical process of the present invention, in one section and terminal point PH=2.8, in two sections and terminal point PH=6.2～6.4 o'clock, after five cyclical operations, system reaches stable state.Its result is described below:
(1) in pretreatment tank
Drop into earlier the phosphoric acid by wet process 1m that derives from the ore deposit, Kaiyang
3(wherein contain P
2O
5204g/L, F 12.9g/L, Fe
2O
35.2g/L, Al
2O
35.8g/L, Ca 8.9g/L), pump into again from the molten thick slurry 0.34m that returns at the bottom of the clarifier
3(wherein contain P
2O
596.6g/L, F 4.05g/L, Fe
2O
32.4g/L, Al
2O
32.7g/L), make the dissolving of thick slurry, regulate again the PH=2.2 of system with milk of lime, obtain preliminary treatment clear liquid 1.92m after removing after filtration sediment
3(wherein contain P
2O
5114.6g/L, F 0.94g/L, Fe
2O
30.45g/L, Al
2O
30.49g/L) enter in one section neutralization chamber, do the fertile use of farming after the filter cake drying.
(2) in one section neutralizing well
1.92m from pretreatment process
3Clear liquid continues with the milk of lime neutralization, regulation and control terminal point PH=2.8, and further being removed with precipitated form of impurity such as F, the Fe in the solution, Al pumps into this reaction slurry in the settler at this moment.
(3) in settler
In one section and gained contain solid system, after clarification in 36 hours, obtain upper clear supernate (being purifying phosphoric acid) 2.05m
3(wherein contain P
2O
592.2g/L, F 0.264g/L, P
2O
5/ F=349) and bottom thick slurry 0.34m
3, two strands of materials are pumped into respectively in two sections neutralization chambers and the pretreatment tank.
(4) in two sections neutralizing wells
2.05m from clarifier top
3Clear liquid (being purifying phosphoric acid) is further used lime slurry neutralization, until the terminal point PH=6.2 of system～6.4 end, after filtration, (it consists of P can to obtain 454kg calcium hydrophosphate fodder product after the drying
2O
541.5%wt, Ca 24.2%wt, F 0.119%wt).
In the present embodiment, P in the product
2O
5With respect to the total P in the phosphoric acid by wet process
2O
5, its yield reaches 92.3%.
Claims (1)
1. produce improving one's methods of calcium hydrophosphate fodder for one kind, comprise that mainly the purification of phosphoric acid by wet process and milk of lime neutralisation produce the secondary calcium phosphate two parts, the purification that it is characterized in that said phosphoric acid by wet process is a combination purification technique by " pre-treatment removal of impurities section neutralization purifications-clarification and thick slurry is one by one returned molten " three technological process formations:
Said pre-treatment impurity removal process mainly comprises following two steps: at first will dissolve with phosphoric acid by wet process from the molten thick slurry that returns of clarification operation, form the solution of a homogeneous, neutralize with milk of lime then, the pH=2.2 of regulator solution～2.5, precipitation is removed in the solution about 80% impurity, after filtration in the phosphoric acid solution pump to of disgorging section and cleaning section;
In said one section and process for purifying mainly be to regulate the pH=2.8 of the phosphoric acid solution after the preliminary treatment removal of impurities～3.3 with milk of lime, phosphoric acid solution is further purified, reach P
2O
5The purification requirement of/F 〉=300, the solid system pump that contains of gained is processed to clarifying operation;
It mainly is to make in one section and the solid system that contains of cleaning section gained leaves standstill clarification 24～72 hours in settler that said clarification and thick slurry return molten technology, in the upper clear supernate pump to two of gained section and operation produce secondary calcium phosphate, the thick stock pump of gained carries out thick slurry to pre-treatment removal of impurities operation and returns molten processing.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106487A CN1049403C (en) | 1997-06-25 | 1997-06-25 | Improved method for producing feed grade calcium hydrophosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97106487A CN1049403C (en) | 1997-06-25 | 1997-06-25 | Improved method for producing feed grade calcium hydrophosphate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1172068A CN1172068A (en) | 1998-02-04 |
| CN1049403C true CN1049403C (en) | 2000-02-16 |
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ID=5168725
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97106487A Expired - Fee Related CN1049403C (en) | 1997-06-25 | 1997-06-25 | Improved method for producing feed grade calcium hydrophosphate |
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| Country | Link |
|---|---|
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089250A (en) * | 1992-12-26 | 1994-07-13 | 张小平 | A kind of method and device of producing calcium hydrogen phosphate fodder |
| CN1118332A (en) * | 1994-09-08 | 1996-03-13 | 陈书香 | Wet process for preparing calcium hydrophosphate fodder from phosphoric acid |
| CN1136403A (en) * | 1996-02-01 | 1996-11-27 | 邯郸市磷肥厂 | Method for producing fodder grade calcium hydrophosphate by wet phosphoric acid |
-
1997
- 1997-06-25 CN CN97106487A patent/CN1049403C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1089250A (en) * | 1992-12-26 | 1994-07-13 | 张小平 | A kind of method and device of producing calcium hydrogen phosphate fodder |
| CN1118332A (en) * | 1994-09-08 | 1996-03-13 | 陈书香 | Wet process for preparing calcium hydrophosphate fodder from phosphoric acid |
| CN1136403A (en) * | 1996-02-01 | 1996-11-27 | 邯郸市磷肥厂 | Method for producing fodder grade calcium hydrophosphate by wet phosphoric acid |
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| Publication number | Publication date |
|---|---|
| CN1172068A (en) | 1998-02-04 |
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