CN87102156A - A kind of novel method of producing calcium hydrogen phosphate fodder - Google Patents
A kind of novel method of producing calcium hydrogen phosphate fodder Download PDFInfo
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- CN87102156A CN87102156A CN87102156.0A CN87102156A CN87102156A CN 87102156 A CN87102156 A CN 87102156A CN 87102156 A CN87102156 A CN 87102156A CN 87102156 A CN87102156 A CN 87102156A
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- extraction agent
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Abstract
The present invention be a kind of be the novel method that starting raw material is produced calcium hydrogen phosphate fodder with calcium superphosphate.It by extract, purify, once neutralize, separate, chemical process such as drying, pulverizing realizes.Produce calcium hydrogen phosphate fodder with present method and have characteristics such as technical process is short, waste water is few, product yield height.
Description
The present invention is a kind of novel method of producing calcium hydrogen phosphate fodder.
" the 54th page of method of having put down in writing with mono-calcium phosphate production secondary calcium phosphate of inorganic chemicals industry handbook volume two of volumes such as Tianjin chemical research institute, this method is calcium superphosphate to be added water extraction make mono-calcium phosphate solution, after the defluorinate, neutralize with milk of lime, neutralization divides two sections and carries out, first section gets the fertilizer secondary calcium phosphate, and second section gets the feed secondary calcium phosphate.This method is produced calcium hydrogen phosphate fodder and is adopted two sections neutralizations, and technical process is long, also have partly fertilizer grade product in the product, thereby the feed grade product yield is low (with P
2O
5Collect rate=62.5%).
Task of the present invention is that studying a kind of is starting raw material with calcium superphosphate, and product all is that feed secondary calcium phosphate, product yield height are (with P
2O
5Collect rate=66.7～91.6%), the novel method of the technological process of production is short, extraction agent can be recycled production calcium hydrogen phosphate fodder.
Feature of the present invention is to be raw material with calcium superphosphate, one of aqueous solution such as the muriate of selection potassium, sodium, ammonium or nitrate, water, imitative seawater, dilute hydrochloric acid are made extraction agent, be added in the calcium superphosphate, extract mono-calcium phosphate wherein, this extraction liquid is through after purifying, once neutralize with lime milk solution, obtain the calcium hydrogen phosphate fodder precipitation.
Of the present invention being described in detail as follows:
1. extraction: one of aqueous solution such as selective chlorination potassium, sodium-chlor, ammonium chloride, saltpetre, SODIUMNITRATE, ammonium nitrate, water, imitative seawater, dilute hydrochloric acid are made extraction agent, are added in the calcium superphosphate, extract mono-calcium phosphate wherein.The extraction agent consumption is (weight ratio) calcium superphosphate/extraction agent (with potassium, sodium, an ammonium restatement)=1: 0.02～0.4; Water is 1: 1～6 for the extraction agent consumption.The extraction agent concentration expressed in percentage by weight is: muriate is 2～9%, nitrate is 7～11%, dilute hydrochloric acid is about 0.70%, imitative seawater is a sodium chloride-containing about 2%.50～80 ℃ of extraction temperature.2.5 hours extraction time.Separate then, discard residue phosphogypsum, obtain the extraction liquid of phosphoric acid one calcium.Extractive reaction following (following represent potassium, sodium, ammonium) with R:
(1), extracts with aqueous chloride solution
(2), with nitrate aqueous solution extractive reaction formula:
(3), water extractive reaction formula:
(4), with imitative seawater (the 0.72%NaCl aqueous solution) extractive reaction formula muriate extractive reaction formula.
(5), with diluted hydrochloric acid aqueous solution extractive reaction formula:
2. purification extraction liquid: contain impurity such as arsenic that calcium superphosphate brings, fluorine, sulfate radical in the extraction liquid, when producing calcium hydrogen phosphate fodder, must give earlier removing.
(1), dearsenification: in extraction liquid, add the sodium sulphite dearsenification.The add-on of sodium sulphite is 0.6～1.2% of a calcium superphosphate amount, and the dearsenification temperature is 75 ± 5 ℃, stirs about 1 hour of sedimentation, waste 30 minutes.Its reaction is as follows:
(2), defluorinate: the extraction liquid after the dearsenification adds potassium primary phosphate and silica powder defluorinate.The add-on of potassium primary phosphate is 0.8～1.8% of a calcium superphosphate amount, and the silica powder add-on is 0.5～3% calcium superphosphate amount, and the defluorinate temperature is controlled at 65～80 ℃, stirs 30 minutes, leaves standstill waste about 1 hour.Its reaction formula is as follows:
(3), engaging sulphate: the extraction liquid behind dearsenification, the fluorine, add an amount of barium dihydrogen phosphate solution, stirred 20 minutes, leave standstill and remove slag, remove sulfate radical.React as follows:
3. neutralization: the extraction liquid after will purifying while hot adds lime milk solution and once neutralizes, and neutralization reaction control pH value made the PO in the extraction liquid at 5.5～6.5 o'clock
-3 4Precipitate fully.Through separating filtrate is extraction agent, recycles aborning.Be the calcium hydrogen phosphate fodder product after solid phase drying, the pulverizing.Its reaction formula is as follows:
(1), to the neutralization reaction formula of muriate extraction liquid:
(calcium hydrogen phosphate fodder (III)) (extraction agent (VI))
(2), to the neutralization reaction formula of nitrate extraction liquid:
(3), to the neutralization reaction formula of water extract:
(4), to the neutralization reaction formula of dilute hydrochloric acid extraction liquid:
It is as follows to obtain quality product by the inventive method: (subordinate list 1)
The present invention compares with former method, and following two advantages are arranged:
1. the present invention selects for use the aqueous solution such as muriate, nitrate, dilute hydrochloric acid of potassium, sodium, ammonium to make extraction agent, can be recycled in process of production, thereby lacks than the waste water of former method, reduces environmental pollution.
2. compare with technology during the present invention adopts once and in technology and former method two sections, not only technical process is lacked, and product yield and raw material availability are all much higher than former method.(by the embodiment data preparation) sees the following form:
Embodiment 1
1. take by weighing calcium superphosphate and (contain effective P
2O
516%) 300 grams are put in the beaker, add and contain NH
4The aqueous solution 2000ML of Cl 5% starts agitator at 65 ℃ and stirred 2.5 hours.
2. filter above-mentioned extraction liquid, waste.
3. above-mentioned filtrate is heated to 80 ℃, adds Na
2The S5 gram stirred 20～30 minutes, left standstill 1 hour, and separation is removed slag, and stays filtrate.
4. above-mentioned filtrate is heated to 80 ℃, adds KH
2PO
45 grams, silica powder 30～50 grams stirred 20 minutes, left standstill 1 hour, filtered, removed slag, and stayed filtrate.
5. with an amount of Ba(H
2PO
4)
2Solution is added on above-mentioned filtrate, adds gac 3 grams while hot, stirs leaching filtrate, waste 10～20 minutes.
6. saturated lime milk solution is gently added in the above-mentioned filtrate, the limit edged stirs, and is 6.5 o'clock until pH value, stops to feed in raw material, and produces a large amount of CaHPO this moment
42H
2The O precipitation.
7. the above-mentioned precipitation of centrifugation, with the clear water washing for several times, until washing lotion with 0.5% AgNO
3Till the solution inspection is haze-free.
8. above-mentioned filter cake is being dried below 60 ℃.
9. the secondary calcium phosphate porphyrize of oven dry is crossed 100 mesh sieves, be loaded on then in the plastics bag, get 100 gram products.Quality product is by analysis shown in subordinate list 1.
Embodiment 2
1. take by weighing calcium superphosphate (effective P
2O
5Content 16%), 1 kilogram, put in the plastic tank, add and contain NH
47000 milliliters of the aqueous solution of Cl5.5% stir extraction 2.5 hours down at 65 ℃.
2. filter above-mentioned extraction liquid, discard filter cake.
With above-mentioned filtrate purifying treatment with embodiment 1.
4. gently add lime milk solution in the filtrate behind dearsenification, defluorinate, engaging sulphate, adding to pH value is 6.5, and the limit edged stirs, and produces a large amount of CaHPO this moment
42H
2The O precipitation.
5. the above-mentioned precipitation of centrifugation adds the clear water washing for several times, until washing lotion with 0.5%AgNO
3Till the solution inspection is haze-free.
6. 100 mesh sieves are being dried, pulverize, crossed to above-mentioned filter cake below 60 ℃, packing gets product 270 and restrains then.
Quality product is by analysis shown in subordinate list 1.
Embodiment 3
Present embodiment is the synthesis result of 17 embodiment, is listed in the table below.Now be described as follows:
1. calcium superphosphate (effective P
2O
3Content 16%) charging capacity is 300 grams, and the extraction agent consumption is 2000 milliliters, and the extraction time is 2.5 hours, single extraction.
2. dearsenification, defluorinate, engaging sulphate are operated identical with embodiment 1.
3. neutralization operation is with embodiment 1.
4. wash three times with five times of tap water after getting product, oven dry then, crushing screening is with embodiment 1.
Claims (4)
1, a kind of is the novel method that starting raw material is produced calcium hydrogen phosphate fodder with calcium superphosphate, it is by extraction, purify, neutralization, separate, dry, chemical processes such as pulverizing make, it is characterized in that to select Repone K, sodium-chlor, ammonium chloride, SODIUMNITRATE, ammonium nitrate, water, imitative seawater, one of aqueous solution such as dilute hydrochloric acid are made extraction agent, be added in the calcium superphosphate, extract phosphoric acid-calcium wherein, this extraction liquid is through dearsenification, defluorinate, behind the scavenging process such as engaging sulphate, once neutralize with lime milk solution, obtain the calcium hydrogen phosphate fodder precipitation, filtrate after the separation is extraction agent, recycles in process of production.Its reaction following (following represent potassium, sodium or ammonium) with R:
Extractive reaction
(1), do the reaction of extraction agent with aqueous chloride solution:
(2), make the reaction formula of extraction agent with nitrate aqueous solution:
(3), use water as the reaction formula of extraction agent:
(4), the reaction formula of making extraction agent with imitative seawater is made the reaction formula of extraction agent with aqueous chloride solution.
(5), make the reaction formula of extraction agent with dilute hydrochloric acid:
(1), to the neutralization reaction formula of muriate extraction liquid:
(3), to the neutralization reaction formula of water extract:
(4), to the neutralization reaction formula of dilute hydrochloric acid extraction liquid:
2, according to the extraction process of the novel method of the said production calcium hydrogen phosphate fodder of claim 1, it is characterized in that extraction agent consumption (weight ratio) calcium superphosphate/extraction agent is (with Na
+, K
+Or NH
+ 4Meter) 1: 0.02～0.4, extraction agent (it is outer to dewater) concentration is 1～17%, 50～80 ℃ of extraction agent controlled temperature.
3, according to scavenging process such as the dearsenification of the said novel method of claim 1, defluorinate, engaging sulphates, it is characterized in that: use the sodium sulphite dearsenification, amount of sodium sulfide is 0.6～1.2% of a calcium superphosphate amount, and the dearsenification temperature is 75 ± 5 ℃.Reaction is:
With silica powder and potassium primary phosphate defluorinate, the consumption of silica powder and potassium primary phosphate is respectively 0.5～3% and 0.8～1.8% of calcium superphosphate, and the defluorinate temperature is 65～80 ℃, and reaction formula is:
With an amount of barium dihydrogen phosphate engaging sulphate, reaction formula is:
4, according to the said novel method of claim 1 with once neutralize extraction liquid after purifying of lime milk solution, it is characterized in that neutralization reaction control degree pH value 5.5～6.5, makes the PO in the extraction liquid
-3 4Become the calcium hydrogen phosphate fodder precipitation fully.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87102156A CN1008436B (en) | 1987-03-16 | 1987-03-16 | Production technique of calcium superphosphate fodder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN87102156A CN1008436B (en) | 1987-03-16 | 1987-03-16 | Production technique of calcium superphosphate fodder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN87102156A true CN87102156A (en) | 1988-09-14 |
| CN1008436B CN1008436B (en) | 1990-06-20 |
Family
ID=4813844
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN87102156A Expired CN1008436B (en) | 1987-03-16 | 1987-03-16 | Production technique of calcium superphosphate fodder |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1008436B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744769A (en) * | 2017-02-21 | 2017-05-31 | 瓮福（集团）有限责任公司 | A kind of method that calcium coproduction sulphur ammonium is raised in utilization ardealite production |
-
1987
- 1987-03-16 CN CN87102156A patent/CN1008436B/en not_active Expired
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744769A (en) * | 2017-02-21 | 2017-05-31 | 瓮福（集团）有限责任公司 | A kind of method that calcium coproduction sulphur ammonium is raised in utilization ardealite production |
| CN106744769B (en) * | 2017-02-21 | 2020-10-30 | 瓮福（集团）有限责任公司 | Method for producing feed calcium and co-producing ammonium sulfate by using phosphogypsum |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1008436B (en) | 1990-06-20 |
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