CN1043481A - Technology for calcium bydrogen phosphate forage - Google Patents
Technology for calcium bydrogen phosphate forage Download PDFInfo
- Publication number
- CN1043481A CN1043481A CN 89106617 CN89106617A CN1043481A CN 1043481 A CN1043481 A CN 1043481A CN 89106617 CN89106617 CN 89106617 CN 89106617 A CN89106617 A CN 89106617A CN 1043481 A CN1043481 A CN 1043481A
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- CN
- China
- Prior art keywords
- acid
- calcium
- filter
- normal pressure
- under normal
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/322—Preparation by neutralisation of orthophosphoric acid
Abstract
A kind of chemical novel process of producing calcium hydrogen phosphate fodder, used additives, water and ground phosphate rock are mixed with ore pulp, adding hydrochloric acid reacts and obtains filter acid, remove harmful elements such as fluorine, lead, cadmium, mercury through purification and obtain refining filter acid, add milk of lime in one step and calcium hydrophosphate fodder productive rate 100%, calcium chloride solution is renewable multiplexing or be processed into byproduct.Completely closed loop process does not have useless, poison gas, does not have useless, sewage, and is free from environmental pollution.Quality product and technico-economical comparison are all more advanced.
Description
The invention relates to a kind of chemical process technology of producing calcium hydrophosphate fodder, be specially adapted to lack the area of yellow phosphorus, sulfuric acid, phosphorus concentrate resource.
At present, the external calcium hydrophosphate fodder of producing, be that the raw material technological line (is seen " phosphorus, phosphoric acid and phosphoric acid salt present situation, application and development " generally with the thermal phosphoric acid of electric furnace process yellow phosphorus preparation with the wet technique refinement phosphoric acid that sulfuric acid divides the phosphorus decomposing concentrate to prepare, Chengdu, Sichuan chemical research designing institute, original text is stated from the 18th page of " inorganic chemicals industry " 1989 the 3rd phase).Yellow phosphorus, sulfuric acid, phosphorus concentrate are more in short supply and expensive chemical raw material.
Domestic, Yan Jiukaifa salt acid system precipitate phosphoric acid hydrogen calcium for many years, its Technology is two step neutralisations, the first step neutralization makes precipitated phosphate; The second step neutralization obtains calcium hydrophosphate fodder, about 3: 1 of phosphate fertilizer and feed weight ratio, and promptly the feed productive rate only 25%; The salt acid system " Cy-1 flow process " of Hubei Prov. Chemical Research Inst Yao, king two people exploitation, system adopts salting-out process to produce the intermediates calcium chlorophosphate earlier, reslurry adds the milk of lime metathesis and makes calcium hydrophosphate fodder and calcium chloride again, perhaps be that calcium phosphate dibasic anhydrous (is seen " research of calcium novel process is raised in the production of salt acid system " with the calcium chlorophosphate thermolysis, Hubei Prov. Chemical Research Inst, original text are stated from the 6th page of " inorganic chemicals industry " 1988 the 1st phase).The shortcomings of two step neutralisations are, with harmful element and amounts of insoluble iron such as fluorine, lead, cadmium, mercury, arsenic, aluminium, magnesium phosphoric acid salt are enriched in the precipitated phosphate, work the mischief to farm environment, and simultaneously the calcium hydrophosphate fodder productive rate is low, efficient is poor.Salt acid system " Cy-1 flow process ", technical process is unreasonable, and cold, heat exhaustion are bigger, and the calcium chloride problem is still unresolved, and industrial Practical significance is not good enough.
Purpose of the present invention, be to seek decomposing phosphate rock by chlorhydric acid selective reaction, step neutralization, multiplexing processing method and the condition of calcium chloride regeneration, exploitation salt acid system novel process, realization is a raw material with the Rock Phosphate (72Min BPL) raw ore, one the step in and calcium hydrophosphate fodder productive rate 100%, totally-enclosed working cycle, free from environmental pollution,
Content of the present invention and implementation method are as follows:
1. ore pulp reaction: used additives water glass, water and granularity are mixed with ore pulp (weight ratio in auxiliary agent, water, ore deposit is 1: 18: 45) for the ground phosphate rock of-1mm.With the ore pulp input reactor, stir and to be warming up to 50-70 ℃, add concentration evenly, lentamente and be 30% hydrochloric acid (for the 100-103% of theoretical amount), under the normal pressure sealing condition, reacted 10-20 minute.Reacted ore pulp separates after filtration and obtains filter acid (I), and filter cake is a white residue.The main chemical reactions formula is:
2. purifying: will filter acid (I) input reactor, and stir and be warming up to 35-50 ℃, (sodium-chlor is 1-1.3 with the weight ratio of filter acid (I): 100), reaction is 10-20 minute under condition of normal pressure to add fluorine precipitation agent sodium-chlor.With reacted filter acid (I) input ageing settling bath, the precipitation of ageing at normal temperatures 40-50 hour, the ageing clear liquor is the filter acid (II) after the defluorinate, and throw out is byproduct Na
2SiF
6; To filter acid (II) transportation flow through cation exchange resin column, filter acid at normal temperatures and pressures (II) contact harmful element such as the lead that can remove in 3-5 minute wherein, copper, cadmium, mercury and obtains purified and filter sour (III) with resin.
3. neutralization reaction: will filter acid (III) input reactor, under agitation condition, be warming up to 40-50 ℃, (milk of lime is 0.25-0.30 with the weight ratio of filter acid (III): 1) evenly, to add the milk of lime that concentration is 30-40% lentamente, reaction is 1-2 hour under condition of normal pressure, and the wet cake that filtering separation obtains is calcium hydrophosphate fodder (CaHPO after the oven dry down at≤75 ℃
42H
2O) product, filtrate are the calcium chloride solution of concentration 23-30%.Chemical equation is:
4. reclaiming: calcium chloride solution reclaims, and has two kinds of methods can be for selecting for use or having both use.The one, adopt prior art to be processed into byproduct calcium chloride; The 2nd, the method for reproduction that the present invention develops: to concentration 45-75%, (5-10kg/cm then pressurizes with the calcium chloride solution evaporation concentration
2) spray into thermal decomposition furnace, have water vapor to exist and＞500 ℃ of temperature under, pyrolysis takes place, the HCl of generation and Ca(OH)
2Can be after sharp separation is discharged for multiplexing.Chemical equation is:
The technological process synoptic diagram of invention sees accompanying drawing for details.Description of drawings is as follows:
Square frame is main production process;
Solid line is represented solid materials;
Long and short dash line express liquid material;
Dotted line is represented gas material.
The present invention compared with prior art, major advantage is it take the byproduct hydrochloric acid of chlor-alkali plant and rock phosphate in powder raw ore as raw material, in the step and calcium hydrophosphate fodder productive rate 100%; Calcium chloride is renewable multiplexing, and white residue can be made cement raw material; Closed circulating, without useless, poison gas, without useless, sewage, free from environmental pollution; Product quality and technical-economic index are all more advanced.
Embodiment is as follows:
With Yunnan Jian Shan Rock Phosphate (72Min BPL) and technical hydrochloric acid is raw material, and according to content of the present invention and method processing, the actual techniques index that obtains is as follows:
The main chemical composition of Rock Phosphate (72Min BPL) (%) is P
2O
533.04 CaO 43.00, F 2.77, and MgO 0.24, Fe
2O
30.60, Al
2O
31.24, SiO
214.00 Pb 0.0057, Cu 0.0036.
Drop into: ground phosphate rock 1000g, water glass 22g, water 400g, 30% hydrochloric acid 1882g, sodium-chlor (edible refined salt) 40g.
Output: calcium hydrophosphate fodder 863.07g, byproduct Sodium Silicofluoride 43.84g, calcium chloride (CaCl
22H
2O) 1133g or be reproduced multiplexing.
The key technical indexes: P
2O
5Transformation efficiency 98.23%, P
2O
5Recovery rate 98.01%, harmful element decreasing ratio 〉=97.72%.
Quality product:
Calcium hydrophosphate fodder quality index (%):
Byproduct quality top grade.
Also carried out processing experiment for five kinds with Hubei, Yunnan, other phosphorus ore samples such as external, only needed in the enforcement according to different phosphorus ore chemical compositions, correspondingly adjusted the material ratio that drops into, its final technical indicator is all close.
Claims (7)
1, a kind of chemical process technology of producing calcium hydrogen phosphate fodder adopts decomposing phosphate rock by chlorhydric acid, it is characterized in that following steps
11 used additives water glass, water and granularity are mixed with ore pulp (auxiliary agent, water, ore deposit weight ratio are 1: 18: 45) for the ground phosphate rock of-1mm, under normal pressure and 50-70 ℃, adding concentration is 30% hydrochloric acid, stirs and carries out reaction in 10-20 minute, separates obtaining filter sour (I).
12 filter acid (I) under normal pressure and 35-50 ℃, add sodium-chlor, stir and carry out reaction in 10-20 minute, obtain filter acid (II) through the ageing precipitation, and transportation flow obtains filter acid (III) through cation exchange resin column is refining again.
13 filter acid (III), under normal pressure and 40-50 ℃, adding concentration is the milk of lime of 30-40%, stirs and carries out reaction in 1-2 hour, separates obtaining the calcium hydrophosphate fodder product.
14 with the calcium chloride solution of product separation, evaporation concentration is HCl and Ca (OH) to concentration 50-75% in that steam and temperature＞500 a ℃ following thermolysis is arranged
2
2, according to the method for claim 11, it is characterized in that: adding hydrochloric acid content is the 100-103% of theoretical amount.
3, according to the method for claim 12, it is characterized in that: the amount that adds sodium-chlor is 1-1.30 with the weight ratio of filtering acid (I): 100.
4, according to the method for claim 12, it is characterized in that: the ageing precipitation is to carry out under normal pressure and temperature 40-50 hour.
5, according to the method for claim 12, it is characterized in that: filter acid (II) cation exchange resin column of flowing through is contact 3-5 minute under normal pressure and temperature.
6, according to the method for claim 13, it is characterized in that: adding concentration is that the milk of lime amount of 30-34% and the weight ratio of filter acid (III) are 0.25-0.30: 1.
7, according to the method for claim 14, it is characterized in that: the calcium chloride solution after concentrating should be forced into 5-10kg/cm
2Spray in the thermal decomposition furnace.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106617 CN1019473B (en) | 1989-08-31 | 1989-08-31 | Technology for calcium bydrogen phosphate forage |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89106617 CN1019473B (en) | 1989-08-31 | 1989-08-31 | Technology for calcium bydrogen phosphate forage |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043481A true CN1043481A (en) | 1990-07-04 |
| CN1019473B CN1019473B (en) | 1992-12-16 |
Family
ID=4856810
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89106617 Expired CN1019473B (en) | 1989-08-31 | 1989-08-31 | Technology for calcium bydrogen phosphate forage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1019473B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041812C (en) * | 1996-08-23 | 1999-01-27 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Production method for fodder grade calcium hydrogen phosphate |
| CN1051527C (en) * | 1997-06-10 | 2000-04-19 | 李怀然 | Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate |
| WO2015082468A1 (en) * | 2013-12-02 | 2015-06-11 | Ecophos S.A. | Source of phosphate for agriculture and the food industry |
| WO2015081973A1 (en) * | 2013-12-02 | 2015-06-11 | Ecophos S.A. | Source of phosphate for agriculture and the food industry |
| BE1021886B1 (en) * | 2013-12-02 | 2016-01-25 | Ecophos S.A. | NEW PHOSPHATE SOURCE FOR AGRICULTURE AND FOOD. |
-
1989
- 1989-08-31 CN CN 89106617 patent/CN1019473B/en not_active Expired
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041812C (en) * | 1996-08-23 | 1999-01-27 | 四川绵竹龙蟒矿物质饲料集团有限公司 | Production method for fodder grade calcium hydrogen phosphate |
| CN1051527C (en) * | 1997-06-10 | 2000-04-19 | 李怀然 | Combined depositting defluorinating method for fodder grade calcium hydrophosphate by wet process from phosphate |
| WO2015082468A1 (en) * | 2013-12-02 | 2015-06-11 | Ecophos S.A. | Source of phosphate for agriculture and the food industry |
| WO2015081973A1 (en) * | 2013-12-02 | 2015-06-11 | Ecophos S.A. | Source of phosphate for agriculture and the food industry |
| BE1021886B1 (en) * | 2013-12-02 | 2016-01-25 | Ecophos S.A. | NEW PHOSPHATE SOURCE FOR AGRICULTURE AND FOOD. |
| CN105939962A (en) * | 2013-12-02 | 2016-09-14 | 艾可弗斯股份有限公司 | Source of phosphate for agriculture and the food industry |
| JP2017505280A (en) * | 2013-12-02 | 2017-02-16 | エコフォス・エス・アー | Phosphate source for agriculture and food industry |
| US10464853B2 (en) | 2013-12-02 | 2019-11-05 | Ecophos S.A. | Source of phosphate for agriculture and the food industry |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1019473B (en) | 1992-12-16 |
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