CN104773716A

CN104773716A - Method used for decomposing middle and low-grade phosphorus ore with hydrochloric acid to prepare feed sodium phosphate calcium

Info

Publication number: CN104773716A
Application number: CN201410010019.4A
Authority: CN
Inventors: 姚鼎文; 姚宁
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-01-09
Filing date: 2014-01-09
Publication date: 2015-07-15

Abstract

The invention discloses a method used for decomposing middle and low-grade phosphorus ore with hydrochloric acid so as to prepare feed-grade sodium phosphate calcium. According to the method, chloride calcium phosphate is prepared firstly, and is purified and mixed with table salt; and an obtained mixture is roasted at 800 to 1200 DEG C. Generated calcium chloride is decomposed with sulfuric acid so as to prepare calcium sulfate whisker materials; generated HCl is recycled; and associated elements, such as rare earth elements, iodine, and uranium, in phosphorus ore are enriched and extracted from a salting out mother liquor of a closed circulation.

Description

Hydrochloric acid decomposing medium and low grade manufactures the method for feed sodium phosphate calcium

Technical field

The invention belongs to phosphoric acid by wet process and phosphoric acid salt processing technology, is decompose with hydrochloric acid the technology category that any phosphorus ore manufactures feed phosphate.

Background technology

Sodium phosphate calcium is rarely known by the people at home and abroad as high-grade feed phosphate, but its excellent performance number obtains people's Application and Development.It is applicable to Mammals, and particularly domestic birds and animals is edible, it has animal phosphorus necessarily, calcium nutritive element, also is furnished with sodium element, its phosphorus, calcium, the proportioning very science of sodium three, it is effectively more more convenient than the mixed feed adding secondary calcium phosphate and salt in edible general green fodder on the market that animal absorbs these nutritive elements, learn from animal experiment, if the assimilated efficiency of sodium phosphate calcium is decided to be 100 indexs, that secondary calcium phosphate can only reach the manufacture method of 75 indexs (1) about sodium phosphate calcium, United States Patent (USP) (1) is only had to report a kind of method, namely the P of 142 parts of weight is used ₂o ₅the sodium carbonate of the Si Liaodengji dicalcium phosphate feed grade of=50%, CaO=40% and 53 parts of weight is at 1200 DEG C, and sinter 5 hours, cooling crush forms, and through the qualification of X-diffraction, is high temperature α and low temperature bata CaNaPO ₄mixture, containing P ₂o ₅=44.4%, Ca=25.4%, Na=14.5%, P: Ca: Na=1: 1.3: 0.75. its solubilized 85% in the ammonium citrate of ammonia alkali, according to feed efficiency test, upper proportioning is the most perfect, the feed phosphate that suitable especially ox, sheep and pig use, and its reaction formula is

Summary of the invention

Consider that high-temperature sintering process of the U.S. manufactures the method for sodium phosphate calcium, first will prepare the secondary calcium phosphate of crystal water, P ₂o ₅just can reach more than 50%, along with the rich phosphorus ore of Chinese commodity accelerates exhaustion day by day, the enterprise of domestic employing sulfuric acid wet process calcium hydrophosphate forage all faces the situation that there is lack of raw materials, and therefore the present inventor adopts CY Technology to provide a kind of method manufacturing sodium phosphate calcium, and concrete steps are:

1) the huge P of standing stock is decomposed with hydrochloric acid ₂o ₅any mid low grade phosphate rock of>=6wt%;

2) intermediate is first prepared---monocalcium chlorophosphate, is called for short calcium chlorophosphate code name P- _o1;

3) again will with homemade PATS-1 type scavenging agent purification, after purification, solution returns decomposing phosphate rock operation.

4) by final CaNaPO ₄in product P: Ca: Na=1: 1.3: 0.75 (weight ratio) adds purification P- ₀₁, salt and Paris white companion close evenly, and sinter 1 hour at 800-1200 DEG C, cool levigate, be feed grade sodium phosphate calcium, composition is in Table-2; .P ₂o ₅the phosphorus ore of=17%, P ₂o ₅yield can reach 95%.

5) the HCl gas that sintering is released passes into P- _o1mother liquor salts out muriate, and salting-out mother liquor returns decomposing phosphate rock;

6) muriate is with sulfuric acid decomposition, and wherein calcium sulfate worry is washed and obtained pure CaSO ₄2H ₂o, calcium sulfate crystal whisker material is made through autoclave pressurized, heated, market price is not at 1200-6000 yuan/ton etc., in papermaking, plastics, rubber and building materials plasterboard etc., can have the market of up to ten million ton every year, this just thoroughly can solve current sulfuric acid wet process calcium hydrogen phosphate fodder enterprise and discharge the phosphogypsum and calcium hydrogen phosphate fodder technique P that are difficult to dispose in a large number ₂o ₅the difficult problem that yield is not high.

7) filter the HCl that the mother liquor of calcium sulfate contains, heating is driven away the muriate of lower circulation of saltouing, and the vitriol of iron magnalium adds milk of lime and generates iron aluminum-magnesium hydroxide and calcium sulfate, can the raw material of making cement.Such HCl can be recycled, and has the phosphorus ore of the associated elements such as rare earth, iodine and uranium, can enrichment and extraction from upper salting-out mother liquor.Reaction equation is

Decomposing phosphate rock: Ca ₅f (PO ₄) ₃+ 10HCl → 3H ₃pO ₄+ 5CaCl ₂+ HF ↑

Analyse P- _o1: H ₃pO ₄+ CaCl ₂→ CaClH ₂pO ₄h ₂o ↓+HCl

Sintering:

Muriatic sulfuric acid decomposition:

CaCl ₂+H ₂SO ₄→2HCl↑+CaSO ₄·2H ₂O↓

MgCl ₂+H ₂SO ₄→2HCl↑+MgSO ₄

2AlC1 ₃+3H ₂SO ₄→6HCl↑+Al ₂(SO ₄) ₃

2FeCl ₃+3H ₂SO ₄→6HCl↑+Fe ₂(SO ₄) ₃

Iron aluminium sulfate and milk of lime react:

MgSO ₄+Ca(OH) ₂→CaSO ₄·2H ₂O↓+Mg(OH) ₂↓

Al(SO ₄) ₃+3Ca(OH) ₂→3CaSO ₄·2H ₂O↓+Al(OH) ₃↓

Fe(SO ₄) ₃+3Ca(OH) ₂→3CaSO ₄·2H ₂O↓+Fe(OH) ₃↓

Figure of description is this process flow sheet.Ground phosphate rock is in decomposition _-1middle hydrochloric acid decomposes through diafiltration _-1diafiltration, discharges white residue, and the fluoro-gas that reaction is discharged absorbs to react with sodium salt solution at absorption place use water again and generates Sodium Silicofluoride byproduct.Decomposed solution adds crystal and is analysing P ₀₁calcium chlorophosphate (P is separated out at place _-01), through press filtration, at purification P ₀₁pulverize at roasting place roasting ball milling place with quantitative salt and lime powder mix after place's purification diafiltration and be sodium phosphate calcium product.Roasting is discharged enter to saltout sentence P containing H C I gas _-01mother liquor absorbs, and salts out muriate, in decomposition _-2place, by itself and sulfuric acid reaction, obtains calcium sulfate precipitation thing, manufactures calcium sulfate crystal whisker material in diafiltration place diafiltration to whiskerizing place.Calcium sulfate mother liquor is driven the H C I place of analysing of also desalting out of in the de-H C I place's heating of heating and to be saltoutd muriate, and the mother liquor deviating from H C I contains magnesium iron aluminium salt sentences lime slurry neutralization in reaction again, and the iron aluminium calcium magnesium slag made can be used as the raw material of manufacture of cement.Salting-out mother liquor returns decomposition _-1place's decomposing phosphate rock, forms mother liquor and H C I closed circulation flow process.

Table-1P- _o1purification composition (wt.%)

Table-2 sodium phosphate calcium analyzes (% by weight)

Embodiment

Table-3 phosphorus ores used (wt.%)

Take 1000 grams of ground phosphate rock slowly to drop into and be heated to heated and stirred in 1900 grams of concentrated hydrochloric acids of nearly 60 DEG C, add ore deposit and finish insulated and stirred 15 minutes again, the fluoro-gas that reaction produces absorbs to react with NaCl solution with water again and generates Na ₂siF ₆product, slip filtered while hot is washed, and obtain wet white residue 406 grams, decomposed solution 1960 grams adds crystal seed and separates out 669 grams of P- _o1(P ₂o ₅=20.4%) .1271 gram of P- _o1mother liquor, at upper P- _o1in add 200 grams of PATS-1 type scavenging agents making beating purifications, removal of impurities, pressures consider to obtain and purify P- _o1430 grams (table-1), after purification, solution returns decomposing phosphate rock.Get 100 grams of purification P- _o1add 26 grams of salt (purity 95%) and 10 grams of Paris whites (purity 95%) stir, 820 ± 10 DEG C of roastings 1 hour cooling levigate 67.3 grams of white powders, be accredited as α and β sodium phosphate calcium mixture through X diffraction, record P=19.4% (P ₂o ₅=44.4%) Ca=25.1% (CaO=35.14%) Na=14.3%, P: Ca: Na=1: 1.29: 0.74 (table-2), passes into P-by the hydrogenchloride that sodium phosphate calcium processed produces _o1mother liquor, salts out muriate, and salting-out mother liquor returns decomposing phosphate rock, and muriate is with sulfuric acid decomposition, and wherein calcium sulfate worry is washed and obtained pure CaSO ₄2H ₂o, makes calcium sulfate crystal whisker material 571 grams through autoclave pressurized, heated, and known crystal length-to-diameter ratio i.e. as well product more than 50, this sample length-to-diameter ratio reaches 81, and explanation is it will have a good sale potential product.Isolate CaSO ₄2H ₂after O is the vitriol of iron magnalium, and hydrogenchloride is driven in first heating out of, then adds milk of lime reaction, forms the mixture of iron aluminum-magnesium hydroxide and gypsum, can make cement raw material.

Second time reaction, namely in first time cyclical operation, start supplementary concentrated hydrochloric acid 300ml and decompose 1000 grams of ground phosphate rock together with the muriatic mother liquor of saltouing of turning one's head (with phosphoric acid and hydrochloric acid and a small amount of muriate), the same first set reaction of operating method, obtains sodium phosphate calcium product 413 grams of (P ₂o ₅=44.1%, CaO=35.1%, Na=14.2%), p: Ca: Na=1: 1.3: 0.74.Operate down by this schedule of operation always.

Reference

[1]USP3,658,549Apr.25，1972 。

Claims

1. with hydrochloric acid decomposed P ₂o ₅any phosphorus ore of>=6wt%, first in decomposed solution, separate out an intermediate product---monocalcium chlorophosphate (is called for short calcium chlorophosphate code name P- ₀₁).

2. according to step 1 the method that describes be with PATS-1 type scavenging agent purification P- ₀₁.

3. according to step 2 the method that describes be by final CaNaPO ₄in product P: Ca: Na=1: 1.3: 0.75 (weight ratio) adds purification P- ₀₁, salt and Paris white companion close evenly, sinter 1 hour at 800-1200 DEG C, and the fluorine-containing of discharge contains HCl gas, passes into P- ₀₁mother liquor salts out muriate, and salting-out mother liquor returns decomposing phosphate rock.Calcining matter cools, and is levigately feed grade sodium phosphate calcium product.

4. according to step 3 the method that describes, muriate is with sulfuric acid decomposition, and wherein calcium sulfate is considered to wash and obtained pure CaSO ₄2H ₂o, makes calcium sulfate crystal whisker material through autoclave pressurized, heated, and phosphogypsum mother liquor heats the HCl driven out of and goes salting-out procedures, and wet solid phase and milk of lime react, and the mixture of the oxyhydroxide and gypsum that become iron magnalium is discharged.

5. according to step 3 the method that describes, extract the associated elements such as rare earth, iodine and uranium phosphorus ore from the mother liquor enrichment of separating out after muriate.