CN107089649A

CN107089649A - The method that hydrochloric acid decomposing medium and low grade manufactures polyphosphoric acids and APP

Info

Publication number: CN107089649A
Application number: CN201610100899.3A
Authority: CN
Inventors: 姚鼎文; 姚宁; 雷硤
Original assignee: Individual
Current assignee: Individual
Priority date: 2016-02-18
Filing date: 2016-02-18
Publication date: 2017-08-25

Abstract

The present invention introduces a kind of method for manufacturing polyphosphoric acids and APP, is to decompose any mid low grade phosphate rock using hydrochloric acid, with milk of lime and decomposed solution, extracted again with TBP, polyphosphoric acids is made in pure water back extraction, concentration polymerization, in polyphosphoric acids, lead to ammonia, aggregate into APP.HF is driven in the white fertilizer mashing that raffinate aqueous phase is produced with neutralizing plus hydrochloric acid back dissolving, heating out of, and solution salts out chloride, diafiltration, salting-out mother liquor and wash water return to decomposing phosphate rock, and chloride is dissolved with water, plus milk of lime is neutralized, diafiltration, filtrate wash water condensing crystallizing generation anhydrous calcium chloride.Wet solid phase adds dissolving with hydrochloric acid, with N₂₃₅Extract iron, iron oxide red is made in the heating of its blowing air by absorbing ammonia generation ferric ammonium.Raffinate aqueous phase leads to ammonia and produces magnesium hydroxide, and no boron magnesia is made through diafiltration roasting.Filtrate thermal decomposition after filtering produces alumdum, gas phase cooling generation ammonium chloride.Calcium chloride and white residue are generated into high activity siliceous fertilizer and hydrogen chloride in medium temperature roast, the latter returns to decompose white fertilizer.

Description

The method that hydrochloric acid decomposing medium and low grade manufactures polyphosphoric acids and APP

Technical field：

The invention belongs to wet phosphoric acid purifying and polymerization technique, be with decomposing phosphate rock by chlorhydric acid obtain it is wet Method phosphoric acid is with organic solvent extracting and purifying and the technology category of polymerization.

Background technology：

Polyphosphoric acids is a series of mixture of phosphoric acid polymerization things, by its P₂O₅Content is different, with H₃PO₄Meter, its product specification generally has 105~117% etc. a variety of.

Polyphosphoric acid product is one of fine phosphorus chemical product, application field be related to agricultural, light industry, The fields such as oil, chemical industry, medicine, food, spices, such as manufacture high-purity phosphoric acid, beverage additive, In terms of phosphorous agricultural chemicals, refractory material, analytical reagent, corrosion inhibitor and metal cleaner.In stone In oily industry, using polyphosphoric acid as catalyst, propylene tetramer is produced, for high-knock rating gasoline. It is used as cyclizing agent, acylating agent, catalyst and dehydrating agent in organic synthesis.Other polyphosphoric acids conduct While phosphoric acid is used, as having supercooling property compared with common thermal phosphoric acid, even in much lower At a temperature of storage remain to keep liquid and corrosivity is small.Transport the P of per unit weight₂O₅Transport ratio Common phosphate transport expense is to save 40%, and long distance transportation cost advantage is especially prominent.

China's polyphosphoric acids production focuses primarily upon Jiangsu, Shanghai, Zhejiang, Guangxi and Yunnan Province. Current about 440,000 tons/year of production capacity, 390,000 tons of yield, wherein being advised with Jiangsu a company device Mould is maximum, up to 100,000 tons/year.

At present, domestic polyphosphoric acids production technology mainly has two kinds：One kind is passed through by raw material of yellow phosphorus Burning hydration control hydrauture, produces polyphosphoric acids；Another is with thermal phosphoric acid and P₂O₅For Raw material, polymerisation purification is carried out and obtained polyphosphoric acids by heating.

Ammonium polyphosphate APP can be write as (NH₄PO₃) n, it is a kind of important Halogen phosphorus flame retardant, Due to there is two kinds of elements of phosphorus and nitrogen, flame retardant effect is phosphorous better than single, single nitrogenous fire retardant, and by The murder by poisoning of halogen is not produced when fire-retardant, so being the developing direction of fire retardant and leading from now on Product.

The purposes of APP, low polymerization degree can be used as high-concentration phosphoric acid ammonium compound fertilizer and extinguishing chemical former Material, higher degrees of polymerization mostly makees fabric, timber, engineering plastics, rubber, electric wire, cable Fire retardant.

Current production method, mainly there is following several：

1st, polyphosphoric acid ammoniation process

2、P₂O₅-NH₃-H₂O high temperature gas-phase reaction methods

3、NH₃、P₂O₅(NH₄)₂HPO₄Condensation method

4th, in the presence of APP, phosphoric acid and ammonification condensation method

5、NH₄H₂PO₄With CO (NH₂)₂Condensation method

6、(NH₄)₃PO₄And P₂O₅Condensation method

7th, phosphoric acid and urea condensation method

Hydrochloric acid Wet Phosphoric Acid Market is once aggregated into poly by this technique using the polyfurnace of oneself research and development Phosphoric acid, and then reacted with ammonia, aggregate into the APP that the degree of polymerization is 100-400.

The content of the invention：

The present invention is the method that any phosphorus ore, manufacture polyphosphoric acids and APP are decomposed using hydrochloric acid, Concretely comprise the following steps：

0001 decomposes the full mesh phosphorus ore of mistake 40 with hydrochloric acid, and its reaction temperature is 80 degree Celsius or so, salt Sour consumption is 105% times of the theoretical acid consumption summation of all metal oxides in phosphorus ore, reaction time It is stirred for 30 minutes to add miberal powder to finish.

0002, with industrial filter cloth heat filtering and washing, obtains decomposed solution and white residue.

0003 in milk of lime and decomposed solution is to PH=1-3, to filter to get filtrate and wet solid phase (white fertile).

0004 filtrate is with TBP: boat coal=1: 1 extractant extraction, and oil phase is with aqueous phase volume ratio 3-5: 1 extraction temperature is 10-45 degree Celsius, and extraction time is 4-5 minutes, is extracted using three cross-flows Take.

The organic phase that 0005 extraction has phosphoric acid is washed with strip liquor, and consumption is the 3-5% of organic phase volume, Totally three times, material temperature 10-45 degree Celsius, wash time 5 minutes.

0006 is stripped three times with organic phase volume 10-15% pure water, water temperature 10-45 degree Celsius, instead 5 minutes extraction time.

Strip liquor is concentrated under reduced pressure into P by 0007₂O₅>=62% obtains industrial phosphoric acid.

0008 adds P with thermal phosphoric acid₂O₅The polyfurnace material of polymerization polyphosphoric acids processed is with stainless steel Can, and during the polymerization of the hydrochloric acid wet method concentrated phosphoric acid of this technique, find to all including stainless steel Metal is not corrosion-resistant, and finally trying out graphite material can be with corrosion resistant and high temperature resistant, but has seepage, uses General impermeable graphite material does heating and resistance to can only arrive 100° centigrade both at home and abroad at present, and this work Skill polymerization temperature is at more than 200 degree Celsius, and the author works out a kind of blocking method, reaches Celsius 1000 degree also non-leakage, successfully polymerize P₂O₅>=84% water white transparency glop poly phosphorus Acid.During with sulfuric acid wet process phosphoric acid polymerization, P can only achieve₂O₅=70% black or dark-brown stiff Liquid, and P₂O₅Loss more than 50%.

0009 by polyphosphoric acids and anhydrous gas ammonia in the tubular polyfurnace of homemade high temperature resistant, it is Celsius 310-320 degree hot polymerization synthesizes APP product.

0010 will be beaten in TBP raffinates aqueous phase and decomposed solution with the wet solid phase (white fertilizer) that produces, plus Dissolving with hydrochloric acid, heating is driven HF gases out of and absorbed into the absorber of decomposing phosphate rock by chlorhydric acid process, goes Anhydrous HF processed.

The upper solution of 0011 cooling, separates out a large amount of metal chloride crystallizations, and separation, elution, crystallization are female Liquid and wash water return to decomposing phosphate rock.

The metal chloride of 0012 separation is dissolved in water, and is neutralized with milk of lime and arrives PH=6-7, crosses diafiltration Wash, filtrate and wash water condensing crystallizing are into high-grade anhydrous calcium chloride (CaCl₂=95.8%).

Add dissolving with hydrochloric acid with the metal hydroxides produced in 0013, with N₂₃₅Extractant extracts iron.

0014 is passed through gas ammonia in extraction iron organic phase, and the ferric ammonium separating, washing blowing air of generation is roasted Burn and obtain iron oxide red (Fe₂O₃=98.2%).

0015 is passed through gas ammonia in extraction iron raffinate aqueous phase, produces magnesium hydrate precipitate, diafiltration, roasting And obtain without boron activated magnesia (MgO=95.3%).

The filtrate wash water of 0016 filtering magnesium hydroxide produces alumina in 150~250 degree of spray pyrolysis Celsius Powder (Al₂O₃=95.1%).

Pyrolysis gas phase refrigerated separation is obtained ammonium chloride by 0017.

0018 when calcium chloride dull sale, by crystallization calcium chloride and white residue mix, Celsius 810-820 degree is calcined half an hour, obtains siliceous fertilizer and hydrogen chloride, and the latter returns to acidifying and decomposes white fertilizer.

Brief description of the drawings：

Fig. 1 is that hydrochloric acid decomposing medium and low grade manufactures polyphosphoric acids and APP process chart.

The full ground phosphate rock for crossing 40 mesh, which is put into, to be heated in 60 degree Celsius of hydrochloric acid, hydrochloric acid dosage For 105% times of the theoretical acid consumption summation of phosphorus ore metal oxide, the insulated and stirred again after miberal powder is finished 30 minutes, the fluoro-gas of generation is absorbed with water went anhydrous HF processed, filters while hot, white residue washing After stack, can be used as sand and use, decomposed solution add while hot milk of lime neutralize arrive PH=1-3, removal of impurities The wet solid phase (white fertilizer) produced is pending, and the decomposed solution that part is neutralized is with TBP: boat coal=1: 1 Extractant is extracted, material temperature 10-45 degree Celsius, oil phase: aqueous phase=3-5: 1, extraction time 4-5 minutes, Cross current solvent extraction three times, oil phase is washed three times with strip liquor, and consumption is the 3-5% of oil phase volume, 5 points Clock, material temperature is 10-45 degree Celsius, and organic phase is stripped with organic phase volume 10%-15% pure water, Stripping times are 5 minutes, and water temperature is 10-45 degree Celsius, totally three times, strip liquor is concentrated under reduced pressure To P₂O₅>=62% obtains industrial phosphoric acid, and it is homemade that industrial phosphoric acid is put into 200-250 degree Celsius It polymerize in high temperature resistant polyfurnace and obtains P₂O₅>=84% polyphosphoric acids, it is existed with anhydrous gas ammonia It polymerize and obtains chain length 100-1000 APP in 310-320 self-control high temperature resistant polyfurnace. The white fertilizer for adding dissolving with hydrochloric acid above to produce in TBP raffinate aqueous phases, heating drives HF out of and removes phosphorite stope Anhydrous HF processed is absorbed in the absorber of process, cooling solution separates out a large amount of metal chloride crystallizations, taken out Filter elution, crystallization mother liquor and wash water return to decomposing phosphate rock, and be dissolved in water this metal chloride, plus stone Grey breast, which is neutralized, arrives PH=6-7, produces iron aluminum-magnesium hydroxide, diafiltration, filtrate and wash water concentration granulation High-grade anhydrous calcium chloride is produced, iron aluminum-magnesium hydroxide is added into dissolving with hydrochloric acid, with N₂₃₅Extractant Extract iron 15 minutes, material temperature 10-45 degree Celsius separates extraction iron organic phase, is passed through gas ammonia, produces iron Ammonium salt, produces iron oxide red, under extraction iron extractant is returned by the roasting of ferric ammonium separating, washing blowing air Secondary extraction iron, the extraction iron raffinate aqueous phase ventilation ammonia of separation, is settled out magnesium hydroxide, through diafiltration roasting Obtain without boron activated magnesia, filtrate in 150~250 degree of spray roastings Celsius, that is, obtains aluminium with wash water Oxygen powder, gas phase cools down to obtain ammonium chloride.

When calcium chloride dull sale, by crystallization calcium chloride and white residue mix, in 810-820 Celsius Degree roasting half an hour, siliceous fertilizer and hydrogen chloride are obtained, the latter returns to acidifying and decomposes white fertilizer.

Embodiment：

Table 1, raw ore composition

Title	P₂O₅	CaO	MgO	Fe₂O₃	Al₂O₃	F	Al
								Weight %	12.3	30.75	10.05	1.22	0.58	1.9	24.9

Claim 1000 grams of full mesh ground phosphate rock of mistake 40, pour into slowly and heated 60 degree 1881 milliliters Celsius Reacted in 30% technical hydrochloric acid, finish again insulated and stirred 30 minutes, fluoro-gas water, which absorbs, goes system Anhydrous HF, heat filtering washs to obtain 2490 grams of wet 361 grams of white residue, filtrate and wash water, with milk of lime Neutralize decomposed solution arrive PH=2, suction filtration, 2100 grams of filtrate is with tributyl phosphate: navigate coal=1: 1 body 6300 milliliters of extractant extractions of product, 28 degree Celsius of material temperature, extraction time 5 minutes carries out three altogether Secondary cross current solvent extraction, load organic phases are with water: 85% phosphoric acid=4: the wash liquid that 1 (volume) is prepared Three times, each consumption is 315 milliliters, when circulate operation is set up, is washed with strip liquor, 26 degree Celsius of water temperature, the organic phase purified with water temperature 26 degree of 630 milliliters of pure water back extraction Celsius, Totally three times, strip liquor is concentrated under reduced pressure to obtain 178 grams of P₂O₅=62.3% industrial phosphoric acid, takes 100 grams Industrial phosphoric acid, in the homemade high temperature resistant crucible of 200-250 degree Celsius polymerize 1 hour, obtain 70 grams of P₂O₅=84.8% polyphosphoric acids, takes 50 grams of polyphosphoric acids, in 310-320 degree Celsius Homemade high temperature resistant crucible in, lead to anhydrous gas ammonia half an hour, cooling wash away short chain and accessory substance, Dried in 60-70 Celsius, obtain 41 grams of APPs, it is 375 to survey the degree of polymerization.Raffinate aqueous phase with it is white Fertilizer mashing dissolving with hydrochloric acid, heating drive HF out of, into the absorber of decomposing phosphate rock process in absorb, go Anhydrous HF processed, solution cooling separates out a large amount of metal chloride crystallizations, and magma filtering elution, crystallization is female Liquid returns to decomposing phosphate rock with wash water, and metal chloride is dissolved in water, and is neutralized with milk of lime and arrives PH= 6-7, diafiltration, filtrate wash water concentration granulates to obtain 1021 grams of anhydrous calcium chloride (purity 95.8%), gold Category hydroxide adds dissolving with hydrochloric acid, with N₂₃₅Extractant extracts iron, separation extraction iron organic phase, with ammoniacal liquor Back extraction generation ferric ammonium, be isolated washing blowing air be calcined 11.2 grams of purity be 98.2% oxygen Change iron oxide red.The extractant that ammoniacal liquor back extraction generation ferric ammonium is isolated returns to the metal of extraction subsequent cycle The acidifying solution of hydroxide, raffinate aqueous phase ventilation ammonia during extraction iron, produces magnesium hydroxide and aluminate, Magnesium hydroxide is filtered, washing is calcined without 95.2 grams of boron active oxidation magnesium powder (MgO=95.3%), The solution of filtration washing obtains alumdum (Al in 240~250 degree of spray roastings Celsius₂O₃=95.1%) 5.5 grams, the NH of gas phase distillation will be calcined₄Solid ammonium chloride is collected to obtain in Cl coolings.By 1021g without Water calcium chloride and the dry white residue mixs of 611g, are calcined half an hour in 810-820 degree Celsius, obtain high work Property siliceous fertilizer 1023g and hydrogen chloride 643g, by hydrogen chloride negative pressure absorbing to white fertilizer mashing retort, Decompose white fertilizer.

Table 2, polyphosphoric acids analysis

Title

P₂O₅

Fe ions

SO₄

Cl ions

Pb

Density

White standard %

≥84

≤0.001

≤0.05

0.001

0.01

2.1/ normal temperature

This handicraft product

84.5

0.001

0.0

0.001

2.1/ normal temperature

Table 3, APP analysis

Technical indicator	LSGAPP02-1	LSGAPP02-2	This handicraft product
				Outward appearance	White powder	White powder	White powder
P₂O₅% >=	71	71	71.8
				N% >=	14	14	14.5
Decomposition temperature DEG C ＞	270	270	275
				Moisture % ＜	0.25	0.25	0.24
Solubility g/100ml (25 DEG C of water slurries)≤	0.5	0.5	0.4
				PH value (10% aqueous solution)	6.5-7.5	6.5-7.5	6.5
25 DEG C of ＜ of viscosity (10% aqueous solution)	20	100	75
				Particle diameter (μm)	10-15	10-15	13

Table 4, industrial anhydrous calcium chloride analysis (weight %)

Claims

1. a kind of method that polyphosphoric acids and APP are manufactured with hydrochloric acid decomposing medium and low grade, its Feature, method, step are：

Any phosphorus ore is decomposed with technical hydrochloric acid or hydrogen chloride.

2. in milk of lime and decomposed solution is to PH=1-3, to filter to obtain decomposed solution and wet solid phase (white fertile).

3. the method described according to claim 2, with tributyl phosphate: boat coal=1: 1 extraction Agent is 10-45 degree Celsius, oil phase: aqueous phase=3-4: 1 extracting and purifying decomposed solution 5 minutes in material temperature.

4. method is described according to claim 3, using water: 85% phosphoric acid volume ratio is prepared as 4: 1 Phosphoric acid,diluted, washed during circulate operation with strip liquor by the 3-5% material temperatures 10-45 degree Celsius of oil phase volume Wash organic phase, 5 minutes.

5. the method described according to claim 4, using 10-45 degree water Celsius as organic phase body Long-pending 10-15% pure water back extraction organic phase 5 minutes.

6. the method described according to claim 5, strip liquor is concentrated under reduced pressure and is aggregated to P₂O₅ >=84% and obtain polyphosphoric acids.

7. being passed through gas ammonia in polyphosphoric acids, then aggregate into APP (APP).

8. the method described according to claim 2, the raffinate aqueous phase that TBP is extracted and white fertilizer Hydrochloric acid back dissolving is added in mashing, and heating drives HF out of and removes phosphorus ore decomposition gas absorption plant, together absorbs Go anhydrous HF processed.

9. the method described according to claim 8, the HF driven out of solution is cooled to Celsius 20 degree or so, separate out a large amount of metal chloride crystalline solid.

10. the method described according to claim 9, magma is filtered and eluted, filtrate and wash water Decomposing phosphate rock is returned to, metal chloride reacts with milk of lime, generation iron aluminum-magnesium hydroxide and chlorination High-grade anhydrous calcium chloride is made with wash water concentration in calcium, suction filtration, washing, filtrate.

11. the method described according to claim 10, by metal hydroxides plus dissolving with hydrochloric acid, With N₂₃₅Extractant extracts iron, and material temperature 10-30 degree Celsius extracts 15 minutes, oil phase: aqueous phase=1: 1.

12. the method described according to claim 11, will extract the organic phase separation of iron, lead to ammonia Generate ferric ammonium, the extractant of separation return iron in the iron magnalium chloride of extraction subsequent cycle from Son.

13. the method described according to claim 12, ferric ammonium washing blowing air roasting is given birth to Into iron oxide red and ammonia, ammonia returns to front suction ammonia.

14. the method described according to claim 13, leads to ammonia by extraction iron raffinate aqueous phase, separates out Magnesium hydrate precipitate and aluminate.

15. the method described according to claim 14, magnesium hydroxide is filtered, wash, roasting Burn and obtain no boron active oxidation magnesium powder.

16. the method described according to claim 15, by aluminate solution Celsius 150~250 Degree thermally decomposes to generate Al₂O₃, it is separated into alumdum.

17. the method described according to claim 16, chlorination is collected to obtain by roasting gas phase cooling Ammonium.

18. the method described according to claim 10, the calcium chloride of separation can be mixed with white residue Close, be calcined half an hour in 800-1000 degree Celsius, obtain siliceous fertilizer and hydrogen chloride gas, the latter returns to White fertilizer is decomposed in acidifying.