CN85102403A - Produce potassium phosphate salt with Rock Phosphate (72Min BPL) and potassium bearing rock - Google Patents
Produce potassium phosphate salt with Rock Phosphate (72Min BPL) and potassium bearing rock Download PDFInfo
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- CN85102403A CN85102403A CN85102403.3A CN85102403A CN85102403A CN 85102403 A CN85102403 A CN 85102403A CN 85102403 A CN85102403 A CN 85102403A CN 85102403 A CN85102403 A CN 85102403A
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Abstract
Produce potassium phosphate salt (or potassium ammonium phosphate) with Rock Phosphate (72Min BPL) and potassium bearing rock, it is characterized in that the ore that all undissolved potassium bearing rock symbiotic phosphorus potassium symbiotic ore of nitric acid, phosphoric acid, chloroazotic acid or this two kinds of ores exist respectively is a raw material with Rock Phosphate (72Min BPL) and sulfuric acid, hydrochloric acid.At first divide phosphorus decomposing potassium symbiosis breeze or ground phosphate rock with dilute hydrochloric acid; Acid decomposition liquid is produced precipitated superphosphate through adding milk of lime (or limestone powder) suspension; Acid decompose slag or potassium bearing rock powder or sour decompose slag add potassium bearing rock powder (material A) and produce sal enixum through the batching roasting, then the precipitated superphosphate that makes and sal enixum are reacted under acidic conditions and make phosphoric acid potassium salt product, this product is mainly made fertilizer usefulness, and ore tailing is used to make cement and by-product gypsum.
Description
The invention relates to the ore that exists respectively with Rock Phosphate (72Min BPL) and sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the symbiotic phosphorus potassium symbiotic ore of all undissolved potassium bearing rock of chloroazotic acid (to call potassium bearing rock in the following text) and this two kinds of ores is raw material, the method production potassium phosphate salt of employing chemical (or potassium ammonium phosphate, down together) Chemicals.
As everyone knows, potassium phosphate salt is a kind of high-efficiency compound fertilizer, industrial purposes is arranged also.The method of producing potassium phosphate salt at present is a lot, mainly contains following several:
(1) neutralisation: make with phosphoric acid and potassium hydroxide (or salt of wormwood) neutralization reaction, this method has been used more than 100 year, is still adopting so far, referring to 1 page of " inorganic chemicals industry " 83 years 9 phase.
(2) double decomposition: make with phosphoric acid and Repone K metathesis reflection, referring to 1 page of " inorganic chemicals industry " 83 years 9 phase.
(3) direct method: with Rock Phosphate (72Min BPL), Repone K, sulfuric acid is that raw material is made, referring to 54 pages of " chemical fertilizer industry " 1978 3 phases.
Preceding two kinds of methods are that raw materials cost is higher with phosphoric acid, sylvite or potash all.Though the third method directly adopts Rock Phosphate (72Min BPL), this Rock Phosphate (72Min BPL) must be phosphorous of high grade, and iron, aluminium, magnesium addition content is low or the high-quality phosphorus ore handled through ore dressing, and still to need the higher Repone K of cost be raw material.
45 pages of " Sichuan chemical industry " 1980 the 2nd phases reported and decomposed with hydrochloric acid in the grade phosphorus mine stone flour, acid decomposition liquid adds milk of lime (or limestone powder) suspension and produces precipitated superphosphate; Add sulfuric acid system sal enixum by commodity Repone K; Produce the method for potassium phosphate salt at last by precipitated superphosphate and sal enixum reaction.This arts demand commodity Repone K and existence have the handling problem of the by product calcium chloride of pollution to environment.
Rock Phosphate (72Min BPL) and potassium bearing rock be Rock Phosphate (72Min BPL) and the symbiotic phosphorus potassium of potassium bearing rock symbiotic ore particularly, general phosphorous grade is low, iron, aluminium, magnesium addition content height are produced the standard that phosphoric acid by wet process is estimated phosphorus ore by general: ratio * 100%＜8% of ferric oxide ten aluminium sesquioxides and Vanadium Pentoxide in FLAKES in ore; Ratio * 100%＜the 3-5% of magnesium oxide and Vanadium Pentoxide in FLAKES.All substantially exceed this ratio by the many Rock Phosphate (72Min BPL) of this requirement, phosphorus potassium symbiotic ore is all the more so.This class ore of phosphorus potassium mineral intergrowth generally is difficult to processing treatment, and it is little still to be considered to extraction value so far.Along with the exploitation of higher-grade Rock Phosphate (72Min BPL) and soluble potassium salt mine expends, how to utilize this class ore to cause people's attention gradually, many investigators are being devoted to the research of this respect: domestic have factory once to decompose with phosphoric acid or other mineral acids after high-temperature fusion shrend, pulverizing with phosphorus potassium symbiotic ore, produce potassium phosphate salt, test is not achieved success; Domestic unit is also arranged is raw material with similar ore, decomposes with vitriolate of tartar and sulfuric acid and directly produces potassium primary phosphate, because the iron in the ore, the influence of aluminium impurity, test is not also achieved success.
The objective of the invention is to utilize Rock Phosphate (72Min BPL) and potassium bearing rock particularly low from phosphorous grade, extract phosphorus potassium in Rock Phosphate (72Min BPL) that iron, aluminium, magnesium addition are high and the symbiotic phosphorus potassium ore of potassium bearing rock and make high-load potassium phosphate salt, this method is that prior art does not have.
It is raw material with Rock Phosphate (72Min BPL) with the ore that potassium bearing rock symbiotic phosphorus potassium symbiotic ore or this two kinds of ores exist respectively that feature of the present invention provides a kind of, produces the method for potassium phosphate salt:
(1) Rock Phosphate (72Min BPL) and potassium bearing rock symbiotic phosphorus potassium symbiotic ore or rock phosphate powder are broken into the 20-120 order, the preferential 40-80 order of selecting, in reactor with contain hydrogenchloride 6-25%(% meter by weight) dilute hydrochloric acid, under 20-60 ℃ of condition decomposition reaction 5-130 minute, preferential selection 10-30 minute, obtain the acid decomposition liquid of phosphoric acid and calcium chloride and the sour decompose slag of iron content, aluminium impurity and potassium bearing rock, thereby the phosphorus in the phosphorus potassium mineral intergrowth and iron, aluminium impurity and potassium bearing rock are separated.
(2) contain the acid decomposition liquid of phosphoric acid and calcium chloride, by adding the reaction of milk of lime (or limestone powder) suspension, neutralization phosphoric acid wherein, sedimentation is filtered and is obtained precipitated superphosphate (CaHPO then
42H
2O), make phosphorus obtain enrichment, filtrate is calcium chloride solution.
(3) sour decompose slag or potassium bearing rock powder or sour decompose slag are added potassium bearing rock powder (being material A) 1 part (by weight), allocate filtrate calcium chloride 0.3-0.8 part (by calcium chloride weight) of precipitation separation calcium phosphate into, lime powder (or limestone powder) 1-5 part (by weight) is preferentially selected 1.5-3.5 part (by weight) to make and is carried the potassium roasting material; To carry the potassium roasting material places High Temperature Furnaces Heating Apparatus 700 ℃ of-1500 ℃ of following roastings 3 hours-10 minutes, or from the tail gas of roasting system cement, reclaim Repone K, or will carry potassium roasting material water extraction after the roasting, leaching liquid is the mixed solution that contains Repone K and calcium chloride, soaks slag and makes to make cement raw material.The mixed solution adding sulfuric acid reaction of Repone K and calcium chloride is removed calcium chloride earlier generate gypsum (calcium sulfate, together following) and filter out gypsum, again with Repone K (or the Repone K that from the tail gas of roasting system cement, reclaims) and sulfuric acid reaction, produce sal enixum, the hydrogenchloride of emitting is recycled into the hydrochloric acid circulation and is used to decompose raw ore, and gypsum is for paying product.
(4) sal enixum that makes and the precipitated superphosphate that before makes are reacted the acid mixed solution that generates potassium phosphate salt and phosphoric acid under acidic conditions.
(5) in the acid mixed solution that makes: add a small amount of potassium hydroxide neutralization phosphoric acid wherein, and further remove tertiary iron phosphate, aluminium impurity, get the potassium phosphate salt crystal product through Crystallization Separation; Add ammonium hydroxide neutralization phosphoric acid wherein, further remove tertiary iron phosphate, aluminium impurity, get the potassium ammonium phosphate crystal product through Crystallization Separation; Solvent (hereinafter to be referred as solvent B) the absorption phosphoric acid wherein that adds absorption phosphoric acid such as methyl alcohol or ethanol or propyl alcohol or butanols or primary isoamyl alcohol or acetone, isolate solid phosphoric acid sylvite product, solvent distillation B and phosphoric acid mixed solution obtain phosphoric acid product, and solvent B is recovered utilization.
The precipitated superphosphate that makes in the inventive method process, calcium chloride, Repone K, vitriolate of tartar (adding sulfuric acid reaction by Repone K makes), carrying tailings, gypsum, the phosphoric acid of potassium roasting material after potassium is carried in roasting all can be separately as product utilization or sale.
Because the present invention has effectively utilized the phosphorus potassium production higher-grade potassium phosphate salt in the ore that Rock Phosphate (72Min BPL) and potassium bearing rock symbiotic phosphorus potassium symbiotic ore and this two kinds of ores exist respectively, there be not pollution and the handling problem of calcium chloride to environment, use no or little commodity sylvite, potash, raw ore and by product are fully utilized, thereby product cost reduces significantly than additive method in addition.There is a phosphorus potassium mineral intergrowth in Sichuan, more than 10 hundred million tons of reconnaissance geological survey reserves.
By the accompanying drawing of specification sheets of the present invention is to be used to describe the present invention to use ore that Rock Phosphate (72Min BPL) and potassium bearing rock symbiotic phosphorus potassium symbiotic ore or this two kinds of ores exist the respectively simple and easy flow process as the raw material production potassium phosphate salt.
By the flow process of accompanying drawing dilute hydrochloric acid (line 20) is added and to add phosphorus potassium symbiosis breeze again in the reactor (1) or rock phosphate powder (line 21) carries out sour decomposition reaction, isolate sour decompose slag (line 22) and acid decomposition liquid (line 23) then, acid decomposition liquid sent into add milk of lime (or limestone powder) suspension (line 24) in the reactor (2) again and carry out neutralization reaction, separating reaction slip then, filter residue is precipitated superphosphate (line 25), and filtrate is calcium chloride (line 26); Calcium chloride is concentrated the back, and to add potassium bearing rock powder (line 26,27) with sour decompose slag or potassium bearing rock powder or sour decompose slag in blender loader (3) be that material A, lime powder (or limestone powder, line 28) fit in and carry potassium roasting material (line 29); To carry and send into water (line 30) leaching in the leaching groove (5) after the potassium roasting material is sent into the middle roasting of high-temperature roasting stove (4), leach liquor is Repone K, calcium chloride mixed solution (line 31), separate and soak slag (line 32) immersion liquid, soak slag and make the system cement raw material, immersion liquid is sent into reactor (6) adding sulfuric acid (line 33) and is removed with calcium chloride reaction generation gypsum (line 34), Repone K and sulfuric acid reaction are produced sal enixum (line 35), and the hydrogenchloride of generation (line 36) is recycled into hydrochloric acid and is used to decompose raw ore; Sal enixum is reacted generation gypsum (line 37) and potassium phosphate salt and phosphoric acid mixed solution (line 38) at reactor (7) and precipitated superphosphate under acidic conditions, gypsum is removed, mixed solution is sent into reactor (8): further remove tertiary iron phosphate, aluminium impurity if add potassium hydroxide (dotted line 39) neutralization phosphoric acid wherein, condensing crystal is isolated potassium phosphate salt crystal product (line 40); If add ammonium hydroxide (dotted line 39) neutralization phosphoric acid wherein, further remove tertiary iron phosphate, aluminium impurity, condensing crystal is isolated potassium ammonium phosphate crystal product (line 40); If add solvent B(dotted line 39) absorb phosphoric acid wherein, potassium phosphate salt is separated out, through separate potassium phosphate salt solid phase prod (line 40).Solvent distillation B and phosphoric acid mixed solution reclaim solvent B and utilize, obtain phosphoric acid product simultaneously.
The dotted line of reactor in the accompanying drawing (8) represents to add different chemical substances.
(line 41) of high-temperature roasting stove (4) expression is reclaimed Repone K in the accompanying drawing from the tail gas of roasting system cement.
Embodiment: by the flow process of accompanying drawing of the present invention, with chemical constitution is table 1 fineness 20-120 purpose phosphorus potassium symbiosis breeze 1000 grams, with dilute hydrochloric acid decomposition reaction in 5000 ml beakers, obtain sour decompose slag and acid decomposition liquid, acid decomposition liquid is poured in 5000 ml beakers again, add milk of lime and carry out neutralization reaction, and filter to isolate precipitated superphosphate, filtrate is calcium chloride solution.(the main chemical constitution (weight %) of precipitated superphosphate relatively sees Table 1 for raw ore, sour decompose slag).Calcium chloride, the lime that obtains in material A and the process is mixed with carries the potassium roasting material, carry the potassium roasting material and use water extraction after the roasting in the leaching groove in retort furnace, filtering separation is removed and is soaked slag.Immersion liquid adds excess sulfuric acid and generates gypsum in 5000 ml beakers, make sal enixum after removing gypsum.At last with the precipitated superphosphate that makes previously and sal enixum in 5000 ml beakers under acidic conditions reaction make potassium phosphate salt and phosphoric acid, gypsum mixture slurry, filter to isolate gypsum and get potassium phosphate salt and phosphoric acid mixed solution.This mixed solution adds potassium hydroxide neutralization phosphoric acid wherein in 5000 ml beakers, further remove tertiary iron phosphate, aluminium impurity, and Crystallization Separation gets phosphoric acid potassium salt product 226 grams.Outward appearance is a white crystal, all is water-soluble, and its chemical constitution sees Table 2.
The invention is not restricted to the scope of present embodiment.
Subordinate list 1: raw ore, sour decompose slag, the main comparable chemical constitution of precipitated superphosphate (% meter by weight) are relatively
Subordinate list 2: product potassium phosphate salt (potassium primary phosphate) main chemical (weight %)
Claims (8)
1, produces potassium phosphate salt with Rock Phosphate (72Min BPL) and potassium bearing rock, it is characterized in that making the acid decomposition liquid of phosphoric acid and calcium chloride, in acid decomposition liquid, add milk of lime (or limestone powder) suspension and produce precipitated superphosphate (CaHPO with dilute hydrochloric acid decomposing phosphate rock stone and sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, the symbiotic phosphorus potassium symbiotic ore of all undissolved potassium bearing rock of chloroazotic acid (abbreviation potassium bearing rock) or Rock Phosphate (72Min BPL) raw ore powder
42H
2O), utilize the filtrate calcium chloride complex acid decompose slag of precipitation separation calcium phosphate or potassium bearing rock powder or sour decompose slag to add potassium bearing rock powder (material A), lime powder (or limestone powder) is mixed with carries the potassium roasting material, carry the potassium roasting material at the high temperature kiln roasting, or from roasting tail gas, reclaim Repone K, or obtain containing Repone K with the potassium roasting material of carrying after the water extraction roasting, the solution of calcium chloride, after this solution adding sulfuric acid is removed calcium chloride, produce sal enixum by Repone K, react the mixing solutions of making potassium phosphate salt and phosphoric acid by sal enixum and precipitated superphosphate under acidic conditions again, this mixed solution makes phosphoric acid potassium salt product through different processing treatment.
2, according to the method for claim 1, the dilute hydrochloric acid concentration that it is characterized in that decomposing the raw ore powder is to contain hydrogenchloride 6-25%(by weight).
3, according to the method for claim 1 and 2, the ratio of components that it is characterized in that carrying the potassium roasting material is material A (by weight): calcium chloride (by effective ingredient weight): lime powder (or limestone powder, all by weight)=1: 0.3～0.8: 1-5.
4, according to the method for claim 1 and 3, it is characterized in that carrying the maturing temperature of potassium roasting material in High Temperature Furnaces Heating Apparatus is 700 ℃-1500 ℃.
5, according to the method for claim 1 and 4, it is characterized in that in potassium phosphate salt and phosphoric acid mixed solution, adding potassium hydroxide neutralization phosphoric acid wherein, make the potassium phosphate salt crystal product.
6, according to the method for claim 1 and 4, it is characterized in that in potassium phosphate salt and phosphoric acid mixed solution, adding ammonium hydroxide neutralization phosphoric acid wherein, make the potassium ammonium phosphate crystal product.
7, according to the method for claim 1 and 4, it is characterized in that in the mixed solution of potassium phosphate salt and phosphoric acid, adding methyl alcohol or ethanol or propyl alcohol or butanols or primary isoamyl alcohol or acetone (title solvent B) absorption phosphoric acid wherein and isolate the potassium phosphate salt solid phase prod, solvent distillation B and phosphoric acid mixed solution, reclaim solvent B, obtain phosphoric acid simultaneously.
8, according to the method for claim 1 and 7, tailings, Repone K, gypsum, the phosphoric acid of it is characterized in that precipitated superphosphate, calcium chloride, carrying after potassium is carried in the roasting of potassium roasting material all can use for product separately or sell.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102403 CN1014052B (en) | 1985-04-01 | 1985-04-01 | Preparation of potassium phosphate from phosphorus ore and potassic rock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 85102403 CN1014052B (en) | 1985-04-01 | 1985-04-01 | Preparation of potassium phosphate from phosphorus ore and potassic rock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN85102403A true CN85102403A (en) | 1986-09-24 |
| CN1014052B CN1014052B (en) | 1991-09-25 |
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ID=4792485
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 85102403 Expired CN1014052B (en) | 1985-04-01 | 1985-04-01 | Preparation of potassium phosphate from phosphorus ore and potassic rock |
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| Country | Link |
|---|---|
| CN (1) | CN1014052B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098827C (en) * | 1998-12-30 | 2003-01-15 | 南京理工大学 | Natural phosphate fertilizer and its wet preperation process |
| CN102887731A (en) * | 2012-09-25 | 2013-01-23 | 李成哲 | Potassium-containing ore for fertilizer and preparation method and application thereof |
| CN113173584A (en) * | 2021-04-21 | 2021-07-27 | 武汉工程大学 | Resource comprehensive utilization method of phosphorus tailings and potassium feldspar |
-
1985
- 1985-04-01 CN CN 85102403 patent/CN1014052B/en not_active Expired
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1098827C (en) * | 1998-12-30 | 2003-01-15 | 南京理工大学 | Natural phosphate fertilizer and its wet preperation process |
| CN102887731A (en) * | 2012-09-25 | 2013-01-23 | 李成哲 | Potassium-containing ore for fertilizer and preparation method and application thereof |
| CN102887731B (en) * | 2012-09-25 | 2014-11-05 | 李成哲 | Potassium-containing ore for fertilizer and preparation method and application thereof |
| CN113173584A (en) * | 2021-04-21 | 2021-07-27 | 武汉工程大学 | Resource comprehensive utilization method of phosphorus tailings and potassium feldspar |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1014052B (en) | 1991-09-25 |
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