CN1095055A - Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method - Google Patents
Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method Download PDFInfo
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- CN1095055A CN1095055A CN 93111802 CN93111802A CN1095055A CN 1095055 A CN1095055 A CN 1095055A CN 93111802 CN93111802 CN 93111802 CN 93111802 A CN93111802 A CN 93111802A CN 1095055 A CN1095055 A CN 1095055A
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- phosphogypsum
- ammonium
- tartar
- ammonia
- ammonium chloride
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 43
- 238000000034 method Methods 0.000 title claims abstract description 40
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 36
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 230000008569 process Effects 0.000 title claims abstract description 17
- 208000006558 Dental Calculus Diseases 0.000 title claims abstract description 15
- 235000019270 ammonium chloride Nutrition 0.000 title claims abstract description 14
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 28
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004176 ammonification Methods 0.000 claims abstract description 10
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 239000000463 material Substances 0.000 claims abstract description 6
- 230000004087 circulation Effects 0.000 claims abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 20
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 19
- 239000012452 mother liquor Substances 0.000 claims description 19
- 239000011591 potassium Substances 0.000 claims description 19
- 229910052700 potassium Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 16
- 238000007670 refining Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000002425 crystallisation Methods 0.000 claims description 9
- 230000008025 crystallization Effects 0.000 claims description 9
- 239000012141 concentrate Substances 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 230000001839 systemic circulation Effects 0.000 claims description 3
- 150000001721 carbon Chemical class 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 26
- 239000000460 chlorine Substances 0.000 abstract description 17
- 229910021529 ammonia Inorganic materials 0.000 abstract description 13
- 238000005516 engineering process Methods 0.000 abstract description 10
- 229910052801 chlorine Inorganic materials 0.000 abstract description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003337 fertilizer Substances 0.000 abstract description 5
- 230000009466 transformation Effects 0.000 abstract description 4
- 238000005303 weighing Methods 0.000 abstract description 2
- 239000004254 Ammonium phosphate Substances 0.000 abstract 1
- 229910000148 ammonium phosphate Inorganic materials 0.000 abstract 1
- 235000019289 ammonium phosphates Nutrition 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 20
- 239000002994 raw material Substances 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000012065 filter cake Substances 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005496 tempering Methods 0.000 description 3
- 229920002472 Starch Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000001166 ammonium sulphate Substances 0.000 description 2
- 229910000019 calcium carbonate Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 235000012204 lemonade/lime carbonate Nutrition 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000008107 starch Substances 0.000 description 2
- 235000019698 starch Nutrition 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- MKKVKFWHNPAATH-UHFFFAOYSA-N [C].N Chemical compound [C].N MKKVKFWHNPAATH-UHFFFAOYSA-N 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 235000011116 calcium hydroxide Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000000618 nitrogen fertilizer Substances 0.000 description 1
- 238000012946 outsourcing Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/04—Fertilisers containing potassium from minerals or volcanic rocks
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05C—NITROGENOUS FERTILISERS
- C05C3/00—Fertilisers containing other salts of ammonia or ammonia itself, e.g. gas liquor
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
Abstract
The invention provides a kind of novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method, the ammonium sulfate factory that is fit to 1000-30000 ton/year scale produces the no chlorine mixed fertilizer of top grade.It is characterized in that making carbon supplying agenty with bicarbonate of ammonia, this agent is with after phosphogypsum mixes in conversion tank, and under the condition of ratio 〉=500 of slurry circulation amount and ammonification material times and ammonia material pH6-8, the normal temperature micro-negative pressure operation is finished the aminating reaction process.This technology solid-state CO of bicarbonate of ammonia institute's fixed
2Replace traditional gaseous state for carbon, simplify and processing unit and operational condition that extensive phosphogypsum transforms, can be at normal temperature with near in the saturated ammoniumsulphate soln, the transformation efficiency of acquisition＞96% and than weighing 1.2 ammonium phosphate solution, ammonia yield＞98%.
Description
The present invention relates to a kind of phosphogypsum conversion method and produce the improvement technology of vitriolate of tartar and ammonium chloride.This technology is particularly suitable for the high-grade no chlorine (Cl of middle or small ammonium sulfate factory's production in 1000-30000 ton/year
-) mixed fertilizer.
Traditional phosphogypsum conversion method is that gaseous state supplies carbon for the carbon mode, and its reaction formula is:
Processing condition are: 3 hours reaction times, temperature of reaction 55-60 ℃, solid-to-liquid ratio 1: 3, slip pH value 〉=8, recycle ratio 12-15, CaCO
3Dried slag/the m of intensity filter 600-650Kg
2.hr, its ammonium sulfate filtrate proportion 1.16, ammonia yield 96%, phosphogypsum transformation efficiency 96%.It is with carbonic acid gas (CO
2) and liquefied ammonia (NH
3) make sal volatile ((NH
4)
2CO
3), phosphogypsum and (NH
4)
2CO
3Solution reaction transforms and generates ammoniumsulphate soln ((NH
4)
2SO
4), this solution through concentrate, crystallization, separate solid ammonium sulfate, ammonium sulfate again through Repone K (kcl) saltout, replace, separate, drying just produces vitriolate of tartar (K
2SO
2) and ammonium chloride (NH
4Cl).This technology is fit to＞30000 tons/year the high-grade no chlorine mixed fertilizer of large-scale ammonium sulfate factory's production.Because of its conversion procedure has adopted complicated purifying flue gas and NH
3Reaction generates (NH
4)
2CO
3The tooling device of solution promptly relies on the CO after purifying
2With NH
3Under strict process equipment and operational condition, obtain (NH
4)
2CO
3) solution, do not hold so gaseous state instead is not difficult to support technically for carbon, and must have certain industrial scale and could form effective benefit.At present, be the small nitrogenous fertilizer plant of raw material with the Sweet natural gas, the CO in all necessary outsourcing part limestone kiln
2, realize carbon balance.And CO
2Commodity valency (300 yuan/ton) in the technological process by CO that stack gas provided
210 times, so the expense of raw materials height and is difficult to reach ammonia carbon and reacts prerequisite stringent condition.This shows with traditional phosphogypsum conversion method and produce K
2SO
4And NH
4Cl technology is not suitable on a small scale, and ammonium sulfate factory produces no chlorine mixed fertilizer.
Purpose of the present invention is intended to overcome the deficiency of above-mentioned traditional phosphogypsum conversion method, with solid-state CO
2Replacing traditional gaseous state is mechanism for carbon, provide a kind of for the carbon mode easily support hold, and in being fit to, the novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method used of ammonium sulfate factory on a small scale.
The objective of the invention is to finish like this: refining through thick phosphogypsum, transform, concentrate, operations such as crystallization, separation make solid ammonium sulfate, this ammonium sulfate is replaced through Repone K again, be that ammonium is analysed, after potassium analyses, through separate, drying process obtains product-vitriolate of tartar and ammonium chloride.It is solid-state for carbon for the carbon mode, adopt bicarbonate of ammonia to make carbon supplying agenty in the conversion procedure, after this carbon supplying agenty and refining phosphogypsum mix in the two slurry of double flute systemic circulation conversion tank, be under at least 500 times the control condition at the ratio of slurry circulation amount and ammonification material, the normal temperature micro-negative pressure operation, finish the aminating reaction whole process, its reaction formula is:
Its ammonium sulfate is replaced through Repone K, finishes that ammonium is analysed, potassium is analysed reaction process, and its reaction formula is:
In conversion procedure: ammonification speed pH value is 6-8, and the normal temperature of normal temperature micro-negative pressure operation is 20-55 ℃, and the reaction times is 5-8 hour, and solid-to-liquid ratio is 1: 3-6, NH
4HCO
3/ NH
3=1(molecular ratio), ammonium ion is excessive is 20%.
Ammonium is analysed and is analysed operation with potassium and be cold saltouing, and the female liquefied heavy of its ammonium is that 1.15-1.18, potassium mother liquor proportion are 1.14-1.17.
The present invention compares with traditional phosphogypsum conversion method, owing to use the solid-state CO of bicarbonate of ammonia institute's fixed
2Replace gaseous state for carbon, thereby simplified and processing unit and operational condition that extensive phosphogypsum transforms, that is: cancelled CO
2Treating process, do the ammonia source the also available ammoniacal liquor of liquefied ammonia, can operate, can obtain higher ammoniumsulphate soln, ammonification material speed pH value wide ranges etc. at normal temperatures.The present invention is technic index after tested: the quality of ammonium sulfate filtrate proportion 〉=1.20, phosphogypsum transformation efficiency＞96%, ammonia yield＞98%, potassium yield＞95%, product vitriolate of tartar and ammonium chloride all meets the technical grade national standard.This technology since have solid-state for carbon technique easily support hold, processing unit and operational condition require not too strict, and raw material extensively reaches raw material and expends that low (" K per ton sees attached list
2SO
4Raw material consumption ") etc. characteristics, be fit to middle or small ammonium sulfate factory and produce high-grade no chlorine mixed fertilizer.The scale of this technology can obtain economic benefit for producing the 1000-30000 vitriolate of tartar per year.Its economic benefit improves about 30% than traditional sulphur phosphogypsum conversion method (identical output).This technology is for turning waste into wealth, i.e. new way has been opened up in the utilization of refuse phosphogypsum.
Below in conjunction with accompanying drawing the present invention is elaborated:
Accompanying drawing is a technological process block-diagram of the present invention.
Embodiment one: referring to accompanying drawing.This technology comprises that thick phosphogypsum is refining, carbonization, wash and starch and wash again, modified, concentrated, crystallization, separation, thick KCl is refining, ammonium is analysed, separate, dry, potassium is analysed, separation, drying process are finished whole process of production, acquisition vitriolate of tartar, ammonium chloride product.The thick phosphogypsum of its raw material, bicarbonate of ammonia, liquefied ammonia (or ammoniacal liquor), sulfuric acid, thick potassium chloride dosage part by weight are about 50: 11: 3(or 10): 1: 23, each operation process was as follows:
1. thick phosphogypsum is refining: thick phosphogypsum is added in the vertical countercurrent washing groove, and added the water upruss of 4 times of amounts by the bottom at this groove and contact molten wherein solubility (the water-soluble P in the phosphogypsum that goes with phosphogypsum slightly
2O
5＜0.02%), the less impurity of proportion goes out with the formal floating mat of muddy liquid.The muddy liquid of discharging is through the settlement separate sediment that discards, and clear liquid neutralizes with milk of lime, with CaHPO
42H
2The O form reclaims wherein phosphoric acid salt, and mother liquor returns rinse bath, the refining phosphogypsum slip that rinse bath is discharged after filtration, separate, its filtrate is returned rinse bath.
2. transform: the refining phosphogypsum of wet basis enters in the two slurry of the special closed double flute systemic circulation conversion tank, behind the bicarbonate of ammonia thorough mixing that adds, in ratio＞500 of slurry circulation amount and ammonification material times, ammonification speed pH value keeps 6, solid-to-liquid ratio 1: 3.5, liquid phase proportion＞1.2, NH
4HCO
3/ NH
3=1(molecular ratio), under the control condition of ammonium ion excessive 20%, and, separate obtaining ammonium sulfate filtrate and filter cake after filtration 22 ℃ of little negative reactions 8 hours.Its filtrate enters subsider, and through settlement separate ammonium sulfate clear liquid and the muddy liquid of getting, this muddy liquid returns conversion tank.The tail gas that produces in conversion process absorbs through the absorption tower, and is extracted out by blower fan.Calcium sulfate particle in this operation phosphogypsum is subjected to the effect of centrifugal force and raising force simultaneously in conversion tank, the ratio that can obtain slurry circulation amount and feeding quantity reaches the high-speed displacement more than 500 times.With the less solid NH of solubleness
4HCO
3Replace the bigger weight (NH of solubleness
4)
2CO
3Solution has been realized 2NH
4 +/ SO
4 =The excessive condition of 〉=1.2 ammonia, its excess of ammonia are washed and starched through clear water again and are washed operation and all reclaim.Therefore this conversion reaction can be in lower temperature with near in the saturated ammoniumsulphate soln, obtains＞96% transformation efficiency and than weighing 〉=1.20 ammonium sulfate filter value, measures and the use isolation technique of saltouing for realizing that the little negative pressure of normal temperature reduces to concentrate, and obtains product K respectively
2SO
4And NH
4Cl has created condition.
3. wash and starch again and wash: the ammonium sulfate filter cake enters stock tank again, add with 1: 1 clear water amount of filter cake washing (wash water proportion＞1.03) the calcium carbonate filter cake of N＜0.03% (the calcium sulfate intensity filter is the dried slag/m of 650Kg
2Hr) and light ammonium sulfate filtrate, this filtrate is returned conversion tank, and calcium carbonate filter cake discards, or makes cement raw material.
4. modified: it is 6 to carry out modifier treatment by pH value in modified groove that the ammonium sulfate clear liquid is used the sulfuric acid that comes out through the absorption tower.
5. concentrate, crystallization, separation, drying: the ammonium sulfate clear liquid after modified enters sulphur ammonium thickener and adopts vacuum-evaporation to concentrate (109 ℃ of thickening temperatures) to water content 40%.Concentrate the back in the condenser crystallization, its crystallization outlet temperature≤50 ℃.In whizzer, separate behind the ammonium sulfate crystallization, solid, the mother liquor of ammonium sulfate are separated.Its mother liquor (proportion 1.24) returns thickener, and solid gets commodity ammonium sulfate after drying.
6. thick KCl is refining: with K
2The thick KCl of O content＞60% adds in the generator, be warming up to the employing insulation of boiling back 80-90 ℃ of pressure filter press filtration with mother liquor that returns and the clear water dissolving (50g/100g water) that replenishes, get thermal purification liquid and filter residue, its filter residue discards, the crystallization when being cooled to 25 ℃ of thermal purification liquid is filtered to such an extent that wet basis is originally made with extra care KCl and mother liquor, and this mother liquor returns generator.
7. ammonium analyse, separate, drying: wet basis ammonium sulfate enters ammonium and analyses tempering tank, contact with the potassium mother liquor that adds, through cold saltout react after the NH in the potassium mother liquor
4Cl separates out, and gets NH after separating after filtration
4Cl and ammonium mother liquor (proportion 1.17), NH
4The Cl drying just obtains product NH
4Cl.This NH
4K in the Cl product
2O content is 1%.
8. potassium analyse, separate, drying: the ammonium mother liquor enters potassium and analyses tempering tank and contact with the refining KCl of the wet basis of adding, through cold saltout react after, more after filtration, separate K
2SO
4With potassium mother liquor (proportion 1.16), the potassium mother liquor adds ammonium and analyses tempering tank, K
2SO
4Obtain product K after drying
2SO
4This K
2SO
4In the product: K
2O＞50%, Cl
-＜2.5%(agricultural grade), Cl
-＜0.25%(technical grade), moisture＜1%.
Embodiment two: referring to accompanying drawing.Raw material consumption: 2000 kilograms of thick phosphogypsums, 500 kilograms in bicarbonate of ammonia, 100 kilograms in liquefied ammonia, 40 kilograms in sulfuric acid, 900 kilograms in thick Repone K.Ammonification speed pH value keeps 7 in conversion procedure, solid-to-liquid ratio 1: 4.5,35 ℃ of temperature of reaction, 7 hours reaction times.Wash that the lime carbonate intensity filter is the dried slag/m of 700Kg in the operation washing and starching again
2Hr.Analyse potassium mother liquor proportion 1.14 in the operation at potassium.Analyse in the operation at ammonium, ammonium mother liquor proportion is 1.15.Other is identical with embodiment one, obtains product K
2SO
41 ton, NH
40.6 ton of CL.
Embodiment three: referring to accompanying drawing.Raw material consumption: thick phosphogypsum 2000g, bicarbonate of ammonia 450g, agricultural ammoniacal liquor 500g(20%NH
3), sulfuric acid 50g, thick Repone K 900g.Internal circulating load is 500 times, ammonification speed pH value maintenance 8 with the ammonia residual ratio in conversion procedure, solid-to-liquid ratio 1: 6,5 hours reaction times, 53 ℃ of temperature of reaction.Wash that the lime carbonate intensity filter is the dried slag/m of 800Kg in the operation washing and starching again
2Hr.Analyse at potassium that potassium mother liquor proportion is 1.17 in the operation.Analyse at ammonium that ammonium mother liquor proportion is 1.1.8 in the operation.Other is still identical with embodiment one.Obtain product K
2SO
4985g, NH
4Cl 608g.
K per ton
2SO
4Raw material consumption
Subordinate list
| Raw material | The tradition Using Phosphogypsum Conversion Method | This new technology | ||
| Consumption (ton) | The amount of money (unit) | Consumption (ton) | The amount of money (unit) | |
| Sulfuric acid | 0.04 | 13.60 | 0.04 | 13.60 |
| Ardealite | 2 | 10.00 | 2 | 10.00 |
| Carbonic hydroammonium | 0.45 | 126 | ||
| Liquefied ammonia | 0.2 | 200 | 0.10 | 100 |
| Carbon dioxide | 0.25 | 75 | ||
| Potassium chloride | 0.90 | 720 | 0.9 | 720 |
| Add up to | 1018.60 | 969.60 | ||
Claims (4)
1, a kind of novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method, refining through thick phosphogypsum, transform, concentrate, crystallization, operations such as separation get solid ammonium sulfate, this ammonium sulfate is analysed through ammonium again, potassium is analysed, separate, drying process obtains product vitriolate of tartar and ammonium chloride, it is characterized in that: adopt bicarbonate of ammonia to make carbon supplying agenty in the conversion procedure, after this carbon supplying agenty and refining phosphogypsum mix in the two slurry of double flute systemic circulation conversion tank, at slurry circulation amount and ammonification material than being under the control condition of 6-8 at least 500 times and ammonification speed pH value, the normal temperature micro-negative pressure operation, finish the aminating reaction whole process, its reaction formula is:
2, novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method according to claim 1, it is characterized in that: control condition also comprises solid-to-liquid ratio 1: 3-6, NH
4HCO
3/ NH
3=1, ammonium ion is excessive 20%, and the normal temperature of operational condition is 20-55 ℃, reaction times 5-8 hour.
3, novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method according to claim 1 is characterized in that: CaCO
3Intensity filter is the dried slag/m of 650-800Kg
2.hr.
4, novel process of producing vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method according to claim 1 is characterized in that: ammonium is analysed and is analysed operation with potassium and be cold saltouing, and its ammonium mother liquor proportion is that 1.15-1.18, potassium mother liquor proportion are 1.14-1.17.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111802 CN1095055A (en) | 1993-05-08 | 1993-05-08 | Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111802 CN1095055A (en) | 1993-05-08 | 1993-05-08 | Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method |
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| Publication Number | Publication Date |
|---|---|
| CN1095055A true CN1095055A (en) | 1994-11-16 |
Family
ID=4989560
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|---|---|---|---|
| CN 93111802 Pending CN1095055A (en) | 1993-05-08 | 1993-05-08 | Produce the novel process of vitriolate of tartar and ammonium chloride with the phosphogypsum conversion method |
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|---|---|
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041619C (en) * | 1995-02-20 | 1999-01-13 | 李永 | Process for producing potassium sulfate by plaster stone conversion method |
| CN101554998B (en) * | 2008-06-20 | 2011-06-29 | 陈明顺 | Method and equipment system for preparing sulfur trioxide from gypsum |
| CN102372292A (en) * | 2010-08-20 | 2012-03-14 | 中国地质大学（北京） | Technology for preparing potassium sulfate with potassium-rich mother liquid and phosphogypsum |
| CN102616812A (en) * | 2012-04-09 | 2012-08-01 | 瓮福（集团）有限责任公司 | Device for producing ammonium sulfate with ammonium bicarbonate as main raw material |
| CN111410212A (en) * | 2020-03-09 | 2020-07-14 | 安徽海德化工科技有限公司 | Method for recycling sulfuric acid production wastewater |
| EP4299553A1 (en) * | 2022-06-30 | 2024-01-03 | SABIC Global Technologies B.V. | Production of nitrogen, potassium, sulfur nutrient through de-carbonization and utilization of calcium sulfate |
-
1993
- 1993-05-08 CN CN 93111802 patent/CN1095055A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041619C (en) * | 1995-02-20 | 1999-01-13 | 李永 | Process for producing potassium sulfate by plaster stone conversion method |
| CN101554998B (en) * | 2008-06-20 | 2011-06-29 | 陈明顺 | Method and equipment system for preparing sulfur trioxide from gypsum |
| CN102372292A (en) * | 2010-08-20 | 2012-03-14 | 中国地质大学（北京） | Technology for preparing potassium sulfate with potassium-rich mother liquid and phosphogypsum |
| CN102372292B (en) * | 2010-08-20 | 2013-11-27 | 中国地质大学（北京） | Process for producing potassium sulfate by using potassium-rich mother liquor and phosphogypsum |
| CN102616812A (en) * | 2012-04-09 | 2012-08-01 | 瓮福（集团）有限责任公司 | Device for producing ammonium sulfate with ammonium bicarbonate as main raw material |
| CN111410212A (en) * | 2020-03-09 | 2020-07-14 | 安徽海德化工科技有限公司 | Method for recycling sulfuric acid production wastewater |
| EP4299553A1 (en) * | 2022-06-30 | 2024-01-03 | SABIC Global Technologies B.V. | Production of nitrogen, potassium, sulfur nutrient through de-carbonization and utilization of calcium sulfate |
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