CN102963874B - Method for producing industrial-grade potassium dihydrogen phosphate (KH2PO4) by wet method purified phosphoric acid and potassium sulfate - Google Patents
Method for producing industrial-grade potassium dihydrogen phosphate (KH2PO4) by wet method purified phosphoric acid and potassium sulfate Download PDFInfo
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- CN102963874B CN102963874B CN201210487348.9A CN201210487348A CN102963874B CN 102963874 B CN102963874 B CN 102963874B CN 201210487348 A CN201210487348 A CN 201210487348A CN 102963874 B CN102963874 B CN 102963874B
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- phosphoric acid
- potassium
- potassium sulfate
- filtrate
- potassium dihydrogen
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000000034 method Methods 0.000 title claims abstract description 48
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 46
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 title claims abstract description 32
- 229910052939 potassium sulfate Inorganic materials 0.000 title claims abstract description 32
- 235000011151 potassium sulphates Nutrition 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 21
- 235000019796 monopotassium phosphate Nutrition 0.000 title claims abstract description 19
- 229910000402 monopotassium phosphate Inorganic materials 0.000 title claims abstract description 12
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 title claims abstract description 11
- 239000007836 KH2PO4 Substances 0.000 title abstract 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 title abstract 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 24
- 239000000706 filtrate Substances 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 239000000047 product Substances 0.000 claims abstract description 15
- 239000011575 calcium Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 239000007787 solid Substances 0.000 claims abstract description 7
- 229910052700 potassium Inorganic materials 0.000 claims description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 27
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 26
- 239000011591 potassium Substances 0.000 claims description 26
- 239000013078 crystal Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000012065 filter cake Substances 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000006227 byproduct Substances 0.000 claims description 4
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 4
- 238000004062 sedimentation Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 5
- 239000011574 phosphorus Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 4
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000002002 slurry Substances 0.000 abstract 2
- 239000000463 material Substances 0.000 abstract 1
- 229910019142 PO4 Inorganic materials 0.000 description 18
- 239000010452 phosphate Substances 0.000 description 18
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- 239000007788 liquid Substances 0.000 description 13
- 239000002893 slag Substances 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 9
- 239000010440 gypsum Substances 0.000 description 6
- 229910052602 gypsum Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 238000009991 scouring Methods 0.000 description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 5
- 238000006477 desulfuration reaction Methods 0.000 description 5
- 230000023556 desulfurization Effects 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000004537 pulping Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005352 clarification Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 239000002367 phosphate rock Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000009413 insulation Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 206010019332 Heat exhaustion Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- VVJRSSJSRXEOQL-UHFFFAOYSA-N calcium;potassium;sulfuric acid;hydrate Chemical compound O.[K].[K].[Ca].OS(O)(=O)=O.OS(O)(=O)=O VVJRSSJSRXEOQL-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229940080286 lowsium Drugs 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
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- Processing Of Solid Wastes (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for producing industrial-grade potassium dihydrogen phosphate (KH2PO4) by wet method purified phosphoric acid and potassium sulfate, belonging to the field of phosphorus chemical industry. The method comprises the following steps: a. adding potassium sulfate in wet method purified phosphoric acid and fully dissolving potassium sulfate, wherein the addition amount of potassium sulfate based on mole ratio is that p:K is 0.6-1.2:1; b, adding calcium carbonate slurry with solid content of 50-90% in the solution obtained from the step a, stirring for reaction, wherein the reaction temperature is controlled to 60-90 DEG C, the addition amount of the calcium carbonate slurry based on mole ratio is that Ca:S is 0.6-1.2; c. filtering a mixed material system which is obtained by the reaction in the step b; and d. adjusting the pH value of the filtrate obtained from the step c to 4-5, and then concentrating and crystallizing, thus obtaining the potassium dihydrogen phosphate product. The method is simple in process, easy to control and industrially apply, low in cost and high in yield; and the yield of P2O5 can be up to over 96% and the yield of K2O can be up to over 98%.
Description
Technical field
The invention belongs to phosphorous chemical industry field, be specifically related to a kind of method of Wet Phosphoric Acid Market and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen.
Background technology
Phosphate industry is a large branch of chemical industry, KH
2p0
4it is the staple product of phosphate industry.Pure phosphoric acid potassium dihydrogen is containing potassium oxide (K
2o) 34.6%, Vanadium Pentoxide in FLAKES (P
2o
5) 52.2%.Potassium primary phosphate (KH
2pO
4) be a kind of rhomboidal crystal of colourless or white band gloss, can be water-soluble, react acid, be insoluble to alcohol.Due to the character that it is special, potassium primary phosphate is a kind of important chemical goods, has a wide range of applications in industries such as agricultural, industry, food, medicine.
1821, potassium primary phosphate was produced out first, and it first neutralization reaction occurs by phosphoric acid and solution of potassium carbonate, and then crystallization obtains.Originally, prepare potassium primary phosphate in this way, just as theoretical investigation, not used for commercial use.Until eighties of last century sixties, countries in the world just start to carry out deep research to the theoretical basis of its process and technique, propose several production technique, as neutralisation, KCl and phosphoric acid high temperature double decomposition, and ion exchange method, solvent extration etc.
At present, main method and the quality thereof of producing potassium primary phosphate have following:
1, neutralisation: in the enterprise of existing potassium primary phosphate, major part adopts neutralisation technique, this method technical process is simple, technology maturation, facility investment is few, stable and reliable product quality, but with thermal phosphoric acid and potassium hydroxide for raw material, expensive, production cost is too high, makes its use range receive certain limitation.
2, Repone K high temperature double decomposition: owing to being take KCl as raw material, therefore there is certain cost advantage, but production process heat exhaustion is very large, and equipment corrosion is serious, also quality product can be caused poor because of side reaction.
3, solvent extration technical process is simple, and scale is changeable, and react under low temperature, equipment corrosion is little, and cost is low, pollutes without " three wastes ", and shortcoming is that organic solvent is expensive, still has now the loss of solvent and the problem of inactivation to fail to be solved well.
4, conversion method: with technical grade phposphate Repone K, obtain potassium primary phosphate, by-product hydrochloric acid, this method temperature of reaction is high, and corrosion protection of equipment is difficult to reach a standard.
5, ion exchange method: utilize ion exchange resin respectively to H
2pO
4 -and K
+absorption and regeneration process generate potassium primary phosphate, the disadvantage of this production method is that the water yield of evaporation is too large, and energy consumption is too high.
6, direct method: directly use ground phosphate rock, sulfuric acid and KCl production potassium primary phosphate is that early seventies is carried on by Irish Ge Erding company and Yi Er company of this race of the U.S..The greatest problem of this method is that ground phosphate rock fluorine content is high, generates the potassium silicofluoride of indissoluble in reaction process, and add and generate a part of syngenite, the loss of potassium reaches more than 20%, cannot reach a standard economically.Also because ground phosphate rock impurity is many, cause potassium primary phosphate of poor quality.
Due to aforesaid method drawback separately, up to the present, also do not have fairly large production line, cause the potassium primary phosphate source of goods on market in short supply, product price remains high always.Applicant is according to practical situation, (Wet Phosphoric Acid Market is with strong acid and phosphorus ore direct reaction to develop purifying phosphoric acid in a wet process, because its foreign matter content is high, so also through decolouring, extraction treatment, obtained after reducing foreign matter content) be raw material, the potassium hydroxide adopting potassium sulfate to substitute high price carries out the production technique of potassium primary phosphate.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of method of Wet Phosphoric Acid Market and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, and the method production cost is low, yield is high, be easy to industrial applications.
The technical solution adopted for the present invention to solve the technical problems is: the method using Wet Phosphoric Acid Market and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, is characterized in that comprising the steps:
A, in Wet Phosphoric Acid Market, add potassium sulfate make it dissolve completely, the add-on ratio of potassium sulfate: P ︰ K=0.6 ~ 1.2 ︰ 1;
B, by solid content be 50 ~ 90% calcium carbonate slip join stirring reaction in the solution of step a gained, controlling temperature of reaction is 60 ~ 90 DEG C, the add-on ratio of calcium carbonate slip: Ca ︰ S=0.6 ~ 1.2 ︰ 1;
C, step b is reacted after the mixture system that obtains filter, obtain filtrate and filter cake; Filter cake is byproduct phosphogypsum through washing;
D, by the filtrate potassium hydroxide aqueous solution of step c gained or Wet Phosphoric Acid Market adjust ph to 4 ~ 5, then condensing crystal obtains potassium dihydrogen phosphate product.
Wherein, in aforesaid method step a, the temperature of carrying out dissolving when adding potassium sulfate in Wet Phosphoric Acid Market is 70 ~ 80 DEG C, is incubated 5 ~ 10 minutes again after dissolving.
Wherein, in aforesaid method step a, the add-on ratio of potassium sulfate: P ︰ K=1.05 ~ 1.15 ︰ 1.
Wherein, in aforesaid method step b, calcium carbonate slip is joined the temperature of reacting in the solution of step a gained and controls at 70 ~ 80 DEG C.
Wherein, in aforesaid method step b, the add-on ratio of calcium carbonate slip: Ca ︰ S=0.8 ~ 1.1 ︰ 1.
Wherein, in aforesaid method step c, gained filtrate is also through settlement treatment, makes not filter the removing of close grain sedimentation thoroughly in filtrate.
Further, the settling time is 12 ~ 24 hours.
Wherein, in aforesaid method steps d, by step c gained filtrate adjust ph to 4.2 ~ 4.7.
Wherein, in aforesaid method steps d, the concrete steps of condensing crystal are: the filtrate after adjust ph is sent into vacuum vaporation system and concentrates, controlling slip proportion is 1.40 ~ 1.45, then be cooled to 30 ~ 40 DEG C and separate out potassium dihydrogen phosphate crystal, then through centrifugation, the obtained potassium dihydrogen phosphate product of oven dry.
The invention has the beneficial effects as follows: the present invention in a wet process purifying phosphoric acid and cheap potassium sulfate is raw material, and Wet Phosphoric Acid Market foreign matter content is low, can reduce the loss of phosphorus in production process, and potassium sulfate substitutes potassium hydroxide as raw material, reduces costs.Meanwhile, the present invention first allows potassium sulfate be dissolved completely in phosphoric acid, makes it exist with ionic condition, participate in reaction after slurrying calcium carbonate again, reaction can be made more thorough, avoid wrapping up phenomenon, and calcium carbonate meeting is preferential and sulfate radical reacts, and generates the calcium sulfate of indissoluble, inhibits CaHPO
42H
2the generation of O, reduce further the loss of phosphorus.Further, the strict Controlling Technology parameter of the present invention, can obtain the dihydrate gypsum that particle is thick, be easy to separation, also can improve the yield of Vanadium Pentoxide in FLAKES.Therefore, production process of the present invention simple, be easy to control and industrial applications, with low cost, yield is high, P
2o
5yield can reach more than 96%, K
2o yield can reach more than 98%.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of the specific embodiment of the invention, and KDP is potassium primary phosphate.
Embodiment
The present invention selects Wet Phosphoric Acid Market operational path, be conceived to the raw material using relative low price, adopt relatively gentle reaction conditions also to make every effort to higher yield, provide a kind of practical, can be mass-produced, the production method of potassium primary phosphate economic again.Production process mainly contains moltenly to join, slurrying desulfurization, to filter and the step such as the washing of slag, the condensing crystal of the stillness of night.
1, moltenly to join
Wet Phosphoric Acid Market is added in the reactor of a band heating unit, start agitator and be warming up to 70 ~ 80 DEG C; This temperature is that temperature is too low, and potassium sulfate can not dissolve completely in order to potassium sulfate can better be dissolved.
Potassium sulfate adds reactor (preferred P ︰ K=1.05 ~ 1.15 ︰ 1) by the mol ratio that P ︰ K is 0.6 ~ 1.2 ︰ 1, and potassium sulfate dissolves rear insulation reaction 5 ~ 10 minutes completely, obtains one containing K
+, PO
4 3-, SO
4 2+isoionic mixing solutions.And the insulation after potassium sulfate dissolving all exists with ionic condition in order to ensure component each in slip, reduce the parcel in follow-up pulping process and entrainment loss.
H
3PO
4+K
2SO
4=2K
++PO
4 3-+SO
4 2++3H
+
2, slurrying desulfurization
(1) first added water by high-quality calcium carbonate powders and make the slip that solid content is 50% ~ 90%, required moisture comes from the slag washing water of subsequent handling;
(2) slip is slowly added in 1 clear solution obtained, constantly stir slip, guarantee that removal of bubbles is thorough.The add-on of calcium carbonate.
The add-on of calcium carbonate presses the SO in Ca ion and slip
4 2-radiometer, i.e. the ratio of Ca and S, experiment shows, when the calcium carbonate added bring into the molar ratio of Ca and S be 0.6 ~ 1.2 time, sweetening effectiveness is good, most preferably 0.8 ~ 1.1.If this place's calcium carbonate add-on deficiency can cause SO in slip
4 2-content is higher, affects the main content of product; And calcium carbonate adds too much, then unnecessary Ca will combine with phosphoric acid, forms calcium phosphate salt, separates out, affect P with the form precipitated
2o
5yield.
(3) Controlling System temperature of reaction 60 ~ 90 DEG C, preferably 70 ~ 80 DEG C, guarantee that gypsum produces two water crystallization things, particle is thick; 30 minutes reaction times was advisable.
Principal reaction has:
CaCO
3+SO
4 2++H
+=CaSO
4↓+CO
2↑+H
2O
Process simultaneously also can with certain side reaction, and along with adding gradually of calcium carbonate, solution ph constantly rises, the Fe of trace in purifying phosphoric acid
3+, A1
3+, Mg
2+, F
-, S0
4 2-can with CaS0 Deng impurity
42H
20, CaF
2, A1P0
4, FeP0
4form Deng salt is precipitated out.Be difficult in the process avoid the phosphorus having part with Ca (H
2pO
4)
2form separate out, cause P
2o
5loss.
3, the washing of filtration and slag
(1) slip after having reacted pumps into filter equipment and filters.This filter plant can be band filter, also can be plate-and-frame filter press;
(2) gained clear liquid enters subsider, can slowly stir in subsider, makes not filter in the stillness of night thin brilliant crystallization again thoroughly and precipitates with the form of postprecipitation salt.Settling time is 12 ~ 24 hours, and the clear liquid foreign matter content after sedimentation can be down to less than 1%;
(3) a certain amount of P is contained in filter residue
2o
5and K
2the useful components such as O, need through secondary washing, guarantee P wherein
2o
5content is down to less than 0.5%.The gypsum tailings of high-quality can be used as building materials, mould etc. and directly uses.
The residue washing water water yield: a wash water add-on: be preferably 1 times of the quantity of slag.
Two wash water add-ons: be preferably 0.5 times of the quantity of slag.
4, the accurate adjustment of clear liquid and condensing crystal
Its pH value is adjusted to 4 ~ 5 by the sedimentation clear liquid potassium hydroxide aqueous solution of above-mentioned (2) gained or Wet Phosphoric Acid Market, preferably 4.2 ~ 4.7; Pump into vacuum vaporation system again to concentrate, controlling slip proportion is 1.40 ~ 1.45.The low meeting of slip pH value herein causes part P
2o
5still exist with the form of phosphoric acid, cannot crystallization, and then affect P
2o
5yield; Slip pH value height can cause having part dipotassium hydrogen phosphate to generate, thus causes the main content of product defective.
Be cooled to 30 ~ 40 DEG C and separate out potassium primary phosphate crystallization, this temperature is selected to be because if temperature is too high, potassium dihydrogen product then cannot be made enough to separate out, and although temperature too low single crystallization yield improves but industrially to drop to lower temperature and need long time, force the required energy consumption of cooling also better in addition, waste energy consumption; Again through centrifugation, oven dry, obtained potassium dihydrogen phosphate product.
Below by embodiment, the specific embodiment of the present invention is further described, but not therefore by protection scope of the present invention restriction in one embodiment.
Embodiment one
This example P ︰ K mol ratio=0.6 ︰ 1, Ca ︰ SO
4mol ratio=0.8 ︰ 1, in Wet Phosphoric Acid Market used, each component concentration is as shown in table 1:
Table 1 Wet Phosphoric Acid Market indices
| Project | P 2O 5 | Fe | As | Mg | F | SO 4 |
| Index/% | 20.12 | 0.0097 | 0.0014 | 0.03 | 0.0054 | 0.19 |
Test potassium sulfate used, potassium hydroxide, calcium carbonate is analytical pure, main content is more than 98;
(1) moltenly to join
Taking 1000g Wet Phosphoric Acid Market adds in the reactor of a band heating unit, start agitator and be warming up to 70 ~ 80 DEG C, then taking potassium sulfate 420g and add dissolving, being incubated 5 ~ 10 minutes after the entry to be completely, guarantee to dissolve completely, and each component exists all in the form of an ion;
(2) slurrying desulfurization
Take high-quality calcium carbonate powders 192.8g, add the slurrying of 128.5g water, be configured to the calcium carbonate slip that solid content is about 60%;
Slip is slowly added in 1 clear solution obtained, constantly stir slip, guarantee that removal of bubbles is thorough.
Controlling System temperature of reaction 70 ~ 80 DEG C, guarantee that gypsum produces two water crystallization things, particle is thick; Reaction times is 30 minutes;
Obtain slip 1525.1g.
(3) washing with slag is filtered
Slip after having reacted carries out suction filtration, obtains filtrate 1164g, filter residue 361g;
Gained clear liquid places clarification in cool place place, and clear liquid pH value is 5.3;
The whole plasm scouring again of filter cake, bath water amount is 361g, obtains filter residue 342g filtrate 380g after suction filtration;
The whole secondary of filter cake plasm scouring again, bath water amount is 171g, the filter residue 324g of suction filtration, filtrate 189g;
Washings returns pulping system, containing P in slag
2o
5be 0.9%, K2O be 0.4%.
(4) accurate adjustment of clear liquid and condensing crystal
Get (3) gained clear liquor, add secondary wet process purifying phosphoric acid 666.76g; Recording KDP slip pH value is 4.32, to its condensing crystal, obtains concentrated solution 825.1g, slip proportion 1.40.Obtain KDP crystallization 550g through cooling down Crystallization Separation, crystalline mother solution 226g, after drying, sample presentation analysed preparation quality is in table 2.System P as calculated
2o
5transformation efficiency (i.e. yield) be 96.4%; System K
2the transformation efficiency (i.e. yield) of O is 98.03%.
Embodiment two
This example P ︰ K mol ratio=1.1 ︰ 1, Ca ︰ SO4 mol ratio=0.9 ︰ 1, Wet Phosphoric Acid Market indices is as table 1.
(1) moltenly to join
Taking 1000g Wet Phosphoric Acid Market adds in the reactor of a band heating unit, start agitator and be warming up to 70 ~ 80 DEG C, then taking potassium sulfate 229g and add dissolving, being incubated 5 ~ 10 minutes after the entry to be completely, guarantee to dissolve completely, and each component exists all in the form of an ion;
(2) slurrying desulfurization
Take high-quality calcium carbonate powders 118.31g, add the slurrying of 78.87g water, be configured to the calcium carbonate slip that solid content is about 60%;
Slip is slowly added in 1 clear solution obtained, constantly stir slip, guarantee that removal of bubbles is thorough.
Controlling System temperature of reaction 70 ~ 80 DEG C, guarantee that gypsum produces two water crystallization things, particle is thick; Reaction times is 30 minutes;
Obtain slip 1290g.
(3) washing with slag is filtered
Slip after having reacted carries out suction filtration, obtains filtrate 1068g, filter residue 222g.
Gained clear liquid places clarification in cool place place, and clear liquid pH value is 3.51;
The whole plasm scouring again of filter cake, bath water amount is 222g, obtains filter residue 210g filtrate 234g after suction filtration;
The whole secondary of filter cake plasm scouring again, bath water amount is 105g, the filter residue 199g of suction filtration, filtrate 116g;
Washings returns pulping system, containing P in slag
2o
5be 0.7%, K2O be 0.4%.
(4) accurate adjustment of clear liquid and condensing crystal
Get (3) gained clear liquor, add potassium hydroxide 11.61g; Recording KDP slip pH value is 4.29, to its condensing crystal, obtains concentrated solution 720g, slip proportion 1.40.Obtain KDP crystallization 251g through cooling down Crystallization Separation, crystalline mother solution 461g, after drying, sample presentation analysed preparation quality is in table 2.System P as calculated
2o
5transformation efficiency be 99.1%, system K
2the transformation efficiency of O is 98.7%.
Embodiment three
This example P ︰ K mol ratio=1.2 ︰ 1, Ca ︰ SO4 mol ratio=1.1 ︰ 1, Wet Phosphoric Acid Market indices is as table 1.
(1) moltenly to join
Taking 1000g Wet Phosphoric Acid Market adds in the reactor of a band heating unit, start agitator and be warming up to 70 ~ 80 DEG C, then taking potassium sulfate 210g and add dissolving, being incubated 5 ~ 10 minutes after the entry to be completely, guarantee to dissolve completely, and each component exists all in the form of an ion;
(2) slurrying desulfurization
Take high-quality calcium carbonate powders 132.6g, add the slurrying of 88.3g water, be configured to the calcium carbonate slip that solid content is about 60%;
Slip is slowly added in 1 clear solution obtained, constantly stir slip, guarantee that removal of bubbles is thorough.
Controlling System temperature of reaction 70 ~ 80 DEG C, guarantee that gypsum produces two water crystallization things, particle is thick; Reaction times is 30 minutes;
Obtain slip 1280g.
(3) washing with slag is filtered
Slip after having reacted carries out suction filtration, obtains filtrate 1032g, filter residue 248g.
Gained clear liquid places clarification in cool place place, and clear liquid pH value is 3.02;
The whole plasm scouring again of filter cake, bath water amount is 248g, obtains filter residue 235g filtrate 261g after suction filtration;
The whole secondary of filter cake plasm scouring again, bath water amount is 118g, the filter residue 224g of suction filtration, filtrate 129g;
Washings returns pulping system, containing P in slag
2o
5be 0.8%, K2O be 0.4%.
(4) accurate adjustment of clear liquid and condensing crystal
Get (3) gained clear liquor, add potassium hydroxide 21.29g; Recording KDP slip pH value is 4.40, to its condensing crystal, obtains concentrated solution 688g, slip proportion 1.41.Obtain KDP crystallization 256g through cooling down Crystallization Separation, crystalline mother solution 275.1g, after drying, sample presentation analysed preparation quality is in table 2.System P as calculated
2o
5transformation efficiency be 99.1%, system K
2the transformation efficiency of O is 99.8%.
The each embodiment product index of table 2
P in byproduct phosphogypsum in embodiment one, two and three
2o
5content be respectively 0.9%, 0.7%, 0.7%; K
2the content of O is respectively 0.4%, 0.3%, 0.5%; Because phosphoric acid by wet process have passed through primary purification process, do not detect other foreign ions, CaSO
4main content reaches more than 90%, and quality is more excellent.
From embodiment, the present invention, by reasonable disposition principle, Controlling Technology process and parameter, makes P
2o
5yield can reach more than 96%, K
2o yield can reach more than 98%, product potassium primary phosphate and phosphogypsum foreign matter content few, quality is high, and technological process is simple, is easy to industrial applications.
Claims (3)
1. use the method for Wet Phosphoric Acid Market and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, it is characterized in that comprising the steps:
A, in Wet Phosphoric Acid Market, add potassium sulfate make it dissolve completely, the add-on ratio of potassium sulfate: P ︰ K=1.05 ~ 1.15 ︰ 1; The temperature of carrying out dissolving when adding potassium sulfate in Wet Phosphoric Acid Market is 70 ~ 80 DEG C, is incubated 5 ~ 10 minutes again after dissolving;
B, by solid content be 50 ~ 90% calcium carbonate slip join stirring reaction in the solution of step a gained, controlling temperature of reaction is 70 ~ 80 DEG C, the add-on ratio of calcium carbonate slip: Ca ︰ S=0.8 ~ 1.1 ︰ 1;
C, step b is reacted after the mixture system that obtains filter, obtain filtrate and filter cake; Filter cake is byproduct phosphogypsum through washing; Filtrate is also through settlement treatment, and make not filter the removing of close grain sedimentation thoroughly in filtrate, the settling time is 12 ~ 24 hours;
D, by the filtrate potassium hydroxide aqueous solution of step c gained or Wet Phosphoric Acid Market adjust ph to 4 ~ 5, then condensing crystal obtains potassium dihydrogen phosphate product.
2. the method for Wet Phosphoric Acid Market according to claim 1 and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, is characterized in that: in steps d, by step c gained filtrate adjust ph to 4.2 ~ 4.7.
3. the method for Wet Phosphoric Acid Market according to claim 1 and potassium sulfate production PHOSPHORIC ACID TECH.GRADE potassium dihydrogen, it is characterized in that: in steps d, the concrete steps of condensing crystal are: the filtrate after adjust ph is sent into vacuum vaporation system and concentrates, controlling slip proportion is 1.40 ~ 1.45, then be cooled to 30 ~ 40 DEG C and separate out potassium dihydrogen phosphate crystal, then through centrifugation, the obtained potassium dihydrogen phosphate product of oven dry.
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| CN106430132A (en) * | 2016-11-04 | 2017-02-22 | 湖北三宁化工股份有限公司 | Method for preparing monopotassium phosphate and co-product ammonium sulfate by circulation method |
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| CN112758906A (en) * | 2020-12-31 | 2021-05-07 | 谢坪 | Process for producing potassium dihydrogen phosphate |
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| CN116216673B (en) * | 2022-12-29 | 2024-12-10 | 瓮福（集团）有限责任公司 | A production process of potassium dihydrogen phosphate |
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