CN105154979B - A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity - Google Patents
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity Download PDFInfo
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- CN105154979B CN105154979B CN201510597990.6A CN201510597990A CN105154979B CN 105154979 B CN105154979 B CN 105154979B CN 201510597990 A CN201510597990 A CN 201510597990A CN 105154979 B CN105154979 B CN 105154979B
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 244
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 122
- 238000000034 method Methods 0.000 title claims abstract description 49
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 230000008569 process Effects 0.000 title claims abstract description 18
- 239000006227 byproduct Substances 0.000 title claims abstract description 17
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 254
- 238000006243 chemical reaction Methods 0.000 claims abstract description 139
- 239000007787 solid Substances 0.000 claims abstract description 109
- 239000007788 liquid Substances 0.000 claims abstract description 78
- 239000010440 gypsum Substances 0.000 claims abstract description 51
- 229910052602 gypsum Inorganic materials 0.000 claims abstract description 51
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 238000000605 extraction Methods 0.000 claims abstract description 37
- 239000002367 phosphate rock Substances 0.000 claims abstract description 34
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000006210 lotion Substances 0.000 claims abstract description 31
- 238000005406 washing Methods 0.000 claims abstract description 31
- 239000011574 phosphorus Substances 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 29
- 238000002386 leaching Methods 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 28
- 239000000126 substance Substances 0.000 claims abstract description 27
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 26
- 239000003607 modifier Substances 0.000 claims abstract description 21
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 15
- 229910000389 calcium phosphate Inorganic materials 0.000 claims abstract description 12
- YYRMJZQKEFZXMX-UHFFFAOYSA-L calcium bis(dihydrogenphosphate) Chemical compound [Ca+2].OP(O)([O-])=O.OP(O)([O-])=O YYRMJZQKEFZXMX-UHFFFAOYSA-L 0.000 claims abstract description 10
- 229940062672 calcium dihydrogen phosphate Drugs 0.000 claims abstract description 10
- 235000019691 monocalcium phosphate Nutrition 0.000 claims abstract description 10
- 239000000706 filtrate Substances 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 41
- 238000006396 nitration reaction Methods 0.000 claims description 40
- 239000002002 slurry Substances 0.000 claims description 36
- 239000000047 product Substances 0.000 claims description 34
- 238000007865 diluting Methods 0.000 claims description 21
- 239000002253 acid Substances 0.000 claims description 18
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000012546 transfer Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 239000010452 phosphate Substances 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 3
- 229930002839 ionone Natural products 0.000 claims 1
- 150000002499 ionone derivatives Chemical class 0.000 claims 1
- 239000000344 soap Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 44
- 238000010790 dilution Methods 0.000 description 43
- 239000012895 dilution Substances 0.000 description 43
- 230000008676 import Effects 0.000 description 22
- 239000002994 raw material Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 239000000284 extract Substances 0.000 description 10
- 230000035611 feeding Effects 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- -1 phosphogypsum dihydrate Chemical class 0.000 description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000005864 Sulphur Substances 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 6
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 6
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 6
- 239000001509 sodium citrate Substances 0.000 description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 244000248349 Citrus limon Species 0.000 description 5
- 235000005979 Citrus limon Nutrition 0.000 description 5
- NJXVPIZBZLQQPB-UHFFFAOYSA-N N1=CC=CC2=CC=CC=C12.[Mo] Chemical compound N1=CC=CC2=CC=CC=C12.[Mo] NJXVPIZBZLQQPB-UHFFFAOYSA-N 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 150000002576 ketones Chemical class 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229960005069 calcium Drugs 0.000 description 4
- 239000011575 calcium Substances 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 239000006071 cream Substances 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 239000004337 magnesium citrate Substances 0.000 description 3
- 229960005336 magnesium citrate Drugs 0.000 description 3
- 235000002538 magnesium citrate Nutrition 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 235000019341 magnesium sulphate Nutrition 0.000 description 3
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 description 3
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 3
- 229910000165 zinc phosphate Inorganic materials 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 2
- 229960001714 calcium phosphate Drugs 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 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 2
- 239000002699 waste material Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The present invention relates to a kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, phosphoric acid and ground phosphate rock are added in extraction tank after extractive reaction, sulfuric acid is added to continue to react, 30%~50% calcium ion is set to generate dihydrate gypsum, dihydrate gypsum feeding is turned in brilliant groove, crystal modifier is added, 30%~50% common αsemiwatergypsum whisker is obtained.Other 50%~70% calcium ion is present in phosphoric acid leaching liquid with the form of calcium dihydrogen phosphate, phosphoric acid leaching liquid is imported into decalcification reactive tank after separation, after the sulfuric acid solution that addition washing lotion dilutes, then first decalcification carries out solid turning the brilliant reaction generation high whiteness αsemiwatergypsum whisker of high-purity.The present invention had both reduced the content of phosphorus in accessory substance αsemiwatergypsum whisker, and the industrialized production of the common αsemiwatergypsum whisker of phosphoric acid by wet process by-product and the high whiteness αsemiwatergypsum whisker of high-purity is realized again, different demand of industrial production and the market demand can be met.
Description
Technical field
The present invention relates to a kind of production method of αsemiwatergypsum whisker, and in particular to one kind production phosphoric acid by wet process by-product α half
The method of water crystal whisker of gypsum and the high whiteness αsemiwatergypsum whisker of high-purity.
Background technology
αsemiwatergypsum whisker has higher intensity and use value.Calcium sulfate crystal whiskers have compared with other chopped fibers
The advantages of affinity of the polymer such as high temperature resistant, resist chemical, good toughness, intensity height and rubber plastic is strong, and price
Minimum in whisker, there is the unrivaled cost performance of other whiskers only the 1/200~1/300 of the whisker such as carborundum, using model
Enclose widely, be a kind of function admirable, cheap green material, with the very strong market competitiveness.
Chinese patent document CN1584130A (application numbers：200410024348.0) disclose one kind stone is manufactured in phosphoric acid
The method of cream whisker.This method is to carry out leaching chemical reaction, control using the phosphoric acid that excessive concentration is 30~40% and phosphorus ore
Temperature processed is 50-95 DEG C, by the reaction of 2-4 hours, separates liquid phase and is filtered, and obtains containing H3PO43-4mol/L,
Ca2+0.8-1.2mol/L phosphoric acid leaching liquid.Phosphoric acid leaching liquid is gradually added into the sulfuric acid solution that concentration is 30-35%,
Stirring reaction 120~150 minutes under conditions of 50~100 DEG C.Then above-mentioned crystal whisker of gypsum suspension is filtered, washed with boiling water
Afterwards, dried at a temperature of 120~200 DEG C.Although this method can produce semi-hydrated gypsum whisker or anhydrous gypsum whisker, the party
The deficiency of method is that the content of phosphorus pentoxide in the crystal whisker of gypsum generated is about 0.5% or so, is difficult to using this method into one
The phosphorus content of step reduction whisker.
Chinese patent document CN1796285A (application numbers：200410093472.2) disclose a kind of preparation of crystal whisker of gypsum
Method, it is characterized in that：The preparation method of the crystal whisker of gypsum comprises the following steps, and chemical gypsum is purified to dihydrate gypsum by a.；
B. the chemical gypsum of purification is added water levigate, the slurry of acquisition squeezes into glassed steel reaction vessels；C. hydrochloric acid or chlorine are added into it again
Salt, boils to gypsum dissolution；D. the solution of dissolving is recrystallized into dihydrate gypsum whisker by stirring, cooling；E. crystallization is produced
Thing is dried；F. the neutralized processing of dihydrate gypsum whisker dried, obtains wet dihydrate gypsum whisker primary product.This method is only obtained
Dihydrate gypsum whisker is obtained, it is necessary to further be dehydrated or turn crystalline substance, the higher semi-hydrated gypsum whisker of use value could be obtained.
Chinese patent document CN103526277A (application numbers：201310508201.8) disclose a kind of manufacture cross section and be
Hexagon and the method with low phosphorus content crystal whisker of gypsum.This method includes forming steps, the calcium phosphate solution of calcium phosphate solution
The step of with sulfuric acid reaction and the forming steps of half water or crystal whisker of gypsum.This method is only limitted to the laboratory research stage, does not apply
In industrialization large-scale production.
By retrieval, having not yet to see phosphoric acid by wet process can be while the industrialization of two kinds of αsemiwatergypsum whiskers of by-product be extensive
The Patents and report of production technology and method.
The content of the invention
Cause ardealite for phosphorus content height in the accessory substance phosphogypsum dihydrate whisker of above-mentioned phosphoric acid by wet process in the prior art
Value is low, and in the prior art without while can be with the present situation of the production method of two kinds of αsemiwatergypsum whiskers of by-product, originally
Invention provides a kind of side for producing the common αsemiwatergypsum whisker of phosphoric acid by wet process by-product and the high whiteness αsemiwatergypsum whisker of high-purity
Method, had both reduced the content of phosphorus in accessory substance αsemiwatergypsum whisker, and phosphorus content is reduced to less than 0.1%, wet method is realized again
The industrialization large-scale production of the common αsemiwatergypsum whisker of phosphoric acid by-product and the high whiteness αsemiwatergypsum whisker of high-purity, can meet
Different demand of industrial production and the market demand.
Technical scheme is as follows：
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include following steps：
(1) after mixing phosphoric acid and ground phosphate rock, extractive reaction is carried out under stirring condition, after extractive reaction is complete, sulphur is added
Acid solution, the addition control of sulfuric acid solution makes 30%~50% calcium ion generate dihydrate gypsum, in addition 50%~70% calcium
Ion exists with the form of calcium dihydrogen phosphate, continues stirring reaction, obtains extraction slurry；Slurry separation of solid and liquid will be extracted, phosphorus is obtained
Acid leaching liquid A and slurry B；
(2) the phosphoric acid leaching liquid A obtained in step (1) is mixed into progress decalcification reaction with sulfuric acid solution, after the completion of reaction,
Separation of solid and liquid, obtains solid C and filtrate D；D points of obtained filtrate is four parts, is respectively used to step (1) extractive reaction, step
(3) turn brilliant reaction, step (4) and turn brilliant reaction, as phosphoric acid finished product；
(3) the solid C obtained in step (2) is added into filtrate D, sulfuric acid solution and crystal modifier to carry out turning brilliant reaction, reaction
After finishing, separation of solid and liquid is carried out, solid E and filtrate F is obtained；Turn in brilliant reaction system comprising mixing that sulfuric acid and phosphoric acid are constituted
Acid, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 12~20%, and phosphoric acid is with P2O5Meter accounts for the mass fraction of nitration mixture
20~30%；
Obtained filtrate F is mixed into progress circulation with solid C and turns brilliant reaction, solid E is with 80~100 DEG C of hot wash
Afterwards, solid G and washing lotion H are obtained；Washing lotion H is used for diluting concentrated sulfuric acid and provides sulfuric acid solution, and solid G is the high whiteness α of high-purity half
Water crystal whisker of gypsum；
(4) the slurry B obtained in step (1) is added into filtrate D, sulfuric acid solution and crystal modifier to carry out turning brilliant reaction, reaction
After finishing, separation of solid and liquid is carried out, solid I and filtrate J is obtained；Turn in brilliant reaction system comprising mixing that sulfuric acid and phosphoric acid are constituted
Acid, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 12~20%, and phosphoric acid is with P2O5Meter accounts for the mass fraction of nitration mixture
20~30%；
By J points of two parts of filtrate, it is respectively used to step (1) extractive reaction, the brilliant reaction of progress circulation turn is mixed with slurry B；
Solid I obtains solid K and washing lotion L with after 80~100 DEG C of hot wash；It is molten that washing lotion L is used for diluting concentrated sulfuric acid offer sulfuric acid
Liquid, solid K is αsemiwatergypsum whisker.
According to currently preferred, the fineness of ground phosphate rock is 80~100 mesh in step (1), and the concentration of phosphoric acid is with H3PO4Meter
For 20~35wt%, the solid-liquid mass ratio of ground phosphate rock and phosphoric acid used is 1:15~45.
According to currently preferred, extractive reaction and the reaction temperature added after sulfuric acid solution are 50 in step (1)
~80 DEG C, 1.5~6h of extractive reaction time is added and is continued 1~3h of stirring reaction after sulfuric acid solution.
It is 20~40wt% according to the concentration of currently preferred, described sulfuric acid solution used.
According to currently preferred, the concentration of phosphoric acid is 2~4mol/L in phosphoric acid leaching liquid A in step (1), calcium ion
Concentration is 0.5~2.0mol/L.
According to currently preferred, extractive reaction and the reaction that adds after sulfuric acid solution are in extraction tank in step (1)
Carry out.
According to currently preferred, decalcification reaction temperature is 60 DEG C~130 DEG C in step (2), the reaction time 1.5~
7.5h。
According to currently preferred, the volume ratio of phosphoric acid leaching liquid A and sulfuric acid solution is 1 in step (2)：3~5.
According to currently preferred, decalcification reaction progress in decalcification reactive tank in step (2).
According to currently preferred, the solid mass ratio of liquid of step (3) and (4) transfer crystalline substance reaction is (2~20)：1.
According to currently preferred, step (3) and the brilliant reaction temperature of (4) transfer are 40 DEG C~130 DEG C, when turning brilliant reaction
Between be 1~9h.
According to currently preferred, the crystal modifier described in step (3) and (4) is containing Al3+、Fe3+、Mg2+、K+、Na+、
NH4 +One in the water-soluble phosphate of ion, sulfate, nitrate, citrate, alkylbenzenesulfonate, alkyl fatty hydrochlorate
Plant or two or more combinations.
According to currently preferred, in step (3) and (4), the addition of described crystal modifier, which is accounted for, turns a brilliant reaction system matter
The 0.1~1.0% of amount.
According to currently preferred, step (3) and the reaction of (4) transfer crystalline substance progress in brilliant groove is turned.
According to currently preferred, the brilliant reaction system maintenance turn of vapours importing turn of washing lotion H and L diluting concentrated sulfuric acid generation
Brilliant required temperature and heat.
According to the present invention, ground phosphate rock generates calcium dihydrogen phosphate, the phosphorus of generation by acid decomposed by phosphoric acid in step (1) extractive reaction
Acid dihydride calcium dissolves in phosphoric acid, adds a certain amount of sulfuric acid solution, calcium dihydrogen phosphate in liquid phase is reacted with sulfate radical, generation
Dihydrate gypsum, the addition of the invention by controlling sulfuric acid solution makes calcium ion in reaction system have 30%~50% generation two
Water crystal whisker of gypsum, further turns brilliant into common αsemiwatergypsum by turning brilliant reaction；50%~70% calcium ion is present in di(2-ethylhexyl)phosphate
In hydrogen calcium, by reacting decalcification with sulfuric acid solution, by turning the brilliant reaction generation high whiteness high-quality αsemiwatergypsum whisker of high-purity.
The key that the present invention prepares high-strength αsemiwatergypsum is to select suitable solution system respectively to balance each other gypsum to adjust
Section, crystal modifier of the present invention is containing Al3+、Fe3+、Mg2+、K+、Na+、NH4 +The water-soluble phosphate of ion, sulfate, nitrate,
One or both of citrate, alkylbenzenesulfonate, alkyl fatty hydrochlorate are mixed above, and these contain turn crystalline substance of cation
Agent is conducive to the formation and growth of needle-like or fibrous αsemiwatergypsum whisker crystalline form under conditions of mixture of sulfuric phosphoric acid.
Common αsemiwatergypsum whisker produced by the invention and the high whiteness high-quality αsemiwatergypsum whisker of high-purity are after calcining
The filler and skeleton of common product and high-end product can be done.
Washing lotion is used for diluting concentrated sulfuric acid by the present invention, and one side washing lotion recycles the generation for avoiding waste liquid, on the other hand
The thermogenetic steam of dilution of the concentrated sulfuric acid is made full use of, steam is imported and turns brilliant reaction system maintenance turn brilliant required a temperature and heat
Amount, realizes the recycling of the heat of dilution, factually border production calculation, the common αsemiwatergypsum whisker of 100,000 tons of annual production and 100,000 tons
The production line of the high whiteness αsemiwatergypsum whisker of high-purity, cost-saved about 1,400,000 yuan using the heat of dilution of the concentrated sulfuric acid.
The present invention has the advantage that and beneficial effect：
1. the technique of the present invention realizes calcium resource classified utilization, 30%~50% common αsemiwatergypsum can be produced
Whisker, and 50%~70% high-purity, high whiteness, high-quality αsemiwatergypsum whisker are produced simultaneously.
2. the present invention can use mid low grade phosphate rock, the phosphor resource in phosphorus ore and calcium resource is set all to obtain effective profit
With reduction production cost improves the utilization rate of phosphorus in phosphorus ore, phosphorus content exists in two produced kind αsemiwatergypsum whisker
Less than 0.1%.
3. the present invention prepares αsemiwatergypsum morphology and can controlled, it can be prepared not by the formula for adjusting crystal modifier
With the αsemiwatergypsum whisker of draw ratio, the different market demands can be applicable.
4. present invention process strong applicability, changes available for industrialization large-scale production or to existing phosphoric acid production technique
Make, different industrialization production requirements and the market demand can be met.
5. whole production process is produced without waste residue, waste water, the problem of sulphur dioxide of phosphor chemical industry ardealite discharge is solved, is had preferably
Environmental benefit and economic benefit.
Brief description of the drawings
Fig. 1 is phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum crystalline substance of high-purity in the embodiment of the present invention
The process flow diagram of palpus.
Embodiment
Below by specific embodiment and the present invention will be described in more detail with reference to accompanying drawing, it is necessary to be pointed out that with
Lower embodiment is it is not intended that limiting the scope of the invention, the person skilled in the art in the field is according in the invention described above
Protection scope of the present invention should be belonged to by holding some the nonessential modifications and adaptations made.
Embodiment 1
Raw material 1：Phosphorus ore, collecting location：Open phosphorus in Guizhou；
Raw material 2：Sodium citrate, it is commercially available；
Raw material 3：Aluminum sulfate, it is commercially available；
Raw material 4：Dodecyl sodium sulfate, it is commercially available；
Raw material 5：Sulfuric acid, concentration is 97%, commercially available；
The diluting concentrated sulfuric acid that it is 97wt% with concentration that sulfuric acid solution used, which is, in embodiment is obtained, in sulfuric acid dilution trap
It is middle to carry out.
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include step as follows：
(1) excessive phosphoric acid and ground phosphate rock are added in extraction tank, the solid-liquid mass ratio of ground phosphate rock and phosphoric acid is 1：17, phosphorus
The concentration of acid is 20wt%, under conditions of being stirred continuously, after progress extractive reaction is complete, adds the sulfuric acid that concentration is 30wt%
Solution, controls the addition of sulfuric acid, continues to react, obtains extraction slurry；About 30% calcium ion is set to generate dihydrate gypsum, in addition
70% calcium ion is present in extraction slurry with the form of calcium dihydrogen phosphate, then will extract slurry through filter separation of solid and liquid,
Obtain phosphoric acid leaching liquid A and slurry B.Phosphoric acid is 2.5mol/L wherein in phosphoric acid leaching liquid, and calcium ion is 0.6mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported into decalcification reactive tank, added in decalcification reactive tank
It is that the concentration that 20wt% phosphoric acid solutions dilute is 30wt% sulfuric acid solutions with concentration, maintains temperature to be stirred reaction at 85 DEG C
2h, generation crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter separation of solid and liquid, obtains solid C and filtrate
D, D points of obtained filtrate is four parts, and part, which is imported, to be turned to carry out turning brilliant reaction in brilliant groove I, and part, which is imported, to be turned to carry out in brilliant groove II
Turn brilliant reaction, part imports in extraction tank and extracts rock phosphate in powder, partly send into sour storehouse as phosphoric acid finished product.
(3) solid C feedings turn in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, control
It is 2 to turn the solid mass ratio of liquid in brilliant groove I:1, turn the nitration mixture constituted in brilliant groove I comprising sulfuric acid and phosphoric acid, wherein, sulfuric acid is with H2SO4Meter
The mass fraction for accounting for nitration mixture is 13%, and phosphoric acid is with P2O5The mass fraction that meter accounts for nitration mixture is 21%；By a turn brilliant reaction system quality hundred
Divide than meter, add after crystal modifier sodium citrate 0.11%, dodecyl sodium sulfate 0.03% and aluminum sulfate 0.42%, remain warm
Degree carries out turning brilliant reaction 2h at 100 DEG C, after completion of the reaction, carries out separation of solid and liquid through filter, obtains solid E and filtrate F, filtrate
F, which is imported, to be turned to continue to turn brilliant reaction in brilliant groove I.Solid E is added after 80~100 DEG C of hot washes, obtains solid G and washing lotion H, solid
G is the high whiteness αsemiwatergypsum whisker of high-purity.Washing lotion H, which is imported, is used to diluting concentrated sulfuric acid, the sulphur being diluted in sulfuric acid dilution trap
Acid solution part, which is imported in extraction tank, continues to extract rock phosphate in powder, and part imports decalcification reactive tank and continues decalcification reaction, and part is imported
Turn to participate in turning crystalline substance reaction in brilliant groove I, it is to turn that part, which imports the steam for turning to participate in turning to produce in brilliant reaction, dilution in crystalline substance groove II,
Brilliant groove I turns the brilliant offer of groove II heat of reaction.
(4) the slurry B obtained in above-mentioned steps (1) feedings are turned in brilliant groove II, lead-in portion filtrate D, portion filtrate J,
Dilution heat of sulfuric acid in part of sulfuric acid dilution trap, it is quality 2 to control the liquid-solid ratio turned in brilliant groove II:1, turn to include sulphur in brilliant groove II
The nitration mixture that acid and phosphoric acid are constituted, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 15%.Phosphoric acid is with P2O5Meter accounts for nitration mixture
Mass fraction be 22%.Based on brilliant reaction system mass percent is turned, crystal modifier sodium citrate 0.11%, 12 is then added
Sodium alkyl sulfonate 0.03% and aluminum sulfate 0.42%, maintain temperature to carry out turning brilliant reaction 2h, after completion of the reaction, warp at 100 DEG C
Belt filter carries out separation of solid and liquid, obtains solid I and filtrate J, and filtrate J parts are imported into extraction tank continues to extract ground phosphate rock,
Part, which is imported, to be turned to continue to turn brilliant reaction in brilliant groove II.Solid I obtains solid K and washing lotion L after 80~100 DEG C of hot washes, Gu
Body K is common αsemiwatergypsum whisker, can directly add water and the plasterings such as plasterboard, gypsum block, gypsum component are made.Wash
Liquid L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation：
The quinoline molybdenum lemon ketone gravimetric method detection of product phosphoric acid liquid, concentration 24%wt；The common αsemiwatergypsum whisker P of product2O5
Content 0.06%wt, the high whiteness αsemiwatergypsum whisker P of high product purity2O5Content 0.05%wt；
The common αsemiwatergypsum whisker of product under 200 times of light microscopes be in needle-like or threadiness, draw ratio be 10~
15.Whiteness value is 80.2, and αsemiwatergypsum Whisker Content mass ratio is 87%；
The high whiteness αsemiwatergypsum whisker of high product purity is in needle-like or threadiness, draw ratio under 200 times of light microscopes
For 10~15, whiteness value is 95.6, and αsemiwatergypsum Whisker Content mass ratio is 99.98%.
Embodiment 2
Raw material 1：Phosphorus ore, collecting location：Open phosphorus in Guizhou；
Raw material 2：Sodium citrate, it is commercially available；
Raw material 3：Ferric sulfate, it is commercially available；
Raw material 4：Sulfuric acid, concentration is 97%, commercially available；
The diluting concentrated sulfuric acid that it is 97wt% with concentration that sulfuric acid solution used, which is, in embodiment is obtained, in sulfuric acid dilution trap
It is middle to carry out.
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include step as follows：
(1) solid-liquid mass ratio that ground phosphate rock and excessive phosphoric acid are added into ground phosphate rock and phosphoric acid in extraction tank is 1：20, phosphorus
The concentration of acid is 24wt%, under conditions of being stirred continuously, after progress extractive reaction is complete, adds the sulfuric acid that concentration is 26wt%
Solution, controls the addition of sulfuric acid, continues to react, obtains extraction slurry；About 50% calcium ion is set to generate dihydrate gypsum, in addition
50% calcium ion is present in extraction slurry with the form of calcium dihydrogen phosphate, then will extract slurry through filter separation of solid and liquid,
Obtain phosphoric acid leaching liquid A and slurry B.Phosphoric acid is 2.3mol/L wherein in phosphoric acid leaching liquid, and calcium ion is 0.8mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported into decalcification reactive tank, added in decalcification reactive tank
It is that the concentration that 24wt% phosphoric acid solutions dilute is 26wt% sulfuric acid solutions with concentration, maintains temperature to be stirred reaction at 90 DEG C
2h, generation crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter separation of solid and liquid, obtains solid C and filtrate
D, D points of obtained filtrate is four parts, and part, which is imported, to be turned to carry out turning brilliant reaction in brilliant groove I, and part, which is imported, to be turned to carry out in brilliant groove II
Turn brilliant reaction, part imports in extraction tank and extracts rock phosphate in powder, partly send into sour storehouse as phosphoric acid finished product.
(3) solid C feedings turn in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, control
It is 3 to turn the solid mass ratio of liquid in brilliant groove I:1, turn the nitration mixture constituted in brilliant groove I comprising sulfuric acid and phosphoric acid, wherein, sulfuric acid is with H2SO4Meter
The mass fraction for accounting for nitration mixture is 16%, and phosphoric acid is with P2O5The mass fraction that meter accounts for nitration mixture is 26%；By a turn brilliant reaction system quality hundred
Divide than meter, add after crystal modifier sodium citrate 0.12%, ferric sulfate 0.20%, maintain temperature to turn a brilliant reaction 3h in 110 DEG C of progress,
After completion of the reaction, separation of solid and liquid is carried out through filter, obtains solid E and filtrate F, filtrate F, which is imported, to be turned to continue to turn brilliant anti-in brilliant groove I
Should.Solid E is added after 80~100 DEG C of hot washes, obtains solid G and washing lotion H, solid G is the high water stones of whiteness α half of high-purity
Cream whisker.Washing lotion H, which is imported, is used to diluting concentrated sulfuric acid in sulfuric acid dilution trap, the sulfuric acid solution part being diluted imports extraction tank relaying
Continuous extraction rock phosphate in powder, part imports decalcification reactive tank and continues decalcification reaction, and part, which is imported, to be turned to participate in turning brilliant reaction, portion in brilliant groove I
The steam for dividing importing to turn to participate in producing in a turn crystalline substance reaction, dilution in brilliant groove II provides reaction to turn crystalline substance groove I or a turn brilliant groove II
Heat.
(4) the slurry B obtained in above-mentioned steps (1) feedings are turned in brilliant groove II, lead-in portion filtrate D, portion filtrate J,
Dilution heat of sulfuric acid in part of sulfuric acid dilution trap, it is quality 3 to control the liquid-solid ratio turned in brilliant groove II:1, turn to include sulphur in brilliant groove II
The nitration mixture that acid and phosphoric acid are constituted, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 16%.Phosphoric acid is with P2O5Meter accounts for nitration mixture
Mass fraction be 26%.Based on brilliant reaction system mass percent is turned, then add crystal modifier sodium citrate 0.12% and
Ferric sulfate 0.20%, maintains temperature to carry out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, carries out separation of solid and liquid through filter, obtain
To solid I and filtrate J, filtrate J parts are imported into extraction tank and continue to extract ground phosphate rock, part, which is imported, to be turned to continue to turn crystalline substance in brilliant groove II
Reaction.Solid I obtains solid K and washing lotion L after 80~100 DEG C of hot washes, and solid K is common αsemiwatergypsum whisker,
It can directly add water and the plasterings such as plasterboard, gypsum block, gypsum component are made.Washing lotion L imports sulfuric acid dilution trap and is used for diluting
The concentrated sulfuric acid.
Result of implementation：
The quinoline molybdenum lemon ketone gravimetric method detection of product phosphoric acid liquid, concentration 22%wt；The common αsemiwatergypsum whisker P of product2O5
Content 0.05%wt, the high whiteness αsemiwatergypsum whisker P of high product purity2O5Content 0.05%wt.
The common αsemiwatergypsum whisker of product under 200 times of light microscopes be in needle-like or threadiness, draw ratio be 20~
25.Whiteness value is 80.4, and αsemiwatergypsum Whisker Content mass ratio is 88%.
The high whiteness αsemiwatergypsum whisker of high product purity is in needle-like or threadiness, draw ratio under 200 times of light microscopes
For 20~25, whiteness value is 95.6, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 3
Raw material 1：Phosphorus ore, collecting location：Open phosphorus in Guizhou；
Raw material 2：Magnesium citrate, it is commercially available；
Raw material 3：Aluminum sulfate, it is commercially available；
Raw material 4：Sulfuric acid, concentration is 97%, commercially available；
The diluting concentrated sulfuric acid that it is 97wt% with concentration that sulfuric acid solution used, which is, in embodiment is obtained, in sulfuric acid dilution trap
It is middle to carry out.
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include step as follows：
(1) solid-liquid mass ratio that ground phosphate rock and excessive phosphoric acid are added into ground phosphate rock and phosphoric acid in extraction tank is 1：22, phosphorus
The concentration of acid is 25wt%, under conditions of being stirred continuously, after progress extractive reaction is complete, adds the sulfuric acid that concentration is 26wt%
Solution, controls the addition of sulfuric acid, continues to react, obtains extraction slurry；About 70% calcium ion is set to generate dihydrate gypsum, in addition
30% calcium ion is present in extraction slurry with the form of calcium dihydrogen phosphate, then will extract slurry through filter separation of solid and liquid,
Obtain phosphoric acid leaching liquid A and slurry B.Phosphoric acid is 2.3mol/L wherein in phosphoric acid leaching liquid, and calcium ion is 0.6mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported into decalcification reactive tank, added in decalcification reactive tank
It is that the concentration that 25wt% phosphoric acid solutions dilute is 26wt% sulfuric acid solutions with concentration, maintains temperature to be stirred reaction at 100 DEG C
2h, generation crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter separation of solid and liquid, obtains solid C and filtrate
D, D points of obtained filtrate is four parts, and part, which is imported, to be turned to carry out turning brilliant reaction in brilliant groove I, and part, which is imported, to be turned to carry out in brilliant groove II
Turn brilliant reaction, part imports in extraction tank and extracts rock phosphate in powder, partly send into sour storehouse as phosphoric acid finished product.
(3) solid C feedings turn in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, control
It is 4 to turn the solid mass ratio of liquid in brilliant groove I:1, turn the nitration mixture constituted in brilliant groove I comprising sulfuric acid and phosphoric acid, wherein, sulfuric acid is with H2SO4Meter
The mass fraction for accounting for nitration mixture is 14%, and phosphoric acid is with P2O5The mass fraction that meter accounts for nitration mixture is 23%；By a turn brilliant reaction system quality hundred
Divide than meter, add after crystal modifier magnesium citrate 0.12%, aluminum sulfate 0.21%, maintain temperature to turn a brilliant reaction 3h in 110 DEG C of progress,
After completion of the reaction, separation of solid and liquid is carried out through filter, obtains solid E and filtrate F, filtrate F, which is imported, to be turned to continue to turn brilliant anti-in brilliant groove I
Should.Solid E is added after 80~100 DEG C of hot washes, obtains solid G and washing lotion H, solid G is the high water stones of whiteness α half of high-purity
Cream whisker.Washing lotion H, which is imported, is used to diluting concentrated sulfuric acid in sulfuric acid dilution trap, the sulfuric acid solution part being diluted imports extraction tank relaying
Continuous extraction rock phosphate in powder, part imports decalcification reactive tank and continues decalcification reaction, and part, which is imported, to be turned to participate in turning brilliant reaction, portion in brilliant groove I
The steam for dividing importing to turn to participate in producing in a turn crystalline substance reaction, dilution in brilliant groove II provides reaction to turn crystalline substance groove I or a turn brilliant groove II
Heat.
(4) the slurry B obtained in above-mentioned steps (1) feedings are turned in brilliant groove II, lead-in portion filtrate D, portion filtrate J,
Dilution heat of sulfuric acid in part of sulfuric acid dilution trap, it is quality 3 to control the liquid-solid ratio turned in brilliant groove II:1, turn to include sulphur in brilliant groove II
The nitration mixture that acid and phosphoric acid are constituted, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 14%.Phosphoric acid is with P2O5Meter accounts for nitration mixture
Mass fraction be 23%.Based on brilliant reaction system mass percent is turned, then add crystal modifier magnesium citrate 0.12% and
Aluminum sulfate 0.21%, maintains temperature to carry out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, carries out separation of solid and liquid through filter, obtain
To solid I and filtrate J, filtrate J parts are imported into extraction tank and continue to extract ground phosphate rock, part, which is imported, to be turned to continue to turn crystalline substance in brilliant groove II
Reaction.Solid I obtains solid K and washing lotion L after 80~100 DEG C of hot washes, and solid K is common αsemiwatergypsum whisker,
It can directly add water and the plasterings such as plasterboard, gypsum block, gypsum component are made.Washing lotion L imports sulfuric acid dilution trap and is used for diluting
The concentrated sulfuric acid.
Result of implementation：
The quinoline molybdenum lemon ketone gravimetric method detection of product phosphoric acid liquid, concentration 22%wt；The common αsemiwatergypsum whisker P of product2O5
Content 0.04%wt, the high whiteness αsemiwatergypsum whisker P of high product purity2O5Content 0.03%wt.
The common αsemiwatergypsum whisker of product under 200 times of light microscopes be in needle-like or threadiness, draw ratio be 30~
40.Whiteness value is 80.8, and αsemiwatergypsum Whisker Content mass ratio is 86%.
The high whiteness αsemiwatergypsum whisker of high product purity is in needle-like or threadiness, draw ratio under 200 times of light microscopes
For 30~40, whiteness value is 95.9, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 4
Raw material 1：Phosphorus ore, collecting location：Open phosphorus in Guizhou；
Raw material 2：Ferric sulfate, it is commercially available；
Raw material 3：Sodium carboxymethylcellulose, it is commercially available；
Raw material 4：Sulfuric acid, concentration is 97%, commercially available；
The diluting concentrated sulfuric acid that it is 97wt% with concentration that sulfuric acid solution used, which is, in embodiment is obtained, in sulfuric acid dilution trap
It is middle to carry out.
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include step as follows：
(1) solid-liquid mass ratio that ground phosphate rock and excessive phosphoric acid are added into ground phosphate rock and phosphoric acid in extraction tank is 1：25, phosphorus
The concentration of acid is 26wt%, under conditions of being stirred continuously, after progress extractive reaction is complete, adds the sulfuric acid that concentration is 26wt%
Solution, controls the addition of sulfuric acid, continues to react, obtains extraction slurry；About 60% calcium ion is set to generate dihydrate gypsum, in addition
40% calcium ion is present in extraction slurry with the form of calcium dihydrogen phosphate, then will extract slurry through filter separation of solid and liquid,
Obtain phosphoric acid leaching liquid A and slurry B.Phosphoric acid is 2.7mol/L wherein in phosphoric acid leaching liquid, and calcium ion is 0.7mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported into decalcification reactive tank, added in decalcification reactive tank
It is that the concentration that 26wt% phosphoric acid solutions dilute is 26wt% sulfuric acid solutions with concentration, maintains temperature to be stirred reaction at 90 DEG C
2h, generation crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter separation of solid and liquid, obtains solid C and filtrate
D, D points of obtained filtrate is four parts, and part, which is imported, to be turned to carry out turning brilliant reaction in brilliant groove I, and part, which is imported, to be turned to carry out in brilliant groove II
Turn brilliant reaction, part imports in extraction tank and extracts rock phosphate in powder, partly send into sour storehouse as phosphoric acid finished product.
(3) solid C feedings turn in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, control
It is 5 to turn the solid mass ratio of liquid in brilliant groove I:1, turn the nitration mixture constituted in brilliant groove I comprising sulfuric acid and phosphoric acid, wherein, sulfuric acid is with H2SO4Meter
The mass fraction for accounting for nitration mixture is 15%, and phosphoric acid is with P2O5The mass fraction that meter accounts for nitration mixture is 25%；By a turn brilliant reaction system quality hundred
Divide than meter, add after crystal modifier ferric sulfate 0.20%, sodium carboxymethylcellulose 0.07%, maintain temperature to turn crystalline substance in 110 DEG C of progress
2h is reacted, after completion of the reaction, separation of solid and liquid is carried out through filter, solid E and filtrate F is obtained, filtrate F imports a turn brilliant groove I and relayed
It is continuous to turn brilliant reaction.Solid E is added after 80~100 DEG C of hot washes, obtains solid G and washing lotion H, solid G is high-purity Gao Bai
Spend αsemiwatergypsum whisker.Washing lotion H, which is imported, is used to diluting concentrated sulfuric acid in sulfuric acid dilution trap, the sulfuric acid solution part being diluted is imported
Continue to extract rock phosphate in powder in extraction tank, part imports decalcification reactive tank and continues decalcification reaction, and part, which is imported, to be turned to participate in turning in brilliant groove I
Crystalline substance reacts, and partly imports the steam for turning to be produced in brilliant groove II in the brilliant reaction of participation turn, dilution for turn crystalline substance groove I or turns brilliant groove II
Heat of reaction is provided.
(4) the slurry B obtained in above-mentioned steps (1) feedings are turned in brilliant groove II, lead-in portion filtrate D, portion filtrate J,
Dilution heat of sulfuric acid in part of sulfuric acid dilution trap, it is quality 5 to control the liquid-solid ratio turned in brilliant groove II:1, turn to include sulphur in brilliant groove II
The nitration mixture that acid and phosphoric acid are constituted, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 15%.Phosphoric acid is with P2O5Meter accounts for nitration mixture
Mass fraction be 25%.Based on brilliant reaction system mass percent is turned, crystal modifier ferric sulfate 0.20%, carboxymethyl are then added
After sodium cellulosate 0.07%, maintain temperature to carry out turning brilliant reaction 2h at 110 DEG C, after completion of the reaction, solid-liquid point is carried out through filter
From obtaining solid I and filtrate J, filtrate J parts are imported into extraction tank continues to extract ground phosphate rock, part, which is imported, to be turned a brilliant groove II and relay
It is continuous to turn brilliant reaction.Solid I obtains solid K and washing lotion L after 80~100 DEG C of hot washes, and solid K is common αsemiwatergypsum
Whisker, can directly add water and the plasterings such as plasterboard, gypsum block, gypsum component are made.Washing lotion L imports sulfuric acid dilution trap and is used for
Diluting concentrated sulfuric acid.
Result of implementation：
The quinoline molybdenum lemon ketone gravimetric method detection of product phosphoric acid liquid, concentration 26%wt；The common αsemiwatergypsum whisker P of product2O5
Content 0.06%wt, the high whiteness αsemiwatergypsum whisker P of high product purity2O5Content 0.04%wt.
The common αsemiwatergypsum whisker of product under 200 times of light microscopes be in needle-like or threadiness, draw ratio be 40~
45.Whiteness value is 82.6, and αsemiwatergypsum Whisker Content mass ratio is 87%.
The high whiteness αsemiwatergypsum whisker of high product purity is in needle-like or threadiness, draw ratio under 200 times of light microscopes
For 40~45, whiteness value is 97.4, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 5
Raw material 1：Phosphorus ore, collecting location：Open phosphorus in Guizhou；
Raw material 2：Trbasic zinc phosphate, it is commercially available；
Raw material 3：Magnesium sulfate, it is commercially available；
Raw material 5：Sulfuric acid, concentration is 97%, commercially available；
The diluting concentrated sulfuric acid that it is 97wt% with concentration that sulfuric acid solution used, which is, in embodiment is obtained, in sulfuric acid dilution trap
It is middle to carry out.
A kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, bag
Include step as follows：
(1) solid-liquid mass ratio that ground phosphate rock and excessive phosphoric acid are added into ground phosphate rock and phosphoric acid in extraction tank is 1：20, phosphorus
The concentration of acid is 25wt%, under conditions of being stirred continuously, after progress extractive reaction is complete, adds the sulfuric acid that concentration is 27wt%
Solution, controls the addition of sulfuric acid, continues to react, obtains extraction slurry；About 50% calcium ion is set to generate dihydrate gypsum, in addition
50% calcium ion is present in extraction slurry with the form of calcium dihydrogen phosphate, then will extract slurry through filter separation of solid and liquid,
Obtain phosphoric acid leaching liquid A and slurry B.Phosphoric acid is 2.2mol/L wherein in phosphoric acid leaching liquid, and calcium ion is 0.9mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported into decalcification reactive tank, added in decalcification reactive tank
It is that the concentration that 25wt% phosphoric acid solutions dilute is 27wt% sulfuric acid solutions with concentration, maintains temperature to be stirred reaction at 90 DEG C
2h, generation crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter separation of solid and liquid, obtains solid C and filtrate
D, D points of obtained filtrate is four parts, and part, which is imported, to be turned to carry out turning brilliant reaction in brilliant groove I, and part, which is imported, to be turned to carry out in brilliant groove II
Turn brilliant reaction, part imports in extraction tank and extracts rock phosphate in powder, partly send into sour storehouse as phosphoric acid finished product.
(3) solid C feedings turn in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, control
It is 6 to turn the solid mass ratio of liquid in brilliant groove I:1, turn the nitration mixture constituted in brilliant groove I comprising sulfuric acid and phosphoric acid, wherein, sulfuric acid is with H2SO4Meter
The mass fraction for accounting for nitration mixture is 20%, and phosphoric acid is with P2O5The mass fraction that meter accounts for nitration mixture is 30%；By a turn brilliant reaction system quality hundred
Divide than meter, add after crystal modifier trbasic zinc phosphate 0.09%, magnesium sulfate 0.21%, maintain temperature to turn a brilliant reaction 3h in 110 DEG C of progress, instead
After should finishing, separation of solid and liquid is carried out through filter, solid E and filtrate F is obtained, filtrate F, which is imported, to be turned to continue to turn brilliant anti-in brilliant groove I
Should.Solid E is added after 80~100 DEG C of hot washes, obtains solid G and washing lotion H, solid G is the high water stones of whiteness α half of high-purity
Cream whisker.Washing lotion H, which is imported, is used to diluting concentrated sulfuric acid in sulfuric acid dilution trap, the sulfuric acid solution part being diluted imports extraction tank relaying
Continuous extraction rock phosphate in powder, part imports decalcification reactive tank and continues decalcification reaction, and part, which is imported, to be turned to participate in turning brilliant reaction, portion in brilliant groove I
The steam for dividing importing to turn to participate in producing in a turn crystalline substance reaction, dilution in brilliant groove II provides reaction to turn crystalline substance groove I or a turn brilliant groove II
Heat.
(4) the slurry B obtained in above-mentioned steps (1) feedings are turned in brilliant groove II, lead-in portion filtrate D, portion filtrate J,
Dilution heat of sulfuric acid in part of sulfuric acid dilution trap, it is quality 6 to control the liquid-solid ratio turned in brilliant groove II:1, turn to include sulphur in brilliant groove II
The nitration mixture that acid and phosphoric acid are constituted, wherein, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 20%.Phosphoric acid is with P2O5Meter accounts for nitration mixture
Mass fraction be 30%.Based on brilliant reaction system mass percent is turned, crystal modifier trbasic zinc phosphate 0.09%, magnesium sulfate are then added
After 0.21%, maintain temperature to carry out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, separation of solid and liquid is carried out through filter, consolidate
Body I and filtrate J, imports extraction tank by filtrate J parts and continues to extract ground phosphate rock, part, which is imported, to be turned to continue to turn brilliant anti-in brilliant groove II
Should.Solid I obtains solid K and washing lotion L after 80~100 DEG C of hot washes, and solid K is common αsemiwatergypsum whisker, can
Directly add water and the plasterings such as plasterboard, gypsum block, gypsum component are made.Washing lotion L imports sulfuric acid dilution trap and is used for diluting dense
Sulfuric acid.
Result of implementation：
The quinoline molybdenum lemon ketone gravimetric method detection of product phosphoric acid liquid, concentration 21%wt；The common αsemiwatergypsum whisker P of product2O5
Content 0.07%wt, the high whiteness αsemiwatergypsum whisker P of high product purity2O5Content 0.06%wt.
The common αsemiwatergypsum whisker of product under 200 times of light microscopes be in needle-like or threadiness, draw ratio be 50~
60.Whiteness value is 81.6, and αsemiwatergypsum Whisker Content mass ratio is 86%.
The high whiteness αsemiwatergypsum whisker of high product purity is in needle-like or threadiness, draw ratio under 200 times of light microscopes
For 50~60, whiteness value is 96.8, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Claims (10)
1. a kind of method for producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and the high whiteness αsemiwatergypsum whisker of high-purity, including
Following steps：
(1) after mixing phosphoric acid and ground phosphate rock, extractive reaction is carried out under stirring condition, after extractive reaction is complete, sulfuric acid is added molten
Liquid, the addition control of sulfuric acid solution makes 30%~50% calcium ion generate dihydrate gypsum, in addition 50%~70% calcium ion
Exist with the form of calcium dihydrogen phosphate, continue stirring reaction, obtain extraction slurry；Slurry separation of solid and liquid will be extracted, phosphoric acid leaching is obtained
Take liquid A and slurry B；
(2) the phosphoric acid leaching liquid A obtained in step (1) is mixed into progress decalcification reaction, after the completion of reaction, solid-liquid with sulfuric acid solution
Separation, obtains solid C and filtrate D；D points of obtained filtrate is four parts, is respectively used to step (1) extractive reaction, step (3) and turns
Crystalline substance reaction, step (4) turn brilliant reaction, are used as phosphoric acid finished product；
(3) the solid C obtained in step (2) is added into filtrate D, sulfuric acid solution and crystal modifier to carry out turning brilliant reaction, reaction is finished
Afterwards, separation of solid and liquid is carried out, solid E and filtrate F is obtained；Turn the nitration mixture constituted in brilliant reaction system comprising sulfuric acid and phosphoric acid, its
In, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 12~20%, and phosphoric acid is with P2O5Meter account for the mass fraction of nitration mixture for 20~
30%；
Obtained filtrate F is mixed into progress circulation with solid C and turns brilliant reaction, solid E is obtained with after 80~100 DEG C of hot wash
To solid G and washing lotion H；Washing lotion H is used for diluting concentrated sulfuric acid and provides sulfuric acid solution, and solid G is the high whiteness αsemiwatergypsum of high-purity
Whisker；
(4) the slurry B obtained in step (1) is added into filtrate D, sulfuric acid solution and crystal modifier to carry out turning brilliant reaction, reaction is finished
Afterwards, separation of solid and liquid is carried out, solid I and filtrate J is obtained；Turn the nitration mixture constituted in brilliant reaction system comprising sulfuric acid and phosphoric acid, its
In, sulfuric acid is with H2SO4The mass fraction that meter accounts for nitration mixture is 12~20%, and phosphoric acid is with P2O5Meter account for the mass fraction of nitration mixture for 20~
30%；
By J points of two parts of filtrate, it is respectively used to step (1) extractive reaction, the brilliant reaction of progress circulation turn is mixed with slurry B；Solid I
After 80~100 DEG C of hot washes, solid K and washing lotion L are obtained；Washing lotion L is used for diluting concentrated sulfuric acid and provides sulfuric acid solution, solid
K is αsemiwatergypsum whisker.
2. according to the method described in claim 1, it is characterised in that the fineness of ground phosphate rock is 80~100 mesh, phosphorus in step (1)
The concentration of acid is with H3PO420~35wt% is calculated as, the solid-liquid mass ratio of ground phosphate rock and phosphoric acid used is 1:15~45.
3. according to the method described in claim 1, it is characterised in that extractive reaction and added in step (1) after sulfuric acid solution
Reaction temperature be 50~80 DEG C, 1.5~6h of extractive reaction time is added and is continued stirring reaction 1~3h after sulfuric acid solution.
4. according to the method described in claim 1, it is characterised in that the concentration of phosphoric acid is 2 in phosphoric acid leaching liquid A in step (1)
~4mol/L, the concentration of calcium ion is 0.5~2.0mol/L.
5. according to the method described in claim 1, it is characterised in that decalcification reaction temperature is 60 DEG C~130 DEG C in step (2),
1.5~7.5h of reaction time.
6. according to the method described in claim 1, it is characterised in that the volume of phosphoric acid leaching liquid A and sulfuric acid solution in step (2)
Than for 1：3~5.
7. according to the method described in claim 1, it is characterised in that step (3) and the solid mass ratio of liquid of (4) transfer crystalline substance reaction are equal
For (2~20)：1.
8. according to the method described in claim 1, it is characterised in that step (3) and the brilliant reaction temperature of (4) transfer be 40 DEG C~
130 DEG C, it is 1~9h to turn the brilliant reaction time.
9. according to the method described in claim 1, it is characterised in that the crystal modifier described in step (3) and (4) is containing Al3+、
Fe3+、Mg2+、K+、Na+、NH4 +Water-soluble phosphate, sulfate, nitrate, citrate, alkylbenzenesulfonate, the alkyl of ion
One or both of soap is mixed above.
10. according to the method described in claim 1, it is characterised in that in step (3) and (4), the addition of described crystal modifier
Account for and turn the 0.1~1.0% of brilliant reaction system quality.
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| CN105543975A (en) * | 2015-12-30 | 2016-05-04 | 常州合肥工业大学研究院 | Method for synthesizing calcium carbonate nanocrystal whiskers on basis of sodium carboxymethyl cellulose and potassium chloride |
| CN108502861B (en) * | 2018-06-25 | 2019-02-22 | 中化重庆涪陵化工有限公司 | Utilize the method and crystallization in motion agent of low-grade phosphate ore production concentrated phosphoric acid coproduction semi-hydrated gypsum whisker |
| CN109112635A (en) * | 2018-08-10 | 2019-01-01 | 瓮福化工科技有限公司 | A method of quickly preparing semi-hydrated gypsum whisker and anhydrous gypsum whisker using ardealite |
| CN109385664B (en) * | 2018-12-17 | 2020-08-04 | 武汉纺织大学 | Preparation method of phosphogypsum whisker |
| CN111559754B (en) * | 2020-04-21 | 2023-06-06 | 贵州大学 | Method for decomposing phosphate rock acidolysis solution by nitric acid to remove calcium and obtain byproduct alpha-type building gypsum |
| CN114275803A (en) * | 2022-01-28 | 2022-04-05 | 贵州大学 | Method for deeply removing calcium and byproduct alpha high-strength gypsum from frozen acidolysis solution in nitrophosphate fertilizer process |
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| JPS5834413B2 (en) * | 1976-02-17 | 1983-07-26 | 三菱化学株式会社 | Method for producing α-type hemihydrate gypsum having needle-like crystals from phosphoric acid by-product dihydrate gypsum |
| JPS59137317A (en) * | 1983-01-27 | 1984-08-07 | Toyo Soda Mfg Co Ltd | Manufacture of needlelike alpha-hemihydrate gypsum |
| CN1314840C (en) * | 2004-06-14 | 2007-05-09 | 青岛科技大学 | Method for producing land plaster whiskers from phosphoric acid |
| CN102303852B (en) * | 2011-04-19 | 2013-01-09 | 江苏瑞和化肥有限公司 | Method for producing phosphoric acid and gypsum whiskers by wet process |
| CN103086335B (en) * | 2013-02-05 | 2014-06-18 | 瓮福（集团）有限责任公司 | Method for production of phosphoric acid and combined production of a-hemihydrate gypsum through dehydrate-hemihydrate wet phosphoric acid technology |
| CN103436950B (en) * | 2013-09-16 | 2016-03-16 | 金正大生态工程集团股份有限公司 | The production method of a kind of decomposing phosphate rock by chlorhydric acid co-producing sulfuric acid calcium pyroborate and ammophos |
| CN103626143A (en) * | 2013-11-29 | 2014-03-12 | 晏明朗 | Method for wet production of phosphoric acid and byproduct, namely white gypsum |
| CN104556189A (en) * | 2014-12-25 | 2015-04-29 | 湖北祥云(集团)化工股份有限公司 | Method for producing white gypsum being by-product of wet process phosphoric acid |
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