CN105154979A - Method for producing wet-process phosphoric acid and coproducing alpha-semi-hydrated gypsum whisker and high-purity high-whiteness alpha-semi-hydrated gypsum whisker - Google Patents
Method for producing wet-process phosphoric acid and coproducing alpha-semi-hydrated gypsum whisker and high-purity high-whiteness alpha-semi-hydrated gypsum whisker Download PDFInfo
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- CN105154979A CN105154979A CN201510597990.6A CN201510597990A CN105154979A CN 105154979 A CN105154979 A CN 105154979A CN 201510597990 A CN201510597990 A CN 201510597990A CN 105154979 A CN105154979 A CN 105154979A
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 256
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 128
- 239000010440 gypsum Substances 0.000 title claims abstract description 58
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 58
- 238000000034 method Methods 0.000 title claims abstract description 57
- 238000004519 manufacturing process Methods 0.000 title abstract description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 219
- 238000006243 chemical reaction Methods 0.000 claims abstract description 150
- 239000007787 solid Substances 0.000 claims abstract description 85
- 238000000605 extraction Methods 0.000 claims abstract description 45
- 239000013078 crystal Substances 0.000 claims abstract description 42
- 239000002367 phosphate rock Substances 0.000 claims abstract description 34
- 238000005406 washing Methods 0.000 claims abstract description 33
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 25
- 239000006227 byproduct Substances 0.000 claims abstract description 17
- 150000004683 dihydrates Chemical class 0.000 claims abstract description 16
- 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 12
- 235000019691 monocalcium phosphate Nutrition 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims description 66
- 239000000706 filtrate Substances 0.000 claims description 61
- 239000000203 mixture Substances 0.000 claims description 59
- 239000001117 sulphuric acid Substances 0.000 claims description 46
- 235000011149 sulphuric acid Nutrition 0.000 claims description 46
- 238000006396 nitration reaction Methods 0.000 claims description 42
- 239000000047 product Substances 0.000 claims description 34
- 239000006210 lotion Substances 0.000 claims description 31
- 238000000926 separation method Methods 0.000 claims description 28
- 238000007865 diluting Methods 0.000 claims description 26
- 238000002386 leaching Methods 0.000 claims description 26
- 239000003607 modifier Substances 0.000 claims description 21
- -1 wherein Substances 0.000 claims description 18
- 239000002893 slag Substances 0.000 claims description 16
- 239000002002 slurry Substances 0.000 claims description 15
- 239000001506 calcium phosphate Substances 0.000 claims description 13
- 229910000150 monocalcium phosphate Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 239000000126 substance Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 6
- 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
- 229910019142 PO4 Inorganic materials 0.000 claims description 3
- 125000000217 alkyl group Chemical group 0.000 claims description 3
- 150000002500 ions Chemical class 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
- 229920002472 Starch Polymers 0.000 claims description 2
- 238000013019 agitation Methods 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 23
- 239000011574 phosphorus Substances 0.000 abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 21
- 229910000389 calcium phosphate Inorganic materials 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract 3
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 abstract 1
- 230000008676 import Effects 0.000 description 51
- 238000010790 dilution Methods 0.000 description 48
- 239000012895 dilution Substances 0.000 description 48
- 239000002994 raw material Substances 0.000 description 21
- 239000000284 extract Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 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
- 239000000725 suspension Substances 0.000 description 6
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 6
- 229940038773 trisodium citrate Drugs 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
- 150000002576 ketones Chemical class 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 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
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000011734 sodium Substances 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
- 229910000831 Steel Inorganic materials 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
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Inorganic materials [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 230000000865 phosphorylative effect Effects 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 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
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a method for producing wet-process phosphoric acid and coproducing alpha-semi-hydrated gypsum whisker and high-purity high-whiteness alpha-semi-hydrated gypsum whisker, which comprises the following steps: adding phosphoric acid and ground phosphorite into an extraction tank to perform extraction reaction, adding sulfuric acid to continue reaction until 30-50% of calcium ions generate dihydrate gypsum, sending the dihydrate gypsum into a crystal transformation tank, and adding a crystal transformation agent to obtain 30-50% of common alpha-semi-hydrated gypsum whisker; and separating the rest 50-70% of calcium ions which exist in the phosphoric acid extracting solution in the form of calcium biphosphate, introducing the phosphoric acid extracting solution into a decalcification reaction tank, adding a sulfuric acid solution diluted by washing liquor, decalcifying, and carrying out crystal transformation reaction on the solid to generate the high-purity high-whiteness alpha-semi-hydrated gypsum whisker. The method lowers the phosphorus content in the byproduct alpha-semi-hydrated gypsum whisker, implements the industrial production of the coproducts common alpha-semi-hydrated gypsum whisker and high-purity high-whiteness alpha-semi-hydrated gypsum whisker from the wet-process phosphoric acid, and can satisfy different industrial production requirements and market demands.
Description
Technical field
The present invention relates to a kind of production method of αsemiwatergypsum whisker, be specifically related to a kind of method of producing phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker.
Background technology
αsemiwatergypsum whisker has higher intensity and use value.Calcium sulfate crystal whiskers is compared with other staple fibres, have high temperature resistant, resist chemical, good toughness, intensity are high, with the advantage such as the affinity of the polymkeric substance such as rubber plastic is strong, and price is minimum in whisker, be only 1/200 ~ 1/300 of the whiskers such as silicon carbide, there is the unrivaled cost performance of other whiskers, range of application widely, is a kind of excellent property, cheap green material, has the very strong market competitiveness.
Chinese patent document CN1584130A (application number: 200410024348.0) disclose a kind of method manufacturing crystal whisker of gypsum in phosphoric acid.The method be use excessive concentration be 30 ~ 40% phosphoric acid and phosphorus ore carry out leaching chemical reaction, control temperature is 50-95 DEG C, through the reaction of 2-4 hour, separates liquid phase and is also filtered, obtain containing H
3pO
43-4mol/L, Ca
2+the phosphoric acid leaching liquid of 0.8-1.2mol/L.Phosphoric acid leaching liquid being added gradually concentration is in the sulphuric acid soln of 30-35%, stirring reaction 120 ~ 150 minutes under the condition of 50 ~ 100 DEG C.Then above-mentioned crystal whisker of gypsum suspension filtered, with after boiling water washing, dry at the temperature of 120 ~ 200 DEG C.Although the method can produce semi-hydrated gypsum whisker or dehydrated gyp-whisker, the deficiency of the method is that the content of Vanadium Pentoxide in FLAKES in the crystal whisker of gypsum generated is about about 0.5%, and application the method is difficult to the phosphorus content reducing whisker further.
Chinese patent document CN1796285A (application number: the preparation method 200410093472.2) disclosing a kind of crystal whisker of gypsum, is characterized by: the preparation method of described crystal whisker of gypsum comprises the following steps, and chemical gypsum is purified to dihydrate gypsum by a.; B. add water levigate by the chemical gypsum of purification, the slurry of acquisition squeezes into glassed steel reaction vessels; C. again to adding hydrochloric acid or villaumite in it, boil to gypsum dissolution; D. the solution of dissolving is gone out dihydrate gypsum whisker through stirring, cooling recrystallization; E. crystallized product is dried; F. the dihydrate gypsum whisker dried, through neutralizing treatment, obtains wet dihydrate gypsum whisker primary products.The method only obtains dihydrate gypsum whisker, needs dehydration further or turns brilliant, could obtain the semi-hydrated gypsum whisker that use value is higher.
Chinese patent document CN103526277A (application number: 201310508201.8) disclose a kind of cross section that manufactures and be hexagon and the method with low phosphorus content crystal whisker of gypsum.The method comprises the forming steps of calcium phosphate solution, calcium phosphate solution and the step of sulfuric acid reaction and the forming steps of half water or crystal whisker of gypsum.The method is only limitted to the laboratory study stage, is not applied to industrialization scale operation.
Through retrieval, having not yet to see phosphoric acid by wet process can simultaneously the industrialization large-scale production process of by-product two kinds of αsemiwatergypsum whiskers and the Patents of method and report.
Summary of the invention
Low for the high phosphogypsum utility value that causes of phosphorus content in the by product phosphogypsum dihydrate whisker of phosphoric acid by wet process in above-mentioned prior art, and not having in prior art simultaneously can the present situation of production method of by-product two kinds of αsemiwatergypsum whiskers, the invention provides a kind of method of producing the common αsemiwatergypsum whisker of phosphoric acid by wet process by-product and high purity high whiteness αsemiwatergypsum whisker, both the content of phosphorus in by product αsemiwatergypsum whisker had been reduced, phosphorus content is made to be reduced to less than 0.1%, achieve again the industrialization scale operation of the common αsemiwatergypsum whisker of phosphoric acid by wet process by-product and high purity high whiteness αsemiwatergypsum whisker, different demand of industrial productions and the market requirement can be met.
Technical scheme of the present invention is as follows:
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise the following steps:
(1) by after phosphoric acid and ground phosphate rock mixing, extractive reaction is carried out under agitation condition, after extractive reaction is complete, add sulphuric acid soln, the add-on of sulphuric acid soln controls make 30% ~ 50% calcium ion generate dihydrate gypsum, other 50% ~ 70% calcium ion exists with the form of monocalcium phosphate, continues stirring reaction, obtains extraction slip; Slip solid-liquid separation will be extracted, obtain phosphoric acid leaching liquid A and slag slurry B;
(2) mixed with sulphuric acid soln by the phosphoric acid leaching liquid A obtained in step (1) and carry out decalcification reaction, after having reacted, solid-liquid separation, obtains solid C and filtrate D; The filtrate D obtained is divided into four parts, is respectively used to step (1) extractive reaction, step (3) turns brilliant reaction, step (4) turns brilliant reaction, as phosphoric acid finished product;
(3) the solid C obtained in step (2) is added filtrate D, sulphuric acid soln and crystal modifier to carry out turning brilliant reaction, after completion of the reaction, carry out solid-liquid separation, obtain solid E and filtrate F; Turn in brilliant reaction system the nitration mixture all comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 12 ~ 20%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 20 ~ 30%;
Mixed with solid C by the filtrate F obtained and carry out circulation and turn brilliant reaction, solid E, with after the hot wash of 80 ~ 100 DEG C, obtains solid G and washing lotion H; Washing lotion H is used for diluting concentrated sulfuric acid provides sulphuric acid soln, and solid G is high purity high whiteness αsemiwatergypsum whisker;
(4) slag obtained in step (1) slurry B is added filtrate D, sulphuric acid soln and crystal modifier to carry out turning brilliant reaction, after completion of the reaction, carry out solid-liquid separation, obtain solid I and filtrate J; Turn in brilliant reaction system the nitration mixture all comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 12 ~ 20%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 20 ~ 30%;
Divide two portions by filtrate J, be respectively used to step (1) extractive reaction, starch B with slag and mix and carry out circulation and turn brilliant reaction; Solid I, with after the hot wash of 80 ~ 100 DEG C, obtains solid K and washing lotion L; Washing lotion L is used for diluting concentrated sulfuric acid provides sulphuric acid soln, and solid K is αsemiwatergypsum whisker.
Preferred according to the present invention, in step (1), the fineness of ground phosphate rock is 80 ~ 100 orders, and the concentration of phosphoric acid is with H
3pO
4count 20 ~ 35wt%, the solid-liquid mass ratio of ground phosphate rock used and phosphoric acid is 1:15 ~ 45.
Preferred according to the present invention, in step (1), extractive reaction and the temperature of reaction after adding sulphuric acid soln are 50 ~ 80 DEG C, and extractive reaction time 1.5 ~ 6h, continues stirring reaction 1 ~ 3h after adding sulphuric acid soln.
Preferred according to the present invention, the concentration of described sulphuric acid soln used is 20 ~ 40wt%.
Preferred according to the present invention, in step (1), in phosphoric acid leaching liquid A, the concentration of phosphoric acid is 2 ~ 4mol/L, and the concentration of calcium ion is 0.5 ~ 2.0mol/L.
Preferred according to the present invention, in step (1), extractive reaction and the reaction after adding sulphuric acid soln are carried out in extraction tank.
Preferred according to the present invention, in step (2), decalcification temperature of reaction is 60 DEG C ~ 130 DEG C, reaction times 1.5 ~ 7.5h.
Preferred according to the present invention, in step (2), the volume ratio of phosphoric acid leaching liquid A and sulphuric acid soln is 1:3 ~ 5.
Preferred according to the present invention, in step (2), decalcification reaction is carried out in decalcification reactive tank.
Preferred according to the present invention, the liquid-solid mass ratio of step (3) and the reaction of (4) transfer crystalline substance is (2 ~ 20): 1.
Preferred according to the present invention, step (3) and the brilliant temperature of reaction of (4) transfer are 40 DEG C ~ 130 DEG C, and turn brilliant reaction times is 1 ~ 9h.
Preferred according to the present invention, step (3) and the crystal modifier described in (4) are containing Al
3+, Fe
3+, Mg
2+, K
+, Na
+, NH
4 +one or more combinations in the water-soluble phosphate of ion, vitriol, nitrate, Citrate trianion, alkylbenzene sulfonate, alkyl fatty hydrochlorate.
Preferred according to the present invention, in step (3) and (4), the addition of described crystal modifier accounts for 0.1 ~ 1.0% of turn brilliant reaction system quality.
Preferred according to the present invention, step (3) and the reaction of (4) transfer crystalline substance are carried out in turn brilliant groove.
Preferred according to the present invention, the hot steam that washing lotion H and L diluting concentrated sulfuric acid produce imports a turn brilliant reaction system and maintains the temperature and heat that turn needed for crystalline substance.
According to the present invention, in step (1) extractive reaction, ground phosphate rock is generated monocalcium phosphate by phosphorolytic cleavage, the monocalcium phosphate generated dissolves in phosphoric acid, add a certain amount of sulphuric acid soln, monocalcium phosphate and sulfate radical in liquid phase are reacted, generates dihydrate gypsum, the present invention is by controlling the add-on of sulphuric acid soln, making calcium ion in reaction system have 30% ~ 50% to generate dihydrate gypsum whisker, turning the common αsemiwatergypsum of brilliant one-tenth further by turning crystalline substance reaction; 50% ~ 70% calcium ion is present in monocalcium phosphate, through reacting decalcification with sulphuric acid soln, generates high purity high whiteness high-quality αsemiwatergypsum whisker by turning brilliant reaction.
The key that the present invention prepares high-strength αsemiwatergypsum selects suitable solution system respectively to balance each other to gypsum to regulate, and crystal modifier of the present invention is containing Al
3+, Fe
3+, Mg
2+, K
+, Na
+, NH
4 +one or more mixing in the water-soluble phosphate of ion, vitriol, nitrate, Citrate trianion, alkylbenzene sulfonate, alkyl fatty hydrochlorate, these contain cationic crystal modifier under the condition of mixture of sulfuric phosphoric acid, are conducive to formation and the growth of needle-like or fibrous αsemiwatergypsum whisker crystalline form.
The common αsemiwatergypsum whisker that the present invention produces and high purity high whiteness high-quality αsemiwatergypsum whisker can do filler and the skeleton of common goods and high-end goods after calcining.
Washing lotion is used for diluting concentrated sulfuric acid by the present invention, washing lotion recycles the generation avoiding waste liquid on the one hand, make full use of the thermogenetic steam of dilution of the vitriol oil on the other hand, steam is imported a turn brilliant reaction system and maintains the temperature and heat that turn needed for crystalline substance, realize dilution pick up the heat, border production calculation factually, the production line of the common αsemiwatergypsum whisker of annual production 100000 tons and 100,000 tons of high purity high whiteness αsemiwatergypsum whiskers, utilizes cost-saved about 1,400,000 yuan of the heat of dilution of the vitriol oil.
The advantage that the present invention has and beneficial effect:
1. technique of the present invention achieves calcium resource classified utilization, can produce the common αsemiwatergypsum whisker of 30% ~ 50%, and produces 50% ~ 70% high purity, high whiteness, high-quality αsemiwatergypsum whisker simultaneously.
2. the present invention can use mid low grade phosphate rock, and the phosphor resource in phosphorus ore and calcium resource are all utilized effectively, and reduce production cost, improve the utilization ratio of phosphorus in phosphorus ore, in the two kinds of αsemiwatergypsum whiskers produced, phosphorus content is below 0.1%.
3. the present invention prepares αsemiwatergypsum morphology and can control, and can be prepared the αsemiwatergypsum whisker of different length-to-diameter ratio, can be suitable for the different market requirements by the formula adjusting crystal modifier.
4. present invention process suitability is strong, can be used for industrialization scale operation or transforms existing phosphoric acid production technique, can meet different industrialization production requirements and the market requirement.
5. whole production process produces without waste residue, waste water, solves a difficult problem for sulphur dioxide of phosphor chemical industry phosphogypsum discharge, has good environmental benefit and economic benefit.
Accompanying drawing explanation
Fig. 1 is the process flow diagram of phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker in the embodiment of the present invention.
Embodiment
Below by specific embodiment, also the present invention will be described in more detail by reference to the accompanying drawings; it is important to point out that following examples can not be interpreted as limiting the scope of the invention, some nonessential improvement that the person skilled in the art in this field does according to the invention described above content and adjustment must belong to protection scope of the present invention.
Embodiment 1
Raw material 1: phosphorus ore, collecting location: phosphorus is opened in Guizhou;
Raw material 2: Trisodium Citrate, commercially available;
Raw material 3: Tai-Ace S 150, commercially available;
Raw material 4: sodium laurylsulfonate, commercially available;
Raw material 5: sulfuric acid, concentration is 97%, commercially available;
The diluting concentrated sulfuric acid that sulphuric acid soln used in embodiment is with concentration is 97wt% obtains, and carries out in sulfuric acid dilution trap.
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise 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, the concentration of phosphoric acid is 20wt%, under the condition constantly stirred, carry out extractive reaction completely after, add the sulphuric acid soln that concentration is 30wt%, control the add-on of sulfuric acid, continue reaction, obtain extraction slip; Make about 30% calcium ion generate dihydrate gypsum, other 70% calcium ion is present in extraction slip with the form of monocalcium phosphate, then will extract slip through filter solid-liquid separation, obtains phosphoric acid leaching liquid A and slag slurry B.Wherein in phosphoric acid leaching liquid, phosphoric acid is 2.5mol/L, and calcium ion is 0.6mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported decalcification reactive tank, the concentration added in decalcification reactive tank with concentration is the dilution of 20wt% phosphoric acid solution is 30wt% sulphuric acid soln, holding temperature carries out stirring reaction 2h at 85 DEG C, generating crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter solid-liquid separation, obtain solid C and filtrate D, the filtrate D obtained is divided into four parts, part imports to turn in brilliant groove I carries out turning brilliant reaction, part imports to turn in brilliant groove II carries out turning brilliant reaction, part imports in extraction tank and extracts Rock Phosphate (72Min BPL), part sends into sour storehouse as phosphoric acid finished product.
(3) solid C sends into and turns in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, and controlling to turn liquid-solid mass ratio in brilliant groove I is 2:1, and turn in brilliant groove I nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 13%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 21%; By turning brilliant reaction system mass percent, after adding crystal modifier Trisodium Citrate 0.11%, sodium laurylsulfonate 0.03% and Tai-Ace S 150 0.42%, holding temperature carries out turning brilliant reaction 2h at 100 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid E and filtrate F, filtrate F imports to turn in brilliant groove I and continues to turn brilliant reaction.Solid E obtains solid G and washing lotion H after adding 80 ~ 100 DEG C of hot washes, and solid G is high purity high whiteness αsemiwatergypsum whisker.Washing lotion H imports in sulfuric acid dilution trap in order to diluting concentrated sulfuric acid, imported in extraction tank by the sulphuric acid soln part of diluting and continue extraction Rock Phosphate (72Min BPL), part imports decalcification reactive tank and continues decalcification reaction, part imports to turn in brilliant groove I and participates in turning brilliant reaction, part imports to turn in brilliant groove II and participates in turning brilliant reaction, and the steam produced in dilution provides heat of reaction for turning brilliant groove I or turning brilliant groove II.
(4) the slag slurry B obtained in above-mentioned steps (1) is sent in turn brilliant groove II, lead-in portion filtrate D, portion filtrate J, dilution heat of sulfuric acid in part of sulfuric acid dilution trap, controlling the liquid-solid ratio turned in brilliant groove II is quality 2:1, turn in brilliant groove II nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 15%.Phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 22%.By turning brilliant reaction system mass percent, then crystal modifier Trisodium Citrate 0.11%, sodium laurylsulfonate 0.03% and Tai-Ace S 150 0.42% is added, holding temperature carries out turning brilliant reaction 2h at 100 DEG C, after completion of the reaction, solid-liquid separation is carried out through belt filter, obtain solid I and filtrate J, filtrate J part is imported extraction tank and continues extraction ground phosphate rock, part imports to turn in brilliant groove II and continues to turn brilliant reaction.Solid I, after 80 ~ 100 DEG C of hot washes, obtains solid K and washing lotion L, and solid K is common αsemiwatergypsum whisker, and can directly add water plasterings such as making plasterboard, gypsum block, gypsum component.Washing lotion L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation:
Product phosphoric acid liquid quinoline molybdenum lemon ketone weighting method detects, concentration 24%wt; Product common αsemiwatergypsum whisker P
2o
5content 0.06%wt, high product purity high whiteness αsemiwatergypsum whisker P
2o
5content 0.05%wt;
The common αsemiwatergypsum whisker of product is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 10 ~ 15.Whiteness value is 80.2, and αsemiwatergypsum Whisker Content mass ratio is 87%;
High product purity high whiteness αsemiwatergypsum whisker is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 10 ~ 15, and whiteness value is 95.6, and αsemiwatergypsum Whisker Content mass ratio is 99.98%.
Embodiment 2
Raw material 1: phosphorus ore, collecting location: phosphorus is opened in Guizhou;
Raw material 2: Trisodium Citrate, commercially available;
Raw material 3: ferric sulfate, commercially available;
Raw material 4: sulfuric acid, concentration is 97%, commercially available;
The diluting concentrated sulfuric acid that sulphuric acid soln used in embodiment is with concentration is 97wt% obtains, and carries out in sulfuric acid dilution trap.
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise step as follows:
(1) solid-liquid mass ratio ground phosphate rock and excessive phosphoric acid being added ground phosphate rock and phosphoric acid in extraction tank is 1:20, the concentration of phosphoric acid is 24wt%, under the condition constantly stirred, carry out extractive reaction completely after, add the sulphuric acid soln that concentration is 26wt%, control the add-on of sulfuric acid, continue reaction, obtain extraction slip; Make about 50% calcium ion generate dihydrate gypsum, other 50% calcium ion is present in extraction slip with the form of monocalcium phosphate, then will extract slip through filter solid-liquid separation, obtains phosphoric acid leaching liquid A and slag slurry B.Wherein in phosphoric acid leaching liquid, phosphoric acid is 2.3mol/L, and calcium ion is 0.8mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported decalcification reactive tank, the concentration added in decalcification reactive tank with concentration is the dilution of 24wt% phosphoric acid solution is 26wt% sulphuric acid soln, holding temperature carries out stirring reaction 2h at 90 DEG C, generating crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter solid-liquid separation, obtain solid C and filtrate D, the filtrate D obtained is divided into four parts, part imports to turn in brilliant groove I carries out turning brilliant reaction, part imports to turn in brilliant groove II carries out turning brilliant reaction, part imports in extraction tank and extracts Rock Phosphate (72Min BPL), part sends into sour storehouse as phosphoric acid finished product.
(3) solid C sends into and turns in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, and controlling to turn liquid-solid mass ratio in brilliant groove I is 3:1, and turn in brilliant groove I nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 16%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 26%; By turning brilliant reaction system mass percent, after adding crystal modifier Trisodium Citrate 0.12%, ferric sulfate 0.20%, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid E and filtrate F, filtrate F imports to turn in brilliant groove I and continues to turn brilliant reaction.Solid E obtains solid G and washing lotion H after adding 80 ~ 100 DEG C of hot washes, and solid G is high purity high whiteness αsemiwatergypsum whisker.Washing lotion H imports in sulfuric acid dilution trap in order to diluting concentrated sulfuric acid, imported in extraction tank by the sulphuric acid soln part of diluting and continue extraction Rock Phosphate (72Min BPL), part imports decalcification reactive tank and continues decalcification reaction, part imports to turn in brilliant groove I and participates in turning brilliant reaction, part imports to turn in brilliant groove II and participates in turning brilliant reaction, and the steam produced in dilution provides heat of reaction for turning brilliant groove I or turning brilliant groove II.
(4) the slag slurry B obtained in above-mentioned steps (1) is sent in turn brilliant groove II, lead-in portion filtrate D, portion filtrate J, dilution heat of sulfuric acid in part of sulfuric acid dilution trap, controlling the liquid-solid ratio turned in brilliant groove II is quality 3:1, turn in brilliant groove II nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 16%.Phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 26%.By turning brilliant reaction system mass percent, then crystal modifier Trisodium Citrate 0.12% and ferric sulfate 0.20% is added, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid I and filtrate J, filtrate J part is imported extraction tank and continues extraction ground phosphate rock, part imports to turn in brilliant groove II and continues to turn brilliant reaction.Solid I, after 80 ~ 100 DEG C of hot washes, obtains solid K and washing lotion L, and solid K is common αsemiwatergypsum whisker, and can directly add water plasterings such as making plasterboard, gypsum block, gypsum component.Washing lotion L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation:
Product phosphoric acid liquid quinoline molybdenum lemon ketone weighting method detects, concentration 22%wt; Product common αsemiwatergypsum whisker P
2o
5content 0.05%wt, high product purity high whiteness αsemiwatergypsum whisker P
2o
5content 0.05%wt.
The common αsemiwatergypsum whisker of product is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 20 ~ 25.Whiteness value is 80.4, and αsemiwatergypsum Whisker Content mass ratio is 88%.
High product purity high whiteness αsemiwatergypsum whisker is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 20 ~ 25, and whiteness value is 95.6, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 3
Raw material 1: phosphorus ore, collecting location: phosphorus is opened in Guizhou;
Raw material 2: magnesium citrate, commercially available;
Raw material 3: Tai-Ace S 150, commercially available;
Raw material 4: sulfuric acid, concentration is 97%, commercially available;
The diluting concentrated sulfuric acid that sulphuric acid soln used in embodiment is with concentration is 97wt% obtains, and carries out in sulfuric acid dilution trap.
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise step as follows:
(1) solid-liquid mass ratio ground phosphate rock and excessive phosphoric acid being added ground phosphate rock and phosphoric acid in extraction tank is 1:22, the concentration of phosphoric acid is 25wt%, under the condition constantly stirred, carry out extractive reaction completely after, add the sulphuric acid soln that concentration is 26wt%, control the add-on of sulfuric acid, continue reaction, obtain extraction slip; Make about 70% calcium ion generate dihydrate gypsum, other 30% calcium ion is present in extraction slip with the form of monocalcium phosphate, then will extract slip through filter solid-liquid separation, obtains phosphoric acid leaching liquid A and slag slurry B.Wherein in phosphoric acid leaching liquid, phosphoric acid is 2.3mol/L, and calcium ion is 0.6mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported decalcification reactive tank, the concentration added in decalcification reactive tank with concentration is the dilution of 25wt% phosphoric acid solution is 26wt% sulphuric acid soln, holding temperature carries out stirring reaction 2h at 100 DEG C, generating crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter solid-liquid separation, obtain solid C and filtrate D, the filtrate D obtained is divided into four parts, part imports to turn in brilliant groove I carries out turning brilliant reaction, part imports to turn in brilliant groove II carries out turning brilliant reaction, part imports in extraction tank and extracts Rock Phosphate (72Min BPL), part sends into sour storehouse as phosphoric acid finished product.
(3) solid C sends into and turns in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, and controlling to turn liquid-solid mass ratio in brilliant groove I is 4:1, and turn in brilliant groove I nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 14%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 23%; By turning brilliant reaction system mass percent, after adding crystal modifier magnesium citrate 0.12%, Tai-Ace S 150 0.21%, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid E and filtrate F, filtrate F imports to turn in brilliant groove I and continues to turn brilliant reaction.Solid E obtains solid G and washing lotion H after adding 80 ~ 100 DEG C of hot washes, and solid G is high purity high whiteness αsemiwatergypsum whisker.Washing lotion H imports in sulfuric acid dilution trap in order to diluting concentrated sulfuric acid, imported in extraction tank by the sulphuric acid soln part of diluting and continue extraction Rock Phosphate (72Min BPL), part imports decalcification reactive tank and continues decalcification reaction, part imports to turn in brilliant groove I and participates in turning brilliant reaction, part imports to turn in brilliant groove II and participates in turning brilliant reaction, and the steam produced in dilution provides heat of reaction for turning brilliant groove I or turning brilliant groove II.
(4) the slag slurry B obtained in above-mentioned steps (1) is sent in turn brilliant groove II, lead-in portion filtrate D, portion filtrate J, dilution heat of sulfuric acid in part of sulfuric acid dilution trap, controlling the liquid-solid ratio turned in brilliant groove II is quality 3:1, turn in brilliant groove II nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 14%.Phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 23%.By turning brilliant reaction system mass percent, then crystal modifier magnesium citrate 0.12% and Tai-Ace S 150 0.21% is added, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid I and filtrate J, filtrate J part is imported extraction tank and continues extraction ground phosphate rock, part imports to turn in brilliant groove II and continues to turn brilliant reaction.Solid I, after 80 ~ 100 DEG C of hot washes, obtains solid K and washing lotion L, and solid K is common αsemiwatergypsum whisker, and can directly add water plasterings such as making plasterboard, gypsum block, gypsum component.Washing lotion L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation:
Product phosphoric acid liquid quinoline molybdenum lemon ketone weighting method detects, concentration 22%wt; Product common αsemiwatergypsum whisker P
2o
5content 0.04%wt, high product purity high whiteness αsemiwatergypsum whisker P
2o
5content 0.03%wt.
The common αsemiwatergypsum whisker of product is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 30 ~ 40.Whiteness value is 80.8, and αsemiwatergypsum Whisker Content mass ratio is 86%.
High product purity high whiteness αsemiwatergypsum whisker is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 30 ~ 40, and whiteness value is 95.9, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 4
Raw material 1: phosphorus ore, collecting location: phosphorus is opened in Guizhou;
Raw material 2: ferric sulfate, commercially available;
Raw material 3: Xylo-Mucine, commercially available;
Raw material 4: sulfuric acid, concentration is 97%, commercially available;
The diluting concentrated sulfuric acid that sulphuric acid soln used in embodiment is with concentration is 97wt% obtains, and carries out in sulfuric acid dilution trap.
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise step as follows:
(1) solid-liquid mass ratio ground phosphate rock and excessive phosphoric acid being added ground phosphate rock and phosphoric acid in extraction tank is 1:25, the concentration of phosphoric acid is 26wt%, under the condition constantly stirred, carry out extractive reaction completely after, add the sulphuric acid soln that concentration is 26wt%, control the add-on of sulfuric acid, continue reaction, obtain extraction slip; Make about 60% calcium ion generate dihydrate gypsum, other 40% calcium ion is present in extraction slip with the form of monocalcium phosphate, then will extract slip through filter solid-liquid separation, obtains phosphoric acid leaching liquid A and slag slurry B.Wherein in phosphoric acid leaching liquid, phosphoric acid is 2.7mol/L, and calcium ion is 0.7mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported decalcification reactive tank, the concentration added in decalcification reactive tank with concentration is the dilution of 26wt% phosphoric acid solution is 26wt% sulphuric acid soln, holding temperature carries out stirring reaction 2h at 90 DEG C, generating crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter solid-liquid separation, obtain solid C and filtrate D, the filtrate D obtained is divided into four parts, part imports to turn in brilliant groove I carries out turning brilliant reaction, part imports to turn in brilliant groove II carries out turning brilliant reaction, part imports in extraction tank and extracts Rock Phosphate (72Min BPL), part sends into sour storehouse as phosphoric acid finished product.
(3) solid C sends into and turns in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, and controlling to turn liquid-solid mass ratio in brilliant groove I is 5:1, and turn in brilliant groove I nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 15%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 25%; By turning brilliant reaction system mass percent, after adding crystal modifier ferric sulfate 0.20%, Xylo-Mucine 0.07%, holding temperature carries out turning brilliant reaction 2h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid E and filtrate F, filtrate F imports to turn in brilliant groove I and continues to turn brilliant reaction.Solid E obtains solid G and washing lotion H after adding 80 ~ 100 DEG C of hot washes, and solid G is high purity high whiteness αsemiwatergypsum whisker.Washing lotion H imports in sulfuric acid dilution trap in order to diluting concentrated sulfuric acid, imported in extraction tank by the sulphuric acid soln part of diluting and continue extraction Rock Phosphate (72Min BPL), part imports decalcification reactive tank and continues decalcification reaction, part imports to turn in brilliant groove I and participates in turning brilliant reaction, part imports to turn in brilliant groove II and participates in turning brilliant reaction, and the steam produced in dilution provides heat of reaction for turning brilliant groove I or turning brilliant groove II.
(4) the slag slurry B obtained in above-mentioned steps (1) is sent in turn brilliant groove II, lead-in portion filtrate D, portion filtrate J, dilution heat of sulfuric acid in part of sulfuric acid dilution trap, controlling the liquid-solid ratio turned in brilliant groove II is quality 5:1, turn in brilliant groove II nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 15%.Phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 25%.By turning brilliant reaction system mass percent, then after adding crystal modifier ferric sulfate 0.20%, Xylo-Mucine 0.07%, holding temperature carries out turning brilliant reaction 2h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid I and filtrate J, filtrate J part is imported extraction tank and continues extraction ground phosphate rock, part imports to turn in brilliant groove II and continues to turn brilliant reaction.Solid I, after 80 ~ 100 DEG C of hot washes, obtains solid K and washing lotion L, and solid K is common αsemiwatergypsum whisker, and can directly add water plasterings such as making plasterboard, gypsum block, gypsum component.Washing lotion L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation:
Product phosphoric acid liquid quinoline molybdenum lemon ketone weighting method detects, concentration 26%wt; Product common αsemiwatergypsum whisker P
2o
5content 0.06%wt, high product purity high whiteness αsemiwatergypsum whisker P
2o
5content 0.04%wt.
The common αsemiwatergypsum whisker of product is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 40 ~ 45.Whiteness value is 82.6, and αsemiwatergypsum Whisker Content mass ratio is 87%.
High product purity high whiteness αsemiwatergypsum whisker is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 40 ~ 45, and whiteness value is 97.4, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Embodiment 5
Raw material 1: phosphorus ore, collecting location: phosphorus is opened in Guizhou;
Raw material 2: zinc phosphate, commercially available;
Raw material 3: magnesium sulfate, commercially available;
Raw material 5: sulfuric acid, concentration is 97%, commercially available;
The diluting concentrated sulfuric acid that sulphuric acid soln used in embodiment is with concentration is 97wt% obtains, and carries out in sulfuric acid dilution trap.
Produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise step as follows:
(1) solid-liquid mass ratio ground phosphate rock and excessive phosphoric acid being added ground phosphate rock and phosphoric acid in extraction tank is 1:20, the concentration of phosphoric acid is 25wt%, under the condition constantly stirred, carry out extractive reaction completely after, add the sulphuric acid soln that concentration is 27wt%, control the add-on of sulfuric acid, continue reaction, obtain extraction slip; Make about 50% calcium ion generate dihydrate gypsum, other 50% calcium ion is present in extraction slip with the form of monocalcium phosphate, then will extract slip through filter solid-liquid separation, obtains phosphoric acid leaching liquid A and slag slurry B.Wherein in phosphoric acid leaching liquid, phosphoric acid is 2.2mol/L, and calcium ion is 0.9mol/L.
(2) the phosphoric acid leaching liquid A obtained in above-mentioned steps (1) is imported decalcification reactive tank, the concentration added in decalcification reactive tank with concentration is the dilution of 25wt% phosphoric acid solution is 27wt% sulphuric acid soln, holding temperature carries out stirring reaction 2h at 90 DEG C, generating crystal whisker of gypsum is suspended in phosphoric acid, by crystal whisker of gypsum suspension through filter solid-liquid separation, obtain solid C and filtrate D, the filtrate D obtained is divided into four parts, part imports to turn in brilliant groove I carries out turning brilliant reaction, part imports to turn in brilliant groove II carries out turning brilliant reaction, part imports in extraction tank and extracts Rock Phosphate (72Min BPL), part sends into sour storehouse as phosphoric acid finished product.
(3) solid C sends into and turns in brilliant groove I, lead-in portion filtrate D, the dilution heat of sulfuric acid in part of sulfuric acid dilution trap, and controlling to turn liquid-solid mass ratio in brilliant groove I is 6:1, and turn in brilliant groove I nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 20%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 30%; By turning brilliant reaction system mass percent, after adding crystal modifier zinc phosphate 0.09%, magnesium sulfate 0.21%, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, carry out solid-liquid separation through filter, obtain solid E and filtrate F, filtrate F imports to turn in brilliant groove I and continues to turn brilliant reaction.Solid E obtains solid G and washing lotion H after adding 80 ~ 100 DEG C of hot washes, and solid G is high purity high whiteness αsemiwatergypsum whisker.Washing lotion H imports in sulfuric acid dilution trap in order to diluting concentrated sulfuric acid, imported in extraction tank by the sulphuric acid soln part of diluting and continue extraction Rock Phosphate (72Min BPL), part imports decalcification reactive tank and continues decalcification reaction, part imports to turn in brilliant groove I and participates in turning brilliant reaction, part imports to turn in brilliant groove II and participates in turning brilliant reaction, and the steam produced in dilution provides heat of reaction for turning brilliant groove I or turning brilliant groove II.
(4) the slag slurry B obtained in above-mentioned steps (1) is sent in turn brilliant groove II, lead-in portion filtrate D, portion filtrate J, dilution heat of sulfuric acid in part of sulfuric acid dilution trap, controlling the liquid-solid ratio turned in brilliant groove II is quality 6:1, turn in brilliant groove II nitration mixture comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 20%.Phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 30%.By turning brilliant reaction system mass percent, then after adding crystal modifier zinc phosphate 0.09%, magnesium sulfate 0.21%, holding temperature carries out turning brilliant reaction 3h at 110 DEG C, after completion of the reaction, solid-liquid separation is carried out through filter, obtain solid I and filtrate J, filtrate J part is imported extraction tank and continues extraction ground phosphate rock, part imports to turn in brilliant groove II and continues to turn brilliant reaction.Solid I, after 80 ~ 100 DEG C of hot washes, obtains solid K and washing lotion L, and solid K is common αsemiwatergypsum whisker, and can directly add water plasterings such as making plasterboard, gypsum block, gypsum component.Washing lotion L imports sulfuric acid dilution trap and is used for diluting concentrated sulfuric acid.
Result of implementation:
Product phosphoric acid liquid quinoline molybdenum lemon ketone weighting method detects, concentration 21%wt; Product common αsemiwatergypsum whisker P
2o
5content 0.07%wt, high product purity high whiteness αsemiwatergypsum whisker P
2o
5content 0.06%wt.
The common αsemiwatergypsum whisker of product is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 50 ~ 60.Whiteness value is 81.6, and αsemiwatergypsum Whisker Content mass ratio is 86%.
High product purity high whiteness αsemiwatergypsum whisker is in needle-like or threadiness under 200 times of opticmicroscopes, and length-to-diameter ratio is 50 ~ 60, and whiteness value is 96.8, and αsemiwatergypsum Whisker Content mass ratio is 99.99%.
Claims (10)
1. produce a method for phosphoric acid by wet process by-product αsemiwatergypsum whisker and high purity high whiteness αsemiwatergypsum whisker, comprise the following steps:
(1) by after phosphoric acid and ground phosphate rock mixing, extractive reaction is carried out under agitation condition, after extractive reaction is complete, add sulphuric acid soln, the add-on of sulphuric acid soln controls make 30% ~ 50% calcium ion generate dihydrate gypsum, other 50% ~ 70% calcium ion exists with the form of monocalcium phosphate, continues stirring reaction, obtains extraction slip; Slip solid-liquid separation will be extracted, obtain phosphoric acid leaching liquid A and slag slurry B;
(2) mixed with sulphuric acid soln by the phosphoric acid leaching liquid A obtained in step (1) and carry out decalcification reaction, after having reacted, solid-liquid separation, obtains solid C and filtrate D; The filtrate D obtained is divided into four parts, is respectively used to step (1) extractive reaction, step (3) turns brilliant reaction, step (4) turns brilliant reaction, as phosphoric acid finished product;
(3) the solid C obtained in step (2) is added filtrate D, sulphuric acid soln and crystal modifier to carry out turning brilliant reaction, after completion of the reaction, carry out solid-liquid separation, obtain solid E and filtrate F; Turn in brilliant reaction system the nitration mixture all comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 12 ~ 20%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 20 ~ 30%;
Mixed with solid C by the filtrate F obtained and carry out circulation and turn brilliant reaction, solid E, with after the hot wash of 80 ~ 100 DEG C, obtains solid G and washing lotion H; Washing lotion H is used for diluting concentrated sulfuric acid provides sulphuric acid soln, and solid G is high purity high whiteness αsemiwatergypsum whisker;
(4) slag obtained in step (1) slurry B is added filtrate D, sulphuric acid soln and crystal modifier to carry out turning brilliant reaction, after completion of the reaction, carry out solid-liquid separation, obtain solid I and filtrate J; Turn in brilliant reaction system the nitration mixture all comprising sulfuric acid and phosphoric acid composition, wherein, sulfuric acid is with H
2sO
4the massfraction that meter accounts for nitration mixture is 12 ~ 20%, and phosphoric acid is with P
2o
5the massfraction that meter accounts for nitration mixture is 20 ~ 30%;
Divide two portions by filtrate J, be respectively used to step (1) extractive reaction, starch B with slag and mix and carry out circulation and turn brilliant reaction; Solid I, with after the hot wash of 80 ~ 100 DEG C, obtains solid K and washing lotion L; Washing lotion L is used for diluting concentrated sulfuric acid provides sulphuric acid soln, and solid K is αsemiwatergypsum whisker.
2. method according to claim 1, is characterized in that, in step (1), the fineness of ground phosphate rock is 80 ~ 100 orders, and the concentration of phosphoric acid is with H
3pO
4count 20 ~ 35wt%, the solid-liquid mass ratio of ground phosphate rock used and phosphoric acid is 1:15 ~ 45.
3. method according to claim 1, is characterized in that, in step (1), extractive reaction and the temperature of reaction after adding sulphuric acid soln are 50 ~ 80 DEG C, and extractive reaction time 1.5 ~ 6h, continues stirring reaction 1 ~ 3h after adding sulphuric acid soln.
4. method according to claim 1, is characterized in that, in step (1), in phosphoric acid leaching liquid A, the concentration of phosphoric acid is 2 ~ 4mol/L, and the concentration of calcium ion is 0.5 ~ 2.0mol/L.
5. method according to claim 1, is characterized in that, in step (2), decalcification temperature of reaction is 60 DEG C ~ 130 DEG C, reaction times 1.5 ~ 7.5h.
6. method according to claim 1, is characterized in that, in step (2), the volume ratio of phosphoric acid leaching liquid A and sulphuric acid soln is 1:3 ~ 5.
7. method according to claim 1, is characterized in that, the liquid-solid mass ratio of step (3) and the reaction of (4) transfer crystalline substance is (2 ~ 20): 1.
8. method according to claim 1, is characterized in that, step (3) and the brilliant temperature of reaction of (4) transfer are 40 DEG C ~ 130 DEG C, and turn brilliant reaction times is 1 ~ 9h.
9. method according to claim 1, is characterized in that, step (3) and the crystal modifier described in (4) are containing Al
3+, Fe
3+, Mg
2+, K
+, Na
+, NH
4 +one or more mixing in the water-soluble phosphate of ion, vitriol, nitrate, Citrate trianion, alkylbenzene sulfonate, alkyl fatty hydrochlorate.
10. method according to claim 1, is characterized in that, in step (3) and (4), the addition of described crystal modifier accounts for and turns 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 |
| CN108502861A (en) * | 2018-06-25 | 2018-09-07 | 中化重庆涪陵化工有限公司 | Method and the crystallization in motion agent of concentrated phosphoric acid coproduction semi-hydrated gypsum whisker are produced using low-grade phosphate ore |
| 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 |
| CN109385664A (en) * | 2018-12-17 | 2019-02-26 | 武汉纺织大学 | A kind of preparation method of ester exchange at phosphorus |
| CN111559754A (en) * | 2020-04-21 | 2020-08-21 | 贵州大学 | Method for removing calcium and byproduct alpha-type building gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| 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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| CN111559754A (en) * | 2020-04-21 | 2020-08-21 | 贵州大学 | Method for removing calcium and byproduct alpha-type building gypsum by decomposing phosphate rock acidolysis solution with nitric acid |
| 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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