WO2017045520A1 - 一种湿法磷酸副产α半水石膏的生产方法 - Google Patents
一种湿法磷酸副产α半水石膏的生产方法 Download PDFInfo
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- WO2017045520A1 WO2017045520A1 PCT/CN2016/096941 CN2016096941W WO2017045520A1 WO 2017045520 A1 WO2017045520 A1 WO 2017045520A1 CN 2016096941 W CN2016096941 W CN 2016096941W WO 2017045520 A1 WO2017045520 A1 WO 2017045520A1
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- solid
- acid
- phosphoric acid
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- slurry
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 158
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 79
- 238000000034 method Methods 0.000 title claims abstract description 69
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 130
- 239000007788 liquid Substances 0.000 claims abstract description 63
- 239000007787 solid Substances 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 53
- 239000011268 mixed slurry Substances 0.000 claims abstract description 43
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 239000002367 phosphate rock Substances 0.000 claims abstract description 41
- 238000000605 extraction Methods 0.000 claims abstract description 37
- 239000013078 crystal Substances 0.000 claims abstract description 36
- 239000002002 slurry Substances 0.000 claims abstract description 35
- 239000000843 powder Substances 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 230000009466 transformation Effects 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000010790 dilution Methods 0.000 claims abstract description 14
- 239000012895 dilution Substances 0.000 claims abstract description 14
- 239000006227 byproduct Substances 0.000 claims description 32
- 239000000243 solution Substances 0.000 claims description 18
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 16
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 14
- 239000000706 filtrate Substances 0.000 claims description 12
- ZOMBKNNSYQHRCA-UHFFFAOYSA-J calcium sulfate hemihydrate Chemical compound O.[Ca+2].[Ca+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZOMBKNNSYQHRCA-UHFFFAOYSA-J 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 8
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 8
- 239000001509 sodium citrate Substances 0.000 claims description 8
- 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 claims description 8
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 7
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- -1 alkyl fatty acid salt Chemical class 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 6
- 238000007865 diluting Methods 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 5
- 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 claims description 5
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 5
- 238000003113 dilution method Methods 0.000 claims description 5
- 239000000194 fatty acid Substances 0.000 claims description 5
- 229930195729 fatty acid Natural products 0.000 claims description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 5
- 239000010452 phosphate Substances 0.000 claims description 5
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 229910000358 iron sulfate Inorganic materials 0.000 claims description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000011505 plaster Substances 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000004317 sodium nitrate Substances 0.000 claims description 4
- 235000010344 sodium nitrate Nutrition 0.000 claims description 4
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 claims description 3
- 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 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 210000002858 crystal cell Anatomy 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 2
- 235000021317 phosphate Nutrition 0.000 claims 3
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 239000007790 solid phase Substances 0.000 claims 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 1
- 239000010440 gypsum Substances 0.000 abstract description 40
- 229910052602 gypsum Inorganic materials 0.000 abstract description 40
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 12
- 239000011574 phosphorus Substances 0.000 abstract description 12
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 12
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 abstract description 11
- 239000000126 substance Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 21
- 150000004683 dihydrates Chemical class 0.000 description 12
- 239000002699 waste material Substances 0.000 description 4
- 239000004566 building material Substances 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- ULTDZDJQQBGHTI-UHFFFAOYSA-N di(quinoxalin-2-yl)methanone Chemical compound C1=CC=CC2=NC(C(C=3N=C4C=CC=CC4=NC=3)=O)=CN=C21 ULTDZDJQQBGHTI-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910052708 sodium Inorganic materials 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
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 235000010689 Lufa Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- DWSKLNHACTWZQD-UHFFFAOYSA-N O.O.O.O.O.P(=O)(O)(O)O.P(=O)(O)(O)O Chemical compound O.O.O.O.O.P(=O)(O)(O)O.P(=O)(O)(O)O DWSKLNHACTWZQD-UHFFFAOYSA-N 0.000 description 1
- QCJQWJKKTGJDCM-UHFFFAOYSA-N [P].[S] Chemical compound [P].[S] QCJQWJKKTGJDCM-UHFFFAOYSA-N 0.000 description 1
- 239000002535 acidifier Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000000701 coagulant Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000004175 phosphorus cycle Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000013517 stratification Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
- C01B25/223—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen only one form of calcium sulfate being formed
- C01B25/226—Hemihydrate process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/222—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen
- C01B25/228—Preparation by reacting phosphate-containing material with an acid, e.g. wet process with sulfuric acid, a mixture of acids mainly consisting of sulfuric acid or a mixture of compounds forming it in situ, e.g. a mixture of sulfur dioxide, water and oxygen one form of calcium sulfate being formed and then converted to another form
- C01B25/229—Hemihydrate-dihydrate process
- C01B25/2295—Hemihydrate-dihydrate process the conversion being performed in one or more vessels different from those used for reaction after separation of phosphoric acid
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/18—Phosphoric acid
- C01B25/22—Preparation by reacting phosphate-containing material with an acid, e.g. wet process
- C01B25/2204—Arrangements of vessels used in reacting phosphate-containing material in wet process
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F11/00—Compounds of calcium, strontium, or barium
- C01F11/46—Sulfates
- C01F11/466—Conversion of one form of calcium sulfate to another
Definitions
- the invention belongs to the technical field of a production method of wet process phosphoric acid, in particular to a method for producing ⁇ -hemihydrate gypsum by-product of wet process phosphoric acid.
- wet-process phosphoric acid generally refers to a sulfuric acid method of wet-process phosphoric acid, that is, phosphoric acid produced by decomposing phosphate rock with sulfuric acid. More than 80% of the phosphoric acid in China is produced by the wet-process two-aqueous process.
- the dihydrate process has the characteristics of simple process, mature technology and strong adaptability to ore types. It is especially suitable for medium and low grade ores and is dominant in the production of wet process phosphoric acid. However, there are still some insurmountable defects in the process of dihydrate process.
- the by-produced phosphogypsum is subject to many restrictions due to its high phosphorus content, and only a small part is used to produce low-grade and low-quality gypsum building materials and cement.
- the coagulant, most of the phosphogypsum is discarded and stored, causing serious pollution and waste. Therefore, the conventional wet-process phosphoric acid process needs to be further improved to reduce the phosphorus content in the phosphogypsum and thus to be converted into a more valuable product.
- the Chinese Patent Publication No. CN103626143A discloses a method for producing a by-product of phosphoric acid by-product in a wet process by first stirring a phosphate rock (pulp) and phosphoric acid at 45 ° C to 70 ° C to form a mixed slurry containing solid impurities; After continuous or intermittent precipitation, a mixed solution of phosphoric acid and calcium phosphate salt and a thick slurry containing solid impurities are separated; under stirring, sulfuric acid is added to react with the separated mixed solution of phosphoric acid and calcium phosphate, and the precipitate is separated and separated to obtain phosphoric acid and white. plaster.
- the invention obtains the product phosphoric acid and white gypsum without the formation of phosphogypsum, eliminates the pollution of the gypsum gypsum stack to the atmosphere, soil and groundwater, and the by-product dihydrate white gypsum has high purity and high whiteness value.
- the invention still needs to discharge the acid insoluble matter residue, which is difficult to handle, and the produced dihydrate white gypsum needs to be dehydrated or crystallized to be used as a ⁇ -gypsum or alpha-gypsum product with a relatively high added value.
- CN102001636A discloses a method for producing a wide concentration of phosphoric acid and clean gypsum by a medium and low grade phosphate rock wet process, which provides a semi-aqueous-dihydrate process method, by-product high quality building half.
- Water gypsum or functional dihydrate gypsum enables better development and utilization of low-grade phosphate rock.
- the invention still needs to discharge solid waste residue and dihydrate gypsum equivalent to the amount of clean gypsum, which is difficult to use.
- Chinese Patent Publication No. CN1421385 discloses a method for producing a hemihydrate-dihydrate phosphoric acid.
- the invention divides the sulfuric acid into two places by controlling the precipitation rate of calcium in the reaction tank; a part of sulfuric acid is added to the mixed acidifier and mixed with the dilute phosphoric acid, and then added to the second reaction tank; another part of sulfuric acid is added to the dilute phosphoric acid tank,
- the alpha hemihydrate gypsum is first prepared, and then the alpha hemihydrate gypsum is converted into dihydrate gypsum.
- the by-product gypsum of the invention is still dihydrate gypsum which is difficult to directly use.
- CN 103086335A discloses a method for producing a phosphoric acid co-produced ⁇ -hemihydrate gypsum by a dihydrate-semi-water wet process phosphoric acid process, and a wet-process phosphoric acid concentration ⁇ (P 2 O 5 ) produced by a two-water process.
- the phosphoric acid concentration ⁇ (P 2 O 5 ) produced by the semi-aqueous process is 10% to 15%
- the co-produced semi-aqueous phosphogypsum crystal water is 5% ⁇ 7%
- the mass percentage of free P 2 O 5 in gypsum is less than 0.4%
- its crystal form is ⁇ -hemihydrate phosphogypsum.
- the method can not control the aspect ratio of ⁇ -hemihydrate gypsum under the condition of dihydrate-semi-water transcrystallization. Although ⁇ -hemihydrate gypsum products can be produced, the ⁇ -hemihydrate gypsum product has low strength, the application of the product is limited, and the phosphorus in the product The content is still high.
- the problems existing in the prior art are: first, it is still necessary to discharge waste such as acid insoluble matter; second, the by-product gypsum is dihydrate, and it is necessary to be processed to become ⁇ -hemihydrate gypsum or ⁇ -hemihydrate gypsum. The higher value of the product; the third is that the obtained alpha hemihydrate gypsum product has low strength and high phosphorus content, which limits its high-end application.
- the present invention provides a method for producing ⁇ -hemihydrate gypsum by-product of wet process phosphoric acid in view of the deficiencies of the prior art.
- the method eliminates the discharge of phosphogypsum and acid-insoluble matter through process innovation, reduces the phosphorus content in gypsum, improves the utilization rate of phosphorus, and obtain ⁇ -hemihydrate gypsum products which can be directly applied to building materials industry. .
- a method for producing ⁇ -hemihydrate gypsum by-product of wet process phosphoric acid comprising the following steps:
- step S2) separating the mixed slurry A obtained in step S1) from 0 to 2/3 of the volume for solid-liquid separation to obtain clear liquid B and solid C;
- the solid-liquid mass ratio of the phosphate rock to the dilute sulfuric acid in the step S1) is 1: (2-10).
- the temperature of the extraction reaction in the step S1) is 30 ° C to 95 ° C; the extraction reaction time is 15 to 60 min.
- the crystallizing agent is a water-soluble phosphate, a water-soluble sulfate, a water-soluble nitrate, a water-soluble citrate, a water-soluble alkylbenzenesulfonate, a water-soluble alkyl fatty acid salt or a water-soluble organic
- a carboxylate the water-soluble phosphate, a water-soluble sulfate, a water-soluble nitrate, a water-soluble citrate, a water-soluble alkylbenzenesulfonate, a water-soluble alkyl fat
- the acid salt and the water-soluble organic carboxylate each independently contain one or more of Al 3+ , Fe 3+ , Mg 2+ , K + , Na + and NH 4 + .
- the temperature of the crystal transformation reaction in the step S3) is 60 ° C to 130 ° C; the time of the crystal transformation reaction is 1.5 to 7.5 h.
- the liquid-solid mass ratio of the solid C and the remaining mixed slurry mixed with the dilute sulfuric acid in the step S3) is (2-6):1.
- the mass fraction of phosphoric acid in the liquid phase after mixing the solid C and the remaining mixed slurry with the dilute sulfuric acid in step S3) is 16% to 25% in terms of P 2 O 5 , and the mass of sulfuric acid in terms of H 2 SO 4 The score is 8% to 12%.
- a method for producing ⁇ -hemihydrate gypsum by-product of wet-process phosphoric acid comprises the following steps:
- the mixed slurry A obtained in the step (1) is separated from the volume of 0 to 2/3 to carry out solid-liquid separation to obtain the clear liquid B and the solid C, and the clear liquid B is sent to the acid storage as the finished phosphoric acid, and the solid C and The remaining mixed slurry is transferred together to the crystallizing tank;
- the whole system is made into some circulation system by the step (2), and the phosphoric acid formed in the step (1) is excessive in the subsequent crystal transformation process, and not only the partial phosphoric acid product is obtained through the step (2), but also the product is ensured.
- the smoothness of the phosphorus cycle of the entire system is ensured.
- the fineness of the phosphate rock in the step (1) is 80 to 100 mesh, and the content of phosphorus pentoxide in the phosphate rock is 10% to 40% by mass.
- the mass concentration of the dilute sulfuric acid in the step (1) and the step (3) is 20% to 40%, and further preferably, the mass concentration of the dilute sulfuric acid is 20% to 35%.
- the mass fraction of sulfate ions in the mixed slurry A in the step (1) is less than 1%.
- the liquid-solid mass ratio of the mixed acid solution and the slurry after decalcification in the step (3) is 2 to 6:1, that is, the solid C, and the remaining mixed slurry is mixed with the diluted sulfuric acid added.
- the liquid-solid mass ratio is 2-6:1; wherein the liquid phosphoric acid accounts for 16% to 25% of the mixed acid in terms of P 2 O 5 , and the sulfuric acid accounts for 8%-12 in the mixed acid of H 2 SO 4 . %; further preferably, the liquid-solid mass ratio of the mixed acid solution and the slurry after decalcification in the step (3) is 3 to 5:1, wherein the liquid phosphoric acid accounts for 18% to 23% of the mixed acid in terms of P 2 O 5 . %, sulfuric acid accounts for 9% to 10% of the mixed acid in terms of H 2 SO 4 .
- the crystallizing agent in the step (3) refers to a water-soluble phosphate, sulfate, nitric acid containing Al 3+ , Fe 3+ , Mg 2+ , K + , Na + , NH 4 + ions.
- a salt, a citrate, an alkylbenzenesulfonate, an alkyl fatty acid salt or an organic carboxylate is included in the step (3).
- the crystallizing agent added in the step (3) is a combination of sodium citrate, iron sulfate, sodium lignin sulfonate; or a combination of sodium nitrate, magnesium sulfate, sodium dodecyl sulfate; or phosphoric acid a combination of sodium, aluminum sulfate, sodium lignin sulfonate; or a combination of ammonium nitrate, magnesium sulfate, sodium chloride.
- the crystallizer combination is one of the following by mass ratio:
- the total amount of the crystallizing agent added in the step (3) is from 0.1% to 1.0% by mass of the mixed slurry.
- the temperature of the hot water in the step (4) is from 80 ° C to 90 ° C.
- the drying temperature in the step (4) is from 110 ° C to 180 ° C, and further preferably, the drying temperature is from 110 ° C to 130 ° C.
- the steam generated in the dilution process in the step (5) is introduced into the crystal cell in the step (3) to provide the heat of reaction.
- a method for producing ⁇ -hemihydrate gypsum by-product of wet-process phosphoric acid comprises the following steps:
- the mixed slurry A obtained in the step (1) is separated from the volume of 1/6 by a filter to carry out solid-liquid separation to obtain a clear liquid B and a solid C, and the separated clear liquid B is sent as a finished phosphoric acid into the acid storage. Solid C is transferred to the crystallizer along with the remaining mixed slurry;
- the principle of the invention is that the phosphate rock powder is firstly decomposed by the mixed acid of sulfuric acid and phosphoric acid, so that the calcium ions in the phosphate rock are all formed into dihydrate gypsum, the crystallizing agent is added, the condition is controlled in the sulfur-phosphorus mixed acid solution, and the ⁇ -half water is directly prepared. plaster.
- the invention relates to a chemical reaction formula:
- the crystal transformation condition of the invention is in a mixed acid solution in the presence of phosphoric acid and sulfuric acid.
- the environment of the strong acid solution can dissolve the dihydrate gypsum, and the water molecules are discharged during the recombination process to form a new one.
- the crystal nucleus and can make the small crystal nucleus dissolve, the large crystal nucleus grows again, which is the generality of the same crystal growth.
- the compounding crystallizer of the present invention can promote the crystal form of gypsum to grow in the desired hexagonal short column direction, and wash with a solvent such as ethanol or water without changing the crystal shape which has been formed. It can maintain its original shape in the water for a long time, and has the same characteristics as the ⁇ -water gypsum produced by the hydrothermal method.
- the ⁇ -hemihydrate gypsum of the invention can be dried into gypsum powder or directly added with water without a drying step to form gypsum products such as gypsum board, gypsum block and gypsum component.
- the invention uses the washing liquid to dilute the concentrated sulfuric acid, on the one hand, the washing liquid is recycled and utilized to avoid the generation of the waste liquid, on the other hand, the steam generated by the dilution heat of the concentrated sulfuric acid is fully utilized, and the steam is introduced into the crystal changing tank to maintain the rotation required.
- the invention can produce ⁇ -semi-water gypsum products which can be directly applied to the building materials industry, and can realize industrialized continuous large-scale production, and solves the problem that the phosphogypsum caused by the conventional wet-process phosphoric acid is difficult to handle.
- Phosphogypsum produced by the conventional wet-process phosphoric acid has high phosphorus content, and the present invention reduces the phosphorus content in the by-produced ⁇ -hemihydrate gypsum to less than 0.1%, thereby improving the utilization ratio of phosphorus in the phosphate rock.
- ⁇ -hemihydrate gypsum prepared by the invention can be controlled, and ⁇ -hemihydrate gypsum with different aspect ratios can be prepared by adjusting the formula of the crystal conversion agent, which can be applied to different market demands.
- the invention fully utilizes the steam generated by the dilution heat of concentrated sulfuric acid to realize the recycling of the dilution heat, thereby saving the production cost, saving energy and reducing emissions.
- All the components in the phosphate rock powder of the invention can be fully utilized, and no environmental pollutants such as waste water and waste phosphogypsum are produced.
- the extraction process of the invention does not require precipitation stratification, which greatly shortens the reaction and aging in the extraction tank. The time required to increase production efficiency.
- FIG. 1 is a schematic view showing the process flow of a method for producing ⁇ -hemihydrate gypsum by-product of wet-process phosphoric acid according to the present invention.
- the chemical reagents used in the examples of the present invention are all commercially available, and the reagent concentration and the mineral component content are all mass percentages.
- Example 1 The phosphate rock collection site is phosphorus in Guizhou; the phosphorus pentoxide content in the phosphate rock is about 32%.
- a method for producing ⁇ -hemihydrate gypsum by-product of wet process phosphoric acid the steps are as follows:
- the phosphate rock powder and the dilute sulfuric acid with a mass concentration of 20% are first added to the extraction tank at a solid-liquid mass ratio of 1:4.
- the fineness of the phosphate rock powder is 100 mesh, and the phosphorus pentoxide content in the phosphate rock is 32. %, under continuous stirring, the extraction bath temperature was controlled at 80 ° C for extraction reaction for 30 minutes to obtain a mixed slurry A.
- the mixed slurry A obtained in the step (1) is separated from the volume of 1/6 by a filter to carry out solid-liquid separation to obtain a clear liquid B and a solid C, and the separated clear liquid B is sent as a finished phosphoric acid into the acid storage. Solid C is transferred to the crystallizer along with the remaining mixed slurry.
- the mixed acid slurry D obtained in the step (3) is subjected to solid-liquid separation to obtain a solid E and a filtrate F, and the solid E is washed with hot water at 85 ° C to obtain a washing liquid H and a solid G, and the solid G is dried by a drying fan.
- the drying temperature is 110 ° C, which is ⁇ -hemihydrate gypsum.
- the product phosphoric acid was detected by the quinoxalyl ketone gravimetric method at a concentration of 27% by weight.
- the product alpha hemihydrate gypsum P 2 O 5 content was 0.06 wt%.
- the product ⁇ -water gypsum meets the industry standard of JC/T 2038-2010. It has a hexagonal short column shape under a 200x optical microscope, the aspect ratio is 1-2, the measured 2h flexural strength is 9.5MPa, and the dry flexural strength is 17MPa.
- the dry compressive strength is 95 MPa, the initial setting time is 8 min, and the final setting time is 17 min.
- Example 2 The phosphate rock collection site is Guizhou Lufa; the phosphorus pentoxide content in the phosphate rock is 27%.
- a method for producing ⁇ -hemihydrate gypsum by-product of wet process phosphoric acid the steps are as follows:
- the mixed slurry A obtained in the step (1) is separated into a volume of 2/3 by a filter to carry out solid-liquid separation to obtain a clear liquid B and a solid C, and the separated clear liquid B is sent as a finished phosphoric acid into the acid storage. Solid C is transferred to the crystallizer along with the remaining mixed slurry.
- the mixed acid slurry D obtained in the step (3) is subjected to solid-liquid separation by a belt filter to obtain a solid E and a filtrate F, and the solid E is washed with hot water at 90 ° C to obtain a washing liquid H and a solid G, and a solid G Drying by a drying fan, the drying temperature is 110 ° C, which is ⁇ -hemihydrate gypsum;
- the product phosphoric acid liquid was detected by the quinoxalyl ketone gravimetric method at a concentration of 22% by weight.
- the product alpha hemihydrate gypsum P 2 O 5 content was 0.08 wt%.
- the product ⁇ -hemihydrate gypsum meets the industry standard of JC/T 2038-2010. It has a hexagonal short column shape under a 200x optical microscope, and the aspect ratio is 2 ⁇ 3.
- the 2h flexural strength is 8.0MPa and the dry bending strength is 15MPa.
- the dry compressive strength is 75 MPa, the initial setting time is 9 min, and the final setting time is 18 min.
- gypsum powder having an aspect ratio of ⁇ 10 or less can be obtained by the present invention. It can be seen that the form of ⁇ -hemihydrate gypsum prepared by the invention can be controlled, and ⁇ -water gypsum powder with different aspect ratios can be prepared by adjusting the formula of the crystal conversion agent, which is suitable for different market demands.
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Abstract
Description
Claims (17)
- 一种湿法磷酸副产α半水石膏的生产方法,其特征在于,包括如下步骤:S1)将磷矿粉与稀硫酸混合进行萃取反应,得到混合浆料A;S2)将步骤S1)中得到的混合浆料A分出体积的0~2/3进行固液分离,得到清液B与固体C;S3)将所述固体C及余下的混合浆料与稀硫酸混合,再加入转晶剂,加热进行转晶反应,得到混合料浆D;S4)将步骤S3)中得到的混合料浆D过滤,得到α半水石膏。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤S1)中磷矿粉与稀硫酸的固液质量比为1:(2~10)。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤S1)中萃取反应的温度为30℃~95℃;萃取反应的时间为15~60min。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述转晶剂为水溶性磷酸盐、水溶性硫酸盐、水溶性硝酸盐、水溶性柠檬酸盐、水溶性烷基苯磺酸盐、水溶性烷基脂肪酸盐或水溶性有机羧酸盐中的一种或几种复配;所述水溶性磷酸盐、水溶性硫酸盐、水溶性硝酸盐、水溶性柠檬酸盐、水溶性烷基苯磺酸盐、水溶性烷基脂肪酸盐与水溶性有机羧酸盐各自独立地含有Al3+、Fe3+、Mg2+、K+、Na+与NH4 +中的一种或几种。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤S3)中转晶反应的温度为60℃~130℃;转晶反应的时间为1.5~7.5h。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤S3)中固体C及余下的混合浆料与稀硫酸混合后的液固质量比为(2~6):1。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,步骤S3)中固体C及余下的混合浆料与稀硫酸混合后的液相中磷酸以P2O5 计的质量分数为16%~25%,硫酸以H2SO4计的质量分数为8%~12%。
- 如权利要求1所述的湿法磷酸副产α半水石膏的生产方法生产方法,其特征在于,包括如下步骤:(1)先将磷矿粉和稀硫酸按固液质量比1:2~10加入到萃取槽中,将萃取槽温度控制在30℃~95℃下进行萃取反应15~60分钟,得到混合料浆A;(2)将步骤(1)中得到的混合料浆A分出体积的0~2/3进行固液分离得清液B和固体C,清液B作为成品磷酸送入酸库,固体C与剩下的混合料浆一起转移到转晶槽中;(3)向转晶槽中加入稀硫酸,控制脱钙后液相磷酸中液固比以及P2O5和H2SO4的含量,得混合后料浆,然后加入转晶剂,维持转晶槽温度在60℃~130℃条件下进行转晶反应1.5~7.5小时,得到混酸料浆D;(4)将步骤(3)中得到的混酸料浆D进行固液分离,得到固体E和滤液F,用热水洗涤固体E,得到洗液H和固体G,将固体G干燥后即得α半水石膏;(5)将步骤(4)的滤液F导入步骤(1)萃取槽继续萃取磷矿粉;洗液H导入硫酸稀释槽中用以稀释浓硫酸,被稀释的硫酸溶液用于步骤(1)中萃取工序和步骤(3)中转晶工序。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(1)中磷矿粉细度为80~100目,磷矿粉中五氧化二磷含量为质量分数10%~40%。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(1)和步骤(3)中稀硫酸质量浓度为20%~40%,进一步优选的,稀硫酸质量浓度为20%~35%。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(1)中混合料浆A中硫酸根离子的质量分数小于1%。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(3)中脱钙后混酸溶液和渣浆的液固质量比为2~6:1,其中液体磷酸以P2O5计占混酸的质量分数为16%~25%,硫酸以H2SO4计占混酸的质量分数为8%~12%;进一步优选的,步骤(3)中脱钙后混酸溶液和渣浆的液固 质量比为3~5:1,其中液体磷酸以P2O5计占混酸的质量分数为18%~23%,硫酸以H2SO4计占混酸的质量分数为9%~10%。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(3)中转晶剂是指含有Al3+、Fe3+、Mg2+、K+、Na+、NH4+离子的水溶性磷酸盐、硫酸盐、硝酸盐、柠檬酸盐、烷基苯磺酸盐、烷基脂肪酸盐或有机羧酸盐中的一种或几种复配。
- 如权利要求13所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,步骤(3)中加入的转晶剂为柠檬酸钠、硫酸铁、木质磺酸钠的组合;或者为硝酸钠、硫酸镁、十二烷基磺酸钠的组合;或者为磷酸钠、硫酸铝、木质磺酸钠的组合;或者为硝酸铵、硫酸镁、氯化钠的组合;所述步骤(3)中加入的转晶剂总含量占混合后料浆质量的0.1%~1.0%;所述转晶剂组合按质量比为下列之一:a.柠檬酸钠:硫酸铁:木质磺酸钠=1.00:1.50~2.00:0.30~0.90;b.硝酸钠:硫酸镁:十二烷基磺酸钠=1.00:1.50~2.00:0.30~0.90;c.磷酸钠:硫酸铝:木质磺酸钠=1.00:1.50~2.00:0.40~0.90;d.硝酸铵:硫酸镁:氯化钠=1.00:1.60~2.20:0.50~0.80。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(4)中热水的温度为80℃~90℃;所述步骤(4)中的干燥温度为110℃~180℃,进一步优选的,干燥温度为110℃~130℃。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,所述步骤(5)中稀释过程中产生的蒸汽导入步骤(3)中转晶槽中提供反应热量。
- 如权利要求8所述的湿法磷酸副产α半水石膏的生产方法,其特征在于,包括如下步骤:(1)先将磷矿粉和质量浓度为20%稀硫酸按固液质量比1:4加入到萃取槽中,磷矿粉细度为100目,磷矿中五氧化二磷含量为32%,在不断搅拌下,将萃取槽温度控制在80℃下进行萃取反应30分钟,得到混合料浆A;(2)将步骤(1)中得到的混合料浆A分出体积的1/6经过滤机进行固液分离得清液B和固体C,分离出的清液B作为成品磷酸送入酸库,固体C与 剩下的混合料浆一起转移到转晶槽中;(3)向转晶槽中加入质量浓度为20%稀硫酸,控制脱钙后混酸溶液和渣浆的液固质量比为6:1,其中液体磷酸中P2O5的浓度占混酸的质量分数为20%,硫酸以H2SO4计占混酸的质量分数为9%,得混合后料浆;然后加入转晶剂硫酸铁占混合后料浆质量的0.23%、柠檬酸钠占混合后料浆质量的0.12%以及木质磺酸钠占混合后料浆质量的0.08%,维持转晶槽温度在110℃条件下进行转晶反应3小时,得到混酸料浆D;(4)将步骤(3)中得到的混酸料浆D进行固液分离,得到固体E和滤液F,用85℃热水洗涤固体E,得到洗液H和固体G,固体G经干燥风机干燥,干燥温度为110℃,即为α半水石膏;(5)将步骤(4)的滤液F导入步骤(1)萃取槽继续萃取磷矿粉;洗液H导入硫酸稀释槽中用以稀释浓硫酸,被稀释的硫酸溶液分为两部分,分别用于步骤(1)中萃取反应、步骤(3)中转晶反应;稀释过程中产生的蒸汽导入转晶槽中提供反应热量。
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CA2998908A CA2998908C (en) | 2015-09-18 | 2016-08-26 | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process |
US15/760,851 US10745278B2 (en) | 2015-09-18 | 2016-08-26 | Method for producing phosphoric acid and by-producing alpha-hemihydrate gypsum by wet-process |
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Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102303852A (zh) * | 2011-04-19 | 2012-01-04 | 江苏瑞和化肥有限公司 | 一种湿法磷酸联产石膏晶须的方法 |
CN103086335A (zh) * | 2013-02-05 | 2013-05-08 | 瓮福(集团)有限责任公司 | 一种二水-半水湿法磷酸工艺生产磷酸联产a-半水石膏的方法 |
CN104355560A (zh) * | 2014-10-21 | 2015-02-18 | 金正大生态工程集团股份有限公司 | 一种α-高强石膏粉的生产方法 |
CN105253867A (zh) * | 2015-09-18 | 2016-01-20 | 金正大生态工程集团股份有限公司 | 一种湿法磷酸副产α半水石膏的生产方法 |
Family Cites Families (18)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3653826A (en) * | 1967-09-21 | 1972-04-04 | Nissan Chemical Ind Ltd | Process for the production of phosphoric acid at a high concentration and a gypsum by-product of improved quality |
JPS5230959B2 (zh) | 1972-11-25 | 1977-08-11 | ||
US4196172A (en) * | 1976-07-07 | 1980-04-01 | Occidental Petroleum Corporation | Hemihydrate type phosphoric acid process |
US4501724A (en) * | 1984-02-01 | 1985-02-26 | Goers Associates Inc. | Method for the wet process manufacture of phosphoric acid |
DE3583209D1 (de) | 1984-11-05 | 1991-07-18 | Prayon Dev Sa | Kontinuierliches verfahren zur herstellung von phosphorsaeure und von calciumsulfat. |
JPS63144107A (ja) | 1986-12-08 | 1988-06-16 | Mitsui Toatsu Chem Inc | 高濃度燐酸−半水石こうスラリ−の濾過方法 |
CN1091424C (zh) | 1998-09-08 | 2002-09-25 | 新疆工学院 | 磷矿浆减水晶形调节剂的使用方法 |
CN1340457A (zh) | 2000-09-01 | 2002-03-20 | 山东鲁北企业集团总公司 | 一种磷酸生产工艺 |
CN1176011C (zh) | 2002-12-25 | 2004-11-17 | 云南红磷化工有限责任公司 | 一种半水—二水磷酸的生产方法 |
CN1314840C (zh) | 2004-06-14 | 2007-05-09 | 青岛科技大学 | 在磷酸中制造石膏晶须的方法 |
CN100396599C (zh) | 2004-12-14 | 2008-06-25 | 自贡鸿鹤化工股份有限公司 | 盐酸法生产磷酸联产石膏的方法 |
US7771851B2 (en) | 2005-08-26 | 2010-08-10 | United States Gypsum Company | Gypsum-containing products containing alpha hemihydrate |
CN102001636B (zh) * | 2010-09-26 | 2012-07-25 | 四川大学 | 利用中低品位磷矿湿法生产宽浓度磷酸和洁净石膏的方法 |
CN102126737A (zh) | 2011-01-20 | 2011-07-20 | 山东金正大生态工程股份有限公司 | 利用硫酸氢钾生产硝硫基复合肥副产石膏的方法 |
CN103332664B (zh) | 2013-06-22 | 2015-08-26 | 瓮福(集团)有限责任公司 | 一种半水法湿法磷酸生产工艺 |
CN103626143A (zh) * | 2013-11-29 | 2014-03-12 | 晏明朗 | 生产湿法磷酸副产白石膏的方法 |
CN104211105A (zh) | 2014-09-25 | 2014-12-17 | 瓮福(集团)有限责任公司 | 一种磷石膏生产方法 |
CN104628274A (zh) | 2014-12-03 | 2015-05-20 | 昆明理工大学 | 一种磷石膏制备高强α半水石膏的方法及装置 |
-
2015
- 2015-09-18 CN CN201510595367.7A patent/CN105253867B/zh active Active
-
2016
- 2016-08-26 CA CA2998908A patent/CA2998908C/en active Active
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2018
- 2018-03-18 SA SA518391134A patent/SA518391134B1/ar unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102303852A (zh) * | 2011-04-19 | 2012-01-04 | 江苏瑞和化肥有限公司 | 一种湿法磷酸联产石膏晶须的方法 |
CN103086335A (zh) * | 2013-02-05 | 2013-05-08 | 瓮福(集团)有限责任公司 | 一种二水-半水湿法磷酸工艺生产磷酸联产a-半水石膏的方法 |
CN104355560A (zh) * | 2014-10-21 | 2015-02-18 | 金正大生态工程集团股份有限公司 | 一种α-高强石膏粉的生产方法 |
CN105253867A (zh) * | 2015-09-18 | 2016-01-20 | 金正大生态工程集团股份有限公司 | 一种湿法磷酸副产α半水石膏的生产方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3351506A4 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115448276A (zh) * | 2022-08-16 | 2022-12-09 | 四川龙蟒磷化工有限公司 | 一种电池正极材料前驱体及其制备方法 |
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RU2688514C1 (ru) | 2019-05-21 |
LT3351506T (lt) | 2020-12-10 |
CN105253867A (zh) | 2016-01-20 |
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US10745278B2 (en) | 2020-08-18 |
CN105253867B (zh) | 2017-10-17 |
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EP3351506B1 (en) | 2020-09-30 |
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