CN117004249A - Method for preparing modified light calcium carbonate from phosphogypsum - Google Patents
Method for preparing modified light calcium carbonate from phosphogypsum Download PDFInfo
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- CN117004249A CN117004249A CN202310743057.XA CN202310743057A CN117004249A CN 117004249 A CN117004249 A CN 117004249A CN 202310743057 A CN202310743057 A CN 202310743057A CN 117004249 A CN117004249 A CN 117004249A
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- Prior art keywords
- calcium carbonate
- light calcium
- phosphogypsum
- ammonium
- ammonium lactate
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- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 title claims abstract description 146
- 229910000019 calcium carbonate Inorganic materials 0.000 title claims abstract description 71
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000004251 Ammonium lactate Substances 0.000 claims abstract description 29
- 229940059265 ammonium lactate Drugs 0.000 claims abstract description 29
- 235000019286 ammonium lactate Nutrition 0.000 claims abstract description 29
- RZOBLYBZQXQGFY-HSHFZTNMSA-N azanium;(2r)-2-hydroxypropanoate Chemical compound [NH4+].C[C@@H](O)C([O-])=O RZOBLYBZQXQGFY-HSHFZTNMSA-N 0.000 claims abstract description 29
- GVJHHUAWPYXKBD-UHFFFAOYSA-N (±)-α-Tocopherol Chemical compound OC1=C(C)C(C)=C2OC(CCCC(C)CCCC(C)CCCC(C)C)(C)CCC2=C1C GVJHHUAWPYXKBD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003607 modifier Substances 0.000 claims abstract description 19
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 14
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 12
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 10
- 229930003427 Vitamin E Natural products 0.000 claims abstract description 10
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 10
- WIGCFUFOHFEKBI-UHFFFAOYSA-N gamma-tocopherol Natural products CC(C)CCCC(C)CCCC(C)CCCC1CCC2C(C)C(O)C(C)C(C)C2O1 WIGCFUFOHFEKBI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 10
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 10
- 229940046009 vitamin E Drugs 0.000 claims abstract description 10
- 235000019165 vitamin E Nutrition 0.000 claims abstract description 10
- 239000011709 vitamin E Substances 0.000 claims abstract description 10
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims description 24
- 238000003763 carbonization Methods 0.000 claims description 13
- 239000002270 dispersing agent Substances 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000004090 dissolution Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 238000001728 nano-filtration Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 8
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 8
- 239000012528 membrane Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004064 recycling Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000002893 slag Substances 0.000 claims description 2
- BTURAGWYSMTVOW-UHFFFAOYSA-M sodium dodecanoate Chemical compound [Na+].CCCCCCCCCCCC([O-])=O BTURAGWYSMTVOW-UHFFFAOYSA-M 0.000 claims description 2
- 229940082004 sodium laurate Drugs 0.000 claims description 2
- 239000011247 coating layer Substances 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 8
- 230000002209 hydrophobic effect Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 5
- 238000005452 bending Methods 0.000 abstract description 2
- 238000010000 carbonizing Methods 0.000 abstract 1
- 239000011347 resin Substances 0.000 abstract 1
- 229920005989 resin Polymers 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 34
- 239000003795 chemical substances by application Substances 0.000 description 10
- 229960005069 calcium Drugs 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 9
- 239000004033 plastic Substances 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000012546 transfer Methods 0.000 description 7
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- -1 long-chain fatty acid salts Chemical class 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 238000004062 sedimentation Methods 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000010828 elution Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 235000019270 ammonium chloride Nutrition 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical group [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000006011 modification reaction Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- MKJXYGKVIBWPFZ-UHFFFAOYSA-L calcium lactate Chemical compound [Ca+2].CC(O)C([O-])=O.CC(O)C([O-])=O MKJXYGKVIBWPFZ-UHFFFAOYSA-L 0.000 description 1
- 239000001527 calcium lactate Substances 0.000 description 1
- 229960002401 calcium lactate Drugs 0.000 description 1
- 235000011086 calcium lactate Nutrition 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical group CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000010850 salt effect Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
-
- 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
- C01F11/18—Carbonates
-
- 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
- C01F11/18—Carbonates
- C01F11/185—After-treatment, e.g. grinding, purification, conversion of crystal morphology
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C1/00—Treatment of specific inorganic materials other than fibrous fillers; Preparation of carbon black
- C09C1/02—Compounds of alkaline earth metals or magnesium
- C09C1/021—Calcium carbonates
- C09C1/022—Treatment with inorganic compounds
- C09C1/024—Coating
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/006—Combinations of treatments provided for in groups C09C3/04 - C09C3/12
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/06—Treatment with inorganic compounds
- C09C3/063—Coating
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09C—TREATMENT OF INORGANIC MATERIALS, OTHER THAN FIBROUS FILLERS, TO ENHANCE THEIR PIGMENTING OR FILLING PROPERTIES ; PREPARATION OF CARBON BLACK ; PREPARATION OF INORGANIC MATERIALS WHICH ARE NO SINGLE CHEMICAL COMPOUNDS AND WHICH ARE MAINLY USED AS PIGMENTS OR FILLERS
- C09C3/00—Treatment in general of inorganic materials, other than fibrous fillers, to enhance their pigmenting or filling properties
- C09C3/10—Treatment with macromolecular organic compounds
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/19—Oil-absorption capacity, e.g. DBP values
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention discloses a method for preparing modified light calcium carbonate from phosphogypsum. The method comprises the steps of dissolving phosphogypsum in ammonium lactate solution, filtering to obtain calcium-rich solution, carbonizing by ammonium carbonate to obtain light calcium carbonate, carrying out wet surface modification on the light calcium carbonate by using a compound modifier of polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate, so that a stable high-molecular organic hydrophobic coating layer is formed on the surface of the light calcium carbonate, the lipophilicity of the surface of the light calcium carbonate is increased, the compatibility with resin is better, and the prepared modified light calcium carbonate is filled in a PP material, so that the heat resistance, impact resistance and bending resistance of the PP material can be obviously enhanced.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a method for preparing modified light calcium carbonate from phosphogypsum.
Background
Phosphogypsum is industrial solid waste residue generated in the process of preparing phosphoric acid by a sulfuric acid method, 4-5 phosphogypsum is generated per 1 ton of phosphoric acid, and the main component of phosphogypsum is calcium sulfate dihydrate, and then silicon dioxide, and also contains a small amount of phosphorus and fluorine. Phosphogypsum is high in yield, and the phosphogypsum is piled up to occupy a large amount of land resources by taking piling up as a main disposal mode, and water pollution is easy to cause. Phosphogypsum is a misplaced resource, so that phosphogypsum is treated and recycled, and the production of high-value products can bring environmental benefits and create economic benefits.
At present, in the existing process for preparing calcium carbonate by using phosphogypsum, in the method for co-producing ammonium sulfate and calcium carbonate by using phosphogypsum in the patent CN101492178A, the phosphogypsum and the ammonium carbonate are directly mixed and reacted to prepare modified calcium carbonate and ammonium sulfate, and the method realizes high-value utilization of phosphogypsum, but the prepared modified calcium carbonate contains impurities, and the purity is only 93.13%. The phosphogypsum is dissolved by adopting a phase transfer agent, impurities are removed and carbonized, so that the purity of the calcium carbonate can be improved, in the patent CN114368771A, ammonium chloride is used for dissolving the phosphogypsum, the impurities are removed and carbonized to prepare spherical calcium carbonate, in the patent CN113321232A, the ammonia-containing phase transfer agent is used for dissolving the impurities and carbonized to prepare light calcium carbonate, ammonium sulfate in the phase transfer agent is recovered by adopting evaporation crystallization, the method can obtain purer calcium carbonate, but the energy consumption for recovering the ammonium sulfate by the evaporation crystallization is high, and when the cations of the phase transfer agent are different from those of the carbonization agent, the purity of the product obtained by the evaporation crystallization is low.
The surface of the light calcium carbonate has hydroxyl groups with stronger hydrophilicity and stronger alkalinity, and the hydrophilic oleophobic property ensures that the light calcium carbonate has poor affinity with an organic high polymer, is easy to form aggregates, is unevenly dispersed in the high polymer, influences the using effect, and is necessary to carry out surface modification treatment for improving the reinforcing effect of the light calcium carbonate and the dispersing effect of the light calcium carbonate in plastics. The common surface modifier is stearate, oleate and other long-chain fatty acid salts, the long-chain fatty acid salts and calcium form a precipitate to wrap the surface of calcium carbonate, but the wrapping layer is unstable and is easy to elute in the washing process, so that the effect of the surface modifier in plastic filling is affected, and therefore, the design of the light calcium carbonate surface wrapping layer with stable structure is necessary.
Based on the above, it is necessary to develop a method for preparing modified light calcium carbonate by using phosphogypsum as a raw material, preparing light calcium carbonate by adopting a phase transfer method, selecting a proper separation technology to recycle a phase transfer agent and ammonium sulfate, and carrying out surface modification on the light calcium carbonate to form a stable hydrophobic coating layer on the surface of the light calcium carbonate, thereby improving the surface stability of the light calcium carbonate, enhancing the affinity between the light calcium carbonate and an organic polymer and the dispersibility of the light calcium carbonate in the polymer.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a method for preparing modified light calcium carbonate by phosphogypsum, which can prepare high-purity modified light calcium carbonate by phosphogypsum, effectively separate and recycle phase transfer agent and ammonium sulfate, and the prepared modified light calcium carbonate has uniform and stable surface coating, strong hydrophobicity, uniform dispersion in high polymer, good compatibility, simple preparation process, low cost and good performance of conversion products, and meets the requirements of target markets.
The invention realizes the aim by the following technical scheme:
(1) Adding phosphogypsum into ammonium lactate solution, heating, stirring and dissolving, and filtering after dissolving completely to obtain calcium-rich liquid and high-silicon slag;
(2) Adding a dispersing agent into the calcium-rich liquid obtained in the step (1), slowly dripping an ammonium carbonate solution into the calcium-rich liquid under the heating condition, continuously stirring, filtering after the dripping is finished to obtain light calcium carbonate, separating ammonium lactate and ammonium sulfate from filtrate by adopting a nanofiltration membrane, and recycling the ammonium lactate to the step (1);
(3) And (3) mixing the light calcium carbonate obtained in the step (2), adding a surface modifier into the slurry, heating the slurry, fully stirring for a period of time, filtering, washing and drying to obtain the modified light calcium carbonate.
Preferably, in the step (1), the mass ratio of phosphogypsum to ammonium lactate is 1:2-4, the concentration of ammonium lactate is 15-25 wt%, the dissolution temperature is 40-60 ℃, the stirring speed is 200-400 r/min, and the dissolution time is 0.5-2 h.
Preferably, the dispersing agent in the step (2) is sodium laurate, the dosage is 0.1-0.5 wt%, and the concentration of the ammonium carbonate solution is 2-5wt%. The carbonization reaction temperature is 75-95 ℃, the stirring speed is 200-400 r/min, and the dripping time is 10-30 min.
Preferably, the nanofiltration membrane in the step (2) adopts a nanofiltration membrane with a molecular weight cut-off of 300D, and adopts two-stage nanofiltration.
Preferably, in the step (3), the slurry concentration is 40-60 wt%, the surface modifier is a compound modifier prepared from polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:0.1-1.5:1-5, the dosage is 3-5 wt%, the heating temperature is 75-95 ℃, and the stirring time is 0.5-1 h.
The invention has the beneficial effects that:
1. the invention has simple process flow and lower energy consumption, the whole reaction system forms a closed loop, the ammonium lactate solution is recycled, and no waste is generated;
2. according to the invention, the surface of the light calcium carbonate is modified by adopting the polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate compound modifier by a wet method to form a uniform and stable oleophylic and hydrophobic coating, so that the hydrophobicity and dispersibility of the light calcium carbonate are obviously improved, and when the light calcium carbonate is used as a plastic product filler, the heat resistance, strength and rigidity of the plastic product can be enhanced, and the production cost is reduced; 3. according to the invention, phosphogypsum is prepared into a high-valued modified light calcium carbonate product, so that the phosphogypsum is recycled, the environmental problem caused by phosphogypsum can be effectively relieved, and the economic value is created.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed description of the preferred embodiments
In order to better explain the present invention, the following examples are given as only some embodiments of the present invention, and phosphogypsum used in the examples is taken from a certain phosphorus chemical industry and its composition is shown in the following table:
table 1: phosphogypsum main components:
example 1
(1) Phosphogypsum is added into an ammonium lactate solution with the concentration of 15wt%, and the mass ratio of the phosphogypsum to the ammonium lactate is 1:2, heating to 40 ℃, maintaining the temperature, stirring and dissolving for 2 hours at the stirring speed of 300r/min, and filtering to obtain calcium-enriched liquid;
(2) Adding 0.2wt% of sodium lauryl sulfate into the calcium-enriched liquid obtained in the step (1), heating the calcium-enriched liquid to 80 ℃, keeping the temperature, dripping an ammonium carbonate solution with the concentration of 2wt% into the calcium-enriched liquid for 10min, continuously stirring at the stirring speed of 300r/min, filtering after the dripping is finished to obtain light calcium carbonate, performing two-stage nanofiltration on filtrate by adopting a nanofiltration membrane with the molecular weight cutoff of 300D, recycling ammonium lactate to the step (1), and recycling the ammonium lactate to the step (1), wherein the recovery rate of the ammonium lactate is 91.5%;
(3) And (3) pulping the light calcium carbonate obtained in the step (2), wherein the concentration of the slurry is 40wt%, adding 3wt% of surface modifier which is a compound modifier prepared from polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:1.5:2 into the slurry, heating the slurry to 80 ℃, fully stirring for 0.5h, filtering, washing and drying to obtain the modified light calcium carbonate.
Example 2
The process steps are the same as in example 1, only the ammonium lactate concentration is 20wt%, the mass ratio of phosphogypsum to ammonium lactate is 1:3, the dissolution temperature is 45 ℃, the dissolution time is 1h, the dissolution stirring speed is 200r/min, the consumption of a dispersing agent is 0.3wt%, the carbonization reaction temperature is 85 ℃, the ammonium carbonate concentration is 3wt%, the dripping time is 15min, the carbonization stirring speed is 400r/min, the slurry mixing concentration is 50wt%, the consumption of a surface modifier is 4wt%, the surface modifier is a compound modifier prepared from polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:0.5:3, the modification reaction temperature is 85 ℃, the modification stirring time is 1h, and the recovery rate of ammonium lactate is 91.1%;
example 3
The process steps are the same as in example 1, only ammonium lactate concentration 25wt%, phosphogypsum in ammonium lactate mass ratio 1:4, the dissolution temperature is 50 ℃, the dissolution time is 1h, the consumption of the dispersing agent is 0.4wt%, the carbonization reaction temperature is 90 ℃, the ammonium carbonate concentration is 4wt%, the dripping time is 20min, the carbonization stirring speed is 400r/min, the slurry mixing concentration is 60wt%, the consumption of the surface modifying agent is 4wt%, the surface modifying agent is a compound modifying agent prepared by polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:0.3:3, the modification reaction temperature is 90 ℃, and the recovery rate of ammonium lactate is 91.1%.
Example 4
The process steps are the same as in example 1, only the ammonium lactate concentration is 20wt%, the mass ratio of phosphogypsum to ammonium lactate is 1:4, dissolving temperature 50 ℃, dissolving time 0.5h, dissolving and stirring speed 400r/min, dispersing agent dosage 0.5wt%, carbonization reaction temperature 75 ℃, ammonium carbonate concentration 4wt%, dripping time 20min, carbonization and stirring speed 400r/min, slurry mixing concentration 55wt%, surface modifier dosage 5wt%, and surface modifier is a compound modifier prepared from polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:1:3, modification reaction temperature 95 ℃, modification and stirring time 1h, and recovery rate of ammonium lactate 90.4%.
Comparative example 1
The process steps are the same as in example 1, except that the surface modifier is a mixture of polyvinyl carboxylate and vitamin E polyethylene glycol succinate in a ratio of 1:1, the amount is 3wt%, and the recovery rate of ammonium lactate is 90.7%.
Comparative example 2
The procedure was as in example 1, except that no dispersant was added during carbonization, and the recovery rate of ammonium lactate was 91.2%.
Comparative example 3
The method steps are the same as in example 1, only ammonium chloride is used for dissolving phosphogypsum, and the recovery rate of ammonium chloride is 92.5%.
The modified calcium carbonate obtained in examples 1 to 4 and comparative example 1 was washed with water 6 times, and the elution rate of the hydrophobic coating layer was measured, and the results are shown in Table 2:
table 2: EXAMPLES 1 to 4 elution Rate Experimental data
| Sample of | 1 time | 2 times | 3 times | 4 times | 5 times | 6 times |
| Example 1 | 0.10％ | 0.17％ | 0.17％ | 0.19％ | 0.19％ | 0.19％ |
| Example 2 | 0.09％ | 0.11％ | 0.11％ | 0.11％ | 0.11％ | 0.11％ |
| Example 3 | 0.12％ | 0.15％ | 0.15％ | 0.16％ | 0.16％ | 0.16％ |
| Example 4 | 0.15％ | 0.15％ | 0.16％ | 0.17％ | 0.17％ | 0.17％ |
| Comparative example 1 | 0.95％ | 1.32％ | 1.77％ | 2.52％ | 2.98％ | 3.57％ |
It can be seen from Table 2 that the elution rates of examples 1 to 4 were lower than that of comparative example 1 after each washing, and the elution rates of the respective samples were not changed after 2 washing in examples 1 to 4, indicating that the coating layer on the surface of calcium carbonate was not decreased by washing again after 2 washing, indicating that the coating layer was stable in the liquid phase dispersion system, whereas the elution rate was increased after each washing in comparative example 1, indicating that the coating layer was decreased and the coating layer was unstable. Therefore, the carbon nitride can be added to effectively improve the stability of the coating, and the carbon nitride has high stability and hardness due to the unit cell structure of the carbon nitride, and can form a stable organic coating on the surface of calcium carbonate when being used together with polyvinyl carboxylate and vitamin E polyethylene glycol succinate.
The modified light calcium carbonate of examples 1 to 4 and comparative examples 1 to 3 and the light calcium carbonate of comparative example 4 were subjected to analytical tests to determine the purity, sedimentation volume, oil absorption value using the light calcium carbonate prepared in example 1 as comparative example 4, and the test results are shown in table 3:
table 3: test data for examples and comparative examples
| Sample of | Purity of | Sedimentation volume mL/g | Oil absorption value |
| Example 1 | 98.2％ | 4.5 | 34.4 |
| Example 2 | 97.9％ | 4.8 | 37.5 |
| Example 3 | 97.5％ | 4.4 | 32.8 |
| Example 4 | 97.1％ | 4.9 | 37.9 |
| Comparative example 1 | 98.5％ | 3.9 | 41.2 |
| Comparative example 2 | 98.7％ | 2.5 | 48.1 |
| Comparative example 3 | 97.1％ | 2.2 | 35.4 |
| Comparative example 4 | 99.8％ | 2.8 | 58.9 |
As can be seen from Table 3, the purities of examples 1-4 and comparative examples 1-2 were all 97% or more, demonstrating that high purity modified light calcium carbonate could be produced by this method; the sedimentation volume of example 1 is higher than that of comparative example 4, and the oil absorption value is lower than that of comparative example 4, which shows that the surface of the light calcium carbonate is modified by surface coating so that the surface of the light calcium carbonate becomes more oleophilic and hydrophobic, and the dispersibility in water is better, so that the sedimentation volume is larger, and the oil absorption value of the organic hydrophobic coating layer on the surface of the light calcium carbonate is reduced; the settling volume of example 1 is higher than that of comparative example 2, which shows that the addition of the dispersant in the carbonization process can increase the settling volume of the modified calcium carbonate, which is mainly that the dispersant can be adsorbed on the surface of the calcium carbonate particles to inhibit the growth and agglomeration of the particles, so that the modified light calcium carbonate particles are smaller and have better dispersibility. The sedimentation volume of example 1 is greater than that of comparative example 1, and the oil absorption value is lower than that of comparative example 1, which indicates that the addition of carbon nitride can increase the sedimentation volume of the modified light calcium carbonate and reduce the oil absorption value, which benefits from the addition of carbon nitride to make the coating layer more hydrophobic, more stable in structure and less voids on the surface of the calcium carbonate particles. The indexes of the embodiment 1 are all better than those of the comparative example 3 because ammonium lactate and calcium ions are combined in a complexing form, calcium of calcium lactate is slowly released into a solution and combined with ammonium carbonate to generate calcium carbonate in the carbonization process, the formed calcium carbonate has small particle size and uniform shape, light calcium carbonate can be obtained, ammonium chloride promotes the dissolution of calcium sulfate through a salt effect, calcium exists in an ionic form, and a large amount of calcium ions and ammonium carbonate are combined to easily form particles with large particle size in the carbonization process, so that heavy calcium carbonate is obtained.
Modified light calcium carbonate in examples 1 to 4 was added to polypropylene materials at an addition amount of 20%, equivalent amounts of light calcium carbonate prepared in examples 1 to 4 was added to polypropylene materials at an addition amount of 20% to prepare comparative examples 4 to 7, pure polypropylene materials were prepared as comparative example 8, and performance tests were conducted on examples 1 to 4 and comparative examples 1 to 7, and the results of the performance tests are shown in Table 4:
table 4: comparative and example Performance test experimental data
As can be seen from Table 4, each performance index of comparative examples 4 to 7 is higher than that of comparative example 8, which shows that the addition of light calcium carbonate can improve the tensile strength, flexural strength, impact strength and heat resistance of PP material at the same time, and that the heat resistance, flexural strength and impact strength of comparative example 3 are better than those of comparative example 8, but the tensile strength is lower than that of comparative example 8, which shows that the addition of heavy calcium carbonate can improve the heat resistance and part of mechanical properties of plastic, and cannot improve the tensile strength, flexural strength, impact strength and heat resistance at the same time. All performance indexes of the examples 1-4 are higher than those of the comparative examples 4-7, which shows that after the light calcium carbonate is modified, the compatibility of the light calcium carbonate and the PP material is better, the mechanical property and the heat resistance of the PP material are greatly improved, all performances of the example 1 are better than those of the comparative example 2, the filling effect of the calcium carbonate in the plastic filler can be improved by adding the dispersing agent, all performances of the example 1 are better than those of the comparative example 1, the heat resistance and the impact resistance of the plastic are obviously improved, and the modified light calcium carbonate is added into the plastic to enhance the impact strength, the tensile strength, the bending strength and the heat resistance of the plastic due to the high-temperature-resistant property of the carbon nitride.
The foregoing is illustrative of the present invention and is not to be construed as limiting thereof, but is for the purpose of describing various embodiments of the present invention.
Claims (8)
1. A method for preparing modified light calcium carbonate from phosphogypsum, comprising the following steps:
(1) Adding phosphogypsum into ammonium lactate solution, heating, stirring and dissolving, and filtering after dissolving completely to obtain calcium-rich liquid and high-silicon slag;
(2) Adding a dispersing agent into the calcium-rich liquid obtained in the step (1), slowly dripping an ammonium carbonate solution into the calcium-rich liquid under the heating condition, continuously stirring, filtering after the dripping is finished to obtain light calcium carbonate, separating ammonium lactate and ammonium sulfate from filtrate by adopting a nanofiltration membrane, and recycling the ammonium lactate to the step (1);
(3) And (3) mixing the light calcium carbonate obtained in the step (2), adding a surface modifier into the slurry, heating the slurry, fully stirring for a period of time, filtering, washing and drying to obtain the modified light calcium carbonate.
2. The treatment method according to claim 1, wherein in the step (1), the mass ratio of phosphogypsum to ammonium lactate is 1:2-4, and the concentration of ammonium lactate is 15-25% by weight wt%.
3. The method according to claim 1, wherein the dissolution temperature in the step (1) is 40 to 60 ℃, the stirring speed is 200 to 400r/min, and the dissolution time is 0.5 to 2 hours.
4. The method according to claim 1, wherein the dispersant in the step (2) is sodium laurate, the amount of the dispersant is 0.1-wt% -0.5-wt%, and the concentration of the ammonium carbonate solution is 2-wt% -5-wt%.
5. The method according to claim 1, wherein the carbonization reaction temperature in the step (2) is 75 to 95 ℃, the stirring speed is 200 to 400r/min, and the dropping time is 10 to 30min.
6. The process of claim 1, wherein the nanofiltration membrane of step (2) is a nanofiltration membrane having a molecular weight cut-off of 300D, and wherein two-stage nanofiltration is employed.
7. The treatment method according to claim 1, wherein in the step (3), the concentration of the light calcium carbonate slurry is 40-60-wt%, the surface modifier is a compound modifier obtained by mixing polyvinyl carboxylate, carbon nitride and vitamin E polyethylene glycol succinate according to a ratio of 2:0.1-1.5:1-5, and the dosage is 3-5 wt%.
8. The method according to claim 1, wherein the heating temperature in the step (3) is 75 to 95 ℃ and the stirring time is 0.5 to 1h.
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Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008151991A1 (en) * | 2007-06-15 | 2008-12-18 | Omya Development Ag | Surface-reacted calcium carbonate in combination with hydrophobic adsorbent for water treatment |
| CN101671494A (en) * | 2009-09-19 | 2010-03-17 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| US20130288887A1 (en) * | 2012-04-28 | 2013-10-31 | Zhejiang University | Method for preparing a nano-calcium carbonate slurry from waste gypsum as calcium source, the product and use thereof |
| CN104592551A (en) * | 2015-01-12 | 2015-05-06 | 安徽玉堂雨具有限公司 | Filler capable of enhancing low-temperature resistance of plastic and preparation method thereof |
| CN106927494A (en) * | 2017-03-31 | 2017-07-07 | 贵州省化工研究院 | A kind of method that utilization ardealite directly prepares modified calcium carbonate |
| CN108822714A (en) * | 2018-05-25 | 2018-11-16 | 合肥昂诺新材料有限公司 | A kind of water-repellent paint that hydrophobicity is promoted |
| CN109535772A (en) * | 2018-12-27 | 2019-03-29 | 李绿叶 | A kind of low-viscosity active calcium carbonate and its method of modifying |
| CN113321232A (en) * | 2021-06-16 | 2021-08-31 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| CN115710432A (en) * | 2022-12-15 | 2023-02-24 | 中路交科科技股份有限公司 | Hydrophobic durable high-viscosity modified asphalt and preparation method thereof |
-
2023
- 2023-06-21 CN CN202310743057.XA patent/CN117004249A/en active Pending
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008151991A1 (en) * | 2007-06-15 | 2008-12-18 | Omya Development Ag | Surface-reacted calcium carbonate in combination with hydrophobic adsorbent for water treatment |
| CN101671494A (en) * | 2009-09-19 | 2010-03-17 | 张家界恒亮新材料科技有限公司 | Surface modified calcium carbonate and preparation method thereof |
| CN101993105A (en) * | 2010-12-10 | 2011-03-30 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| US20130288887A1 (en) * | 2012-04-28 | 2013-10-31 | Zhejiang University | Method for preparing a nano-calcium carbonate slurry from waste gypsum as calcium source, the product and use thereof |
| CN104592551A (en) * | 2015-01-12 | 2015-05-06 | 安徽玉堂雨具有限公司 | Filler capable of enhancing low-temperature resistance of plastic and preparation method thereof |
| CN106927494A (en) * | 2017-03-31 | 2017-07-07 | 贵州省化工研究院 | A kind of method that utilization ardealite directly prepares modified calcium carbonate |
| CN108822714A (en) * | 2018-05-25 | 2018-11-16 | 合肥昂诺新材料有限公司 | A kind of water-repellent paint that hydrophobicity is promoted |
| CN109535772A (en) * | 2018-12-27 | 2019-03-29 | 李绿叶 | A kind of low-viscosity active calcium carbonate and its method of modifying |
| CN113321232A (en) * | 2021-06-16 | 2021-08-31 | 合肥工业大学 | Method for preparing light calcium carbonate and co-producing ammonium sulfate from phosphogypsum |
| CN115710432A (en) * | 2022-12-15 | 2023-02-24 | 中路交科科技股份有限公司 | Hydrophobic durable high-viscosity modified asphalt and preparation method thereof |
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