CN111302375A - Method for preparing gypsum whisker and composite flame retardant by taking phosphorus tailings as raw materials - Google Patents
Method for preparing gypsum whisker and composite flame retardant by taking phosphorus tailings as raw materials Download PDFInfo
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- CN111302375A CN111302375A CN202010123203.5A CN202010123203A CN111302375A CN 111302375 A CN111302375 A CN 111302375A CN 202010123203 A CN202010123203 A CN 202010123203A CN 111302375 A CN111302375 A CN 111302375A
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- flame retardant
- composite flame
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- 239000003063 flame retardant Substances 0.000 title claims abstract description 106
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 105
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000011574 phosphorus Substances 0.000 title claims abstract description 41
- 229910052698 phosphorus Inorganic materials 0.000 title claims abstract description 41
- 239000010440 gypsum Substances 0.000 title claims abstract description 34
- 229910052602 gypsum Inorganic materials 0.000 title claims abstract description 34
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 70
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims abstract description 35
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 26
- 239000010452 phosphate Substances 0.000 claims abstract description 26
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 26
- 239000011777 magnesium Substances 0.000 claims abstract description 24
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003607 modifier Substances 0.000 claims abstract description 22
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000011575 calcium Substances 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 10
- 238000013329 compounding Methods 0.000 claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 53
- 238000005406 washing Methods 0.000 claims description 37
- 239000000347 magnesium hydroxide Substances 0.000 claims description 32
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001556 precipitation Methods 0.000 claims description 24
- 230000032683 aging Effects 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 14
- 229940093429 polyethylene glycol 6000 Drugs 0.000 claims description 10
- RYYKJJJTJZKILX-UHFFFAOYSA-M sodium octadecanoate Chemical compound [Na+].CCCCCCCCCCCCCCCCCC([O-])=O RYYKJJJTJZKILX-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 239000004137 magnesium phosphate Substances 0.000 claims description 4
- 229960002261 magnesium phosphate Drugs 0.000 claims description 4
- 229910000157 magnesium phosphate Inorganic materials 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- TZHYBRCGYCPGBQ-UHFFFAOYSA-N [B].[N] Chemical compound [B].[N] TZHYBRCGYCPGBQ-UHFFFAOYSA-N 0.000 claims description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 claims description 2
- 239000007822 coupling agent Substances 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 5
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000003912 environmental pollution Methods 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 38
- 150000001875 compounds Chemical class 0.000 description 30
- 239000003822 epoxy resin Substances 0.000 description 24
- 229920000647 polyepoxide Polymers 0.000 description 24
- 238000003756 stirring Methods 0.000 description 24
- 239000012153 distilled water Substances 0.000 description 18
- 239000000706 filtrate Substances 0.000 description 18
- 238000005303 weighing Methods 0.000 description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 12
- 239000007788 liquid Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 9
- 239000000843 powder Substances 0.000 description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000007865 diluting Methods 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 238000004321 preservation Methods 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 4
- 238000005188 flotation Methods 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- 239000002910 solid waste Substances 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 2
- 239000010459 dolomite Substances 0.000 description 2
- 229910000514 dolomite Inorganic materials 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZHQXROVTUTVPGO-UHFFFAOYSA-N [F].[P] Chemical compound [F].[P] ZHQXROVTUTVPGO-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
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- 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
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/20—Magnesium hydroxide by precipitation from solutions of magnesium salts with ammonia
-
- 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
- C01F5/00—Compounds of magnesium
- C01F5/14—Magnesium hydroxide
- C01F5/22—Magnesium hydroxide from magnesium compounds with alkali hydroxides or alkaline- earth oxides or hydroxides
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- 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
- C08K9/04—Ingredients treated with organic substances
-
- 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
- C08K9/08—Ingredients agglomerated by treatment with a binding agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2217—Oxides; Hydroxides of metals of magnesium
- C08K2003/2224—Magnesium hydroxide
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
Abstract
The invention provides a method for preparing gypsum whisker and a composite flame retardant by taking phosphate tailings as raw materials, which comprises the steps of firstly decomposing the phosphate tailings by using sulfuric acid to obtain acidolysis solution A and phosphogypsum, then separating calcium and magnesium by using a precipitator to obtain acidolysis solution B and gypsum whisker, then oxidizing the acidolysis solution B by using hydrogen peroxide and ammonia water to remove impurities, adding a modifier, and adding an alkaline precipitator at a certain temperature to obtain modified magnesium hydroxide to be compounded with an organic flame retardant to obtain the composite flame retardant. The modified magnesium hydroxide in the prepared composite flame retardant has high compatibility in polymers, and has an organic-inorganic synergistic flame retardant effect by compounding with an organic flame retardant, so that the obtained composite flame retardant has a good flame retardant effect, a new way is provided for resource utilization of phosphorus tailings, the additional value of phosphorus tailings products is greatly improved, the environmental pollution caused by the phosphorus tailings is solved, the ecological environment is improved, and the composite flame retardant has great economic, social and environmental benefits.
Description
Technical Field
The invention relates to the technical field of waste resource utilization, in particular to a method for preparing gypsum whiskers and a composite flame retardant by taking phosphate tailings as raw materials.
Background
The phosphorus tailings mainly come from tailings left after ore dressing and concentrate extraction, and belong to mining solid wastes in industrial solid wastes. The minerals mainly comprise dolomite, fluorine phosphorus ash and quartz, the CaO content of the dolomite is about 30.0-34.0 percent, and P is2O5The content is about 4-8.5%, and the content of MgO is about 12-18%.
As the exploitation of phosphate rock increases, the amount of phosphate tailings also rises rapidly. 0.44t of phosphate tailings can be generated every 1t of phosphate concentrate is produced, the phosphate tailings mainly comprise flotation phosphate tailings, phosphorus slag and phosphate sludge, the flotation phosphate tailings are solid wastes generated after phosphate ore is subjected to a flotation process, the average MgO content is more than 15%, and the magnesium-rich resource is worthy of recycling. At present, the part of tailings is stockpiled in a tailing pond for a long time, so that not only can effective solution and utilization be realized, but also a series of environmental problems can be caused, and the serious current situation of resource waste is caused. Magnesium hydroxide is one of the polymer flame retardants widely used at present, and has the advantages of no toxicity, low smoke, stable chemical property of magnesium oxide generated after decomposition, no secondary pollution and the like. However, magnesium hydroxide produced by the traditional process has serious agglomeration phenomenon, poor dispersion performance, large addition amount and low flame retardant efficiency, so that the application of the magnesium hydroxide as a flame retardant is greatly limited. Therefore, it is very important to modify the surface of magnesium hydroxide to improve the compatibility of magnesium hydroxide powder in the polymer. The tailings contain a large amount of magnesium elements, and the flame-retardant magnesium hydroxide product prepared by recycling the magnesium elements not only can solve the environmental pollution, improve the ecological environment and improve the national soil, but also can create income for enterprises, so that the comprehensive utilization of the phosphorus tailings has huge economic, social and environmental benefits.
Disclosure of Invention
In view of the above, the invention aims to provide a method for preparing gypsum whiskers and a composite flame retardant by using phosphorus tailings as a raw material, so as to solve the problems of low resource utilization rate and low product added value of the existing phosphorus tailings.
In order to achieve the purpose, the technical scheme of the invention is realized as follows:
a method for preparing gypsum whiskers and a composite flame retardant by taking phosphate tailings as raw materials comprises the following steps:
1) mixing the high-magnesium phosphate tailings with sulfuric acid, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out suction filtration and washing to obtain acidolysis solution A and phosphogypsum;
2) adding a precipitator into the acidolysis solution A for precipitation reaction, and after the precipitation reaction is finished, aging, filtering, and washing to obtain acidolysis solution B and gypsum whiskers;
3) adding hydrogen peroxide and ammonia water into the acidolysis solution B, removing impurities, adding a modifier, heating to a certain temperature, adding an alkaline precipitator, carrying out precipitation reaction, and after the precipitation reaction is finished, aging, filtering, washing and drying to obtain magnesium hydroxide;
4) and compounding the magnesium hydroxide and the organic flame retardant to obtain the composite flame retardant.
Optionally, the concentration of the sulfuric acid in the step 1) is 1.68-18.4mol/L, and the mass ratio of the sulfuric acid to the high-magnesium phosphate tailings is (1.01-2) to 1.
Optionally, the reaction temperature of the acidolysis reaction in the step 1) is 20-60 ℃, and the reaction time is 10-60 min; the suction filtration temperature of the suction filtration in the step 1) is 20-60 ℃.
Optionally, the precipitant in the step 2) is one of sulfuric acid, sodium sulfate and sodium bisulfate, and the mass fraction of the precipitant is 5-25%; the addition amount of the precipitant in the step 2) is 1-2.5 times of the amount of calcium in the acidolysis solution A.
Optionally, the reaction temperature of the precipitation reaction in the step 2) is 70-95 ℃, and the reaction time is 0.5-2 h; the aging time of the aging in the step 2) is 2-4 h.
Optionally, the volume ratio of the acidolysis solution B, the hydrogen peroxide and the ammonia water in the step 3) is 1 to (1/200-1/50) to (1/9-4/9).
Optionally, the modifier in step 3) is one of sodium stearate, polyethylene glycol 6000, a coupling agent, and a mixture of sodium stearate and polyethylene glycol 6000.
Optionally, the adding amount of the modifier in the step 3) is 2% -8% of the yield of the magnesium hydroxide, and the temperature rise temperature after the modifier is added is 50-95 ℃; the reaction temperature of the precipitation reaction in the step 3) is 50-95 ℃.
Optionally, in the step 3), the alkaline precipitant is one of ammonia water, sodium hydroxide and potassium hydroxide, and the concentration of the alkaline precipitant is 1-3 mol/L.
Optionally, the organic flame retardant in the step 4) is one of a phosphorus-nitrogen flame retardant, a boron-nitrogen flame retardant, a phosphorus flame retardant and a nitrogen flame retardant, and the addition amount of the organic flame retardant in the composite flame retardant is 2% -10%.
Compared with the prior art, the method for preparing the gypsum whisker and the composite flame retardant by taking the phosphate tailings as the raw materials has the following advantages:
1. the invention utilizes the high-magnesium phosphate tailings to prepare magnesium hydroxide and gypsum whiskers, and adds the modifier in the preparation process, thereby greatly improving the compatibility of the obtained magnesium hydroxide in polymers, compounding the modified magnesium hydroxide with the organic flame retardant, and having organic and inorganic synergistic flame retardant effect, so that the obtained composite flame retardant has good flame retardant effect, provides a new way for resource utilization of the phosphate tailings, greatly improves the additional value of phosphate tailings products, solves the environmental pollution caused by the phosphate tailings, improves the ecological environment, and has huge economic, social and environmental benefits.
2. The preparation method is simple, three major elements of calcium, magnesium and phosphorus in the phosphate tailings can be effectively utilized, the condensate obtained by concentration can be used for process washing water, water resources are saved, and the purpose of accurately utilizing the phosphate tailings is achieved.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate an embodiment of the invention and, together with the description, serve to explain the invention and not to limit the invention. In the drawings:
FIG. 1 is a process flow chart of the present invention for preparing gypsum whisker and composite flame retardant by using phosphate tailings as raw materials.
Detailed Description
It should be noted that the embodiments and features of the embodiments may be combined with each other without conflict.
The present invention will be described in detail below with reference to the drawings and examples.
Example 1
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to 5% of mass fraction, dropwise adding the diluted sulfuric acid into acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.05: 1, starting stirring, gradually generating white precipitate in the solution, heating to 85 ℃ after the addition of the sulfuric acid is finished, reacting for 30min to fully perform precipitation reaction, then aging for 2h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 1.56ml of hydrogen peroxide, heating to 70 ℃, adding 34.67ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of a product magnesium hydroxide 6% (mass fraction), wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 1: 1, heating to 70 ℃, dropwise adding 1.02L of a sodium hydroxide solution with the concentration of 2mol/L, reacting for 1.5h, continuing to react for 15min to fully perform precipitation reaction, then aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 2 percent (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant of the embodiment is 30.2%.
Example 2
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to 9% of mass fraction, dropwise adding into the acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.15: 1, starting stirring, gradually generating white precipitate in the solution, heating to 70 ℃ after the addition of the sulfuric acid is finished, reacting for 35min to fully perform precipitation reaction, then aging for 1.5h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 0.76ml of hydrogen peroxide, heating to 70 ℃, adding 17ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of a product magnesium hydroxide 6% (mass fraction), wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 2: 1, heating to 70 ℃, dropwise adding 2.04L of a sodium hydroxide solution with the concentration of 1mol/L, reacting for 1.5h, continuing to react for 15min, after fully performing precipitation reaction, aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 4% (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant is 31.2%.
Example 3
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to a mass fraction of 13%, dropwise adding the diluted sulfuric acid into acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.25: 1, starting stirring, gradually generating white precipitate in the solution, heating to 75 ℃ after the addition of the sulfuric acid is finished, reacting for 40min to fully perform precipitation reaction, then aging for 1.8h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 0.745ml of hydrogen peroxide, heating to 70 ℃, adding 16.5ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of a product magnesium hydroxide 8% (mass fraction), wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 2: 1, heating to 70 ℃, dropwise adding 1.36L of a sodium hydroxide solution with the concentration of 1.5mol/L, reacting for 1.5h, continuing to react for 15min, fully performing precipitation reaction, aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 5% (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant in the embodiment is 31.5%.
Example 4
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to 17% of mass fraction, dropwise adding into the acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.35: 1, starting stirring, gradually generating white precipitate in the solution, heating to 80 ℃ after the addition of the sulfuric acid is finished, reacting for 55min to fully perform precipitation reaction, then aging for 2.5h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 0.735ml of hydrogen peroxide, heating to 70 ℃, adding 16.3ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of 5% (mass fraction) of the product magnesium hydroxide, wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 1: 1, heating to 70 ℃, dropwise adding 0.927L of a sodium hydroxide solution with the concentration of 2.2mol/L, reacting for 1.5h, continuing to react for 15min, fully performing precipitation reaction, aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 3 percent (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant of the embodiment is 30.5%.
Example 5
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to 21% of mass fraction, dropwise adding into the acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.45: 1, starting stirring, gradually generating white precipitate in the solution, heating to 95 ℃ after the addition of the sulfuric acid is finished, reacting for 50min to fully perform the precipitation reaction, then aging for 2.2h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 0.725ml of hydrogen peroxide, heating to 70 ℃, adding 16.1ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of a product magnesium hydroxide of 7% (mass fraction), wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 1: 1, heating to 70 ℃, dropwise adding 0.816L of a sodium hydroxide solution with the concentration of 2.5mol/L, reacting for 1.5h, continuing to react for 15min, fully performing precipitation reaction, aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 9 percent (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant in the embodiment is 32.8%.
Example 6
As shown in fig. 1, the method for preparing gypsum whiskers and a composite flame retardant from phosphate tailings in this embodiment specifically includes the following steps:
1) weighing 144mL of concentrated sulfuric acid with the mass fraction of 98% (18.4mol/L), placing the concentrated sulfuric acid in a clean three-neck flask, weighing 261.8g of high-magnesium phosphorus tailing powder, gradually adding the high-magnesium phosphorus tailing into the three-neck flask, opening condensed water after the addition of the high-magnesium phosphorus tailing is finished, starting stirring, refluxing at 50 ℃ for 35min, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out heat preservation and suction filtration at 60 ℃, washing the phosphogypsum obtained by suction filtration twice by using 140mL of distilled water, and mixing the primary water washing liquid with the acidolysis filtrate obtained by suction filtration to obtain acidolysis liquid A and phosphogypsum;
2) weighing 7.7mL of 98% sulfuric acid, diluting to 25% of mass fraction, dropwise adding into the acidolysis solution A, wherein the ratio of the addition amount of the sulfuric acid to the mass amount of calcium in the acidolysis solution A is 1.55: 1, starting stirring, gradually generating white precipitate in the solution, heating to 90 ℃ after the addition of the sulfuric acid is finished, reacting for 60min to fully perform precipitation reaction, then aging for 3h, performing suction filtration, washing the calcium sulfate whisker obtained by suction filtration twice with 140mL of distilled water, and mixing the primary water washing solution with the acidified filtrate to obtain acidolysis solution B and gypsum whisker;
3) placing the acidolysis solution B in a dry three-neck flask, starting stirring, adding 0.725ml of hydrogen peroxide, heating to 70 ℃, adding 16.1ml of ammonia water, continuing to react for 15min, performing suction filtration to separate impurities obtained by the reaction, placing filtrate obtained by the suction filtration in the dry three-neck flask, starting stirring, adding a modifier of a product magnesium hydroxide 2% (mass fraction), wherein the modifier is a mixture of sodium stearate and polyethylene glycol 6000 in a mass ratio of 2: 1, heating to 70 ℃, dropwise adding 0.68L of a sodium hydroxide solution with the concentration of 3mol/L, reacting for 1.5h, continuing to react for 15min, after fully performing precipitation reaction, aging to room temperature, performing suction filtration, washing with distilled water and ethanol for three times respectively, and drying to obtain magnesium hydroxide;
4) compounding magnesium hydroxide and an organic flame retardant (DHBAP) to obtain the compound flame retardant.
The compound flame retardant is used in epoxy resin (EP), wherein the addition amount of the organic flame retardant in the compound flame retardant is 10 percent (mass fraction). The epoxy resin (EP) added with the compound flame retardant of the embodiment is subjected to a flame retardant performance test.
Tests show that the limit oxygen index of the compound flame retardant of the embodiment is 33.2%.
The present invention is not limited to the above preferred embodiments, and any modifications, equivalent substitutions, improvements, etc. within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing gypsum whiskers and a composite flame retardant by taking phosphate tailings as raw materials is characterized by comprising the following steps:
1) mixing the high-magnesium phosphate tailings with sulfuric acid, carrying out acidolysis reaction, after the acidolysis reaction is finished, carrying out suction filtration and washing to obtain acidolysis solution A and phosphogypsum;
2) adding a precipitator into the acidolysis solution A for precipitation reaction, and after the precipitation reaction is finished, aging, filtering, and washing to obtain acidolysis solution B and gypsum whiskers;
3) adding hydrogen peroxide and ammonia water into the acidolysis solution B, removing impurities, adding a modifier, heating to a certain temperature, adding an alkaline precipitator, carrying out precipitation reaction, and after the precipitation reaction is finished, aging, filtering, washing and drying to obtain magnesium hydroxide;
4) and compounding the magnesium hydroxide and the organic flame retardant to obtain the composite flame retardant.
2. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material according to claim 1, wherein the concentration of the sulfuric acid in the step 1) is 1.68-18.4mol/L, and the mass ratio of the sulfuric acid to the high-magnesium phosphorus tailings is (1.01-2) to 1.
3. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material according to claim 1, wherein the acidolysis reaction in the step 1) is carried out at a temperature of 20-60 ℃ for 10-60 min; the suction filtration temperature of the suction filtration in the step 1) is 20-60 ℃.
4. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material according to claim 1, wherein the precipitant in the step 2) is one of sulfuric acid, sodium sulfate and sodium bisulfate, and the mass fraction of the precipitant is 5-25%; the addition amount of the precipitant in the step 2) is 1-2.5 times of the amount of calcium in the acidolysis solution A.
5. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw materials according to claim 1, wherein the reaction temperature of the precipitation reaction in the step 2) is 70-95 ℃, and the reaction time is 0.5-2 h; the aging time of the aging in the step 2) is 2-4 h.
6. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material as claimed in claim 1, wherein the volume ratio of the acidolysis solution B, the hydrogen peroxide and the ammonia water in the step 3) is 1: (1/200-1/50) to (1/9-4/9).
7. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material as claimed in claim 1, wherein the modifier in the step 3) is one of sodium stearate, polyethylene glycol 6000, a coupling agent, and a mixture of sodium stearate and polyethylene glycol 6000.
8. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material according to claim 1, wherein the addition amount of the modifier in the step 3) is 2% -8% of the yield of the magnesium hydroxide, and the temperature rise temperature after the modifier is added is 50-95 ℃; the reaction temperature of the precipitation reaction in the step 3) is 50-95 ℃.
9. The method for preparing the gypsum whiskers and the composite flame retardant from the phosphorus tailings as the raw material according to claim 1, wherein the alkaline precipitant in the step 3) is one of ammonia water, sodium hydroxide and potassium hydroxide, and the concentration of the alkaline precipitant is 1-3 mol/L.
10. The method for preparing the gypsum whisker and the composite flame retardant by using the phosphorus tailings as the raw materials according to claim 1, wherein the organic flame retardant in the step 4) is one of a phosphorus-nitrogen flame retardant, a boron-nitrogen flame retardant, a phosphorus flame retardant and a nitrogen flame retardant, and the addition amount of the organic flame retardant in the composite flame retardant is 2-10%.
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