CN117324126A - Phosphogypsum flotation impurity-removing whitening agent and preparation method and process thereof - Google Patents
Phosphogypsum flotation impurity-removing whitening agent and preparation method and process thereof Download PDFInfo
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- CN117324126A CN117324126A CN202210723925.3A CN202210723925A CN117324126A CN 117324126 A CN117324126 A CN 117324126A CN 202210723925 A CN202210723925 A CN 202210723925A CN 117324126 A CN117324126 A CN 117324126A
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- phosphogypsum
- flotation
- whitening agent
- impurity
- trimethyl ammonium
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- 238000005188 flotation Methods 0.000 title claims abstract description 122
- 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 109
- 230000002087 whitening effect Effects 0.000 title claims abstract description 81
- 230000008569 process Effects 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title abstract description 13
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 111
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 62
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012535 impurity Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 42
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims description 22
- -1 vinyl trimethoxy silane acetic acid Chemical compound 0.000 claims description 10
- SZEMGTQCPRNXEG-UHFFFAOYSA-M trimethyl(octadecyl)azanium;bromide Chemical compound [Br-].CCCCCCCCCCCCCCCCCC[N+](C)(C)C SZEMGTQCPRNXEG-UHFFFAOYSA-M 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 4
- 239000002893 slag Substances 0.000 claims description 4
- 238000004537 pulping Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 abstract description 8
- 229910052602 gypsum Inorganic materials 0.000 abstract description 7
- 239000010440 gypsum Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract description 4
- 239000004088 foaming agent Substances 0.000 abstract description 4
- 239000011574 phosphorus Substances 0.000 abstract description 4
- 229910052698 phosphorus Inorganic materials 0.000 abstract description 4
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 3
- 239000000945 filler Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 238000009270 solid waste treatment Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 38
- 230000000052 comparative effect Effects 0.000 description 22
- 238000012360 testing method Methods 0.000 description 14
- 239000006260 foam Substances 0.000 description 12
- 239000012141 concentrate Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 239000005695 Ammonium acetate Substances 0.000 description 5
- 229940043376 ammonium acetate Drugs 0.000 description 5
- 235000019257 ammonium acetate Nutrition 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 229910052604 silicate mineral Inorganic materials 0.000 description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052683 pyrite Inorganic materials 0.000 description 3
- NIFIFKQPDTWWGU-UHFFFAOYSA-N pyrite Chemical compound [Fe+2].[S-][S-] NIFIFKQPDTWWGU-UHFFFAOYSA-N 0.000 description 3
- 239000011028 pyrite Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LPULCTXGGDJCTO-UHFFFAOYSA-N 6-methylheptan-1-amine Chemical compound CC(C)CCCCCN LPULCTXGGDJCTO-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007844 bleaching agent Substances 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- OATFZMZHCHJBGR-UHFFFAOYSA-N ethenoxyperoxysilane Chemical compound C(=C)OOO[SiH3] OATFZMZHCHJBGR-UHFFFAOYSA-N 0.000 description 1
- 238000012921 fluorescence analysis Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZTERWYZERRBKHF-UHFFFAOYSA-N magnesium iron(2+) oxygen(2-) Chemical class [Mg+2].[O-2].[Fe+2].[O-2] ZTERWYZERRBKHF-UHFFFAOYSA-N 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002364 soil amendment Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/018—Mixtures of inorganic and organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/04—Frothers
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Paper (AREA)
Abstract
The invention relates to a phosphogypsum flotation impurity-removing whitening agent and a preparation method and process thereof, belonging to the technical field of phosphorus chemical solid waste treatment. Solves the problems of complex synthesis process, poor whitening effect and weak collecting capacity of phosphogypsum impurity removal whitening flotation collecting agent in the prior art. The phosphogypsum flotation impurity-removing whitening agent comprises the following raw materials in parts by weight: 40-60 parts of vinyl trimethoxy silane, 30-45 parts of acetic acid solution and 10-15 parts of alkyl trimethyl ammonium bromide. The phosphogypsum flotation impurity-removing whitening agent provided by the invention is suitable for strong acid environment, can capture colored organic matters and silicate impurities simultaneously, has the performance of a foaming agent, has the advantages of stable performance, strong collecting capacity, high flotation speed, low consumption and the like, can improve the whiteness of phosphogypsum to about 70% after a flotation process, and can be directly used for PVC filler, beta semi-hydrated gypsum, building wall materials and the like.
Description
Technical Field
The invention belongs to the technical field of phosphorus chemical solid waste treatment, and particularly relates to a phosphogypsum flotation impurity removal whitening agent and a preparation method and process thereof.
Background
Phosphogypsum is the main solid waste of the phosphorus chemical industry, and 4.5-5.5t phosphogypsum is produced on average per 1 ton of wet-process phosphoric acid. Currently, the phosphogypsum stockpiling amount in China exceeds 5000 hundred million tons, and the comprehensive utilization rate is only about 40%. Whiteness is an important factor affecting phosphogypsum application.
Phosphogypsum contains phosphoric acid and impurities such as salts, fluorides, organic matters, quartz, iron-magnesium oxides and the like, and is grey or grey-black, so that the phosphogypsum can only be applied to the fields of cement, chemical raw materials, soil amendments, roadbeds and the like with low added value. The phosphogypsum is subjected to impurity removal and whitening, so that the utilization value of the phosphogypsum can be greatly improved, the phosphogypsum can also replace natural gypsum with limited reserves, the damage of solid waste storage to the ecological environment is reduced, and the resource utilization rate is improved. The flotation method can effectively remove organic substances, quartz and other impurities in phosphogypsum, greatly improve the whiteness of the phosphogypsum, expand the application of the phosphogypsum in the aspects of light thermal insulation gypsum boards, phase-change energy storage materials, building decorations and the like, and improve the application value of the phosphogypsum. Flotation collectors are critical in determining the effectiveness of flotation. Patent CN201510930935.4 discloses a method for preparing phosphogypsum flotation collector by using isooctylamine as raw material, which has stable chemical property and good selectivity, but the synthesis process involves hydrogen, hydrogen peroxide, catalyst and the like, and the process flow is complex. Zhang Lizhen and the like take the dodecyl amine as a collector, and a coarse and fine process is adopted to obtain a product with the dihydrate gypsum content of 97.5 percent, but the whiteness of phosphogypsum is not greatly improved (inorganic salt industry. 2021,53 (06), 171-173+184). Therefore, a novel and efficient phosphogypsum impurity-removing whitening flotation collector is in need.
In conclusion, aiming at the problems of complex synthesis process, poor whitening effect, weak collecting capacity and the like of the existing phosphogypsum impurity removal whitening flotation collecting agent, the development of the phosphogypsum impurity removal whitening agent has very important significance.
Disclosure of Invention
In view of the above analysis, the embodiment of the invention aims to provide an phosphogypsum flotation impurity-removing and whitening agent, and a preparation method and a process thereof, which are used for solving at least one of the problems of complex synthesis process, poor whitening effect, weak collecting capacity and the like of phosphogypsum impurity-removing and whitening flotation collecting agents in the prior art.
The main purpose of the invention is realized by the following technical scheme:
the invention provides an phosphogypsum flotation impurity-removing whitening agent which comprises the following raw materials in parts by weight: 40-60 parts of vinyl trimethoxy silane, 30-45 parts of acetic acid solution and 10-15 parts of alkyl trimethyl ammonium bromide.
Further, the mass fraction of the acetic acid solution is 0.5-5.0%.
Further, the alkyl trimethyl ammonium bromide comprises one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.
The invention also provides a preparation method of the phosphogypsum flotation impurity-removing whitening agent, which is used for preparing the phosphogypsum flotation impurity-removing whitening agent and comprises the following steps:
s1, mixing and stirring vinyl trimethoxy silane and acetic acid solution to obtain a vinyl trimethoxy silane acetic acid solution system;
s2, adding alkyl trimethyl ammonium bromide into the vinyl trimethoxy silane acetic acid solution system, and stirring.
Further, in the step S1, the stirring time is 0.5-3.0h.
Further, in the step S2, the stirring time is 20-60min.
The invention also provides a phosphogypsum flotation impurity removal and whitening process, which adopts the phosphogypsum flotation impurity removal and whitening agent and comprises the following steps:
step 1: mixing phosphogypsum and water according to a certain mass percentage, and stirring and pulping to obtain ore pulp;
step 2: adding a flotation impurity-removing whitening agent with a certain mass into the ore pulp, and continuously stirring;
step 3: and (5) introducing the ore pulp into a flotation machine by adopting a slag pulp pump for flotation.
Further, in the step 1, the mass content of phosphogypsum in the ore pulp is 15-35%.
Further, in the step 2, the dosage of the flotation impurity-removing whitening agent is 80-300g/t based on the mass of phosphogypsum.
Further, in the step 3, the flotation time is 4-8min.
Compared with the prior art, the invention has at least one of the following beneficial effects:
1. the phosphogypsum flotation impurity-removing whitening agent provided by the invention is suitable for strong acid environment, and can simultaneously capture colored organic matters and silicate impurities.
2. The phosphogypsum flotation impurity-removing whitening agent provided by the invention has the performance of a foaming agent, and has the advantages of stable performance, strong collecting capacity, high flotation speed, low dosage and the like.
3. The phosphogypsum flotation impurity removal whitening agent provided by the invention can be directly used for phosphogypsum flotation impurity removal whitening, the whiteness can be improved to 70% after a flotation process is carried out, the step of removing organic matters in advance is not needed, and the phosphogypsum flotation impurity removal whitening agent can be directly used for PVC filler, beta semi-hydrated gypsum, building wall materials and the like.
In the invention, the technical schemes can be mutually combined to realize more preferable combination schemes. Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings are only for purposes of illustrating particular embodiments and are not to be construed as limiting the invention.
FIG. 1 is a flow chart of phosphogypsum flotation according to the present invention;
FIG. 2X-ray diffractometer analysis of phosphogypsum flotation tailings in example 2 of the present invention.
Detailed Description
Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and together with the description serve to explain the principles of the invention, and are not intended to limit the scope of the invention.
The invention provides an phosphogypsum flotation impurity-removing whitening agent which comprises the following raw materials in parts by weight: 40-60 parts of vinyl trimethoxy silane, 30-45 parts of acetic acid solution and 10-15 parts of alkyl trimethyl ammonium bromide.
At present, the phosphogypsum impurity-removing whitening flotation collector has complex synthesis process, poor whitening effect and weak collecting capacity, and compared with the prior art, the flotation impurity-removing whitening collector can simultaneously capture organic matters and silicate impurities; the acid resistance and the heterogeneous ion resistance are strong; the foaming agent has the performance of the foaming agent and the bubble viscosity is low; stable chemical property and strong collecting capacity; the flotation speed is high, the consumption is low, and the problems of complex synthesis process, poor whitening effect and weak collecting capacity of phosphogypsum impurity removal and whitening flotation collecting agents in the prior art are solved.
Specifically, the mass fraction of the acetic acid solution is 0.5-5.0%.
Specifically, the alkyl trimethyl ammonium bromide comprises one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and octadecyl trimethyl ammonium bromide.
It should be noted that the components and the content of the invention can fully exert the synergistic enhancement effect among the components. The phosphogypsum flotation impurity-removing whitening agent is prepared from vinyl trimethoxy silane, acetic acid solution with the mass fraction of 0.5-5.0% and alkyl trimethyl ammonium bromide, wherein the vinyl trimethoxy silane is hydrolyzed in ore pulp to generate Si-OH groups, so that the surfaces of organic matters, pyrite, silicate minerals and the like in the phosphogypsum can be combined together through dehydration condensation, and the surfaces of the impurities are changed from hydrophilic to hydrophobic, thereby promoting flotation separation of the phosphogypsum. The acetic acid solution can increase the solubility of the vinyl trimethoxy silane in the aqueous solution, so that the vinyl trimethoxy silane can be better dispersed in the ore pulp and acts on organic matters, pyrite, silicate minerals and other impurities; on the other hand, the acetic acid solution can also react with alkyl trimethyl ammonium bromide to generate alkyl trimethyl ammonium acetate, so that the collecting performance and the foaming performance of the alkyl trimethyl ammonium acetate are improved. On the one hand, the alkyl trimethyl ammonium bromide can act with silicate minerals to remove the silicate minerals; on the other hand, the foam performance is also achieved, the adhesion of the vinyl trioxysilane and impurity combination on the bubbles is promoted, and the bubbles float and separate along with the adhesion.
The mass fraction of the acetic acid solution is lower than 0.5%, and the acetic acid solution can not completely react with vinyl trimethoxy silane and alkyl trimethyl ammonium bromide in the same parts, so that the synergistic effect of the vinyl trimethoxy silane and the alkyl trimethyl ammonium bromide can not be achieved. The mass fraction is higher than 5.0%, and the residue is remained after the complete action of the catalyst with vinyl trimethoxy silane and alkyl trimethyl ammonium bromide in the same parts, so that on one hand, the pH value of ore pulp is influenced, and the flotation is not facilitated; on the other hand, the waste of acetic acid is caused, the cost is increased, and the method is uneconomical.
The invention also provides a preparation method of the phosphogypsum flotation impurity-removing whitening agent, which is used for preparing the phosphogypsum flotation impurity-removing whitening agent and comprises the following steps:
s1, mixing and stirring vinyl trimethoxy silane and acetic acid solution to obtain a vinyl trimethoxy silane acetic acid solution system;
s2, adding alkyl trimethyl ammonium bromide into the vinyl trimethoxy silane acetic acid solution system, and stirring.
Specifically, in S1, the stirring time is 0.5-3.0h.
Specifically, in S2, the stirring time is 20-60min.
In S1, mixing and stirring vinyl trimethoxy silane and acetic acid solution, on one hand, the solution with good solubility of the vinyl trimethoxy silane can be obtained, and the dispersibility of the vinyl trimethoxy silane in phosphogypsum slurry to be treated is facilitated; on the other hand, during the mixing and stirring process, the vinyl trimethoxy silane is hydrolyzed, and the acetic acid solution can promote the hydrolysis of the vinyl trimethoxy silane and improve the stability of the vinyl trimethoxy silane.
Specifically, the vinyl trimethoxy silane has low solubility in water and high solubility in dilute acetic acid solution, so that the vinyl trimethoxy silane is added into the acetic acid solution to increase the solubility in the solution, and is convenient for better dispersing in ore pulp; on the other hand, the acetic acid solution has the double effects of promoting the hydrolysis of vinyl trimethoxy silane and improving the stability of the vinyl trimethoxy silane.
In S2, alkyl trimethyl ammonium bromide is easy to dissolve in water, and is added into vinyl trimethoxy silane acetic acid solution, and alkyl trimethyl ammonium bromide reacts with acetic acid in the vinyl trimethoxy silane acetic acid solution to generate alkyl trimethyl ammonium acetate, so that the foaming performance of the medicament can be enhanced.
In the step S1, the stirring time is 0.5-3.0h, and the vinyl trimethoxy silane is completely dissolved and reacted in the acetic acid solution within 0.5-3.0h.
In the step S2, the stirring time is 20-60min, and in 20-60min, the alkyl trimethyl ammonium bromide can completely react with acetic acid in the vinyl trimethoxy silane acetic acid solution to generate alkyl trimethyl ammonium acetate, so that the foaming performance of the alkyl trimethyl ammonium acetate is improved. The reaction time is less than 20min, and the reaction of the alkyl trimethyl ammonium bromide and the acetic acid is incomplete; the time is longer than 60min, and the reaction can be ensured to be complete.
The invention also provides a phosphogypsum flotation impurity removal and whitening process, which adopts the phosphogypsum flotation impurity removal and whitening agent and comprises the following steps:
step 1: mixing phosphogypsum and water according to a certain mass percentage, and stirring and pulping to obtain ore pulp;
step 2: adding a flotation impurity-removing whitening agent with a certain mass into the ore pulp, and continuously stirring;
step 3: and (5) introducing the ore pulp into a flotation machine by adopting a slag pulp pump for flotation.
Specifically, in the step 1, the mass percentage of phosphogypsum in the ore pulp is 15-35%.
The phosphogypsum mass content in the ore pulp is lower than 15%, the unit time treatment capacity is lower, the cost is wasted, and the method is uneconomical; the quality content of phosphogypsum in the ore pulp is higher than 35%, the whiteness of phosphogypsum is improved slightly, and the whitening effect is not obvious. In the invention, the mass percentage of phosphogypsum in the ore pulp is 15-35%.
Specifically, the dosage of the added flotation impurity-removing whitening agent is 80-300g/t based on the mass of phosphogypsum;
the dosage of the flotation impurity removal and whitening agent is lower than 80g/t, the impurity removal effect is poor, the whiteness increase range is not large, and the whitening effect is not obvious; the dosage of the flotation impurity-removing whitening agent is higher than 300g/t, so that on one hand, calcium sulfate dihydrate and impurities always float out to cause the waste of the calcium sulfate dihydrate, on the other hand, the whiteness of phosphogypsum flotation products is almost unchanged, and on the other hand, the cost is increased by continuously increasing the dosage of the flotation impurity-removing whitening agent, so that the method is uneconomical. In the invention, the dosage of the flotation impurity-removing whitening agent is 80-300g/t according to the mass ratio of phosphogypsum.
Specifically, the pH value of ore pulp is not required to be regulated in the flotation process;
according to the test, when the pH value of ore pulp is 1.5-3.5, the flotation impurity removal whitening effect is good, and the yield of reverse flotation concentrate is high. Phosphogypsum is derived from a phosphoric acid preparation process, and the original pH value of phosphogypsum pulp is generally between 2.0 and 2.5 and is just within the pH range with a good flotation effect, so that the pH value of pulp is not required to be regulated in the reverse flotation process.
Specifically, in the step 3, the flotation time is 4-8min.
The flotation time is lower than 4min, and the phosphogypsum recovery rate is insufficient. Along with the extension of the flotation time, the phosphogypsum recovery rate is increased, but after the reverse flotation time is higher than 8min, the flotation time is prolonged, the recovery rate is not increased any more, and the quality of the concentrate is reduced. In the invention, the floatation time is 4-8min.
In conclusion, the phosphogypsum flotation impurity removal and whitening agent provided by the invention can be used at normal temperature, is suitable for phosphogypsum raw ore (fresh gypsum) and yard aged phosphogypsum (slag yard gypsum), and can obtain good impurity removal and whitening effects through flotation.
In the following examples, only the parts by weight of the raw material components were changed without changing the preparation method of the flotation impurity-removing whitening agent.
In the following examples, phosphogypsum in Guizhou area was used, the whiteness was 34.0%, and CaSO 4 ·2H 2 The O content was 88.7%, and the soluble phosphorus and soluble fluorine contents were 0.24% and 0.28%, respectively. XRF analysis showed the major impurity P 2 O 5 (1.58wt.％)、Fe 2 O 3 (0.255wt.％)、SiO 2 (4.25wt.％)、Al 2 O 3 (0.23 wt.%) and colored organic matter, etc.
To demonstrate the effect of the change in the weight parts of the raw material components of the flotation impurity removal and whitening agents on the index of phosphogypsum flotation products in the examples, the same phosphogypsum was subjected to flotation tests in the examples, and the flotation process was controlled to be completely consistent. Specifically, in the flotation process, the mass percentage of the phosphogypsum mixed with water is 25%, the dosage of the medicament is 150g/t according to the mass ratio of the phosphogypsum, and the flotation is carried out for 5min. And respectively drying, weighing, testing and the like the flotation tailings and phosphogypsum concentrate. With whiteness of phosphogypsum and CaSO 4 ·2H 2 The O content is an assessment index, and the performance of the flotation impurity-removing whitening agent is clarified.
Example 1
The flotation impurity-removing whitening agent in this embodiment comprises the following raw materials: the raw materials comprise 40 parts of vinyl trimethoxy silane, 45 parts of acetic acid solution with the mass fraction of 0.5% and 15 parts of dodecyl trimethyl ammonium bromide.
The test results show that: the whiteness of phosphogypsum concentrate is 68.2%, caSO4.2H 2 The O content was 93.7%.
Example 2
The flotation impurity-removing whitening agent in this embodiment comprises the following raw materials: the raw materials comprise, by weight, 50 parts of vinyl trimethoxy silane, 35 parts of acetic acid solution with the mass fraction of 1.5% and 15 parts of tetradecyl trimethyl ammonium bromide.
The test result shows that the whiteness of phosphogypsum is 69.4 percent, caSO 4 ·2H 2 The O content is 94.3%, the analysis result of the X-ray diffractometer of the flotation tailings is shown in figure 2, and pyrite, quartz and CaSO are contained in the tailings 4 ·2H 2 O。
Example 3
The raw materials of the flotation impurity-removing and whitening agent in this embodiment are composed of: the raw materials comprise 55 parts of vinyl trimethoxy silane, 35 parts of acetic acid solution with the mass fraction of 2.5% and 10 parts of hexadecyl trimethyl ammonium bromide.
The test result shows that the whiteness of phosphogypsum is 69.9%, caSO 4 ·2H 2 The O content was 94.7%, and the other main components are shown in Table 1.
Table 1X-ray fluorescence analysis results (wt.%) of phosphogypsum concentrate
Example 4
The flotation impurity-removing whitening agent in this embodiment comprises the following raw materials: the raw materials comprise 60 parts of vinyl trimethoxy silane, 30 parts of acetic acid solution with the mass fraction of 5.0% and 10 parts of octadecyl trimethyl ammonium bromide.
The test result shows that the whiteness of phosphogypsum is 70.2 percent, caSO 4 ·2H 2 The O content was 95.2%.
Comparative example 1
The flotation impurity-removing whitening agent in this comparative example is vinyltrimethoxysilane. The vinyltrimethoxysilane can trap colored organic matters to form flocs in the flotation process, but cannot generate a large amount of uniform foam.
Test results show that the whiteness of phosphogypsum concentrate is 47.1 percent, caSO 4 ·2H 2 The O content was 89.4%.
Comparative example 2
The flotation impurity-removing whitening agent in this comparative example comprises the following raw materials: 60 parts of vinyl trimethoxy silane and 40 parts of acetic acid solution with the mass fraction of 1.5%. The vinyltrimethoxysilane can trap colored organic matters to form flocs in the flotation process, but cannot generate a large amount of uniform foam.
The test result shows that the whiteness of phosphogypsum is 48.4 percent, caSO 4 ·2H 2 The O content is 89.8％。
Comparative example 3
The flotation impurity-removing whitening agent in this comparative example was cetyltrimethylammonium bromide. The flotation process can produce a large amount of white uniform foam, but cannot effectively capture the colored organic matters in the slurry.
The test result shows that the whiteness of phosphogypsum is 49.7 percent, caSO 4 ·2H 2 The O content was 91.5%.
Comparative example 4
The flotation impurity-removing whitening agent in this comparative example comprises the following raw materials: 30 parts of acetic acid solution with the mass fraction of 5.0 percent and 70 parts of octadecyl trimethyl ammonium bromide. The flotation process can produce a large amount of uniform froth, but the colored organic matter is dispersed in the pulp and octadecyl trimethyl ammonium bromide is not able to effectively capture it.
The test result shows that the whiteness of phosphogypsum is 54.6 percent, caSO 4 ·2H 2 The O content was 92.3%.
Comparative example 5
The flotation impurity-removing whitening agent in this comparative example comprises the following raw materials: 60 parts of vinyl trimethoxy silane and 40 parts of octadecyl trimethyl ammonium bromide. In the flotation process, the vinyl trimethoxy silane has poor dispersibility in ore pulp, and the colored organic matters have insufficient capturing capability, so that white uniform foam is generated.
The test result shows that the whiteness of phosphogypsum is 55.7 percent, caSO 4 ·2H 2 The O content was 93.4%.
Comparative example 6
The flotation impurity-removing whitening agent in this comparative example comprises the following raw materials: the flotation impurity-removing whitening agent in this comparative example is: acetic acid solution with mass fraction of 5.0%. The flotation process does not generate foam and no impurity floats.
The test result shows that the whiteness of phosphogypsum is 41.5 percent, caSO 4 · 2 H 2 The O content was 90.8%.
Comparative example 7
The flotation impurity-removing whitening collector in this embodiment comprises the following raw materials: the raw materials comprise 20 parts of vinyl trimethoxy silane, 75 parts of acetic acid solution with the mass fraction of 5.0% and 5 parts of dodecyl trimethyl ammonium bromide.
Flotation process: part of the colored organic matters adhere to the surfaces of the bubbles to form black bubbles, but the black bubbles are generated for a short time.
The test result shows that the whiteness of phosphogypsum is 56.6 percent, caSO 4 ·2H 2 The O content was 92.5%.
As is clear from comparative examples 1 and 1, only vinyltrimethoxysilane was used as a flotation impurity-removing and whitening agent, although colored organic matters in phosphogypsum could be captured to form flocs. However, vinyltrimethoxysilane does not have foamability and cannot form a large amount of foam to float out the organic flocs. So the removal rate of the colored organic matters is not high, and the whiteness and CaSO of phosphogypsum concentrate are low 4 ·2H 2 The O content was only 47.1% and 89.4%, respectively.
As is clear from comparative examples 2 and 2, only a mixture of vinyltrimethoxysilane and acetic acid solution with a mass fraction of 1.5% by weight in a ratio of 60:40 was used as a flotation impurity-removing and whitening agent. The flotation phenomenon was the same as in comparative example 1, and the impurities could not be floated by forming a large amount of foam layers. So the whiteness of phosphogypsum concentrate is only 48.4 percent, caSO 4 ·2H 2 The O content was 89.8%.
As is clear from comparative examples 3 and 3, the flotation impurity-removing and whitening agent is only cetyl trimethyl ammonium bromide, which has good foamability, can form a large number of foam layers, has a certain capturing capacity on mineral impurities such as quartz and has good impurity removing effect on quartz and the like. But the removal rate of colored organic matters is low, the whiteness improvement amplitude of phosphogypsum concentrate is not large, and the whiteness improvement amplitude is only 49.7 percent, namely CaSO 4 ·2H 2 The O content was 91.5%.
As is clear from comparative examples 4 and 4, the mixture of octadecyl trimethyl ammonium bromide and acetic acid solution with mass fraction of 5.0% in weight part of 70:30 is used as flotation impurity removal and whitening agent, the foamability is good, the foam is dense, the effect of removing mineral impurities such as quartz is good, but the removal rate of organic substances is low, and the whiteness of phosphogypsum concentrate is low, which is only 54.6%.
In comparative example 5, the mixture of vinyl trimethoxy silane and octadecyl trimethyl ammonium bromide in the weight ratio of 60:40 is used as a flotation impurity-removing and whitening agent, the vinyl trimethoxy silane in the ore pulp in the flotation process has poor dispersibility, the capturing capability of colored organic matters is insufficient, and white uniform foam is generated. In comparative example 6, 5.0% acetic acid solution by mass fraction was used as a flotation impurity-removing and whitening agent, no foam was produced during the flotation process, and no impurity was floated. Comparative example 7 the weight parts of vinyltrimethoxysilane, acetic acid solution with a mass fraction of 5.0% and dodecyltrimethylammonium bromide in the flotation impurity-removing whitening agent are not in the data range of the invention, and part of colored organic matters adhere to the surfaces of bubbles to form black bubbles in the flotation process, but the black bubbles are generated for a short time. The whiteness of phosphogypsum concentrate obtained by the three methods is 55.7%, 41.5% and 56.6%, respectively, which are obviously lower than those of examples 1-4.
The foregoing is only a preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions easily contemplated by those skilled in the art within the technical scope of the present invention should be included in the scope of the present invention.
Claims (10)
1. The phosphogypsum flotation impurity-removing whitening agent is characterized by comprising the following raw materials in parts by weight: 40-60 parts of vinyl trimethoxy silane, 30-45 parts of acetic acid solution and 10-15 parts of alkyl trimethyl ammonium bromide.
2. The phosphogypsum flotation impurity removal and whitening agent according to claim 1, wherein the mass fraction of the acetic acid solution is 0.5-5.0%.
3. The phosphogypsum flotation impurity removal and whitening agent of claim 1, wherein the alkyl trimethyl ammonium bromide comprises one or more of dodecyl trimethyl ammonium bromide, tetradecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide, octadecyl trimethyl ammonium bromide.
4. A method for preparing the phosphogypsum flotation impurity-removing whitening agent, which is used for preparing the phosphogypsum flotation impurity-removing whitening agent according to any one of claims 1 to 3, and is characterized by comprising the following steps:
s1, mixing and stirring vinyl trimethoxy silane and acetic acid solution to obtain a vinyl trimethoxy silane acetic acid solution system;
s2, adding alkyl trimethyl ammonium bromide into the vinyl trimethoxy silane acetic acid solution system, and stirring.
5. The method according to claim 4, wherein in the step S1, the stirring time is 0.5 to 3.0 hours.
6. The method according to claim 4, wherein in the step S1, the stirring time is 20 to 60 minutes.
7. An phosphogypsum flotation impurity removal and whitening process, which adopts the phosphogypsum flotation impurity removal and whitening agent according to any one of claims 1-3 or the phosphogypsum flotation impurity removal and whitening agent prepared according to any one of claims 4-6, and is characterized by comprising the following steps:
step 1: mixing phosphogypsum and water according to a certain mass percentage, and stirring and pulping to obtain ore pulp;
step 2: adding certain mass of phosphogypsum flotation impurity-removing whitening agent into the ore pulp, and continuously stirring;
step 3: and (5) introducing the ore pulp into a flotation machine by adopting a slag pulp pump for flotation.
8. The process according to claim 7, wherein in the step 1, the phosphogypsum is 15-35% by mass.
9. The process according to claim 7, wherein in the step 2, the amount of the agent for removing impurities and whitening flotation is 80-300g/t based on the mass of phosphogypsum.
10. The process according to claim 7, wherein the flotation time is 4-8min in step 3.
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