CN117563783A - Composite flotation reagent for low-rank coal and preparation method thereof - Google Patents
Composite flotation reagent for low-rank coal and preparation method thereof Download PDFInfo
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- CN117563783A CN117563783A CN202311591090.1A CN202311591090A CN117563783A CN 117563783 A CN117563783 A CN 117563783A CN 202311591090 A CN202311591090 A CN 202311591090A CN 117563783 A CN117563783 A CN 117563783A
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- grease
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- 239000003245 coal Substances 0.000 title claims abstract description 103
- 238000005188 flotation Methods 0.000 title claims abstract description 95
- 238000002360 preparation method Methods 0.000 title claims abstract description 41
- 239000003153 chemical reaction reagent Substances 0.000 title claims abstract description 36
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 32
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- IDYWQONQVXWFQP-UHFFFAOYSA-N butan-1-ol;octan-1-ol Chemical compound CCCCO.CCCCCCCCO IDYWQONQVXWFQP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000010775 animal oil Substances 0.000 claims abstract description 19
- 235000015112 vegetable and seed oil Nutrition 0.000 claims abstract description 19
- 239000008158 vegetable oil Substances 0.000 claims abstract description 19
- 239000004519 grease Substances 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 15
- 150000001298 alcohols Chemical class 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000003377 acid catalyst Substances 0.000 claims abstract description 5
- 239000003921 oil Substances 0.000 claims description 58
- 235000019198 oils Nutrition 0.000 claims description 58
- 238000006243 chemical reaction Methods 0.000 claims description 35
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 21
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 14
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 9
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical compound CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 7
- 239000004927 clay Substances 0.000 claims description 7
- 230000018044 dehydration Effects 0.000 claims description 7
- 238000006297 dehydration reaction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229920000570 polyether Polymers 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- JOLVYUIAMRUBRK-UHFFFAOYSA-N 11',12',14',15'-Tetradehydro(Z,Z-)-3-(8-Pentadecenyl)phenol Natural products OC1=CC=CC(CCCCCCCC=CCC=CCC=C)=C1 JOLVYUIAMRUBRK-UHFFFAOYSA-N 0.000 claims description 2
- YLKVIMNNMLKUGJ-UHFFFAOYSA-N 3-Delta8-pentadecenylphenol Natural products CCCCCCC=CCCCCCCCC1=CC=CC(O)=C1 YLKVIMNNMLKUGJ-UHFFFAOYSA-N 0.000 claims description 2
- JOLVYUIAMRUBRK-UTOQUPLUSA-N Cardanol Chemical compound OC1=CC=CC(CCCCCCC\C=C/C\C=C/CC=C)=C1 JOLVYUIAMRUBRK-UTOQUPLUSA-N 0.000 claims description 2
- FAYVLNWNMNHXGA-UHFFFAOYSA-N Cardanoldiene Natural products CCCC=CCC=CCCCCCCCC1=CC=CC(O)=C1 FAYVLNWNMNHXGA-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229920001400 block copolymer Polymers 0.000 claims description 2
- PTFIPECGHSYQNR-UHFFFAOYSA-N cardanol Natural products CCCCCCCCCCCCCCCC1=CC=CC(O)=C1 PTFIPECGHSYQNR-UHFFFAOYSA-N 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 abstract description 30
- 230000000694 effects Effects 0.000 abstract description 26
- 238000011161 development Methods 0.000 abstract description 7
- 239000000047 product Substances 0.000 abstract description 6
- 238000004134 energy conservation Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000001737 promoting effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 28
- 239000003814 drug Substances 0.000 description 21
- -1 carbon ester Chemical class 0.000 description 18
- 239000003795 chemical substances by application Substances 0.000 description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 9
- 239000002283 diesel fuel Substances 0.000 description 7
- 239000008396 flotation agent Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 229940079593 drug Drugs 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 238000011282 treatment Methods 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- 238000009833 condensation Methods 0.000 description 5
- 230000005494 condensation Effects 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 229930195733 hydrocarbon Natural products 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000011221 initial treatment Methods 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 239000002699 waste material Substances 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000003350 kerosene Substances 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 2
- 239000003830 anthracite Substances 0.000 description 2
- 239000002956 ash Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 150000003138 primary alcohols Chemical class 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 238000005809 transesterification reaction Methods 0.000 description 2
- 235000019871 vegetable fat Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000005273 aeration Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000010883 coal ash Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 239000008162 cooking oil Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000032798 delamination Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 235000019197 fats Nutrition 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical compound CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000008194 pharmaceutical composition Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
- 239000007762 w/o emulsion Substances 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
Abstract
The invention relates to a compound flotation reagent for low-rank coal and a preparation method thereof. The preparation method of the invention comprises the following steps: (1) Animal and vegetable oil or grease byproducts react with alcohols under the condition of an acid catalyst to obtain a first-stage reaction liquid; (2) Reacting the first-stage reaction liquid with butanol-octanol raffinate in the presence of alkaline substances to obtain a second-stage reaction liquid; (3) And mixing and stirring the two-stage reaction liquid and the emulsifying agent, and homogenizing to obtain the composite flotation reagent. The compound flotation reagent prepared by the method has better flotation effect on low-rank coal, and compared with the compound reagent prepared by a bio-based low-carbon ester pure product, the compound reagent prepared by the method has the advantages of more stability, lower reagent consumption and higher flotation perfection index. The composite flotation reagent has the advantages of strong safety, environmental friendliness, energy conservation, strong adaptability, good use effect in a low-temperature environment and capability of promoting comprehensive utilization and green development of coal resources.
Description
Technical Field
The invention relates to a compound flotation reagent for low-rank coal and a preparation method thereof.
Background
Along with the continuous exploitation and consumption of high-quality coal resources such as coking coal, fat coal and the like in China, the utilization of low-rank coal and carbon resources has great significance for guaranteeing the coal energy supply in China and realizing the efficient utilization of the low-quality coal resources. With the development of coal mining mechanization, the proportion of micro-fine particles in coal is increased, and a flotation method is one of the most effective methods for sorting fine-particle-grade coal slime and is an effective way for realizing green development of coal resources.
In the coal slime flotation process, the addition of a flotation reagent is of great importance, and the reagent system of a collector, a foaming agent and the two is an important factor influencing the flotation index. The hydrocarbon oil such as diesel oil or kerosene is a common traditional collector in the field of coal slime flotation, has better collecting performance for high-quality coals such as anthracite, coking coal, lean coal and the like with high deterioration degree, but hardly exerts the advantages and has higher drug consumption for low-rank coals with low deterioration degree. Factors that low rank coal is difficult to float with conventional diesel or kerosene collectors are: (1) the deterioration degree of the low-rank coal is low, a large amount of oxygen-containing functional groups on the particle surface of the low-rank coal are easy to form hydrogen bonds with water molecules, a layer of hydration film is easy to wrap on the surface of the coal particles in water, and therefore a nonpolar hydrocarbon oil collector is difficult to attach on the surface of the coal particles; (2) the traditional nonpolar hydrocarbon oil has no solubility and dispersibility, has poor dispersity in water and has low contact efficiency with coal particles.
Increasingly, waste oils are used to prepare biological material coal slime collectors or flotation agents, such as patent CN102172565A, patent CN116637725A, patent CN114870999a, and the like. The coal slime collecting agent or the flotation agent prepared by using the waste oil is improved in different degrees only for the flotation effect of high-quality coals such as anthracite, coking coal, lean coal and the like with high deterioration degree compared with hydrocarbon oil such as diesel oil or kerosene and the like, and is not ideal for improving the flotation effect of low-rank coals with low deterioration degree. In addition, the dispersion effect of the flotation agent or collector in the pulp system at low temperature affects the flotation effect of the flotation agent or collector.
Disclosure of Invention
The invention aims to provide the environment-friendly compound flotation reagent which has better flotation effect on low-rank coal, wide use temperature range, low cost, safety and no toxicity.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a method of preparing a composite flotation reagent for low rank coal, the method comprising the steps of:
(1) Animal and vegetable oil or grease byproducts and alcohols react in the presence of an acid catalyst to obtain a first-stage reaction liquid;
(2) Reacting the first-stage reaction liquid in the step (1) with butanol-octanol raffinate in the presence of alkaline substances to obtain a second-stage reaction liquid;
(3) And (3) mixing and stirring the second-stage reaction liquid in the step (2) with an emulsifying agent, and homogenizing to obtain the compound flotation reagent.
Preferably, the animal and vegetable oil or grease byproducts comprise one or more of swill oil, white clay oil, fatty acid and acidification oil.
Preferably, the alcohol is a primary alcohol, and more preferably a primary alcohol having 1 to 10 carbon atoms.
Preferably, the alcohol is one or more of methanol, ethanol, isopropanol and butanol.
Preferably, the acidic catalyst is one or more of sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid.
Preferably, the butanol-octanol raffinate comprises 10% -18% of n-butanol, 3% -10% of isobutanol, 10% -20% of octanol, 35% -55% of higher alcohols and 10% -20% of other monohydric alcohols.
The butanol-octanol raffinate is a byproduct in the alcohol preparation process, and compared with a pure product reagent compound foaming agent, the cost is relatively lower. The butanol-octanol raffinate can be directly obtained through the market, and the component content of the butanol-octanol raffinate in different batches can slightly fluctuate, but the butanol-octanol raffinate has no influence on the final composite flotation reagent basically.
Preferably, the butanol-octanol raffinate has a moisture of less than 5%, more preferably less than 3%.
Preferably, the alkaline substance is one or more of sodium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate.
Preferably, the emulsifier is one or more of hydroxyl polyethylene oxide block copolymer, heterogeneous fatty alcohol polyoxyethylene ether, cardanol polyoxyethylene ether, fatty acid methyl ester ethoxylate, fatty amine polyoxyethylene ether, block polyether and polyether polyol.
Preferably, in the step (1), the amount of the alcohol is 15% to 30% by mass of the animal and vegetable oil or fat by-product, for example 15%, 16%, 17%, 18%, 19%, 20%, 21%, 22%, 23%, 24%, 25%, 26%, 27%, 28%, 29%, 30%.
Preferably, in the step (1), the amount of the acidic catalyst is 0.2% to 0.8%, for example 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8% of the mass of the animal and vegetable oil or fat by-product.
Preferably, the reaction pressure of step (1) is 0.4 to 1.0Mpa, for example 0.4Mpa, 0.5Mpa, 0.6Mpa, 0.7Mpa, 0.8Mpa, 0.9Mpa, 1.0Mpa.
Preferably, the reaction temperature of the step (1) is 120-180 ℃.
And/or the reaction time of the step (1) is 10-15 min.
Preferably, in the step (2), the butanol-octanol raffinate is used in an amount of 20% -50%, such as 20%, 25%, 30%, 35%, 40%, 45%, 50% of the mass of the animal and vegetable oil or grease byproduct.
Preferably, in the step (2), the alkaline substance is used in an amount of 0.1% to 0.5%, for example, 0.1%, 0.2%, 0.3%, 0.4%, 0.5% of the mass of the animal and vegetable oil or grease byproduct.
Preferably, the reaction temperature of step (2) is 120 to 130 ℃, e.g. 120 ℃, 125 ℃, 130 ℃.
Preferably, the reaction time of the step (2) is 60 to 90 minutes.
Preferably, in the step (3), the amount of the emulsifier is 1% -10%, for example 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10% of the mass of the animal and vegetable oil or grease byproduct.
Preferably, the reaction temperature of step (3) is 40 to 60 ℃, e.g., 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃.
Preferably, the reaction time of the step (3) is 60 to 90 minutes.
Preferably, in the step (3), the homogenizing time is 30-60 min, and the homogenizing temperature is 20-30 ℃. Homogenizing at room temperature.
The composite flotation reagent product obtained by the invention is a tan to tan transparent liquid.
Preferably, the animal and vegetable oil or grease byproduct is a pretreated animal and vegetable oil or grease byproduct, the pretreatment comprising filtration and/or dehydration.
The second aspect of the invention also provides a compound flotation reagent for low rank coal prepared by the above preparation method.
The third aspect of the invention also provides a flotation method of low-rank coal, wherein the flotation method adopts the compound flotation reagent for the low-rank coal for flotation.
Preferably, the low-rank coal is non-caking coal and/or weakly caking coal.
Preferably, the particle size of the weakly caking coal is less than 0.5mm.
Preferably, the dosage of the compound flotation reagent is 400g/t dry coal slime to 600g/t dry coal slime, and more preferably 450g/t dry coal slime to 550g/t dry coal slime.
According to some embodiments, the low-rank coal is a weakly caking coal, and is pretreated to a particle size of less than 0.5mm prior to flotation.
Due to the application of the technical scheme, compared with the prior art, the invention has the following advantages:
the invention introduces the preparation process of the bio-based medium carbon ester, can directly take waste oil from waste cooking oil, swill-cooked dirty oil and the like as raw materials to carry out esterification and transesterification, mixes and stirs the mixture after transesterification with an emulsifying agent, and obtains the compound flotation reagent through homogenization. The composite flotation reagent has the advantages of strong safety, environmental friendliness, energy conservation, strong adaptability, good use effect in a low-temperature environment and capability of promoting comprehensive utilization and green development of coal resources.
Drawings
FIG. 1 is a view showing the state of the pharmaceutical compositions of examples 1 to 4 after being left at normal temperature for 2 months;
fig. 2 is a state diagram of the medicines of comparative examples 1 to 5 after leaving the medicines at room temperature for 2 months.
Detailed Description
The invention is further described below with reference to examples. The present invention is not limited to the following examples. The implementation conditions adopted in the embodiments can be further adjusted according to different requirements of specific use, and the implementation conditions which are not noted are conventional conditions in the industry. The technical features of the various embodiments of the present invention may be combined with each other as long as they do not collide with each other.
Aiming at the development of low-order coal flotation agents, researches show that carbon esters in biological base can be effectively adsorbed with oxygen-containing functional groups on the surface of low-order coal, so that the oxygen-containing functional groups on the surface of coal are masked to play a role in strengthening hydrophobicity. But the following problems exist when the method is truly applied to low-rank coal flotation: on the one hand, the cost of carbon esters in biobased is high, and the refined products are often used in fuels, so that the application in the field of coal slime is limited. On the other hand, the carbon ester in the biological base has no foaming characteristic, but has excellent intersolubility and stability, and can be intersoluble with an alcohol oil foaming agent to influence the flotation effect. In addition, the carbon esters in biobased as flotation agents have poor flotation in low temperature environments.
In order to overcome the problems, the invention provides a novel compound medicament for low-rank coal flotation and a preparation method thereof by combining a preparation process of carbon ester in a biological base, wherein the novel compound medicament has the advantages of wider raw material sources, lower cost, lower medicament consumption and higher flotation perfection index, can effectively improve the flotation effect of low-rank coal, ensures the stability of the compound medicament by adding an emulsifying agent in the preparation process of the compound medicament, effectively improves the use effect at low temperature, does not introduce hydrocarbon oil components, has a closed flash point of more than 70 ℃, is safe and nontoxic, is beneficial to sustainable development, and promotes the comprehensive utilization and green development of coal resources in China.
The technical scheme of the invention is further described below by combining examples and comparative examples.
The raw materials referred to in the following examples and comparative examples were commercially available unless otherwise specified.
The swill-cooked dirty oil used in the following examples and comparative examples was from the oil removal sump of the martial arts hotel in Changzhou; clay oil is purchased from vitamin biotechnology limited (BSAO) in gold altar, usa; the acidified oil was purchased from vieger biotechnology limited (SAO) in gold altar, usa; the butanol-octanol raffinate is purchased from Tianjin Bohai chemical group Co., ltd (the main components are as follows: 10-15% of n-butanol, 3-10% of isobutanol, 10-20% of octanol, 35-55% of higher alcohols, 10-20% of other monohydric alcohols, less than 3% of water, and the contents of each component of the raffinate in different batches fluctuate within the range). The refined biobased lower esters used in the comparative examples were purchased from the Uygur biotechnology Co., ltd (lower esters 1065) in the gold altar area of Changzhou.
The coal slime flotation composite agent based on the bio-based carbon ester preparation process is simply called a composite flotation agent in the invention.
Example 1
The embodiment provides a coal slime flotation composite medicament based on a bio-based medium carbon ester preparation process, which comprises the following preparation methods:
(1) Preliminary treatment is carried out on swill-cooked dirty oil, including filtering and impurity removal by a 2mm filter screen and vacuum dehydration, methanol accounting for 25% of the swill-cooked dirty oil in mass and sulfonic acid accounting for 0.6% of the swill-cooked dirty oil in mass are added into the swill-cooked dirty oil after the preliminary treatment, and the swill-cooked dirty oil is poured into a reaction kettle, the pressure of the reaction kettle is set to be 0.8MPa, the reaction temperature is 170 ℃ and the reaction time is 15min, so that a section of reaction liquid is obtained;
(2) Adding butanol-octanol raffinate accounting for 30% of the mass of the swill-cooked dirty oil and KOH accounting for 0.25% of the mass of the swill-cooked dirty oil into the first-stage reaction liquid in the step (1), and carrying out condensation reflux stirring reaction at the reaction temperature of 125 ℃ for 90min to obtain a second-stage reaction liquid;
(3) Adding fatty alcohol-polyoxyethylene ether (AEO-3) accounting for 5% of the mass of the swill-cooked dirty oil into the second-stage reaction liquid in the step (2), and continuing to stir and mix in a water bath at 50 ℃ for 60min;
(4) Homogenizing the reaction mixture obtained in the step (3) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the compound flotation reagent.
Example 2
The embodiment provides a coal slime flotation composite medicament based on a bio-based medium carbon ester preparation process, which comprises the following preparation methods:
(1) Performing primary treatment on the clay oil, including filtering and impurity removal by a 2mm filter screen and vacuum dehydration, adding 25% of methanol by mass of the clay oil and 0.6% of sulfonic acid by mass of the clay oil into the clay oil after the primary treatment, pouring into a reaction kettle, setting the pressure of the reaction kettle to be 0.8MPa, and reacting at 170 ℃ for 15min to obtain a first-stage reaction liquid;
(2) Adding butanol-octanol raffinate accounting for 30% of the mass of the carclazyte oil and KOH accounting for 0.25% of the mass of the carclazyte oil into the first-stage reaction liquid in the step (1), and carrying out condensation reflux stirring reaction at the reaction temperature of 125 ℃ for 90min to obtain a second-stage reaction liquid;
(3) Adding fatty alcohol polyoxyethylene ether (AEO-3) accounting for 5% of the mass of the carclazyte oil into the second-stage reaction liquid in the step (2), and continuing to stir and mix in a water bath at 50 ℃ for 60min;
(4) Homogenizing the reaction mixture obtained in the step (3) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the compound flotation reagent.
Example 3
The embodiment provides a coal slime flotation composite medicament based on a bio-based medium carbon ester preparation process, which comprises the following preparation methods:
(1) The method comprises the steps of performing primary treatment on swill-cooked dirty oil, including filtering and impurity removal by a 2mm filter screen and vacuum dehydration, adding 25% of ethanol and 0.6% of sulfonic acid into the swill-cooked dirty oil after the primary treatment, pouring the mixture into a reaction kettle, wherein the pressure of the reaction kettle is set to be 0.8MPa, the reaction temperature is 170 ℃, and the reaction time is 15min, so as to obtain a section of reaction liquid;
(2) Adding butanol-octanol raffinate accounting for 30% of the mass of the swill-cooked dirty oil and KOH accounting for 0.25% of the mass of the swill-cooked dirty oil into the first-stage reaction liquid in the step (1), and carrying out condensation reflux stirring reaction at the reaction temperature of 125 ℃ for 90min to obtain a second-stage reaction liquid;
(3) Adding fatty alcohol-polyoxyethylene ether (AEO-3) accounting for 5% of the mass of the swill-cooked dirty oil into the second-stage reaction liquid in the step (2), and continuing to stir and mix in a water bath at 50 ℃ for 60min;
(4) Homogenizing the reaction mixture obtained in the step (3) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the compound flotation reagent.
Example 4
The embodiment provides a coal slime flotation composite medicament based on a bio-based medium carbon ester preparation process, which comprises the following preparation methods:
(1) Preliminary treatment is carried out on swill-cooked dirty oil, including filtering and impurity removal by a 2mm filter screen and vacuum dehydration, methanol accounting for 25% of the swill-cooked dirty oil in mass and sulfonic acid accounting for 0.6% of the swill-cooked dirty oil in mass are added into the swill-cooked dirty oil after the preliminary treatment, and the swill-cooked dirty oil is poured into a reaction kettle, the pressure of the reaction kettle is set to be 0.8MPa, the reaction temperature is 170 ℃ and the reaction time is 15min, so that a section of reaction liquid is obtained;
(2) Adding butanol-octanol raffinate accounting for 30% of the mass of the swill-cooked dirty oil and KOH accounting for 0.25% of the mass of the swill-cooked dirty oil into the first-stage reaction liquid in the step (1), and carrying out condensation reflux stirring reaction at the reaction temperature of 125 ℃ for 90min to obtain a second-stage reaction liquid;
(3) Adding fatty amine polyoxyethylene ether (AC-1205) accounting for 5% of the mass of the swill-cooked dirty oil into the second-stage reaction liquid in the step (2), and continuing to stir and mix in a water bath at 50 ℃ for 60min;
(4) Homogenizing the reaction mixture obtained in the step (3) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the compound flotation reagent.
Comparative example 1
The comparative example provides a coal slime flotation non-composite collector based on a bio-based low-carbon ester preparation process, and the preparation method comprises the following steps:
(1) Preliminary treatment is carried out on swill-cooked dirty oil, including filtering and impurity removal by a 2mm filter screen and vacuum dehydration, methanol accounting for 25% of the swill-cooked dirty oil in mass and sulfonic acid accounting for 0.6% of the swill-cooked dirty oil in mass are added into the swill-cooked dirty oil after the preliminary treatment, and the swill-cooked dirty oil is poured into a reaction kettle, the pressure of the reaction kettle is set to be 0.8MPa, the reaction temperature is 170 ℃ and the reaction time is 15min, so that a section of reaction liquid is obtained;
(2) Adding 10% methanol of the swill-cooked dirty oil and 0.25% KOH of the swill-cooked dirty oil into the first-stage reaction liquid in the step (1), and carrying out water bath condensation reflux stirring reaction at the reaction temperature of 60 ℃ for 90min to obtain a second-stage reaction liquid;
(3) And (3) cooling and layering the two-stage reaction liquid obtained in the step (2), taking an upper liquid, and performing reduced pressure distillation to obtain the coal slime flotation non-composite collector based on the bio-based low-carbon ester preparation process.
Comparative example 2
The comparative example provides a coal slime flotation composite medicament which is not combined with a bio-based medium carbon ester preparation process, and the preparation method comprises the following steps:
(1) The preparation method comprises the following steps: 40 parts of refined bio-based low-carbon ester, 40 parts of butanol-octanol raffinate, 7.5 parts of water, 7.5 parts of glycerol and 5 parts of fatty alcohol polyoxyethylene ether (AEO-3), and pouring the components into the same container in sequence, and stirring and mixing uniformly;
(2) Homogenizing the mixed solution in the step (1) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the bio-based medium carbon ester coal slime flotation composite medicament which is not combined with the production process.
Comparative example 3
The comparative example provides another coal slime flotation composite medicament which is not combined with the preparation process of the carbon ester in the biological base, and the preparation method comprises the following steps:
(1) The preparation method comprises the following steps: 35 parts of refined biological-based low-carbon ester, 35 parts of butanol-octanol raffinate, 12.5 parts of water, 12.5 parts of glycerol and 5 parts of fatty alcohol-polyoxyethylene ether (AEO-3), and pouring the components into the same container in sequence, and stirring and mixing uniformly;
(2) Homogenizing the mixed solution in the step (1) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the bio-based medium carbon ester coal slime flotation composite medicament which is not combined with the production process.
Comparative example 4
The comparative example provides another coal slime flotation composite medicament which is not combined with the preparation process of the carbon ester in the biological base, and the preparation method comprises the following steps:
(1) The preparation method comprises the following steps: 30 parts of refined biological-based low-carbon ester, 30 parts of butanol-octanol raffinate, 17.5 parts of water, 17.5 parts of glycerol and 5 parts of fatty alcohol-polyoxyethylene ether (AEO-3), and pouring the components into the same container in sequence, and stirring and mixing uniformly;
(2) Homogenizing the mixed solution in the step (1) for 60min at a homogenizing temperature of 25 ℃ (room temperature) to obtain the bio-based medium carbon ester coal slime flotation composite medicament which is not combined with the production process.
Comparative example 5
This comparative example provides a coal slime flotation complex formulation based on bio-based medium carbon ester preparation process without emulsifier, the preparation method of which is basically the same as example 1, except that no fatty alcohol polyoxyethylene ether (AEO-3) is added in step (3).
Normal temperature floatation performance test:
the flotation effect evaluation of the flotation unit experiment is mainly based on the following indexes: the clean coal yield, clean coal ash content, flotation perfection index and combustible recovery rate, wherein the clean coal yield is the ratio of the mass of the scraped clean coal to the mass of the floating coal powder and expressed as a percentage; the ash content of the clean coal is measured according to the method for industrial analysis of coal (GB/T212-2008); the flotation perfection index is measured according to the method for evaluating flotation process effect of coal preparation plant (GB/T34164-2017); the recovery rate of combustible is measured according to the method for evaluating floatability of pulverized coal (mud) (GB/T30047-2013).
Flotation unit experiments were performed on the composite type reagent and the non-composite type collector prepared from the composite type reagents prepared in examples 1 to 4 and comparative examples 1 to 5, and diesel oil was used as a control group. The coal sample is weak-viscosity coal, ash content of the feed is 26.73%, the raw coal is crushed, screened, blended and reduced to prepare an analysis coal sample with the grain size smaller than 0.5mm according to a coal sample preparation method (GB/T474-2008), a flotation experiment method is used for performing performance detection according to a coal dust (mud) laboratory unit flotation test method (GB/T4757-2013), a 1.5L XFD type single-tank flotation machine is used as a flotation machine, the impeller rotating speed of the flotation machine is 1800r/min, and the unit aeration quantity is 0.25m 3 /(m 2 Min). The concentration of ore pulp is 80g/L, and the dosage of the composite agent is 500g/t of dry coal slime; non-composite collector matched with secondary octanol foaming agentThe dosage of the non-composite collecting agent is 250g/t of dry coal slime, and the dosage of the sec-octyl alcohol is 250g/t of dry coal slime; the dosage of diesel oil in the control group is 250g/t dry coal slime, and the dosage of the diesel oil in the control group is 250g/t dry coal slime. The results of the flotation test are shown in Table 1.
TABLE 1
Note that: the tests in Table 1 were carried out at room temperature (25 ℃).
Table 1 shows that the flotation effect of examples 1-4 is significantly better than that of the diesel control group, demonstrating that the invention has advantages over diesel for the flotation of low-rank coals.
The flotation effect of the coal slime flotation non-composite collector based on the preparation method of the bio-based low-carbon ester in the comparative example 1 is not as good as that of each example, but is improved compared with other comparative examples and diesel groups, the flotation effect of the coal slime flotation composite agent of the comparative examples 2-4, which is not combined with the preparation process of the bio-based low-carbon ester, is higher than that of diesel, but is still obviously lower than that of the example 1, and the comparative examples 2-4 show that the flotation effect is increased along with the increase of the dosage of the refined bio-based low-carbon ester, so that the cost of the refined bio-based low-carbon ester is higher, and the coal slime flotation composite agent is not suitable for large-scale flotation of low-rank coal. Comparative example 5 shows that the flotation effect is significantly reduced without the addition of an emulsifier, indicating that the addition of an emulsifier helps to improve the dispersion of the agent and improves the flotation effect.
From the above preparation method and the results in Table 1, it can be seen that: (1) In the process of preparing the carbon ester in the biological base, a small amount of oil residue is generated, in the prior art, the oil residue is removed by reduced pressure distillation, but the invention does not perform reduced pressure distillation operation, and the oil residue is left in a final product, so that a certain forward effect is achieved on the flotation effect. (2) The difference between the carbon ester reaction system in the biological base and the monomer is that the substrate, the product and the byproducts in the reaction system are in a mutual conversion relationship, so that the relevance among different components is enhanced, the whole system has higher mixing degree, and the stable and uniform water-in-oil emulsion is easier to prepare, so that the reagent can exert the maximum flotation performance.
And (3) testing low-temperature flotation effect:
the compound agents prepared in example 1, example 4 and comparative example 5 were used to test flotation effect at 5 ℃, and diesel oil was also used as a control, and the test method was the same as above except that the test environment temperature was different, and the details are not repeated here. The test results are shown in Table 2.
TABLE 2
Table 2 examples 1 and 4 show that under low temperature conditions, the clean coal yield, flotation perfection index and combustible recovery rate of the composite agent containing the emulsifier are all higher than that of diesel oil, and that comparative example 5 contains no emulsifier and has poor flotation effect. The emulsifier can improve the dispersibility of the agent, so that the dispersing effect of the agent in a low-temperature ore pulp system is enhanced, and the coal dressing flotation effect can be better enhanced at low temperature.
Stability test:
the medicines prepared in examples 1 to 4 and comparative examples 1 to 5 were uniformly left at room temperature for 2 months, and stability was observed, and the state of the medicines in examples 1 to 4 after being left at room temperature for 2 months was shown in fig. 1, and the state of the medicines in comparative examples 1 to 5 after being left at room temperature for 2 months was shown in fig. 2.
It is evident that examples 1 to 4 are strong in stability and do not delaminate after 2 months of placement. Comparative example 1 is a bio-based low-carbon ester pure product, has no layering phenomenon and has strong stability. Comparative examples 2 to 4 have a tendency to delaminate, the lower the biobased low carbon ester content, the more pronounced the delamination. Comparative example 5 was completely layered and had the worst stability.
The present invention has been described in detail with the purpose of enabling those skilled in the art to understand the contents of the present invention and to implement the same, but not to limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A preparation method of a compound flotation reagent for low-rank coal is characterized by comprising the following steps: the preparation method comprises the following steps: (1) Animal and vegetable oil or grease byproducts and alcohols react in the presence of an acid catalyst to obtain a first-stage reaction liquid; (2) Reacting the first-stage reaction liquid in the step (1) with butanol-octanol raffinate in the presence of alkaline substances to obtain a second-stage reaction liquid; (3) And (3) mixing and stirring the second-stage reaction liquid in the step (2) with an emulsifying agent, and homogenizing to obtain the compound flotation reagent.
2. The method of manufacturing according to claim 1, characterized in that: the animal and vegetable oil or grease byproducts comprise one or more of swill oil, white clay oil, fatty acid and acidified oil;
and/or the alcohol is one or more of methanol, ethanol, isopropanol and butanol;
and/or the acid catalyst is one or more of sulfonic acid, sulfuric acid, phosphoric acid and hydrochloric acid;
and/or the butanol-octanol raffinate comprises 10-18% of n-butanol, 3-10% of isobutanol, 10-20% of octanol, 35-55% of higher alcohols and 10-20% of other monohydric alcohols;
and/or, the water content of the butanol-octanol raffinate is less than 5%;
and/or the alkaline substance is one or more of sodium methoxide, sodium hydroxide, potassium hydroxide, sodium carbonate and potassium carbonate;
and/or the emulsifier is one or more of hydroxyl polyethylene oxide block copolymer, heterogeneous fatty alcohol polyoxyethylene ether, cardanol polyoxyethylene ether, fatty acid methyl ester ethoxylate, fatty amine polyoxyethylene ether, block polyether and polyether polyol.
3. The method of manufacturing according to claim 1, characterized in that: in the step (1), the use amount of the alcohols is 15-30% of the mass of the animal and vegetable oil or grease byproducts;
and/or, in the step (1), the dosage of the acid catalyst is 0.2-0.8% of the mass of the animal and vegetable oil or grease byproducts;
and/or the reaction pressure in the step (1) is 0.4-1.0 Mpa;
and/or, the reaction temperature of the step (1) is 120-180 ℃;
and/or the reaction time of the step (1) is 10-15 min.
4. The method of manufacturing according to claim 1, characterized in that: in the step (2), the dosage of the butanol-octanol raffinate is 20% -50% of the mass of the animal and vegetable oil or grease byproducts;
and/or, in the step (2), the alkaline substance is used in an amount of 0.1-0.5% of the mass of the animal and vegetable oil or grease byproduct;
and/or, the reaction temperature of the step (2) is 120-180 ℃;
and/or the reaction time of the step (2) is 60-90 min.
5. The method of manufacturing according to claim 1, characterized in that:
and/or, in the step (3), the using amount of the emulsifying agent is 1-10% of the mass of the animal and vegetable oil or grease byproduct;
and/or, the reaction temperature of the step (3) is 40-60 ℃;
and/or the reaction time of the step (3) is 60-90 min.
And/or, in the step (3), the homogenizing time is 30-60 min, and the temperature is 20-30 ℃.
6. The method of manufacturing according to claim 1, characterized in that: the compound flotation reagent is a tan or tan transparent liquid.
7. The method of manufacturing according to claim 1, characterized in that: the animal and vegetable oil or grease byproduct is the animal and vegetable oil or grease byproduct after pretreatment, and the pretreatment comprises filtering and/or dehydration.
8. A composite flotation reagent for low rank coal prepared by the preparation method of any one of claims 1 to 7.
9. A method for the flotation of low-rank coal, characterized in that the method comprises the step of carrying out the flotation by using the compound flotation reagent for low-rank coal according to claim 8.
10. The flotation process according to claim 9, wherein the low rank coal is non-caking coal and/or weakly caking coal;
and/or the particle size of the weakly caking coal is less than 0.5mm;
and/or the dosage of the compound flotation reagent for the low-rank coal is 400g/t dry coal slime to 600g/t dry coal slime.
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