CN115584287A - Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof - Google Patents
Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof Download PDFInfo
- Publication number
- CN115584287A CN115584287A CN202211167710.4A CN202211167710A CN115584287A CN 115584287 A CN115584287 A CN 115584287A CN 202211167710 A CN202211167710 A CN 202211167710A CN 115584287 A CN115584287 A CN 115584287A
- Authority
- CN
- China
- Prior art keywords
- nano
- naphthalene
- hydrocarbon fuel
- dispersant
- slurry
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000000446 fuel Substances 0.000 title claims abstract description 91
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 88
- 239000002270 dispersing agent Substances 0.000 title claims abstract description 88
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 78
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 78
- 239000003245 coal Substances 0.000 claims abstract description 55
- 239000002002 slurry Substances 0.000 claims abstract description 55
- -1 1-methylimidazole tetrafluoroborate Chemical compound 0.000 claims abstract description 26
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 claims abstract description 17
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000010008 shearing Methods 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 11
- 239000011268 mixed slurry Substances 0.000 claims description 9
- 238000004945 emulsification Methods 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 8
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- NVVZQXQBYZPMLJ-UHFFFAOYSA-N formaldehyde;naphthalene-1-sulfonic acid Chemical compound O=C.C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 NVVZQXQBYZPMLJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 239000000292 calcium oxide Substances 0.000 claims description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 235000012239 silicon dioxide Nutrition 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 159000000000 sodium salts Chemical class 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 2
- 239000002245 particle Substances 0.000 abstract description 37
- 230000000694 effects Effects 0.000 abstract description 24
- 230000001603 reducing effect Effects 0.000 abstract description 9
- 238000005054 agglomeration Methods 0.000 abstract description 8
- 230000002776 aggregation Effects 0.000 abstract description 8
- 230000008569 process Effects 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 6
- 238000003860 storage Methods 0.000 abstract description 5
- 230000001965 increasing effect Effects 0.000 abstract description 4
- 239000000843 powder Substances 0.000 description 14
- 239000006185 dispersion Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009826 distribution Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000004581 coalescence Methods 0.000 description 4
- 230000001804 emulsifying effect Effects 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 150000002790 naphthalenes Chemical class 0.000 description 3
- 239000003960 organic solvent Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 238000010998 test method Methods 0.000 description 3
- MCTWTZJPVLRJOU-UHFFFAOYSA-O 1-methylimidazole Chemical compound CN1C=C[NH+]=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-O 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- AAXJDARXOMHXJR-UHFFFAOYSA-M potassium;formaldehyde;naphthalene-1-sulfonate Chemical compound [K+].O=C.C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 AAXJDARXOMHXJR-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 102220043159 rs587780996 Human genes 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/18—Organic compounds containing oxygen
- C10L1/192—Macromolecular compounds
- C10L1/198—Macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds homo- or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon to carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/24—Organic compounds containing sulfur, selenium and/or tellurium
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Emergency Medicine (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The invention provides a naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof. The naphthalene dispersant comprises a naphthalene sulfonate polycondensate, 1-methylimidazole tetrafluoroborate and isooctane. The naphthalene dispersant has good viscosity reducing effect and dispersing performance, and mainly has the effects of increasing the adsorbability of the coal surface, improving the hydrophilicity, enabling coal particles to be uniformly dispersed in water, having proper viscosity, and reducing the particle agglomeration phenomenon of nano-scale materials, so that the fluidity of nano-hydrocarbon fuel is improved, and the stability of the performance of nano-hydrocarbon fuel slurry in the storage and transportation processes is ensured.
Description
Technical Field
The invention relates to the field of environment-friendly fuels, in particular to a naphthalene dispersant for preparing a nano hydrocarbon fuel and application thereof.
Background
The nano hydrocarbon fuel is a coal-based fluid fuel which is prepared by pre-treating and refining coal, nano treating and adding hydrogen for enabling by using advanced nano crushing technology and equipment, has the granularity of basic particles of micro-nano level, has higher specific surface area and surface activity, is a novel efficient and clean environment-friendly fuel, and has the characteristics of high combustion efficiency, low pollutant emission and the like. The slurry particles formed after the coal powder is mechanically dispersed by the nanometer set are in a micro nanometer level, the specific surface area and the surface energy are large, the superfine particles can be spontaneously gathered in water to form precipitation or layering, and the apparent viscosity of the slurry is large. The coal particles in the nano hydrocarbon fuel must have a certain particle size and a proper particle size distribution, and have good fluidity so as to be convenient for storage and transportation. Therefore, a proper amount of dispersant needs to be added into the slurry, so that the surfaces of the coal particles are tightly surrounded by dispersant molecules and hydration films, the coal particles are uniformly distributed in water, and the fluidity of the nano hydrocarbon fuel is improved.
However, the particle size of the nano hydrocarbon fuel is micro-nano grade, the surface activity of the superfine particles is obviously different from that of the coal water slurry with the common particle size, and the use of the dispersing agent is also obviously different. At present, china mainly researches on the technology of the dispersant of the coal water slurry, and the research on the nano hydrocarbon fuel dispersant is almost zero.
Disclosure of Invention
The invention mainly aims to provide a naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof, so as to solve the problem of poor dispersing performance of the nano hydrocarbon fuel in the prior art.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a naphthalene-based dispersant for nano hydrocarbon fuel production, the naphthalene-based dispersant comprising a naphthalene sulfonate polycondensate, 1-methylimidazole tetrafluoroborate and isooctane.
Further, the naphthalene dispersant comprises the following components in parts by weight: naphthalenesulfonate polycondensate: 15-32 parts of 1-methylimidazole tetrafluoroborate: 8-12 parts of isooctane: 13 to 17 portions.
Further, the naphthalenesulfonate polycondensate is a potassium salt of naphthalenesulfonate formaldehyde condensate and/or a sodium salt of naphthalenesulfonate formaldehyde condensate.
Further, the 1-methylimidazole tetrafluoroborate is 1-methylimidazole tetrafluoroborate potassium salt and/or 1-methylimidazole tetrafluoroborate sodium salt.
According to another aspect of the invention, a preparation method of nano hydrocarbon fuel pre-slurry is provided, which comprises the following steps: pre-crushing the raw material coal to obtain a pre-crushed raw material; mixing the pre-crushed raw materials, water and the naphthalene dispersant to obtain mixed slurry, and carrying out nano crushing on the mixed slurry to obtain nano hydrocarbon fuel pre-slurry.
Furthermore, the additive amount of the naphthalene dispersant is 3.6-6.1 per mill based on the solid dry weight of the nano hydrocarbon fuel pre-slurry.
Furthermore, the usage amount of the naphthalene series dispersant is 1.5-3.2 wt per mill of naphthalene sulfonate polycondensate, 0.8-1.2 per mill of 1-methylimidazole tetrafluoroborate and 1.3-1.7 per mill of isooctane in the naphthalene series dispersant based on the solid dry weight of the nano hydrocarbon fuel pre-slurry.
Further, the raw material coal comprises the following components in percentage by weight: 43 to 48 percent of carbon, 24 to 32 percent of alumina, 23 to 25 percent of silicon dioxide, 0.2 to 0.4 percent of calcium oxide, 1.5 to 2.5 percent of ferric oxide and the balance of impurities.
Further, before the nano-pulverization, the preparation method further comprises: firstly, the mixed slurry is subjected to ultrasonic pretreatment for 5 to 15 minutes, and then is subjected to shearing emulsification treatment for 15 to 30 minutes.
Furthermore, the ultrasonic pretreatment equipment is an ultrasonic generator, the power is 0.5-5 kilowatts, and the frequency is 20-80 KHZ; preferably, the equipment for shearing and emulsifying treatment is a stirrer, the power is 0.5-5 kilowatts, and the rotating speed is 5000-15000 revolutions per minute.
By applying the technical scheme of the invention, the naphthalene dispersant is used in the preparation process of the nano hydrocarbon fuel, wherein a naphthalene sulfonate condensate molecular structure contains a hydrophobic naphthalene ring and a hydrophilic sulfonic acid group, and is an amphiphilic surfactant, one part of hydrophobic groups are adsorbed on the surfaces of coal particles through electrostatic action, hydrophobic action and other acting forces, and the other part of polar hydrophilic groups are exposed outside and penetrate into water, so that the coal-water relationship is improved, the surface tension of coal is promoted to be reduced, the coalescence among coal powder is reduced, and the dispersion fluidity of nano hydrocarbon fuel slurry is improved. F which can be formed during use of 1-methylimidazolium tetrafluoroborate - The surface dangling bond of the nanocrystal is etched, so that the grinding aiding effect is achieved, and the nano-scale superfine coal powder particles keep uniform and stable performance in water. Isooctane is used as a hydrophobic organic solvent, can assist the naphthalene sulfonate condensate to enhance the adsorption of the naphthalene dispersant on the surface of coal and the dispersion of the nano particles in the synthesis process, thereby leading the naphthalene dispersant to be easily combined with coal powder. The naphthalene dispersant has good viscosity reducing effect and dispersing performance, and mainly has the effects of increasing the adsorbability of the coal surface, improving the hydrophilicity, enabling coal particles to be uniformly dispersed in water, having proper viscosity, and reducing the particle agglomeration phenomenon of nano-scale materials, so that the fluidity of nano-hydrocarbon fuel is improved, and the stability of the performance of nano-hydrocarbon fuel slurry in the storage and transportation processes is ensured.
Detailed Description
It should be noted that the embodiments and features of the embodiments in the present application may be combined with each other without conflict. The present invention will be described in detail with reference to examples.
It should be noted that the relationship between the apparent viscosity and the stability of the nano hydrocarbon fuel is different from the conventional cognition, and many physical properties and chemical properties of the material in the micro-nano state are fundamentally different from those in the conventional state. The finished product of the nano hydrocarbon fuel has the particle size of micro-nano level, and because the specific surface area of the superfine particles is large, the influence of electronic effect, hydroxyl effect, van der waals force and the like on the particles is increased in geometric coefficient, so that the particles are attracted to each other and extruded, namely, the agglomeration phenomenon is generated. It appears in the fluid as a further increase in viscosity, where gravity has little effect on the fluid. For nano hydrocarbon fuel, the function of adding the dispersing agent is mainly to change the fluidity of the nano hydrocarbon fuel, and the main index for representing the effect of the dispersing agent is apparent viscosity. The inventor finds through a large number of experiments and comparisons that the nano hydrocarbon fuel has the tendency that the larger the apparent viscosity is, the better the stability is, and the smaller the apparent viscosity is, the worse the stability is, but the too high viscosity affects the application of the nano hydrocarbon fuel, and the too low viscosity causes the nano hydrocarbon fuel to be influenced by gravity again to generate sedimentation, so that a proper dispersing agent needs to be used to control the viscosity of the nano hydrocarbon fuel within a proper range, preferably 280-320mPa.s, so that the nano hydrocarbon fuel has good dispersing performance and stability on the basis of keeping the characteristics of nano materials.
As described in the background of the invention, the prior art has a problem of poor dispersing performance of nano hydrocarbon fuel. In order to solve the above problems, in an exemplary embodiment of the present invention, there is provided a naphthalene based dispersant for nano hydrocarbon fuel production, including a naphthalene sulfonate polycondensate, 1-methylimidazolium tetrafluoroborate, and isooctane.
The factors influencing the quality of the finished nano hydrocarbon fuel mainly comprise three factors: coal quality of raw materials, solid content of slurry and granularity of finished products. The dispersion state of the nano hydrocarbon fuel particles is one of the main reasons influencing the slurry particle size distribution, and when the dispersion is sufficient, the distribution state of the nano hydrocarbon fuel is more ideal. The naphthalene dispersant of the invention uses amphiphilic naphthalene sulfonate condensate (NSF), so that the coal-water relationship is improved, the coalescence among coal powder is reduced, and the dispersion fluidity of nano hydrocarbon fuel slurry is improved. 1-methylimidazolium tetrafluoroborate ([ Mim ]]BF 4 ) Can form F during use - Etching the surface dangling bond of the nanocrystal to generate the tetrafluoroThe silicon dioxide gas overflows to play a role in grinding aid, so that the nano-scale superfine coal powder particles keep uniform and stable state in water. Isooctane is used as a hydrophobic organic solvent, and can enhance the adsorption of the naphthalene dispersant on the surface of coal, so that the naphthalene dispersant and coal powder are easy to combine.
The invention discloses a composite dispersant mainly based on naphthalene series, which is prepared according to the dispersion requirement of the use working condition on slurry and the combination of the production cost and the subsequent utilization of nano hydrocarbon fuel. The compound dispersant not only has the action mechanism of a single dispersant, but also has the characteristic synergistic interaction characteristic, and has the effect that one is added and the other is more than two, so that the performance of the nano hydrocarbon fuel is more excellent. The naphthalene dispersant has good viscosity reducing effect and dispersing performance, and mainly has the effects of increasing the adsorbability of the coal surface, improving the hydrophilicity, enabling coal particles to be uniformly dispersed in water, having proper viscosity, and reducing the particle agglomeration phenomenon of nano-scale materials, so that the fluidity of nano-hydrocarbon fuel is improved, and the stability of the performance of nano-hydrocarbon fuel slurry in the storage and transportation processes is ensured.
The concentration and the granularity of the nano hydrocarbon fuel finished product are different, the surface activity and the surface energy of slurry are also obviously different, the apparent viscosity and the thickening coefficient are completely different, and the used dispersing agents are different. The dispersing agents with the same components have different proportions and different application methods, and have great influence on the finished product quality of the nano hydrocarbon fuel. In a preferred embodiment, the naphthalene based dispersant comprises, in parts by weight: naphthalenesulfonate polycondensate: 15-32 parts of 1-methylimidazole tetrafluoroborate: 8-12 parts of isooctane: 13 to 17 portions. The naphthalene dispersant is more suitable for the preparation process of the nano hydrocarbon fuel, can better exert the synergistic property of the three components, enables the dispersion effect of slurry to be better, has proper viscosity, and further improves the particle stability of nano materials.
Typically, but not by way of limitation, in the naphthalene dispersants provided herein, the parts by weight of the naphthalene sulfonate polycondensate are, for example, 15 parts, 16 parts, 18 parts, 20 parts, 22 parts, 24 parts, 25 parts, 26 parts, 28 parts, 30 parts, 32 parts, or any two numerical range values; the parts by weight of the 1-methylimidazole tetrafluoroborate are 8 parts, 9 parts, 10 parts, 11 parts, 12 parts or a range value formed by any two numerical values; the weight portion of the isooctane is 13 portions, 14 portions, 15 portions, 16 portions, 17 portions or a range value formed by any two numerical values.
The naphthalenesulfonate polycondensates may be any specific compound known in the art, and in order to provide a better hydrophilic-lipophilic effect of the naphthalene-based dispersants, in a preferred embodiment, the naphthalenesulfonate polycondensates are naphthalenesulfonate formaldehyde condensate potassium salt and/or naphthalenesulfonate formaldehyde condensate sodium salt; preferably, the relative molecular weight of the naphthalene sulfonate polycondensate is 230, so that the surface tension of coal can be further reduced, the agglomeration among coal powder is reduced, and the dispersion flowability of the nano hydrocarbon fuel slurry is enhanced.
Meanwhile, in order to further enhance the etching grinding aid effect of the 1-methylimidazole tetrafluoroborate, in a preferred embodiment, the 1-methylimidazole tetrafluoroborate is 1-methylimidazole tetrafluoroborate potassium salt and/or 1-methylimidazole tetrafluoroborate sodium salt.
In another exemplary embodiment of the present invention, there is also provided a method for preparing a nano hydrocarbon fuel pre-slurry, wherein the nano hydrocarbon fuel pre-slurry is supplemented with hydrogen to obtain a nano hydrocarbon fuel, the method comprising: pre-crushing the raw material coal to obtain a pre-crushed raw material; mixing the pre-crushed raw materials, water and the naphthalene dispersant to obtain mixed slurry, and carrying out nano crushing on the mixed slurry to obtain nano hydrocarbon fuel pre-slurry. Due to the adoption of the naphthalene dispersant, coal particles can be uniformly dispersed in water, the particle agglomeration phenomenon of nano-scale materials is reduced, and the nano-scale materials have proper viscosity, so that the fluidity of the nano-hydrocarbon fuel pre-slurry is improved, and the stability of the property state of the nano-hydrocarbon fuel pre-slurry in the storage and transportation processes is ensured.
In order to further improve the slurry particle size distribution of the nano hydrocarbon fuel, in a preferred embodiment, the naphthalene dispersant is added in an amount of 3.6-6.1 per thousand based on the solid dry weight of the nano hydrocarbon fuel. Wherein the dry solid weight of the nano hydrocarbon fuel pre-slurry refers to the solid content of the slurry. The inventor finds that when the using amount of each component of the naphthalene dispersant is lower than the range, the wettability of the surface of coal particles cannot be obviously improved, the dispersing capacity is limited, the agglomeration phenomenon of the coal particles is obvious, and the viscosity is still high; however, when the amount of each component of the naphthalene-based dispersant is more than the above range, a large amount of the dispersant acts on the surface of the coal particles, the surface water is too strong, an excessively thick hydrated film is formed, and the flow of the coal particles is hindered. Therefore, when the additive amount of each component of the naphthalene dispersant is limited within the above range, the dispersant has excellent viscosity reduction effect on the nano hydrocarbon fuel.
Typically, but not limitatively, the additive amount of the naphthalene dispersant is 3.6 per thousand, 4.0 per thousand, 4.4 per thousand, 4.5 per thousand, 5.0 per thousand, 5.3 per thousand, 5.5 per thousand, 6.0 per thousand, 6.1 per thousand or a range value formed by any two numerical values based on the solid dry weight of the nano hydrocarbon fuel.
The synergy of the amphiphilic surface activity of the naphthalenesulfonate polycondensate and the etching grinding aid effect of the 1-methylimidazole tetrafluoroborate is the main action mode of the naphthalene dispersant, and in a preferred embodiment, the naphthalene dispersant contains 1.5 to 3.2 wt% of naphthalenesulfonate polycondensate, 0.8 to 1.2 wt% of 1-methylimidazole tetrafluoroborate and 1.3 to 1.7 wt% of isooctane based on the solid dry weight of the nano hydrocarbon fuel pre-slurry, so that the naphthalene dispersant can further improve the coal-water relationship and reduce the coalescence among coal powders, thereby further enhancing the dispersion fluidity of the nano hydrocarbon fuel slurry and keeping the nano-scale ultrafine coal powder particles of the invention in a more uniform and stable state in water.
Typically, but not limitatively, the amount of the naphthalenesulfonate polycondensate is 1.5%, 2.0%, 2.5%, 3.0%, 3.2% by weight or any two of the above ranges, the amount of the 1-methylimidazolium tetrafluoroborate is 0.8%, 0.9%, 1.0%, 1.1%, 1.2% or any two of the above ranges, and the amount of the isooctane is 1.3%, 1.4%, 1.5%, 1.6%, 1.7% or any two of the above ranges, based on the dry weight of the nano hydrocarbon fuel.
According to the classification of carbon content, coal is mainly divided into gangue, middling coal, slack coal, clean coal and the like, the carbon content is different, and the contents of main ash components such as silicon dioxide, aluminum oxide, calcium oxide, iron oxide and the like are different, so that the prepared dispersing agent applicable to the nano hydrocarbon fuel is obviously different. Because the surface activity of the ultrafine particles of the powder is obviously enhanced in a micro-nano state, the agglomeration and sedimentation states of slurries with different components are obviously different. The dispersing agents of different types influence the performance of the nano hydrocarbon fuel to a great extent, the dispersing agents and the nano hydrocarbon fuel slurry have obvious matching performance, one dispersing agent can only be suitable for certain slurry meeting the requirements, good dispersing and viscosity reducing effects are achieved on the slurry, and the dispersing effect on unmatched nano hydrocarbon fuel slurry is very little. Thus, in a preferred embodiment, the feed coal comprises, in weight percent: carbon: 43-48%, alumina: 24% -32%, silica: 23% -25%, calcium oxide: 0.2-0.4%, iron oxide: 1.5 to 2.5 percent, and the balance of impurities. The slack coal raw material is sequentially subjected to pre-crushing and nano-crushing to obtain a nano hydrocarbon fuel finished product, the dispersing agent is used in a nano-crushing stage, is a compound dispersing agent mainly based on naphthalene, and is more suitable for the naphthalene dispersing agent, and the concentration of the obtained nano hydrocarbon fuel finished product is 63-65%, and the D50 is less than or equal to 1.0-1.5 mu m.
The naphthalene dispersant is preferably added in a one-time placing mode, and in a preferred embodiment, before the nano-pulverization, the preparation method further comprises the following steps: the mixed slurry is firstly subjected to ultrasonic pretreatment for 5 to 15 minutes and then subjected to shearing emulsification treatment for 15 to 30 minutes, so that the nano hydrocarbon fuel pre-slurry is dispersed more thoroughly, and the naphthalene dispersant is more suitable for exerting the dispersing and viscosity reducing effects.
In order to further improve the dispersing effect of the naphthalene dispersant on the nano hydrocarbon fuel pre-slurry and obtain the nano hydrocarbon fuel pre-slurry with more uniform slurry particle size distribution, the ultrasonic pretreatment equipment is an ultrasonic generator, the power is 0.5-5 kilowatts, and the frequency is 20-80 KHZ. Preferably, the shearing and emulsifying device is a stirrer, the power is 0.5-5 kilowatts, and the rotating speed is 5000-15000 revolutions per minute.
The present application is described in further detail below with reference to specific examples, which should not be construed as limiting the scope of the invention as claimed.
Example 1
In the embodiment, the inner Mongolia quasi-Gell mine area slack coal is used as raw material coal for preparing the nano hydrocarbon fuel.
(1) Pre-crushing the slack coal raw material to obtain a pre-crushed raw material, wherein the specific component of the slack coal is 44% of carbon content by weight percentage; the alumina content is 24 percent; the content of silicon dioxide is 24 percent; the content of calcium oxide is 0.3%; 1.7 percent of ferric oxide, and the balance of impurities;
(2) Mixing the pre-crushed raw materials with water and a naphthalene dispersant, adding the naphthalene dispersant once, then carrying out ultrasonic oscillation for 10 minutes for pretreatment, and then stirring for 20 minutes in a shearing and emulsifying manner to obtain the nano hydrocarbon fuel pre-slurry, wherein the concentration of the finished slurry is 64%, and D50=1.3 μm. Wherein, the adding amount of the naphthalene dispersant is 5.0 per mill based on the solid dry weight of the nano hydrocarbon fuel pre-slurry, wherein the naphthalene dispersant comprises 2.5 per mill of potassium naphthalene sulfonate formaldehyde condensate, 1.0 per mill of 1-methylimidazole sodium tetrafluoroborate and 1.5 per mill of isooctane. The ultrasonic stirring equipment adopts a 1 kilowatt ultrasonic generator with the frequency of 40KHZ; a1 kilowatt stirrer is used for shearing and emulsifying, and the rotation speed is 8000 rpm.
Examples 2 to 7
Examples 2 to 7 differ from example 1 in the amount of each component of the naphthalene dispersant added, as specified in table 1.
TABLE 1
Example 8
Example 8 differs from example 1 in that the sonication pretreatment is carried out for 15 minutes followed by a shearing emulsification treatment for 30 minutes. The power of ultrasonic treatment is 0.5 kilowatt, and the frequency is 80KHZ; the power of the shearing emulsification treatment is 0.5 kilowatt, and the rotating speed is 15000 r/min.
Example 9
Example 9 differs from example 1 in that the sonication pretreatment is carried out for 5 minutes followed by a shearing emulsification treatment for 15 minutes. The power of ultrasonic treatment is 5 kilowatts, and the frequency is 20KHZ; the power of the shearing emulsification treatment is 5 kilowatts, and the rotating speed is 5000 r/min.
Comparative example 1
Comparative example 1 differs from example 1 in that the dispersant is only a naphthalene sulfonate polycondensate.
Comparative example 2
Comparative example 2 differs from example 1 in that the dispersant is only 1-methylimidazolium tetrafluoroborate.
Comparative example 3
Comparative example 3 differs from example 1 in that the dispersant is isooctane only.
The dispersants of examples 1 to 9 and comparative examples 1 to 3 were subjected to a performance test:
(1) According to the fifth part of the GBT18856.5-2008 coal water slurry test method: and (4) stability testing, namely testing the static stability of the nano hydrocarbon fuel after the nano hydrocarbon fuel is kept still for 10 days. Placing a certain amount of uniform nano hydrocarbon fuel sample in a container, standing for 10d under specified conditions, firstly inclining the container to enable the nano hydrocarbon fuel to freely flow out, then vertically inverting the container for 8Min, weighing the mass of the residue in the container, and representing the static stability of the nano hydrocarbon fuel by the mass fraction of the residue of the nano hydrocarbon fuel in the nano hydrocarbon fuel sample.
(2) According to the fourth part of the GBT18856.5-2008 coal water slurry test method: apparent viscosity test method, test at a shear rate of 100s -1 Apparent viscosity of the lower nano hydrocarbon fuel. The apparent viscosity was measured by using a rotary viscometer of the German Hakk VT550 type and averaging 10 sets of data recorded at a shear rate of 100 s-1.
The results of the performance tests of the dispersants of examples 1 to 9 and comparative examples 1 to 3 are shown in table 2.
TABLE 2
The experimental result shows that compared with the original slurry of the nano hydrocarbon fuel without the dispersant, the slurry added with the dispersant of the invention has good stability after standing for 10 days, and the dispersibility of the slurry is improved, which shows that the dispersant of the invention has a certain dispersing effect on the slurry. The experimental result shows that the apparent viscosity of the nano hydrocarbon fuel pre-slurry added with the dispersant is properly reduced compared with that of the non-added virgin pulp, which shows that the dispersant has a certain viscosity reducing effect on the nano hydrocarbon fuel slurry.
From the above description, it can be seen that the above-described embodiments of the present invention achieve the following technical effects: the naphthalene dispersant of the invention uses amphiphilic naphthalene sulfonate condensate (NSF), so that the coal-water relationship is improved, the coalescence among coal powder is reduced, and the dispersion fluidity of nano hydrocarbon fuel slurry is enhanced. 1-methylimidazolium tetrafluoroborate ([ Mim ]]BF 4 ) The method can etch the surface dangling bond of the nanocrystal in the using process, thereby playing a role of grinding aid and ensuring that the nano-scale ultrafine coal powder particles keep uniform and stable state in water. Isooctane is used as a hydrophobic organic solvent, and can enhance the adsorption of the naphthalene dispersant on the surface of coal, so that the naphthalene dispersant and coal powder are easy to combine. Further, it can be seen that the dispersing effect of the dispersant is more excellent when the contents of the respective components or the process parameters are within the preferable range of the present invention.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The naphthalene dispersant for preparing the nano hydrocarbon fuel is characterized by comprising a naphthalene sulfonate polycondensate, 1-methylimidazole tetrafluoroborate and isooctane.
2. The naphthalene dispersant according to claim 1, characterized in that it comprises, in parts by weight:
polycondensate naphthalene sulfonate: 15 to 32 portions of the components are mixed,
1-methylimidazolium tetrafluoroborate: 8 to 12 portions of the mixture, and the mixture,
isooctane: 13 to 17 portions.
3. The naphthalene based dispersant according to claim 1 or 2, characterized in that said naphthalene sulfonate polycondensate is a potassium salt of a naphthalene sulfonic acid formaldehyde condensate and/or a sodium salt of a naphthalene sulfonic acid formaldehyde condensate.
4. The naphthalene based dispersant according to any one of claims 1 to 3, characterized in that said 1-methylimidazole tetrafluoroborate salt is 1-methylimidazole tetrafluoroborate potassium salt and/or 1-methylimidazole tetrafluoroborate sodium salt.
5. The preparation method of the nano-hydrocarbon fuel pre-slurry is characterized by comprising the following steps:
pre-crushing the raw material coal to obtain a pre-crushed raw material;
mixing the pre-crushed raw material, water and the naphthalene dispersant of any one of claims 1 to 4 to obtain mixed slurry, and performing nano-crushing on the mixed slurry to obtain the nano-hydrocarbon fuel pre-slurry.
6. The preparation method of claim 5, wherein the naphthalene dispersant is added in an amount of 3.6 to 6.1% by dry weight based on the solid weight of the nano hydrocarbon fuel pre-slurry.
7. The method as claimed in claim 6, wherein the naphthalene dispersant comprises 1.5 to 3.2 wt% of the naphthalene sulfonate polycondensate, 0.8 to 1.2 wt% of the 1-methylimidazole tetrafluoroborate and 1.3 to 1.7 wt% of isooctane based on the dry solid weight of the nano hydrocarbon fuel pre-slurry.
8. The method according to any one of claims 5 to 7, wherein the raw coal comprises, in weight percent: 43 to 48 percent of carbon, 24 to 32 percent of alumina, 23 to 25 percent of silicon dioxide, 0.2 to 0.4 percent of calcium oxide, 1.5 to 2.5 percent of ferric oxide and the balance of impurities.
9. The production method according to any one of claims 5 to 8, characterized in that, before the nano-pulverization is performed, the production method further comprises: firstly, carrying out ultrasonic pretreatment on the mixed slurry for 5-15 minutes, and then carrying out shearing emulsification treatment for 15-30 minutes.
10. The preparation method according to claim 9, wherein the ultrasonic pretreatment equipment is an ultrasonic generator, the power is 0.5-5 kilowatts, and the frequency is 20-80 KHZ; preferably, the shearing emulsification treatment equipment is a stirrer, the power is 0.5-5 kilowatts, and the rotating speed is 5000-15000 revolutions per minute.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211167710.4A CN115584287B (en) | 2022-09-23 | 2022-09-23 | Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211167710.4A CN115584287B (en) | 2022-09-23 | 2022-09-23 | Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115584287A true CN115584287A (en) | 2023-01-10 |
| CN115584287B CN115584287B (en) | 2023-10-27 |
Family
ID=84777970
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211167710.4A Active CN115584287B (en) | 2022-09-23 | 2022-09-23 | Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115584287B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375546A (en) * | 2023-03-06 | 2023-07-04 | 神华准格尔能源有限责任公司 | Coal-based nano hydrocarbon additive for ammonium nitrate fuel oil explosive, preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4202461A1 (en) * | 1992-01-29 | 1993-08-05 | Huber Fa Michael Muenchen | Suspension polymerisation prodn. of particles or toners - using aq. phase contg. positively-charged silicon di:oxide stabiliser with modification of di:oxide covering on particles |
| CN101550369A (en) * | 2008-12-26 | 2009-10-07 | 新奥新能(北京)科技有限公司 | Water-coal-slurry additive and preparation method thereof |
| US20110233458A1 (en) * | 2010-03-19 | 2011-09-29 | EASTERN MICHIGAN UNIVERSITY Office of Research Development | Nanoparticle dispersions with ionic liquid-based stabilizers |
| KR20120026923A (en) * | 2010-09-10 | 2012-03-20 | 단국대학교 산학협력단 | A method for preparing silver nanoparticles using ionic liquid |
| CN103273077A (en) * | 2013-05-10 | 2013-09-04 | 沈阳化工大学 | Preparing method of [Bmim] BF4 dispersed nano-iron particle |
| CN108690741A (en) * | 2018-05-05 | 2018-10-23 | 孝感寰誉新材科技有限公司 | A kind of cleaning production equipment cleansing composition and preparation method thereof |
| CN109777531A (en) * | 2018-12-24 | 2019-05-21 | 广州建盛建材有限公司 | A kind of naphthalene system coal water slurry dispersing agent and its application |
| CN109810771A (en) * | 2019-01-18 | 2019-05-28 | 湘潭大学 | A kind of ionic liquid and micro-nano solid cooperative reinforcing grinding fluid and preparation method |
| CN113845949A (en) * | 2021-10-27 | 2021-12-28 | 神华准格尔能源有限责任公司 | Nano hydrocarbon fuel preparation and dosing system and method |
| WO2022040425A1 (en) * | 2020-08-19 | 2022-02-24 | Ppg Industries Ohio, Inc. | Dispersions of carbon nanotubes for use in compositions for manufacturing battery electrodes |
-
2022
- 2022-09-23 CN CN202211167710.4A patent/CN115584287B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4202461A1 (en) * | 1992-01-29 | 1993-08-05 | Huber Fa Michael Muenchen | Suspension polymerisation prodn. of particles or toners - using aq. phase contg. positively-charged silicon di:oxide stabiliser with modification of di:oxide covering on particles |
| CN101550369A (en) * | 2008-12-26 | 2009-10-07 | 新奥新能(北京)科技有限公司 | Water-coal-slurry additive and preparation method thereof |
| US20110233458A1 (en) * | 2010-03-19 | 2011-09-29 | EASTERN MICHIGAN UNIVERSITY Office of Research Development | Nanoparticle dispersions with ionic liquid-based stabilizers |
| KR20120026923A (en) * | 2010-09-10 | 2012-03-20 | 단국대학교 산학협력단 | A method for preparing silver nanoparticles using ionic liquid |
| CN103273077A (en) * | 2013-05-10 | 2013-09-04 | 沈阳化工大学 | Preparing method of [Bmim] BF4 dispersed nano-iron particle |
| CN108690741A (en) * | 2018-05-05 | 2018-10-23 | 孝感寰誉新材科技有限公司 | A kind of cleaning production equipment cleansing composition and preparation method thereof |
| CN109777531A (en) * | 2018-12-24 | 2019-05-21 | 广州建盛建材有限公司 | A kind of naphthalene system coal water slurry dispersing agent and its application |
| CN109810771A (en) * | 2019-01-18 | 2019-05-28 | 湘潭大学 | A kind of ionic liquid and micro-nano solid cooperative reinforcing grinding fluid and preparation method |
| WO2022040425A1 (en) * | 2020-08-19 | 2022-02-24 | Ppg Industries Ohio, Inc. | Dispersions of carbon nanotubes for use in compositions for manufacturing battery electrodes |
| CN113845949A (en) * | 2021-10-27 | 2021-12-28 | 神华准格尔能源有限责任公司 | Nano hydrocarbon fuel preparation and dosing system and method |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116375546A (en) * | 2023-03-06 | 2023-07-04 | 神华准格尔能源有限责任公司 | Coal-based nano hydrocarbon additive for ammonium nitrate fuel oil explosive, preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115584287B (en) | 2023-10-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115449417B (en) | Naphthalene compound dispersing agent, activated nano-primary pulp containing naphthalene compound dispersing agent and preparation method of naphthalene compound dispersing agent | |
| Hu et al. | Influence of different dispersants on rheological behaviors of coal water slurry prepared from a low quality coal | |
| CN109904430A (en) | A kind of method for mixing of graphite cathode slurry | |
| CN115584287A (en) | Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof | |
| CN1749195A (en) | Use of tri-isopropanolamine in cement grinding aid | |
| CN111394080A (en) | Thick oil viscosity reducer and using method thereof | |
| CN110323416B (en) | Aqueous negative electrode stability slurry, preparation method thereof, negative electrode plate and lithium battery | |
| WO2019076196A1 (en) | Graphene/trimanganese tetraoxide composite nano lubricating additive and synthesis method thereof | |
| CN114302860A (en) | Dispersion product | |
| CN115558533B (en) | Naphthalene dispersant for preparing nano hydrocarbon fuel and application thereof | |
| CN115572625B (en) | Compound dispersing agent, activated nano-primary pulp containing compound dispersing agent and preparation method of activated nano-primary pulp | |
| Du et al. | Synthesis of a novel amphoteric copolymer and its application as a dispersant for coal water slurry preparation | |
| CN108502876B (en) | Preparation method of graphene composite nano lanthanum oxide oily stable dispersion system | |
| CN103301763B (en) | Method for dispersing nano calcium carbonate powder material in aqueous solution | |
| US20230339760A1 (en) | Method for preparing graphene by mechanical exfoliation and application thereof | |
| CN113171879B (en) | Flotation collector for low-grade molybdenite and preparation method thereof | |
| CN111933903A (en) | Lithium iron phosphate battery positive electrode slurry and preparation method thereof | |
| CN105348572A (en) | Application method for illite smectite clay in rubber | |
| CN113861526B (en) | High-wear-resistance low-heat-generation carbon black masterbatch and preparation method thereof | |
| CN105384969A (en) | High-dispersion zinc oxide and preparation method thereof | |
| CN109251582B (en) | High-performance nano composite heavy calcium carbonate and preparation method thereof | |
| CN112920625A (en) | Modified carbon black and preparation method thereof | |
| CN113801415A (en) | Polytetrafluoroethylene composite micro powder | |
| CN114316655B (en) | Preparation process and application of graphene oxide/nano barium sulfate composite material | |
| CN104610766A (en) | Efficient composite emulsion modifier |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |