CN116515540A - Novel naphthol distillation residue modified coal slurry modifier and preparation method thereof - Google Patents
Novel naphthol distillation residue modified coal slurry modifier and preparation method thereof Download PDFInfo
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- CN116515540A CN116515540A CN202210418002.7A CN202210418002A CN116515540A CN 116515540 A CN116515540 A CN 116515540A CN 202210418002 A CN202210418002 A CN 202210418002A CN 116515540 A CN116515540 A CN 116515540A
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- 239000003250 coal slurry Substances 0.000 title claims abstract description 56
- KJCVRFUGPWSIIH-UHFFFAOYSA-N 1-naphthol Chemical compound C1=CC=C2C(O)=CC=CC2=C1 KJCVRFUGPWSIIH-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000003607 modifier Substances 0.000 title claims abstract description 50
- 238000004821 distillation Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 117
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 63
- 239000003945 anionic surfactant Substances 0.000 claims abstract description 60
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 54
- 150000001875 compounds Chemical class 0.000 claims abstract description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 37
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 36
- 238000003756 stirring Methods 0.000 claims abstract description 29
- 239000000178 monomer Substances 0.000 claims abstract description 22
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 230000004048 modification Effects 0.000 claims abstract description 18
- 238000012986 modification Methods 0.000 claims abstract description 18
- 238000002844 melting Methods 0.000 claims abstract description 10
- 230000008018 melting Effects 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 38
- XUJLWPFSUCHPQL-UHFFFAOYSA-N 11-methyldodecan-1-ol Chemical compound CC(C)CCCCCCCCCCO XUJLWPFSUCHPQL-UHFFFAOYSA-N 0.000 claims description 35
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 30
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 30
- 239000007864 aqueous solution Substances 0.000 claims description 27
- KVCGISUBCHHTDD-UHFFFAOYSA-M sodium;4-methylbenzenesulfonate Chemical compound [Na+].CC1=CC=C(S([O-])(=O)=O)C=C1 KVCGISUBCHHTDD-UHFFFAOYSA-M 0.000 claims description 22
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 21
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 21
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 21
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 19
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 claims description 19
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- -1 N-methyl oleamide taurine salt Chemical class 0.000 claims description 6
- 150000007942 carboxylates Chemical class 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 2
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 2
- MXXDSLLVYZMTFA-UHFFFAOYSA-N octadecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 MXXDSLLVYZMTFA-UHFFFAOYSA-N 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- NPAWNPCNZAPTKA-UHFFFAOYSA-M sodium;propane-1-sulfonate Chemical compound [Na+].CCCS([O-])(=O)=O NPAWNPCNZAPTKA-UHFFFAOYSA-M 0.000 claims description 2
- 150000003900 succinic acid esters Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000003245 coal Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 125000001273 sulfonato group Chemical group [O-]S(*)(=O)=O 0.000 description 6
- 238000009736 wetting Methods 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 4
- 125000001165 hydrophobic group Chemical group 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- PVGBHEUCHKGFQP-UHFFFAOYSA-N sodium;n-[5-amino-2-(4-aminophenyl)sulfonylphenyl]sulfonylacetamide Chemical compound [Na+].CC(=O)NS(=O)(=O)C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 PVGBHEUCHKGFQP-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000005034 decoration Methods 0.000 description 2
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XFRVVPUIAFSTFO-UHFFFAOYSA-N 1-Tridecanol Chemical compound CCCCCCCCCCCCCO XFRVVPUIAFSTFO-UHFFFAOYSA-N 0.000 description 1
- DUIOKRXOKLLURE-UHFFFAOYSA-N 2-octylphenol Chemical group CCCCCCCCC1=CC=CC=C1O DUIOKRXOKLLURE-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920001732 Lignosulfonate Polymers 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- SRSXLGNVWSONIS-UHFFFAOYSA-M benzenesulfonate Chemical compound [O-]S(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-M 0.000 description 1
- 229940077388 benzenesulfonate Drugs 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 241000411851 herbal medicine Species 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-M naphthalene-1-sulfonate Chemical compound C1=CC=C2C(S(=O)(=O)[O-])=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-M 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- KJIOQYGWTQBHNH-UHFFFAOYSA-N undecanol Chemical compound CCCCCCCCCCCO KJIOQYGWTQBHNH-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 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
- C10L1/32—Liquid carbonaceous fuels consisting of coal-oil suspensions or aqueous emulsions or oil emulsions
- C10L1/326—Coal-water suspensions
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
Abstract
The invention relates to the technical field of coal slurry, IPC (industrial personal computer) classification number is C08F, in particular to a novel naphthol distillation residue modified coal slurry modifier and a preparation method thereof. The preparation raw materials of the novel naphthol distillation residue modified coal slurry modifier comprise the following components in parts by weight: 1-10 parts of distillation-rectification residues, 0.2-1 part of silane coupling agent, 80-120 parts of water, 20-45 parts of anionic surfactant, 10-20 parts of phenol, 3-10 parts of alkaline compound, 10-35 parts of formaldehyde and 1-2 parts of auxiliary agent. The preparation method comprises the following steps: under the heating and melting state, adding a silane coupling agent to carry out blending modification on distillation-rectification residues, adding an anionic surfactant to stir and mix, dropwise adding formaldehyde to prepare small monomers, adding water, phenol, liquid sodium hydroxide, dropwise adding residual formaldehyde and adding small monomers and auxiliary agents to a flask to mix, and preparing the novel naphthol distillation residue modified coal slurry modifier.
Description
Technical Field
The invention relates to the technical field of coal slurry, IPC (industrial personal computer) classification number is C08F, in particular to a novel naphthol distillation residue modified coal slurry modifier and a preparation method thereof.
Background
The coal water slurry is a coal water solid-liquid dispersion system prepared by using a physical method to prepare coal, water and a small amount of chemical additives, has good rheological property, stability and thixotropy, and compared with petroleum, the coal water slurry has the advantages of simple preparation process and lower cost, and is widely used as an oil-substituting fuel.
However, in the process of pulping the coal water slurry, because the coal particles are extremely fine and have large specific surface area, and the coal particles are extremely easy to aggregate in the slurry to cause precipitation, the coal water slurry with good stability and fluidity is difficult to prepare, the interface property of the coal water can be changed by adding the dispersing agent, the surface hydrophilicity of the coal particles is improved, the coal particles are uniformly dispersed in water, and the prepared coal water slurry modifier has good dispersion property.
Patent CN109913281A discloses a preparation method of sodium lignin sulfonate dispersant and coal slurry water-coal slurry, which comprises the steps of carrying out a decoration reaction on a decoration agent and water, drying and concentrating to obtain the sodium lignin sulfonate dispersant with waste utilization and good stability, but poor dispersion performance and stability.
Patent CN101543744 discloses a multicomponent composite coal water slurry dispersing agent and application thereof, which is prepared by uniformly mixing naphthalene sulfonate, polyamino carboxylate, polymethacrylate, lignin sulfonate, carbonate and other components according to different weight proportions, and has the excellent performances of material saving, proper viscosity and the like, but poor fluidity.
Disclosure of Invention
In order to solve the problems, the first aspect of the invention provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from, by weight, 1-10 parts of distillation-rectification residues, 0.2-1 part of silane coupling agents, 80-120 parts of water, 20-45 parts of anionic surfactants, 10-20 parts of phenols, 3-10 parts of alkaline compounds, 10-35 parts of formaldehyde and 1-2 parts of auxiliaries.
As a preferable technical scheme, the distillation-rectification residue is subjected to blending modification by a silane coupling agent;
as a preferable technical scheme, the silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane;
as a more preferable technical scheme, the silane coupling agent is vinyl triethoxysilane;
as a preferable technical scheme, the anionic surfactant is one of carboxylate type, sulfonate type, sulfate type and phosphate type anionic surfactants;
as a preferable technical scheme, the sulfonate type anionic surfactant is one of sodium p-toluenesulfonate, sodium 1-propane sulfonate, sodium dodecyl benzene sulfonate, sodium octadecyl benzene sulfonate, N-methyl oleamide taurine salt and succinic acid ester sulfonate or the combination thereof;
as a more preferable technical scheme, the sulfonate type anionic surfactant is a compound of sodium p-methylbenzenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1-1.6:2.3-3.4;
as a preferable technical scheme, the alkaline compound is an aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 2.4-4.13wt%;
as a preferred technical scheme, the formaldehyde is an aqueous solution of formaldehyde, and the concentration of the formaldehyde is 8-14.5wt%;
as a preferable technical scheme, the auxiliary agent is one of or a combination of isomeric decaol polyoxyethylene ether, isomeric undecanol polyoxyethylene ether, isomeric tridecanol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether;
as a more preferable technical scheme, the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 0.5-1.2:1.4-2.7.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 1-10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 0.2-1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add part of formaldehyde into the mixture, controlling the dropwise adding time to be about 40min-1h, and continuously stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding water into another reaction device, heating to 40-50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then starting to slowly dropwise add the rest mass parts of formaldehyde, controlling the dropwise adding speed, finishing dropwise adding for 1.5-2.5h, controlling the temperature in the dropwise adding process to be not more than 80 ℃, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dropwise adding, starting to heat, heating to 93-96 ℃, preserving heat for 3-6h, adding the rest water, stirring and uniformly mixing.
Advantageous effects
(1) The novel naphthol distillation residue modified coal slurry modifier is prepared by mixing distillation-rectification residues, a silane coupling agent, an anionic surfactant and formaldehyde, and then adding water, phenol, liquid sodium hydroxide, residual formaldehyde and an auxiliary agent, and has the advantages of good dispersibility, high stability, low viscosity, good fluidity, good practicability, low energy consumption and the like.
(2) The stability of the prepared naphthol distillation residue modified coal slurry modifier can be improved by adding the silane coupling agent, and particularly when the silane coupling agent is vinyl triethoxysilane, the silane coupling agent can better cooperate with an anionic surfactant and an auxiliary agent, so that the stability of the prepared novel naphthol distillation residue modified coal slurry modifier is improved. The reason is that the vinyl triethoxysilane contains three hydrolyzable ethoxy groups and has vinyl groups with stronger affinity or reaction force with polymer molecules, active groups in the vinyl triethoxysilane can react with hydroxyl groups on the surfaces of particles contained in distillation-rectification residues to form chemical bonds, and the vinyl triethoxysilane also contains vinyl groups which can react with the polymers to form chemical bonds and can cooperate with anionic surfactants, auxiliary agents and the like to enable the distillation-rectification residues to be coupled with the anionic surfactants and the auxiliary agents in a chemical bond mode through a silane coupling agent, so that the substance precipitation in naphthol distillation residues is reduced.
(3) The dispersibility of the prepared naphthol distillation residue modified coal slurry modifier can be improved by adding the anionic surfactant, and particularly the anionic surfactant is the compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the anionic surfactant is 1-1.6:2.3-3.4, the surface tension of the modified coal slurry modifier in the using process can be reduced, thereby improving the dispersing effect of the modified coal slurry modifier by naphthol distillation residues. The reason is probably that the sodium dodecyl benzene sulfonate is of a long-chain structure, the nonpolar lipophilic hydrophobic group contained at one end can act with the hydrophobic group of particles contained in the naphthol distillation-rectification residue, the polar hydrophilic group contained at the other end in the sodium dodecyl benzene sulfonate can adsorb the particles contained in the naphthol distillation-rectification residue and act with polar water molecules, the contact angle between the naphthol distillation-rectification residue and water is reduced, the wettability of the sodium dodecyl benzene sulfonate is increased, the sodium methyl benzene sulfonate is of a short-chain structure, and the sodium dodecyl benzene sulfonate can better adsorb the particles contained in the naphthol distillation-rectification residue in a synergistic effect, so that the dispersibility of the prepared naphthol distillation residue modified coal slurry modifier is further improved. And the long-chain structure of sodium dodecyl benzene sulfonate and the short-chain structure of sodium p-methyl benzene sulfonate are fully stretched in the naphthol distillation residue modified coal slurry modifier to form a better space position effect, so that the naphthol distillation residue modified coal slurry modifier forms a stable and uniformly dispersed solution.
(4) According to the invention, through adding the auxiliary agent, which is synergistic with the anionic surfactant, the preparation of the naphthol distillation residue modified coal slurry modifier with a certain branching degree is facilitated, the surface tension of the prepared naphthol distillation residue modified coal slurry modifier is further reduced, the dispersion effect of the naphthol distillation residue modified coal slurry modifier is improved, and the auxiliary agent is especially the combination of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 0.5-1.2:1.4-2.7, and the prepared naphthol distillation residue modified coal slurry modifier has excellent dispersibility. The reason is probably that the isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether are long-chain polymers with branched structures, and after the isotridecyl alcohol polyoxyethylene ether and the isotridecyl alcohol polyoxyethylene polyoxypropylene ether are compounded, the lowest concentration of a surfactant forming a micelle is more easily achieved, the surfactant can better act with hydrophobic groups of particles contained in naphthol distillation-rectification residues, in addition, the excellent dispersion effect of the compounded benzenesulfonate, the distillation-rectification residues subjected to blending modification by a silane coupling agent and the functional auxiliary agent can be achieved, tiny particles contained in the naphthol distillation-rectification residues can be effectively adsorbed, electrostatic repulsion force is generated to enable the tiny particles to be dispersed, sedimentation and coarsening are avoided, the viscosity of high-concentration coal water slurry is effectively reduced, the fluidity is improved, the service performance is improved, and the energy consumption is reduced.
(5) The invention is characterized in that distillation-rectification residues are heated and melted and are fed by a silane coupling agent
Mixing and modifying, adding an anionic surfactant, stirring and mixing, dropwise adding formaldehyde to prepare a small monomer, adding water, phenol, liquid sodium hydroxide, dropwise adding residual formaldehyde, adding the small monomer and an auxiliary agent to mix, and preparing the novel naphthol distillation residue modified coal slurry modifier.
Detailed Description
Example 1
The embodiment 1 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from the following raw materials in parts by weight.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1:2.3, sodium p-toluenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 2.4 weight percent;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 8wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 0.5:1.4, isotridecyl alcohol polyoxyethylene ether CAS number 69011-36-5, available from Nantong Chen wetting CHEMICAL Co., ltd, isotridecyl alcohol polyoxyethylene polyoxypropylene ether CAS number 78330-23-1, available from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 1 part of distillation-rectification residues, heating to 125 ℃ for melting, adding 0.2 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 4 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 40min, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 60 parts of water into another reaction device, heating to 40 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then starting to slowly dropwise add 6 parts of formaldehyde, controlling the dropwise adding speed, controlling the dropwise adding temperature to be not more than 80 ℃ after 1.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after the dropwise adding is finished, heating to 93 ℃, preserving heat for 3 hours, adding 20 parts of water, and stirring and mixing uniformly.
Example 2
The embodiment 2 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from the following raw materials in parts by weight.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1.6:3.4, sodium p-toluenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 4.13wt%;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 14.5wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 1.2:2.7, the CAS number of the isotridecyl alcohol polyoxyethylene ether is 69011-36-5, purchased from Nantong Chen wetting chemical Co., ltd, the CAS number of the isotridecyl alcohol polyoxyethylene polyoxypropylene ether is 78330-23-1,
purchased from HENAN BON INDUSTRIAL (CHEMICAL) co., LTD.
The weight ratio of the Chinese herbal medicine to the wax matrix is 115:20, a step of;
the second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 14 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 1h, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 90 parts of water into another reaction device, heating to 50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then slowly dripping 21 parts of formaldehyde, controlling dripping speed, controlling the temperature not to exceed 80 ℃ in the dripping process after 2.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dripping, heating to 96 ℃, preserving heat for 6 hours, adding 30 parts of water, and stirring and mixing uniformly.
Example 3
The embodiment 3 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from the following raw materials in parts by weight.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1.3:2.7, sodium p-toluenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 3.1 weight percent;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 11wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 0.8:2.0, isotridecyl alcohol polyoxyethylene ether CAS number 69011-36-5, available from Nantong Chen wetting CHEMICAL Co., ltd, isotridecyl alcohol polyoxyethylene polyoxypropylene ether CAS number 78330-23-1, available from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 6 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 0.5 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 8 parts of formaldehyde into the mixture, controlling the dropwise adding time to be about 50min, and continuing stirring for 1h after the dropwise adding is finished, and taking the mixture as a small monomer for standby;
(2) Adding 75 parts of water into another reaction device, heating to 45 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then starting to slowly dropwise add 12 parts of formaldehyde, controlling the dropwise adding speed, finishing the dropwise adding for 2.0h, controlling the temperature in the dropwise adding process not to exceed 80 ℃, adding the small monomer and the functional auxiliary agent obtained in the step 1 after the dropwise adding is finished, starting to heat, heating to 94 ℃, preserving heat for 4.5h, adding 25 parts of water, and stirring and uniformly mixing.
Comparative example 1
Comparative example 1 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from, by weight, 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formaldehyde and 2 parts of auxiliary agent.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is secondary alkyl sodium sulfonate, with CAS number 68188-18-1, purchased from Shanghai Ding Feng chemical technology Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 4.13wt%;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 14.5wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 1.2:2.7, isotridecyl alcohol polyoxyethylene ether CAS number 69011-36-5, available from Nantong Chen wetting CHEMICAL Co., ltd., isotridecyl alcohol polyoxyethylene polyoxypropylene ether CAS number 78330-23-1, available from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 14 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 1h, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 90 parts of water into another reaction device, heating to 50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then slowly dripping 21 parts of formaldehyde, controlling dripping speed, controlling the temperature not to exceed 80 ℃ in the dripping process after 2.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dripping, heating to 96 ℃, preserving heat for 6 hours, adding 30 parts of water, and stirring and mixing uniformly.
Comparative example 2
Comparative example 2 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from, by weight, 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formaldehyde and 2 parts of auxiliary agent.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 0.4:1.8, sodium p-methylbenzenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 4.13wt%;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 14.5wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 1.2:2.7, isotridecyl alcohol polyoxyethylene ether CAS number 69011-36-5, available from Nantong Chen wetting CHEMICAL Co., ltd., isotridecyl alcohol polyoxyethylene polyoxypropylene ether CAS number 78330-23-1, available from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 14 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 1h, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 90 parts of water into another reaction device, heating to 50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then slowly dripping 21 parts of formaldehyde, controlling dripping speed, controlling the temperature not to exceed 80 ℃ in the dripping process after 2.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dripping, heating to 96 ℃, preserving heat for 6 hours, adding 30 parts of water, and stirring and mixing uniformly.
Comparative example 3
Comparative example 3 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from, by weight, 10 parts of distillation-rectification residue, 1 part of silane coupling agent, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formaldehyde and 2 parts of auxiliary agent.
The distillation-rectification residues are subjected to blending modification by a silane coupling agent;
the silane coupling agent is vinyl triethoxysilane, the CAS number is 78-08-0, and the silane coupling agent is purchased from Shanghai Michelin Biochemical technology Co., ltd;
the anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1.6:3.4, sodium p-toluenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 4.13wt%;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 14.5wt%;
the auxiliary agent is octyl phenol polyoxyethylene ether, the CAS number is 9036-19-5, and the auxiliary agent is purchased from sigma Aldrich (Shanghai) Co.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 14 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 1h, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 90 parts of water into another reaction device, heating to 50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then slowly dripping 21 parts of formaldehyde, controlling dripping speed, controlling the temperature not to exceed 80 ℃ in the dripping process after 2.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dripping, heating to 96 ℃, preserving heat for 6 hours, adding 30 parts of water, and stirring and mixing uniformly.
Comparative example 4
Comparative example 4 provides a novel naphthol distillation residue modified coal slurry modifier, which is prepared from, by weight, 10 parts of distillation-rectification residue, 120 parts of water, 45 parts of anionic surfactant, 20 parts of phenol, 10 parts of alkaline compound, 35 parts of formaldehyde and 2 parts of auxiliary agent.
The anionic surfactant is a sulfonate type anionic surfactant;
the sulfonate type anionic surfactant is a compound of sodium p-toluenesulfonate and sodium dodecyl benzene sulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecyl benzene sulfonate is 1.6:3.4, sodium p-toluenesulfonate CAS number 657-84-1, available from Beijing Baoling technologies Co., ltd., sodium dodecylbenzenesulfonate CAS number 25155-30-0, available from Shanghai Allatin Biochemical technologies Co., ltd;
the alkaline compound is aqueous solution of sodium hydroxide, and the concentration of the alkaline compound is 4.13wt%;
the formaldehyde is an aqueous solution of formaldehyde with a concentration of 14.5wt%;
the auxiliary agent is the compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 1.2:2.7, isotridecyl alcohol polyoxyethylene ether CAS number 69011-36-5, available from Nantong Chen wetting CHEMICAL Co., ltd., isotridecyl alcohol polyoxyethylene polyoxypropylene ether CAS number 78330-23-1, available from HENAN BON INDUSTRIAL (CHEMICAL) CO., LTD.
The second aspect of the invention provides a preparation method of a novel naphthol distillation residue modified coal slurry modifier, which comprises the following steps:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add 14 parts of formaldehyde into the mixture, controlling the dropwise adding time to be 1h, and continuing stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding 90 parts of water into another reaction device, heating to 50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then slowly dripping 21 parts of formaldehyde, controlling dripping speed, controlling the temperature not to exceed 80 ℃ in the dripping process after 2.5 hours, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dripping, heating to 96 ℃, preserving heat for 6 hours, adding 30 parts of water, and stirring and mixing uniformly.
Performance testing
The novel naphthol distillation residue modified coal slurry modifier prepared in the examples 1-3 and the comparative examples 1-4 is respectively put into Qinghai salt lake coal slurry, the addition amount of the novel naphthol distillation residue modified coal slurry modifier is 0.3% of that of the Qinghai salt lake coal slurry, and various indexes such as viscosity, fluidity, dispersibility and stability of the Qinghai salt lake coal slurry are measured, and the test results are shown in Table 1.
Table one: and when the doping amount of the novel naphthol distillation residue modified coal slurry modifier is 0.3%, testing data of viscosity, fluidity, dispersibility and stability of the Qinghai salt lake coal slurry are obtained.
Claims (10)
1. The novel naphthol distillation residue modified coal slurry modifier is characterized by comprising the following preparation raw materials in parts by weight: 1-10 parts of distillation-rectification residues, 0.2-1 part of silane coupling agent, 80-120 parts of water, 20-45 parts of anionic surfactant, 10-20 parts of phenol, 3-10 parts of alkaline compound, 10-35 parts of formaldehyde and 1-2 parts of auxiliary agent.
2. The novel naphthol distillation residue modified coal slurry modifier according to claim 1, wherein the silane coupling agent is one of vinyltriethoxysilane, vinyltrimethoxysilane, and vinyltris (beta-methoxyethoxy) silane.
3. The novel naphthol distillation residue modified coal slurry modifier according to claim 1, wherein the anionic surfactant is one of carboxylate type, sulfonate type, sulfate type and phosphate type surfactants.
4. The novel naphthol distillation residue modified coal slurry modifier according to claim 3, wherein the sulfonate type anionic surfactant is one of sodium p-methylbenzenesulfonate, sodium 1-propane sulfonate, sodium dodecyl benzene sulfonate, sodium octadecyl benzene sulfonate, N-methyl oleamide taurine salt and succinic acid ester sulfonate or a compound thereof.
5. The novel naphthol distillation residue modified coal slurry modifier according to claim 4, wherein the sulfonate type anionic surfactant is a compound of sodium p-methylbenzenesulfonate and sodium dodecylbenzenesulfonate, and the mass ratio of the sulfonate type anionic surfactant to the sodium dodecylbenzenesulfonate is 1-1.6:2.3-3.4.
6. The novel naphthol distillation residue modified coal slurry modifier according to claim 1, wherein the alkaline compound is an aqueous solution of sodium hydroxide having a concentration of 2.4 to 4.13wt%.
7. The novel naphthol distillation residue modified aqueous slurry modifier according to claim 1, wherein the formaldehyde is an aqueous solution of formaldehyde at a concentration of 8 to 14.5wt%.
8. The novel naphthol distillation residue modified coal slurry modifier according to claim 1, wherein the auxiliary agent is one of or a combination of isomeric polyoxyethylene lauryl ether, isomeric polyoxyethylene undecyl ether, isomeric polyoxyethylene tridecyl ether and isotridecyl polyoxyethylene polyoxypropylene ether.
9. The novel naphthol distillation residue modified coal slurry modifier is characterized in that the auxiliary agent is a compound of isotridecyl alcohol polyoxyethylene ether and isotridecyl alcohol polyoxyethylene polyoxypropylene ether, and the mass ratio is 0.5-1.2:1.4-2.7.
10. A process for preparing a novel naphthol distillation residue modified coal slurry modifier according to claim 6, comprising the steps of:
(1) The distillation-rectification residues are blended by a silane coupling agent, and the specific steps are as follows: weighing 1-10 parts of distillation-rectification residues, heating to 125 ℃ for melting, adding 0.2-1 part of silane coupling agent for blending modification, adding anionic surfactant for stirring and mixing, slowly starting to dropwise add part of formaldehyde into the mixture, controlling the dropwise adding time to be about 40min-1h, and continuously stirring for 1h after the dropwise adding is finished to serve as a small monomer for standby;
(2) Adding water into another reaction device, heating to 40-50 ℃, adding phenol according to a proportion, continuing heating, adding aqueous solution of sodium hydroxide according to a proportion at 60 ℃, then starting to slowly dropwise add the rest mass parts of formaldehyde, controlling the dropwise adding speed, finishing dropwise adding for 1.5-2.5h, controlling the temperature in the dropwise adding process to be not more than 80 ℃, adding the small monomer and the functional auxiliary agent obtained in the step 1 after dropwise adding, starting to heat, heating to 93-96 ℃, preserving heat for 3-6h, adding the rest water, stirring and uniformly mixing to obtain the aqueous formaldehyde-free formaldehyde resin.
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