CN113122349A - Coal and heavy oil curing treatment agent and preparation method and application thereof - Google Patents
Coal and heavy oil curing treatment agent and preparation method and application thereof Download PDFInfo
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- CN113122349A CN113122349A CN201911417678.9A CN201911417678A CN113122349A CN 113122349 A CN113122349 A CN 113122349A CN 201911417678 A CN201911417678 A CN 201911417678A CN 113122349 A CN113122349 A CN 113122349A
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 71
- 239000010742 number 1 fuel oil Substances 0.000 title claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 61
- 229920005989 resin Polymers 0.000 claims abstract description 48
- 239000011347 resin Substances 0.000 claims abstract description 48
- 239000007822 coupling agent Substances 0.000 claims abstract description 32
- 239000003245 coal Substances 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000003921 oil Substances 0.000 claims description 51
- 239000001993 wax Substances 0.000 claims description 47
- 229920001568 phenolic resin Polymers 0.000 claims description 30
- 239000005011 phenolic resin Substances 0.000 claims description 30
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 26
- 239000003350 kerosene Substances 0.000 claims description 25
- 239000003208 petroleum Substances 0.000 claims description 22
- 229920000180 alkyd Polymers 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- -1 tert-butyl phenolic resin Chemical compound 0.000 claims description 17
- 239000003822 epoxy resin Substances 0.000 claims description 16
- 229920000647 polyepoxide Polymers 0.000 claims description 16
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 239000004209 oxidized polyethylene wax Substances 0.000 claims description 12
- 235000013873 oxidized polyethylene wax Nutrition 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 10
- LLNBPBDKSXFDFH-UHFFFAOYSA-N O-[aminooxy(dihydroxy)silyl]hydroxylamine Chemical compound NO[Si](ON)(O)O LLNBPBDKSXFDFH-UHFFFAOYSA-N 0.000 claims description 9
- OAMXSIGLYGOOCC-UHFFFAOYSA-N O-trihydroxysilylhydroxylamine Chemical compound NO[Si](O)(O)O OAMXSIGLYGOOCC-UHFFFAOYSA-N 0.000 claims description 8
- 125000001931 aliphatic group Chemical group 0.000 claims description 8
- 229920006271 aliphatic hydrocarbon resin Polymers 0.000 claims description 8
- 229920006272 aromatic hydrocarbon resin Polymers 0.000 claims description 8
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 8
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 8
- NKSJNEHGWDZZQF-UHFFFAOYSA-N ethenyl(trimethoxy)silane Chemical compound CO[Si](OC)(OC)C=C NKSJNEHGWDZZQF-UHFFFAOYSA-N 0.000 claims description 8
- 239000004200 microcrystalline wax Substances 0.000 claims description 8
- 235000019808 microcrystalline wax Nutrition 0.000 claims description 8
- 239000012184 mineral wax Substances 0.000 claims description 8
- 235000019271 petrolatum Nutrition 0.000 claims description 8
- 239000012169 petroleum derived wax Substances 0.000 claims description 8
- 235000019381 petroleum wax Nutrition 0.000 claims description 8
- 229920001169 thermoplastic Polymers 0.000 claims description 8
- 239000004416 thermosoftening plastic Substances 0.000 claims description 8
- 150000003505 terpenes Chemical class 0.000 claims description 6
- 235000007586 terpenes Nutrition 0.000 claims description 6
- DSEKYWAQQVUQTP-XEWMWGOFSA-N (2r,4r,4as,6as,6as,6br,8ar,12ar,14as,14bs)-2-hydroxy-4,4a,6a,6b,8a,11,11,14a-octamethyl-2,4,5,6,6a,7,8,9,10,12,12a,13,14,14b-tetradecahydro-1h-picen-3-one Chemical compound C([C@H]1[C@]2(C)CC[C@@]34C)C(C)(C)CC[C@]1(C)CC[C@]2(C)[C@H]4CC[C@@]1(C)[C@H]3C[C@@H](O)C(=O)[C@@H]1C DSEKYWAQQVUQTP-XEWMWGOFSA-N 0.000 claims description 5
- 239000000047 product Substances 0.000 claims description 5
- HECLRDQVFMWTQS-RGOKHQFPSA-N 1755-01-7 Chemical compound C1[C@H]2[C@@H]3CC=C[C@@H]3[C@@H]1C=C2 HECLRDQVFMWTQS-RGOKHQFPSA-N 0.000 claims description 4
- 239000004698 Polyethylene Substances 0.000 claims description 4
- 239000004743 Polypropylene Substances 0.000 claims description 4
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 4
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000005038 ethylene vinyl acetate Substances 0.000 claims description 4
- 239000012170 montan wax Substances 0.000 claims description 4
- 239000012188 paraffin wax Substances 0.000 claims description 4
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 claims description 4
- 229920000573 polyethylene Polymers 0.000 claims description 4
- 229920001155 polypropylene Polymers 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 229920001187 thermosetting polymer Polymers 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 3
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003830 anthracite Substances 0.000 claims description 2
- 239000002802 bituminous coal Substances 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000003077 lignite Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 25
- 238000010438 heat treatment Methods 0.000 abstract description 18
- 239000007790 solid phase Substances 0.000 abstract description 11
- 230000000704 physical effect Effects 0.000 abstract 1
- 230000009467 reduction Effects 0.000 description 18
- 238000003756 stirring Methods 0.000 description 17
- 238000005516 engineering process Methods 0.000 description 14
- 238000005469 granulation Methods 0.000 description 13
- 230000003179 granulation Effects 0.000 description 13
- 239000010779 crude oil Substances 0.000 description 11
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 6
- 238000004945 emulsification Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000010426 asphalt Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012458 free base Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 231100000989 no adverse effect Toxicity 0.000 description 1
- 239000003027 oil sand Substances 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000003039 volatile agent Substances 0.000 description 1
- 239000002351 wastewater 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
- C10L10/00—Use of additives to fuels or fires for particular purposes
-
- 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
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/14—Function and purpose of a components of a fuel or the composition as a whole for improving storage or transport of the fuel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a coal and heavy oil curing agent and a preparation method and application thereof, wherein the curing agent comprises the following components in parts by weight: 1-20 parts of resin; 1-25 parts of wax substances; 0.5-10 parts of a coupling agent. The present invention also provides a coal and heavy oil modified composition comprising: coal powder, heavy oil and the curing agent. The coal and heavy oil modified composition obtained by the method can be prepared into solid-phase particles after treatment, is convenient to transport, and can recover the original physical properties after heating.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a heavy oil curing technology based on a kerosene co-refining route so as to facilitate long-distance transportation.
Background
In recent years, the heavy and inferior crude oil imported by China is increasingly aggravated, mainly because the price difference of light and heavy crude oil in the global crude oil market is large; in addition, the exploration reserves of the thick oil in the world are about 8150 hundred million tons at present, and account for 70 percent of the residual reserves of the petroleum in the world; mainly distributed in venezuela, canada, russia, usa and china etc., and mainly heavy oil production places such as the west canadian basin, Orinoco heavy oil band and maraca basin, east siberia basin etc. Although the heavy thick oil is low in price, the heavy thick oil has poor normal temperature fluidity and is difficult to pipeline and ship. Taking thick oil of Orimusion as an example, the currently developed technology is emulsified oil, which contains 70% of thick oil of Orimusion and 30% of water and is transported by oil-in-water emulsified liquid, but the emulsified oil has the cost of additionally transporting a large amount of water, and is mainly used as fuel oil, if the subsequent processing needs demulsification and separation, the difficulty and energy consumption are high, and a large amount of waste water is generated, so that the environment is polluted. How to transport heavy oil to domestic processing at low cost is a focus of increasing the benefit of refineries.
The existing crude oil viscosity reduction transportation mainly comprises the process methods of heating viscosity reduction, mixed transportation viscosity reduction, emulsification viscosity reduction, modification viscosity reduction and the like. The heating viscosity reduction is a mode of heating and then conveying crude oil; the viscosity reduction of mixed transportation is to add a diluent into the thick oil so as to reduce the viscosity of the thick oil; the emulsification viscosity reduction is to convert water-in-oil (W/O) crude oil emulsion into oil-in-water (O/W) crude oil emulsion by adding an emulsification viscosity reducer, thereby greatly reducing the viscosity of the crude oil; the upgrading and viscosity reduction mainly comprises the steps of processing the thick oil, and changing heavy hydrocarbon (such as asphalt) into medium or light hydrocarbon, thereby realizing the purpose of viscosity reduction. CN201610324332A discloses a thick oil viscosity reducing composition, a thick oil pour point reducing viscosity reducer and a preparation method thereof, CN201510316957A discloses a crude oil viscosity reducer and a preparation method thereof, and CN20111096721A discloses a thick oil emulsification viscosity reducing method.
At present, the external dependence of crude oil in China is close to 70%, and the problem of energy safety is increasingly serious; coal resources in China are much richer than petroleum resources, the yield of coal in China is expected to exceed 20 hundred million tons in 2020, and the kerosene co-refining technology has received more and more attention in recent years as a means for effectively solving the problems of reasonable utilization of coal and heavy oil processing.
Disclosure of Invention
At present, heavy oil needs to be transported after viscosity reduction, and a plurality of problems exist in the viscosity reduction process, for example, an intermediate heating station needs to be additionally arranged in a heating viscosity reduction transportation mode, the heat energy loss is large, and the cost is increased; the mixed transportation viscosity reduction is only suitable for specific occasions, and light diluent oil is needed; the emulsification and viscosity reduction technology has a plurality of problems in the aspects of emulsion rheology, pipeline design, emulsion dehydration and the like; the upgrading and viscosity reduction technology requires new oil refining devices near oil fields, such as thermal cracking, hydrocracking, coking and the like, and the investment is larger. These problems greatly limit the transport and subsequent use of the feedstock. The applicant has found through research that the problems of the prior art can be solved if a heavy oil product is converted into a solid phase material by adopting a proper means and the solid phase material is transported to a destination in batch like dry bulk goods by modern transportation facilities such as trains, ships and the like, and then the solid phase material can be reduced back to the original state of the oil product by simple treatment without influencing the properties of the solid phase material.
Aiming at the defects in the prior art, the invention aims to provide a coal and heavy oil curing treatment agent, and a preparation method and application thereof. The invention breaks through the bottleneck that viscosity reduction is needed in the transportation of the existing heavy oil pipeline, greatly reduces the transportation cost, enlarges the accessible range of the overseas heavy oil, enables the market of China to use the heavy oil with relatively low price abroad, and provides a heavy oil curing technology based on a kerosene refining route.
The invention provides a coal and heavy oil curing treatment agent, which comprises the following components in parts by weight:
1 to 20 parts of resin
1-25 parts of wax substances
0.5-10 parts of a coupling agent.
In the curing agent, the resin can be one or more of petroleum resin, phenolic resin, alkyd resin and epoxy resin, and the softening point of the selected resin is not lower than 100 ℃. Wherein the petroleum resin can be one or more of C9 petroleum resin, C5/C9 petroleum resin and dicyclopentadiene resin, and the C5/C9 petroleum resin with the softening point of 120-130 ℃ is preferable; the phenolic resin can be one or more of thermoplastic phenolic resin and thermosetting phenolic resin, and is preferably thermoplastic phenolic resin; the alkyd resin can be one or more of short, medium, long and extremely long alkyd resins with four oil degrees, preferably medium oil alkyd resin; the epoxy resin can be one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and aliphatic glycidyl ether epoxy resin, and is preferably aliphatic glycidyl ether epoxy resin.
In the curing agent, the resin is further preferably one or more of a C5/C9 resin, a terpene phenolic resin, a tert-butyl phenolic resin and a pentaerythritol ester. The softening point of the resin is not lower than 110 ℃.
In the curing agent, the wax may be one or more of mineral wax, petroleum wax and synthetic wax, and is preferably synthetic wax. Wherein, the mineral wax can be one or more of montan wax, ozokerite and paraffin wax, and is preferably wax; the petroleum wax can be one or more of microcrystalline wax and petroleum jelly, and is preferably microcrystalline wax; the synthetic wax can be one or more of Fischer-Tropsch wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax and oxidized polyethylene wax; preferably an oxidized polyethylene wax.
In the curing agent, the coupling agent is one of a silane coupling agent and an amino silicic acid coupling agent, and preferably a silane coupling agent. Wherein, the silane coupling agent can be one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane, and is preferably vinyltrimethoxysilane; the amino silicic acid coupling agent can be one or more of monoamino, diamino, triamino and polyamino silicic acid coupling agents, and is preferably a diamino silicic acid coupling agent.
The second aspect of the invention provides a preparation method of a curing agent, which is to uniformly mix required components at 130-200 ℃ to obtain the curing agent.
In a third aspect, the present invention provides a coal and heavy oil modified composition, comprising, in parts by weight:
100-200 parts of pulverized coal
Heavy oil, 200-500 parts
1 to 20 parts of resin
1-25 parts of wax substances
0.5-10 parts of a coupling agent.
In the coal and heavy oil modified composition, the heavy oil has a primary boiling point of generally more than 350 ℃, a softening point of not less than 45 ℃ is controlled, and a softening point of more than 50 ℃ is preferred. The heavy oil can be one or more of residual oil, heavy oil, oil sand and heavy crude oil, and the yield of light fractions at the temperature of less than 220 ℃ is generally not higher than 5%.
In the coal and heavy oil modified composition, the pulverized coal is one or more of anthracite, bituminous coal and lignite, and the mesh number of the pulverized coal is 50-500 meshes, preferably 100-200 meshes.
In the coal and heavy oil modified composition in the curing treatment agent, the resin can be one or more of petroleum resin, phenolic resin, alkyd resin and epoxy resin, and the softening point of the selected resin is not lower than 100 ℃. Wherein the petroleum resin can be one or more of C9 petroleum resin, C5/C9 petroleum resin and dicyclopentadiene resin, and the C5/C9 petroleum resin with the softening point of 120-130 ℃ is preferable; the phenolic resin can be one or more of thermoplastic phenolic resin and thermosetting phenolic resin, and is preferably thermoplastic phenolic resin; the alkyd resin can be one or more of short, medium, long and extremely long alkyd resins with four oil degrees, preferably medium oil alkyd resin; the epoxy resin can be one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and aliphatic glycidyl ether epoxy resin, and is preferably aliphatic glycidyl ether epoxy resin.
In the coal and heavy oil modifying composition, the resin is further preferably one or more of a C5/C9 resin, a terpene phenolic resin, a tert-butyl phenolic resin and a pentaerythritol ester. The softening point of the resin is not lower than 110 ℃.
In the coal and heavy oil modified composition, the wax may be one or more of mineral wax, petroleum wax and synthetic wax, and is preferably synthetic wax. Wherein, the mineral wax can be one or more of montan wax, ozokerite and paraffin wax, and is preferably wax; the petroleum wax can be one or more of microcrystalline wax and petroleum jelly, and is preferably microcrystalline wax; the synthetic wax can be one or more of Fischer-Tropsch wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax and oxidized polyethylene wax; preferably an oxidized polyethylene wax.
In the coal and heavy oil-modifying composition, the coupling agent is one of a silane coupling agent and an aminosilicic acid coupling agent, and a silane coupling agent is preferred. Wherein, the silane coupling agent can be one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane, and is preferably vinyltrimethoxysilane; the amino silicic acid coupling agent can be one or more of monoamino, diamino, triamino and polyamino silicic acid coupling agents, and is preferably a diamino silicic acid coupling agent.
In a fourth aspect, the present invention provides a method for preparing the coal and heavy oil modified composition, the method comprising:
(1) mixing heavy oil raw materials and coal powder at 130-180 ℃ to form a kerosene blend;
(2) fully mixing the kerosene blend obtained in the step (1) with resin, wax substances and a coupling agent at the temperature of 130-180 ℃ and reacting;
(3) and (3) forming the reaction product obtained in the step (2) according to needs to obtain a product.
In the preparation method of the coal and heavy oil modified composition, when the heavy oil raw material and the coal powder are mixed in the step (1), the coal powder can be added all at once or added in multiple times, preferably added in multiple times. The mixing temperature is controlled to be 130-180 ℃, preferably 140-180 ℃, and the mixing time is 0.5-4 h, preferably 1-4 h.
In the above method for preparing the coal and heavy oil modified composition, the forming technique in step (3) may be any one of the forming methods existing in the art, such as one or more of an underwater granulation technique, a steel belt granulation technique, and a slicing granulation technique, according to the product requirements, and preferably, the steel belt granulation technique is selected. The coal and heavy oil modified composition can be prepared into solid particles with the particle size of 3-15 mm.
Compared with the prior art, the invention has the advantages that:
1. in the prior art, heavy oil raw materials are transported through viscosity reduction and then through an oil pipeline, the technical scheme of the invention adopts reverse thinking to convert the mixed raw materials of heavy oil and coal powder into solid-phase particles through solidification treatment and then transport the solid-phase particles, thereby solving the problems of high energy consumption, poor stability and large investment when a viscosity reduction mode is adopted in the prior art. In addition, from another point of view, the technical scheme of the invention overcomes the technical prejudice in the field, because the prior art can only transport through an oil pipeline by reducing the viscosity of the raw materials and keeping the low-temperature fluidity, and the technical scheme of the invention is to solidify the raw materials into solid-phase particles, not reduce the viscosity, but directly convert the solid-phase particles into solid-phase particles for transportation.
2. The coal and heavy oil modified composition obtained by the method can be prepared into solid-phase particles after treatment, is convenient to transport, can be restored to a state capable of being subsequently processed only by heating the coal and heavy oil modified composition after being transported to a destination, has no adverse effect on the properties of a mixture of the coal and the heavy oil, can adjust the viscosity of a material after subsequent heating through the use of a curing treatment agent, and is favorable for subsequent hydrotreatment of a raw material.
3. The curing agent can well couple and crosslink the hydroxyl functional groups on the surface of the coal with other functional groups in the resin, so that a coal-oil space network structure is formed, and the viscosity of the system is increased to meet the granulation requirement; meanwhile, the subsequent heating treatment causes the additive to break, so that the viscosity of the system is obviously reduced; in addition, the wax substance has the characteristics of high low-temperature viscosity and high-temperature viscosity, and the subsequent temperature rise can be beneficial to reducing the viscosity of the system and contributing to the mass and heat transfer effect of the kerosene reaction.
Detailed Description
The invention will be further described with reference to specific embodiments, and the advantages and features of the invention will become apparent as the description proceeds. The examples are illustrative only and do not limit the scope of the invention in any way; it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention, and that such changes and modifications may be made without departing from the spirit and scope of the invention.
The properties of the heavy oil feedstock used in the examples of the present invention and the comparative examples are shown in Table 1, and the properties of the pulverized coal are shown in Table 2.
TABLE 1 heavy oil feedstock Properties
TABLE 2 Industrial and elemental analysis of coal fines
Mad: air drying the base moisture; a. thed: drying the base ash; vdaf: dry ash-free base volatiles
Example 1
Taking 300 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 1, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 6 parts of C5/C9 resin (softening point is 123 ℃), 15 parts of oxidized polyethylene wax and 1.5 parts of bis-amino silicic acid coupling agent into the kerosene mixture, controlling the reaction temperature at 150 ℃, mechanically stirring at 400rad/min for 2 hours, and obtaining a cured coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 2
Taking 300 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 2, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 6 parts of C5/C9 resin (softening point is 123 ℃), 15 parts of oxidized polyethylene wax and 1.5 parts of bis-amino silicic acid coupling agent into the kerosene mixture, controlling the reaction temperature at 160 ℃, mechanically stirring at 400rad/min for 2 hours, and obtaining a cured coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 3
Taking 300 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 2, mixing and heating to 130 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 6 parts of alkyd resin, 15 parts of Fischer-Tropsch wax and 1.5 parts of vinyl triethoxysilane into a kerosene mixture, controlling the reaction temperature at 150 ℃, mechanically stirring at the speed of 400rad/min for 2 hours, and obtaining a solidified coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 4
Taking 300 parts by weight of heavy thick oil raw material, adding 120 parts by weight of 200-mesh coal powder 2, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 10 parts of alkyd resin, 15 parts of Fischer-Tropsch wax and 1.5 parts of vinyl triethoxysilane into a kerosene mixture, controlling the reaction temperature at 170 ℃, and mechanically stirring at the speed of 400rad/min for 2 hours to obtain a solidified coal and heavy oil modified composition; the solidified coal and heavy oil modified composition is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, and the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 5
Taking 500 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 1, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding the kerosene mixture into 20 parts of C5/C9 resin (softening point is 123 ℃), 25 parts of oxidized polyethylene wax and 0.5 part of bis-amino silicic acid coupling agent, controlling the reaction temperature at 170 ℃, and mechanically stirring at 400rad/min for 2 hours to obtain a cured coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 6
Taking 500 parts by weight of heavy oil raw material, adding 200 parts by weight of 200-mesh coal powder 1, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 20 parts of terpene phenolic resin, 25 parts of Fischer-Tropsch wax and 1.5 parts of bis-amino silicic acid coupling agent into the kerosene mixture, controlling the reaction temperature at 180 ℃, mechanically stirring at the speed of 400rad/min for 2 hours, and obtaining a cured coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 7
Taking 200 parts by weight of heavy oil raw material, adding 200 parts by weight of 200-mesh coal powder 1, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 20 parts of terpene phenolic resin, 25 parts of Fischer-Tropsch wax and 1.5 parts of vinyl triethoxysilane into the kerosene mixture, controlling the reaction temperature at 150 ℃, mechanically stirring at the speed of 400rad/min for 2 hours, and obtaining a cured coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Example 8
Taking 200 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 1, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture; adding 10 parts of pentaerythritol ester, 10 parts of Fischer-Tropsch wax and 1.0 part of vinyl triethoxysilane into a kerosene mixture, controlling the reaction temperature at 150 ℃, mechanically stirring at the speed of 400rad/min for 2 hours, and obtaining a solidified coal and heavy oil modified composition; the solidified modified residual oil is prepared into hard particles with the diameter of 5mm by adopting a steel belt granulation technology, and then the hard particles are packaged and transported, wherein the temperature of the solidified residual oil in the generation process is 150 ℃.
Comparative example 1
Taking 300 parts by weight of heavy thick oil raw material, adding 100 parts by weight of 200-mesh coal powder 2, mixing and heating to 150 ℃, mechanically stirring at a speed of 400rad/min for 2 hours to obtain a kerosene mixture.
Comparative example 2
Essentially the same as compared to example 1, except that no oxidized polyethylene wax was added.
Comparative example 3
Essentially the same as in example 1, except that no C5/C9 resin was added.
Comparative example 4
Essentially the same as in example 1, except that no bis-amino silicic acid coupling agent was added.
The cured residues produced in examples 1 to 4 and comparative example 1 were analyzed according to the test methods in the road engineering asphalt and asphalt mixture test protocol (JTGE20-2011) and the results are shown in Table 3.
Table 3 analysis of properties of the cured residue prepared in each example
Claims (20)
1. The curing treatment agent for the coal and the heavy oil comprises the following components in parts by weight:
1 to 20 parts of resin
1-25 parts of wax substances
0.5-10 parts of a coupling agent.
2. The curing agent according to claim 1, wherein: the resin is one or more of petroleum resin, phenolic resin, alkyd resin and epoxy resin, and the softening point of the selected resin is not lower than 100 ℃.
3. The curing agent according to claim 2, wherein: the petroleum resin is one or more of C9 petroleum resin, C5/C9 petroleum resin and dicyclopentadiene resin, and the C5/C9 petroleum resin with the softening point of 120-130 ℃ is preferred; the phenolic resin is one or more of thermoplastic phenolic resin and thermosetting phenolic resin, and is preferably thermoplastic phenolic resin; the alkyd resin is one or more of short, medium, long and extremely long alkyd resins with four oil degrees, preferably medium oil alkyd resin; the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and aliphatic glycidyl ether epoxy resin, and is preferably aliphatic glycidyl ether epoxy resin.
4. The curing agent according to claim 1, wherein: the resin is one or more of C5/C9 resin, terpene phenolic resin, tert-butyl phenolic resin and pentaerythritol ester; the softening point of the resin is not lower than 110 ℃.
5. The curing agent according to claim 1, wherein: the wax substances are one or more of mineral wax, petroleum wax and synthetic wax, and preferably synthetic wax.
6. The curing agent according to claim 5, wherein: the mineral wax is one or more of montan wax, ozokerite and paraffin wax, preferably wax; the petroleum wax is one or more of microcrystalline wax and petroleum jelly, and preferably microcrystalline wax; the synthetic wax is one or more of Fischer-Tropsch wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax and oxidized polyethylene wax; preferably an oxidized polyethylene wax.
7. The curing agent according to claim 1, wherein: the coupling agent is one of a silane coupling agent and an amino silicic acid coupling agent, and preferably is a silane coupling agent.
8. The curing agent according to claim 1, wherein: the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane, and is preferably vinyltrimethoxysilane; the amino silicic acid coupling agent is one or more of monoamino, diamino, triamino and polyamino silicic acid coupling agents, and is preferably a diamino silicic acid coupling agent.
9. A coal and heavy oil modified composition comprising, in parts by weight:
100-200 parts of pulverized coal
Heavy oil, 200-500 parts
1 to 20 parts of resin
1-25 parts of wax substances
0.5-10 parts of a coupling agent.
10. The coal and heavy oil modifying composition of claim 9 wherein: the initial boiling point of the heavy oil is more than 350 ℃, the softening point is controlled to be not less than 45 ℃, and the softening point is preferably more than 50 ℃.
11. The coal and heavy oil modifying composition of claim 9 wherein: the pulverized coal is one or more of anthracite, bituminous coal and lignite.
12. The coal and heavy oil modifying composition of claim 9 wherein: the resin is one or more of petroleum resin, phenolic resin, alkyd resin and epoxy resin, and the softening point of the selected resin is not lower than 100 ℃.
13. The coal and heavy oil modifying composition of claim 12 wherein: the petroleum resin is one or more of C9 petroleum resin, C5/C9 petroleum resin and dicyclopentadiene resin, and the C5/C9 petroleum resin with the softening point of 120-130 ℃ is preferred; the phenolic resin is one or more of thermoplastic phenolic resin and thermosetting phenolic resin, and is preferably thermoplastic phenolic resin; the alkyd resin is one or more of short, medium, long and extremely long alkyd resins with four oil degrees, preferably medium oil alkyd resin; the epoxy resin is one or more of bisphenol A epoxy resin, bisphenol F epoxy resin and aliphatic glycidyl ether epoxy resin, and is preferably aliphatic glycidyl ether epoxy resin.
14. The coal and heavy oil modifying composition of claim 9 wherein: the resin is one or more of C5/C9 resin, terpene phenolic resin, tert-butyl phenolic resin and pentaerythritol ester; the softening point of the resin is not lower than 110 ℃.
15. The coal and heavy oil modifying composition of claim 9 wherein: the wax substances are one or more of mineral wax, petroleum wax and synthetic wax, and preferably synthetic wax.
16. The coal and heavy oil modifying composition of claim 15 wherein: the mineral wax is one or more of montan wax, ozokerite and paraffin wax, and is preferably ozokerite; the petroleum wax is one or more of microcrystalline wax and petroleum jelly, and preferably microcrystalline wax; the synthetic wax is one or more of Fischer-Tropsch wax, polyethylene wax, polypropylene wax, ethylene-vinyl acetate copolymer wax and oxidized polyethylene wax; preferably an oxidized polyethylene wax.
17. The coal and heavy oil modifying composition of claim 9 wherein: the coupling agent is one of a silane coupling agent and an amino silicic acid coupling agent, and preferably is a silane coupling agent.
18. The coal and heavy oil modifying composition of claim 17 wherein: the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane and vinyltris (beta-methoxyethoxy) silane, and is preferably vinyltrimethoxysilane; the amino silicic acid coupling agent is one or more of monoamino, diamino, triamino and polyamino silicic acid coupling agents, and is preferably a diamino silicic acid coupling agent.
19. A process for preparing a coal and heavy oil modified composition as defined in any one of claims 9 to 18, said process comprising:
(1) mixing heavy oil raw materials and coal powder at 130-180 ℃ to form a kerosene blend;
(2) fully mixing the kerosene blend obtained in the step (1) with resin, wax substances and a coupling agent at the temperature of 130-180 ℃ and reacting;
(3) and (3) forming the reaction product obtained in the step (2) according to needs to obtain a product.
20. A process for preparing a coal and heavy oil modified composition according to claim 19, wherein: when the heavy oil raw material and the coal powder are mixed in the step (1), the coal powder is added all at one time or added for multiple times, preferably added for multiple times; the mixing temperature is controlled to be 140-180 ℃, and the mixing time is 0.5-4 h, preferably 1-4 h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023211793A1 (en) * | 2022-04-28 | 2023-11-02 | Baker Hughes Oilfield Operations Llc | Phase change materials to address reversion problems in heavy oils |
| CN117264669A (en) * | 2023-11-22 | 2023-12-22 | 山东新蓝环保科技有限公司 | Fuel additive for cleaning sediment in fuel system and preparation method thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001214032A (en) * | 2000-02-03 | 2001-08-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN1749324A (en) * | 2005-09-30 | 2006-03-22 | 西北师范大学 | Danty composition modified asphalt and its preparing method |
| CN103756259A (en) * | 2014-01-03 | 2014-04-30 | 交通运输部公路科学研究所 | Dry-method asphalt mixture modifier and preparation method thereof as well as asphalt mixture |
| CN104559250A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Thickened asphalt composition and preparation method thereof |
| CN109852079A (en) * | 2018-11-26 | 2019-06-07 | 中设设计集团股份有限公司 | A kind of novel normal-temperature modified asphalt material and its preparation method and application |
| CN110396301A (en) * | 2019-07-30 | 2019-11-01 | 重庆建工住宅建设有限公司 | A kind of warm mix modified pitch and preparation method thereof |
-
2019
- 2019-12-31 CN CN201911417678.9A patent/CN113122349B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001214032A (en) * | 2000-02-03 | 2001-08-07 | Sumitomo Bakelite Co Ltd | Epoxy resin composition and semiconductor device |
| CN1749324A (en) * | 2005-09-30 | 2006-03-22 | 西北师范大学 | Danty composition modified asphalt and its preparing method |
| CN104559250A (en) * | 2013-10-22 | 2015-04-29 | 中国石油化工股份有限公司 | Thickened asphalt composition and preparation method thereof |
| CN103756259A (en) * | 2014-01-03 | 2014-04-30 | 交通运输部公路科学研究所 | Dry-method asphalt mixture modifier and preparation method thereof as well as asphalt mixture |
| CN109852079A (en) * | 2018-11-26 | 2019-06-07 | 中设设计集团股份有限公司 | A kind of novel normal-temperature modified asphalt material and its preparation method and application |
| CN110396301A (en) * | 2019-07-30 | 2019-11-01 | 重庆建工住宅建设有限公司 | A kind of warm mix modified pitch and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 蒲春生等: "《薄层疏松砂岩稠油油藏高效注汽热采技术》", 31 December 2015, 中国石油大学出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023211793A1 (en) * | 2022-04-28 | 2023-11-02 | Baker Hughes Oilfield Operations Llc | Phase change materials to address reversion problems in heavy oils |
| CN117264669A (en) * | 2023-11-22 | 2023-12-22 | 山东新蓝环保科技有限公司 | Fuel additive for cleaning sediment in fuel system and preparation method thereof |
| CN117264669B (en) * | 2023-11-22 | 2024-02-09 | 山东新蓝环保科技有限公司 | Fuel additive for cleaning sediment in fuel system and preparation method thereof |
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