CN105778968A - Method for preparing impregnating pitch, impregnating pitch and application thereof - Google Patents
Method for preparing impregnating pitch, impregnating pitch and application thereof Download PDFInfo
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- CN105778968A CN105778968A CN201610218327.5A CN201610218327A CN105778968A CN 105778968 A CN105778968 A CN 105778968A CN 201610218327 A CN201610218327 A CN 201610218327A CN 105778968 A CN105778968 A CN 105778968A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
- C09J195/00—Adhesives based on bituminous materials, e.g. asphalt, tar, pitch
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
- C10C3/04—Working-up pitch, asphalt, bitumen by chemical means reaction by blowing or oxidising, e.g. air, ozone
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/06—Working-up pitch, asphalt, bitumen by distillation
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Abstract
The invention discloses a method for preparing impregnating pitch, impregnating pitch and application thereof. The method comprises the following steps that 1, extracting solvent is added into direct coal liquefaction residues, and the mixture is sequentially subjected to thermal melting extracting, solid-liquid separating, reduced pressure distillation and solvent recovery treatment to obtain coal liquefaction pitch; 2, heavy oil is added into the coal liquefaction pitch, nitrogen is introduced, the mixture is heated and stirred under the normal pressure, and by means of the thermal polymerization reaction, the impregnating pitch and recovered light oil by-products are obtained, wherein the heavy oil is anthracene oil with the initial boiling point larger than 260 DEG C, vacuum residues and/or catalytic cracking slurry oil; the addition amount of the heavy oil is 20-50 wt% of the coal liquefaction pitch. According to the method, the technology is simple, the condition is mild, equipment is conventional, batch production can be achieved easily, a new path is provided for deep utilization of the direct coal liquefaction residues, pollution to the environment from the direct coal liquefaction residues is reduced, and economy of direct coal liquefaction is improved.
Description
Technical field
The present invention relates to coal liquefaction residue deep process technology field, prepare the method for impregnating pitch, impregnating pitch and application thereof in particular to a kind of.
Background technology
Along with the fast development of national economy, modernization and social development process are constantly accelerated, the consumption figure of oil product is constantly increased by China, greatly exceed the growth rate of the crude oil production same period, causes that petroleum import amount all increases year by year, and has been over from yield.And China is a country that rich coal is oil-poor, make full use of abundant coal resources, the clean coal technology of the advanced person such as development of coal direct liquefaction is to reduce external crude oil is depended on unduly, alleviate one of important channel of China's oil shortage of resources, oil product supply and demand pressure, also it is improve our coal resources utilization rate simultaneously, alleviate pollution that caused by coal burning, promote the Important Action of the energy, economy, harmonious development.
Coal direct liquefaction is by high temperature, high pressure by coal, and under catalyst action, hydrogenation is directly translated into the transport fuel (Petroleum, diesel oil etc.) of cleaning or the clean coal technology of a kind of advanced person of industrial chemicals.The process of DCL/Direct coal liquefaction is usually the granularity that coal is crushed to below 0.15mm in advance, then is made into coal slurry with solvent, and is hydrogenated with under uniform temperature (about 450 DEG C) and high pressure, makes the macromolecular cleavage in coal be hydrogenated into more micromolecular process.In liquefaction process except obtaining the liquiefied product needed, go back some hydrocarbon molecules of by-product, COXDeng the liquefaction residue (also known as coal liquefaction residue) that gas, fresh water (FW) and solid-liquid separation process produce.Liquefied residue generally accounts for about the 30% of coal input quantity.The efficiency of liquefaction process and the economy of whole liquefaction plant and environmental conservation etc. are all had immeasurable impact by the utilization of coal liquefaction residue.Efficient, the feasible method of comprehensive utilization of research coal directly-liquefied residue, extracts the value product economic benefit to improving direct liquefaction process and has important practical significance.
Coal directly-liquefied residue is mainly made up of inanimate matter and organic two parts, and organic matter includes liquefaction heavy oil, bitumen and unconverted coal, mineral that inorganic matter (is commonly referred to ash) and includes in coal and additional catalyst.Liquefaction heavy oil and bitumen in organic species account for the 50% of level of residue, and unconverted coal accounts for the 30% of level of residue, and ash accounts for about 20%.Therefore, the bitumen and mink cell focus that account for 50% in liquefied residue being separated and carry out comprehensive development and utilization, it is feasible for therefrom extracting or prepare more valuable product.
The current utilization to coal liquefaction residue mainly some traditional methods, such as burning, coking liquefaction and gasification hydrogen-producing etc..Directly burn in boiler or kiln as fuel, will affect the economy of coal liquefaction undoubtedly, and the problem that sulfur content higher in liquefied residue will bring environment aspect.Although coking liquefaction adds the liquid oil yield of coal liquefaction craft, but liquefied residue can not obtain the most reasonably utilizing, and the utilization ways of semicoke and coke is very not clear and definite yet.The method that liquefied residue carries out gasification hydrogen-producing is a kind of effective extensive approach utilized, but the high value added utilization potentiality of the bitumen in residue and mink cell focus are embodied, and the ash in residue is up to more than 20%, this brings very big impact will to the deslagging of gasification furnace.
Patent ZL200510047800.X discloses a kind of method preparing carbon nano-material for raw material plasma with coal liquefaction residue.Patent ZL200610012547.9 discloses a kind of method using coal liquefaction residue as road asphalt modifier.ZL200910087907.5 discloses a kind of method utilizing coal directly-liquefied residue to prepare asphalt base carbon fiber.Patent 200910086158.4 discloses a kind of method preparing mesophase pitch with coal liquefaction residue.Said method is all applied to carbon materials field with the bitumen in coal liquefaction residue for raw material, it is not involved with coal directly-liquefied residue and prepares hard pitch and modified related work through solvent naphtha extraction, solid-liquid separation, decompression distillation, and the extracting of residue medium pitch class material is all with expensive pure chemistry reagent for solvent, cost is of a relatively high.Patent 2014100212645 discloses a kind of method utilizing coal directly-liquefied residue to prepare modified pitch.Patent 201410020529X discloses a kind of method utilizing coal directly-liquefied residue normal pressure serialization to prepare modified pitch.Both approaches all have employed coal directly-liquefied residue and separates through solvent naphtha extracted by filtration, its Patent 2014100212645 is through difference, coal liquefaction residue to be extracted filtration grade obtain the coal liquefaction Colophonium of different content of ashes, the modified pitch of various index performance is prepared through high-temperature pressurizing thermal polymerization (>=300 DEG C), patent 201410020529X adopts catalytic reaction principle that the coal liquefaction Colophonium obtained carries out cross-linked polymeric to obtain a kind of modified pitch, above two patents are all not directed to normal pressure thermal polymerization (150～300 DEG C) and prepare impregnating pitch and light oil by-product recovery technique.
Summary of the invention
Preparing the method for impregnating pitch, impregnating pitch and application thereof it is desirable to provide a kind of, the coal liquefaction Colophonium that coal directly-liquefied residue obtains at distilling period is carried out thermal polymerization with mink cell focus by the method, it is achieved that prepare the purpose of impregnating pitch.
To achieve these goals, according to an aspect of the invention, it is provided a kind of method preparing impregnating pitch.The method comprises the following steps: S1, addition extractant in coal directly-liquefied residue, is sequentially carried out thermosol extraction, solid-liquid separation, decompression distillation and solvent recovery and processes, obtains coal liquefaction Colophonium；S2, in coal liquefaction Colophonium add mink cell focus, pass into nitrogen, at ambient pressure heated and stirred, heat polymerization obtains impregnating pitch and the light oil by-product reclaimed；Wherein, mink cell focus is the initial boiling point carbolineum more than 260 DEG C, decompression residuum and/or catalytic cracked oil pulp；And 20～50wt% that the addition of mink cell focus is coal liquefaction Colophonium.
Further, the softening point of coal liquefaction Colophonium is 130～200 DEG C, toluene insolubles content value≤35wt%, quinoline insolubles content value≤1.5wt%, and coking value is 54～68wt.%, content of ashes value≤0.5wt%.
Further, extractant is boiling range is the distillate of 150～405 DEG C.
Further, extractant is one or more in coal tar and distillate thereof.
Further, S1 includes: is mixed according to mass ratio 1:1～1:10 with extractant by coal directly-liquefied residue, obtains mixed liquor；And in a nitrogen atmosphere, with 10 DEG C～30 DEG C/h, mixed liquor being warming up to 80 DEG C～280 DEG C, constant temperature stirring under 0.1～1.0MPa, thermosol extracts, and obtains thermosol and extracts mixture；The time that thermosol extracts is 5～60min, and the speed of constant temperature stirring is 50～300r/min.
Further, S1 adopt the mode of thermal air pressure filtration, Vacuum Heat sucking filtration, cyclonic separation, gravity settling separation and separated carry out solid-liquid separation.
Further, the extract after solid-liquid separation is adopted the mode of distillation or evaporation to carry out solvent recovery process by S1.
Further, the extract after solid-liquid separation is adopted by S1 the mode of air-distillation or decompression distillation carry out solvent recovery process.
Further, the addition of mink cell focus is the 20～50wt% stating coal liquefaction Colophonium.
Further, the mixture of coal liquefaction Colophonium and mink cell focus is warming up to by S2 predetermined temperature, constant temperature normal pressure thermal polymerization.
Further, predetermined temperature is 150～300 DEG C, and heating rate is 1～10 DEG C/min, and the time of thermal polymerization is 2～8 hours.
Further, predetermined temperature is 180～250 DEG C, and heating rate is 5～7 DEG C/min, and the time of thermal polymerization is 4～6 hours.
According to a further aspect in the invention, it is provided that a kind of impregnating pitch.This impregnating pitch adopts any of the above-described kind of method preparing impregnating pitch to be prepared from.
Further, the softening point of impregnating pitch is 80 DEG C～115 DEG C, and toluene insolubles content value is≤22wt%, quinoline insolubles content≤1.0wt%, coking value >=50wt%, content of ashes value≤0.35wt.%.
In accordance with a further aspect of the present invention, it is provided that the application in carbon industry product bonding forming of a kind of above-mentioned impregnating pitch.
Further, carbon industry product includes graphite electrode, Heat Conduction Material and carbon/carbon composite.
Application technical scheme, by coal directly-liquefied residue is carried out thermosol extraction, solid-liquid separation and distillation, obtain a kind of low-ash DCL/Direct coal liquefaction heavy dope, i.e. coal liquefaction Colophonium, then add initial boiling point >=260 DEG C mink cell focus, utilize the mode of normal heating just can prepare the medium and high temperature coal liquefaction impregnating pitch of high added value.The present invention adopts hot melt extracted by filtration separation principle that ash coal direct liquefaction residue is prepared into low ash coal road oil, utilize thermal polymerization simultaneously, coal liquefaction asphalt softening point is reduced by adding mink cell focus, through thermal polymerization, the coal liquefaction Colophonium of high softening-point can be made applicable carbon industry and produce the impregnating pitch of low softening point used, low QI value, high coking value.Preparation technology route is simple, reaction condition is gentle for it, is suitable to industrialized production.
Method technique provided by the present invention is simple, mild condition, equipment are conventional, be prone to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce the coal directly-liquefied residue pollution to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
Accompanying drawing explanation
The Figure of description constituting the part of the application is used for providing a further understanding of the present invention, and the schematic description and description of the present invention is used for explaining the present invention, is not intended that inappropriate limitation of the present invention.In the accompanying drawings:
Fig. 1 illustrates the schematic flow sheet preparing impregnating pitch according to a kind of exemplary embodiments of the present invention.
Detailed description of the invention
It should be noted that when not conflicting, the embodiment in the application and the feature in embodiment can be mutually combined.Describe the present invention below with reference to the accompanying drawings and in conjunction with the embodiments in detail.
According to a kind of typical embodiment of the present invention, as shown in Figure 1, it is provided that a kind of method preparing impregnating pitch.The method comprises the following steps: S1, addition extractant in coal directly-liquefied residue, is sequentially carried out thermosol extraction, solid-liquid separation, decompression distillation and solvent recovery and processes, and obtains containing a kind of low-ash organic heavy dope, i.e. coal liquefaction Colophonium；S2, in coal liquefaction Colophonium add mink cell focus, pass into nitrogen, at ambient pressure heated and stirred, heat polymerization obtains impregnating pitch and the light oil by-product reclaimed；Wherein, mink cell focus is the initial boiling point carbolineum more than 260 DEG C, decompression residuum and/or catalytic cracked oil pulp；And 20～50wt% that the addition of mink cell focus is coal liquefaction Colophonium.
" the organic heavy dope " being previously mentioned in the present invention refers to that coal liquefaction residue distills the obtained a kind of low ash coal liquefaction Colophonium containing organic component through solvent extraction, solid-liquid separation, decompression.
Application technical scheme, by coal directly-liquefied residue is carried out thermosol extraction, solid-liquid separation and distillation, obtain a kind of low-ash DCL/Direct coal liquefaction heavy dope, i.e. coal liquefaction Colophonium, then add initial boiling point >=260 DEG C mink cell focus, utilize the mode of normal heating just can prepare the medium and high temperature coal liquefaction impregnating pitch of high added value.The present invention adopts hot melt extracted by filtration separation principle that ash coal direct liquefaction residue is prepared into low ash coal road oil, coal liquefaction asphalt softening point is reduced by adding mink cell focus, through thermal polymerization, the coal liquefaction Colophonium of high softening-point can be made applicable carbon industry and produce the impregnating pitch of low softening point used, low QI value, high coking value.Preparation technology route is simple, reaction condition is gentle for it, is suitable to industrialized production.
Method of modifying technique provided by the present invention is simple, mild condition, equipment are conventional, be prone to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce the coal directly-liquefied residue pollution to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
In a kind of typical embodiment of the present invention, the softening point of coal liquefaction Colophonium is 130～200 DEG C, toluene insolubles content value≤35wt%, quinoline insolubles content value≤1.5wt%, and coking value is 54～68wt.%, content of ashes value≤0.5wt%.
Preferably, extractant is boiling range is the distillate of 150～405 DEG C.When boiling range≤150 DEG C of distillate, due to big with asphaltene molecule amount gap, can cause that its extraction efficiency is low；When boiling range >=405 DEG C of distillate, in solids-liquid separation step, extractant is difficult to again reclaim.Preferably, extractant is one or more in coal tar and distillate thereof.Coal tar and distillate thereof are due to similar to coal tar pitch molecular structure, and according to the similar principle that mixes, coal tar and distillate thereof for coal directly-liquefied residue extractant, its extraction efficiency is high.A kind of typical embodiment party of the present invention, S1 includes: is mixed according to mass ratio 1:1～1:10 with extractant by coal directly-liquefied residue, obtains mixed liquor；And in a nitrogen atmosphere, with 10 DEG C～30 DEG C/h, mixed liquor being warming up to 80 DEG C～280 DEG C, constant temperature stirring under 0.1～1.0MPa, thermosol extracts, and obtains thermosol and extracts mixture；The time that thermosol extracts is 5～60min, and the speed of constant temperature stirring is 50～300r/min.
Coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with extractant, can ensure that the effect of extraction and solvent recovering rate, if the mass ratio of coal directly-liquefied residue and extractant is higher than 1:1, then it is possible that extractant can not completely by the situation of coal directly-liquefied residue dissolving, cause extracting thorough not, and extractant contained in heavy dope is as content reduces and causes heavy dope softening point；If the mass ratio of coal directly-liquefied residue and extractant is lower than 1:10, then extractant can be caused to waste, increase the cost recovery of follow-up extractant.Considering that high temperature mink cell focus and bitumen reaction are mixed into air and easily catch fire, dangerous, the present invention can pass into N before the reaction in mixed liquor2First get rid of the air in reactor such as stirred tank so that reaction carries out in the absence of oxygen.
The addition of mink cell focus is the 20～50wt% stating coal liquefaction Colophonium, and mink cell focus addition is lower than 20%, and gained impregnating pitch softening point is higher than 115 DEG C, mink cell focus addition > 50%, and gained impregnating pitch softening point is lower than 80 DEG C.
At a kind of typical embodiment of the present invention, step S1 adopt the mode of thermal air pressure filtration, Vacuum Heat sucking filtration, cyclonic separation, gravity settling separation and separated carry out solid-liquid separation.The present invention preferably but is not limited to above-mentioned listed solid-liquid separation method, as long as can be sufficiently separated by solid-liquid and reach desirable effect.When the mode adopting thermal air pressure filtration carries out solid-liquid separation, the temperature of thermal air pressure filtration is 50 DEG C～210 DEG C, it is preferred to 150 DEG C～200 DEG C；The pressure of thermal air pressure filtration is 0.02～101.3KPa or 0.2MPa～1.0MPa.Adopt in said temperature and pressure limit and carry out thermal air pressure filtration, it is possible to largely solid-liquid is easily separated.Except thermal air pressure filtration, when solid-liquid separation adopts cyclonic separation, the temperature of cyclonic separation is 50 DEG C～250 DEG C, and inlet pressure is 0.2MPa～0.6MPa.
A kind of exemplary embodiment according to the present invention, predetermined temperature is 150～300 DEG C, and heating rate is 1～10 DEG C/min, and the time of cross-linked polymeric is 2～8 hours.If predetermined temperature is lower than 150 DEG C, then there will be reactant can not efficient melting, cause stirring uneven, be unfavorable for the quality uniformity of product；If predetermined temperature higher than 300 DEG C, then there will be the light component gasification of reactant, heavy component coking phenomenon, cause heavy dope and interpolation mink cell focus cannot polyreaction preferably, be unfavorable for the carrying out of heat polymerization.Equally, if heating rate is lower than 1 DEG C/min, then there will be heating rate excessively slow, cause that the production time is long, be unfavorable for the raising of production efficiency；If heating rate is higher than 10 DEG C/min, then there will be reactant and be heated uneven, cause the reactant coking of reactor wall place or gasification, be unfavorable for homogeneous reaction.Therefore, through considering, predetermined temperature, heating rate, mixing time are carried out collaborative optimized choice by the present invention, they are limited in above-mentioned scope, it is possible to increase production efficiency, reduce severe reaction conditions degree, contribute to the carrying out of reaction.It is further preferred that predetermined temperature is 180～250 DEG C, heating rate is 5～7 DEG C/min, and the time of cross-linked polymeric is 4～6 hours.
According to a further aspect in the invention, it is provided that a kind of impregnating pitch, this impregnating pitch is adopt any of the above-described kind of method preparing impregnating pitch to be prepared from.The softening point of impregnating pitch prepared by employing the method is 80 DEG C～115 DEG C, and toluene insolubles content value is≤22wt%, quinoline insolubles content≤1.0wt%, coking value >=50wt%, content of ashes value≤0.35wt%.
According to another aspect of the invention, it is provided that any of the above-described kind of impregnating pitch can be applied in carbon industry product bonding forming, such as graphite electrode, Heat Conduction Material, carbon/carbon composite.
Beneficial effects of the present invention is further illustrated below in conjunction with specific embodiment.
Embodiment 1
300Kg coal directly-liquefied residue is added to stirred tank with 750Kg extractant carbolineum (boiling range is 300-405 DEG C), stirs with the speed of 60r/min, fill N2To 0.1MPa, after being warming up to 150 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 30min.Extracting mixture entrance filter and carry out thermal air pressure filtration, filtration temperature is 150 DEG C, and filter pressure is 0.3MPa, and the filter element aperture size of filter is 30 μm.After filtering, collect 180Kg solid filter residue, 867Kg filtrate.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 31.7Kg, reusable edible, and obtaining 146.6Kg solid can coal blending burning or gasification.
Filtrate is sent into vacuum distillation tower, and recovered overhead partial extraction solvent recycles, and collects organic heavy dope that ash is 0.5wt.% at the bottom of tower respectively, softening point is 200 DEG C, toluene insolubles value 35wt%, quinoline insolubles value 1.5wt%, coking value 68wt%.
Organic for 100Kg heavy dope and 34Kg carbolineum (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 300 DEG C with the programming rate of 10 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 300 DEG C of isothermal reaction 2h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 115 DEG C, toluene insolubles value 22wt%, quinoline insolubles value 1.0wt%, coking value 59wt%, and ash value is 0.35wt%.
Embodiment 2
250Kg coal directly-liquefied residue is added to stirred tank with 750Kg coal tar (boiling range is 150-310 DEG C), stirs with the speed of 75r/min, fill N2To 0.3MPa, after being warming up to 170 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 45min.Extracting mixture entrance filter and carry out thermal air pressure filtration, filtration temperature is 120 DEG C, and filter pressure is 0.4MPa, and the filter element aperture size of filter is 40 μm.After filtering, collect 155Kg solid filter residue, 842.8Kg filtrate.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 21.7Kg, reusable edible, and obtaining 130.3Kg solid can coal blending burning or gasification.
Filtrate is sent into vacuum distillation tower, tower top and tower side recovery extractant recycle, at the bottom of tower, collect the organic heavy dope of coal liquefaction that ash is 0.2wt% respectively, softening point is 160 DEG C, toluene insolubles value 30wt%, quinoline insolubles value 1.0wt%, coking value 63wt%.
Organic for 100Kg heavy dope and 22Kg decompression residuum (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 200 DEG C with the programming rate of 5 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 200 DEG C of isothermal reaction 6h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 105 DEG C, toluene insolubles value 18wt%, quinoline insolubles value 0.8wt%, coking value 56wt%, and ash value is 0.1wt%.
Embodiment 3
200Kg coal directly-liquefied residue is added to stirred tank with 800Kg washing oil (boiling range is 220-405 DEG C), stirs with the speed of 85r/min, fill N2To 0.15MPa, after being warming up to 200 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 27min.Extracting mixture entrance filter and carry out thermal vacuum filtration, filtration temperature is 180 DEG C, and filter pressure is 2.9KPa, and the filter element aperture size of filter is 30 μm.After filtering, collect 145Kg solid filter residue, 849Kg filtrate.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 19.7Kg, reusable edible, and obtaining 124.3Kg solid can coal blending burning or gasification.
Filtrate is sent into vacuum distillation tower, tower top and tower side recovery extractant recycle, at the bottom of tower, collect the organic heavy dope of coal liquefaction that ash is 0.1wt% respectively, softening point is 130 DEG C, toluene insolubles value 20wt%, quinoline insolubles value 0.9wt%, coking value 58wt%.
Organic for 100Kg heavy dope and 20Kg catalytic cracked oil pulp (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 150 DEG C with the programming rate of 10 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 150 DEG C of isothermal reaction 10h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 87 DEG C, toluene insolubles value 13wt%, quinoline insolubles value 0.2wt%, coking value 51wt%, and ash value is 0.01wt%.
Embodiment 4
350Kg coal directly-liquefied residue is added to stirred tank with 1000Kg washing oil (boiling range is 200-260 DEG C), stirs with the speed of 55r/min, fill N2To 1MPa, after being warming up to 180 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 50min.Extracting mixture and enter cyclonic separation, separation temperature is 180 DEG C, and pressure is 0.35MPa.After cyclonic separation, collect 303Kg underflow dope, 1039Kg overhead stream clear liquid.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 132Kg, reusable edible, and obtaining 173.6Kg solid can coal blending gasification.
Filtrate is sent into vacuum distillation tower, and recovered overhead extractant recycles, and collects the organic heavy dope of coal liquefaction that ash is 0.2wt% at the bottom of tower respectively, softening point is 170 DEG C, toluene insolubles value 32wt%, quinoline insolubles value 0.9wt%, coking value 58wt%.
Organic for 100Kg heavy dope and 32Kg carbolineum (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 200 DEG C with the programming rate of 6 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 200 DEG C of isothermal reaction 8h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 95 DEG C, toluene insolubles value 15wt%, quinoline insolubles value 0.8wt%, coking value 52wt%, and ash value is 0.03wt%.
Embodiment 5
250Kg coal directly-liquefied residue is added to stirred tank with 250Kg coal tar (boiling range is 150-310 DEG C), stirs with the speed of 50r/min, fill N2To 1MPa, after being warming up to 80 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 5min.Extracting mixture entrance filter and carry out thermal air pressure filtration, filtration temperature is 120 DEG C, and filter pressure is 0.4MPa, and the filter element aperture size of filter is 40 μm.After filtering, collect 155Kg solid filter residue, 842.8Kg filtrate.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 21.7Kg, reusable edible, and obtaining 130.3Kg solid can coal blending burning or gasification.
Filtrate is sent into vacuum distillation tower, tower top and tower side recovery extractant recycle, at the bottom of tower, collect the organic heavy dope of coal liquefaction that ash is 0.2wt% respectively, softening point is 160 DEG C, toluene insolubles value 30wt%, quinoline insolubles value 1.0wt%, coking value 63wt%.
Organic for 100Kg heavy dope and 50Kg decompression residuum (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 180 DEG C with the programming rate of 10 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 200 DEG C of isothermal reaction 6h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 85 DEG C, toluene insolubles value 13wt%, quinoline insolubles value 0.3wt%, coking value 50wt%, and ash value is 0.1wt%.
Embodiment 6
250Kg coal directly-liquefied residue is added to stirred tank with 2500Kg coal tar (boiling range is 150-310 DEG C), stirs with the speed of 300r/min, fill N2To 0.3MPa, after being warming up to 280 DEG C with 10 DEG C～30 DEG C/h, constant temperature stirring extracts 60min.Extracting mixture entrance filter and carry out thermal air pressure filtration, filtration temperature is 120 DEG C, and filter pressure is 0.4MPa, and the filter element aperture size of filter is 40 μm.After filtering, collect 155Kg solid filter residue, 842.8Kg filtrate.
By solid filter residue, being fed through steam stripping unit, liquid portion, after oil-water separation, obtains the extractant of 21.7Kg, reusable edible, and obtaining 130.3Kg solid can coal blending burning or gasification.
Filtrate is sent into vacuum distillation tower, tower top and tower side recovery extractant recycle, at the bottom of tower, collect the organic heavy dope of coal liquefaction that ash is 0.2wt% respectively, softening point is 160 DEG C, toluene insolubles value 30wt%, quinoline insolubles value 1.0wt%, coking value 63wt%.
Organic for 100Kg heavy dope and 22Kg decompression residuum (initial boiling point >=260 DEG C) are added to stirred tank; under nitrogen atmosphere is protected; being warming up to 250 DEG C with the programming rate of 7 DEG C/min, meanwhile, light oil by-product flows into light oil collecting tank along with nitrogen.When at 200 DEG C of isothermal reaction 6h, stopping heating, take out gained coal liquefaction impregnating pitch.The softening point recording product is 108 DEG C, toluene insolubles value 20wt%, quinoline insolubles value 0.8wt%, coking value 57wt%, and ash value is 0.1wt%.
Application case:
Prepared a kind of coal liquefaction impregnating pitch by above-described embodiment 1-6 method, and (sample number is P with the conventional pitch coke oil asphalt in other two market1), (sample number is P to coal tar modified coal tar pitch2) composition and character compare, as shown in table 1.With coal liquefaction impregnating pitch, coal tar mid temperature pitch and coal tar modified coal tar pitch for binding agent, with needle coke for aggregate, carrying out carbonization and graphitization processing by the quality of 3:1 than after kneading and compacting, obtain graphitization carbon-point, sample number into spectrum corresponds to embodiment 1-6 and C respectively1、C2, Physico-chemical tests result is in Table 2.
Table 1
| Sample ID | A% | TI% | QI% | SP℃ | CV% |
| Embodiment 1 | 0.35 | 22 | 1.0 | 115 | 59 |
| Embodiment 2 | 0.1 | 18 | 0.8 | 105 | 56 |
| Embodiment 3 | 0.01 | 13 | 0.2 | 87 | 51 |
| Embodiment 4 | 0.03 | 15 | 0.8 | 95 | 52 |
| Embodiment 5 | 0.1 | 13 | 0.3 | 85 | 50 |
| Embodiment 6 | 0.1 | 20 | 0.1 | 108 | 57 |
| P1 | 0.05 | 19.36 | 4.26 | 85.6 | 49 |
| P2 | 0.08 | 29.18 | 6.78 | 91.5 | 56 |
A: ash；TI: toluene insolubles；QI: quinoline insolubles；SP: softening point；CV: coking value
As it can be seen from table 1 TI, QI content of coal liquefaction impregnating pitch is respectively lower than tar mid temperature pitch and the content of coal tar modified coal tar pitch, its coking value is between tar mid temperature pitch and modified coal tar pitch coking value.Table 2 is the result of the test that these three Colophonium is used as binders for electrodes, table 2 result shows, it is better than traditional binding agent as preparing the carbon-point resistivity that binders for electrodes obtains with coal liquefaction impregnating pitch, other index and coal tar mid temperature pitch and modified coal tar pitch suitable, can meet the requirement of actual production completely.
Table 2
Note: CTE is the coefficient of expansion
As can be seen from the above description, the above embodiments of the present invention achieve following technique effect:
1) by coal directly-liquefied residue is carried out thermosol extraction, solid-liquid separation and distillation, obtain a kind of low-ash DCL/Direct coal liquefaction heavy dope, i.e. coal liquefaction Colophonium, then add initial boiling point >=260 DEG C mink cell focus, utilize the mode of normal heating just can prepare the medium and high temperature coal liquefaction impregnating pitch of high added value.The present invention adopts hot melt extracted by filtration separation principle that ash coal direct liquefaction residue is prepared into low ash coal road oil, utilize air oxidation thermal polymerization simultaneously, coal liquefaction asphalt softening point is reduced by adding mink cell focus, through thermal polymerization, the coal liquefaction Colophonium of high softening-point can be made applicable carbon industry and produce the impregnating pitch of low softening point used, low QI value, high coking value.Preparation technology route is simple, reaction condition is gentle for it, is suitable to industrialized production.
2) the method technique that invention provides is simple, mild condition, equipment are conventional, be prone to amplification produces, deep exploitation for coal directly-liquefied residue provides a kind of new approach, reduce the coal directly-liquefied residue pollution to environment, improve the economy of coal direct liquefaction, there is good market application foreground.
The foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, for a person skilled in the art, the present invention can have various modifications and variations.All within the spirit and principles in the present invention, any amendment of making, equivalent replacement, improvement etc., should be included within protection scope of the present invention.
Claims (15)
1. the method preparing impregnating pitch, it is characterised in that comprise the following steps:
S1, in coal directly-liquefied residue add extractant, be sequentially carried out thermosol extractions, solid-liquid separation, decompression distillation and solvent recovery process, obtain coal liquefaction Colophonium；
S2, in described coal liquefaction Colophonium add mink cell focus, pass into nitrogen, at ambient pressure heated and stirred, heat polymerization obtains impregnating pitch and the light oil by-product reclaimed；
Wherein, described mink cell focus is the initial boiling point carbolineum more than 260 DEG C, decompression residuum and/or catalytic cracked oil pulp；And the 20～50wt% that addition is described coal liquefaction Colophonium of described mink cell focus.
2. method according to claim 1, it is characterised in that the softening point of described coal liquefaction Colophonium is 130～200 DEG C, toluene insolubles content value≤35wt%, quinoline insolubles content value≤1.5wt%, coking value is 54～68wt.%, content of ashes value≤0.5wt%.
3. method according to claim 1, it is characterised in that described extractant is boiling range is the distillate of 150～405 DEG C.
4. method according to claim 1, it is characterised in that described extractant is one or more in coal tar and distillate thereof.
5. method according to claim 1, it is characterised in that described S1 includes:
Described coal directly-liquefied residue is mixed according to mass ratio 1:1～1:10 with described extractant, obtains mixed liquor；And
In a nitrogen atmosphere, with 10 DEG C～30 DEG C/h, described mixed liquor being warming up to 80 DEG C～280 DEG C, constant temperature stirring under 0.1～1.0MPa, thermosol extracts, and obtains thermosol and extracts mixture；
The time that described thermosol extracts is 5～60min, and the speed of described constant temperature stirring is 50～300r/min.
6. method according to claim 1, it is characterised in that adopt the mode of thermal air pressure filtration, Vacuum Heat sucking filtration, cyclonic separation, gravity settling separation and separated to carry out solid-liquid separation in described S1.
7. method according to claim 1, it is characterised in that adopt the mode of distillation or evaporation to carry out solvent recovery process the extract after solid-liquid separation in described S1.
8. method according to claim 7, it is characterised in that the extract after solid-liquid separation adopts in described S1 the mode of air-distillation or decompression distillation carry out solvent recovery process.
9. method according to claim 1, it is characterised in that in described S2, the mixture of described coal liquefaction Colophonium and described mink cell focus is warming up to predetermined temperature, constant temperature normal pressure thermal polymerization.
10. method according to claim 9, it is characterised in that described predetermined temperature is 150～300 DEG C, heating rate is 1～10 DEG C/min, and the time of described thermal polymerization is 2～8 hours.
11. method according to claim 10, it is characterised in that described predetermined temperature is 180～250 DEG C, heating rate is 5～7 DEG C/min, and the time of described thermal polymerization is 4～6 hours.
12. an impregnating pitch, it is characterised in that adopt the method preparing impregnating pitch according to any one of claim 1 to 11 to be prepared from.
13. impregnating pitch according to claim 12, it is characterised in that the softening point of described impregnating pitch is 80 DEG C～115 DEG C, toluene insolubles content value is≤22wt%, quinoline insolubles content≤1.0wt%, coking value >=50wt%, content of ashes value≤0.35wt.%.
14. the application that the impregnating pitch described in a claim 12 or 13 is in carbon industry product bonding forming.
15. application according to claim 14, it is characterised in that described carbon industry product includes graphite electrode, Heat Conduction Material and carbon/carbon composite.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109734458A (en) * | 2019-01-23 | 2019-05-10 | 陕西师范大学 | A kind of synthetic method of asphalt impregnant |
| CN110256858A (en) * | 2019-06-12 | 2019-09-20 | 台州立拓能源有限公司 | Application of the bio-oil as pitch |
| CN110540855A (en) * | 2019-08-29 | 2019-12-06 | 中海沥青股份有限公司 | Petroleum-series impregnating asphalt and preparation method thereof |
| CN111218294A (en) * | 2018-11-27 | 2020-06-02 | 宝武炭材料科技有限公司 | Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN113621396A (en) * | 2020-05-07 | 2021-11-09 | 宝武炭材料科技有限公司 | Preparation method of refined medium-temperature asphalt |
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| CN114836230A (en) * | 2021-02-02 | 2022-08-02 | 圣德光科技发展(北京)有限公司 | Preparation method of adhesive and impregnant |
| CN115572615A (en) * | 2022-09-30 | 2023-01-06 | 中国神华煤制油化工有限公司 | Separation process and separation system for directly liquefying coal into asphaltenes |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281490A (en) * | 2004-03-30 | 2005-10-13 | Osaka Gas Co Ltd | Method for producing optically isotropic pitch |
| CN101445740A (en) * | 2009-01-04 | 2009-06-03 | 北京石油化工学院 | A preparation method of dipping agent pitch |
| CN103756703A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt, method for preparing modified asphalt by using direct liquefied coal residue in normal pressure continuous mode and application of modified coal residue |
| CN103756706A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
-
2016
- 2016-04-08 CN CN201610218327.5A patent/CN105778968A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005281490A (en) * | 2004-03-30 | 2005-10-13 | Osaka Gas Co Ltd | Method for producing optically isotropic pitch |
| CN101445740A (en) * | 2009-01-04 | 2009-06-03 | 北京石油化工学院 | A preparation method of dipping agent pitch |
| CN103756703A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt, method for preparing modified asphalt by using direct liquefied coal residue in normal pressure continuous mode and application of modified coal residue |
| CN103756706A (en) * | 2014-01-16 | 2014-04-30 | 神华集团有限责任公司 | Modified asphalt and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 《危险化学品生产企业从业人员安全技术培训教材》编委会: "《煤化工生产安全操作技术——煤焦油、粗苯的回收与精制》", 31 March 2006 * |
| 常鸿雁等: "《煤液化残渣及其萃取物的热解特性研究》", 《神华科技》 * |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218294B (en) * | 2018-11-27 | 2021-07-23 | 宝武炭材料科技有限公司 | Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point |
| CN111218294A (en) * | 2018-11-27 | 2020-06-02 | 宝武炭材料科技有限公司 | Method for purifying quinoline insoluble coal-series asphalt with high softening point and high softening point |
| CN109734458A (en) * | 2019-01-23 | 2019-05-10 | 陕西师范大学 | A kind of synthetic method of asphalt impregnant |
| CN110256858B (en) * | 2019-06-12 | 2021-08-03 | 台州立拓能源有限公司 | Application of biomass oil as asphalt |
| CN110256858A (en) * | 2019-06-12 | 2019-09-20 | 台州立拓能源有限公司 | Application of the bio-oil as pitch |
| CN110540855A (en) * | 2019-08-29 | 2019-12-06 | 中海沥青股份有限公司 | Petroleum-series impregnating asphalt and preparation method thereof |
| CN110540855B (en) * | 2019-08-29 | 2021-01-15 | 中海沥青股份有限公司 | Petroleum-series impregnating asphalt and preparation method thereof |
| CN113621396A (en) * | 2020-05-07 | 2021-11-09 | 宝武炭材料科技有限公司 | Preparation method of refined medium-temperature asphalt |
| CN111501134A (en) * | 2020-05-28 | 2020-08-07 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN111501134B (en) * | 2020-05-28 | 2022-05-06 | 陕西师范大学 | Method for preparing general-purpose asphalt-based carbon fiber from coal liquefaction residues |
| CN114836230A (en) * | 2021-02-02 | 2022-08-02 | 圣德光科技发展(北京)有限公司 | Preparation method of adhesive and impregnant |
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