CN109181732A - A kind of method that coal tar preparation can spin pitch - Google Patents
A kind of method that coal tar preparation can spin pitch Download PDFInfo
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- CN109181732A CN109181732A CN201811158411.8A CN201811158411A CN109181732A CN 109181732 A CN109181732 A CN 109181732A CN 201811158411 A CN201811158411 A CN 201811158411A CN 109181732 A CN109181732 A CN 109181732A
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- coal tar
- extract
- extractant
- 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
- C10C3/08—Working-up pitch, asphalt, bitumen by selective extraction
-
- 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
Abstract
The method that a kind of preparation of coal tar can spin pitch is that coal tar high-temperature pressure-reduction is distilled to obtain coal tar heavy duty component；It carries out coal tar heavy duty component and level-one extractant that level-one extract liquor and level-one extract remainder is obtained by extraction；Heavy oil is obtained after level-one extract liquor recycling design；Level-one extract remainder is extracted after setting drying with second level extractant, and second level extract liquor and second level extract remainder are obtained；Asphaltene is obtained after second level extract liquor recycling design；Drying second level extract remainder and three-level extractant carry out that three-level extract liquor and three-level extract remainder is obtained by extraction；Three-level extract liquor recycling design obtains preasphaltene after supplying；Asphaltene uniformly mixed with asphaltene be put into fixed bed reactors carry out thermal polycondensation preparation can spin pitch.The present invention has the advantages that skill is simple, solvent easily recycles, is low in cost, high income.
Description
Technical field
The invention belongs to a kind of methods for spinning pitch for preparing asphalt-based carbon fiber, and in particular to one kind is original with coal tar
The method that material preparation can spin pitch.
Background technique
Asphalt base carbon fiber is one kind using asphalt or coal tar pitch as raw material, purification, spinning, pre-oxidation through pitch,
The obtained phosphorus content that is carbonized is greater than 92% special fibre.Since it is with excellent thermodynamic property, it is widely used in military project
And civil field.
Coal tar heavy duty component is a kind of composition and structure is all very complicated and the organic mixture based on aromatic hydrocarbon,
The series of products such as deep processing light oil obtained, heavy constituent are the base stocks of the industries such as synthetic plastic, synthetic fibers.Wherein weigh
Oil, asphalitine (mixture of asphaltene and preasphaltene) are coal tar heavy duty component important components, and heavy oil is coal tar
Heavy distillate accounts for 15% of total weight or so, and heaviness and aromatic ring degree are lower, be typically used as coal liquefaction circulation solvent or
Fuel.Asphalitine (mixture of asphaltene and preasphaltene) accounts for 40% of total weight or so, carbon content with higher and
Aromaticity, therefore it is prone to polymerization or cross-linking reaction, it is suitable for preparing carbon material.And the asphalitine phase in coal tar heavy duty component
Than having in asphalt and artificial synthesized pitch, good fluidity, easy graphitization, cheap, carbonization rate is high and is easy to concentrate
The characteristics of developing to enlarged direction is processed, advantage is had more in terms of carbon material development and utilization.
In order to guarantee that the Carbon fibe haveing excellent performance is made in coal tar heavy duty component, it is necessary first to the weight of low molecular weight therein
Oil, free carbon and solid impurity etc. are separated, and the asphaltene in asphalitine is obtained.Asphaltene be by polycyclic condensed aromatic hydrocarbon and
Its alkyl substituents composition, average molecular weight with higher and armaticity, it is system that phosphorus content is high and polymerization or crosslinking easily occurs
It can be passed through high temperature thermopolymerization, pressurized high-temperature hot polymerization, vacuum high-temperature hot polymerization, the heat of oxidation by the presoma of standby functionality Carbon Materials
The methods of polymerization, crosslinking synthetic method, catalysis synthesis process and hydrogenation modification thermal polymerization, which are made, can spin carbon fiber.Its shortcoming is that pitch
Alkene content in asphalitine is lower, only accounts for~30% or so.Preasphaltene is similar to asphaltene structure, the content in asphalitine
Reach 70% or so, but its molecular weight is larger, when direct thermal polycondensation is easy to happen excessively polymerization and generates secondary quinoline non-soluble
Object.
Summary of the invention
The object of the present invention is to provide a kind of simple process, solvents easily to recycle, low in cost, high income is with coal tar
Raw material prepares the method that can spin pitch.
The present invention is in view of the above-mentioned problems, develop a kind of simple process, solvent easily recycle, low-cost solvent cuts coal
The process route of asphaltene, preasphaltene in tar heavy constituent will prepare the method that can spin pitch, so not after its re-modulation
Preasphaltene can be only made full use of to prepare the characteristic of carbon fiber precursor, and the preparation of coal tar heavy duty component also can be improved to spin
The yield of pitch.
To achieve the above object, a kind of coal tar of the invention prepares the method that can spin pitch, comprising the following steps:
(1) coal tar is distilled through high-temperature pressure-reduction in a kettle, surplus materials is coal tar heavy duty component；
(2) coal tar heavy duty component is added in Soxhlet extractor together with level-one extractant and is extracted, is separated by solid-liquid separation,
Obtain level-one extract liquor and level-one extract remainder；
(3) by the method recycling design of the level-one extract liquor rotary evaporation in step (2) for being recycled, solvent recovery
Steaming excess afterwards is heavy oil；
(4) the level-one extract remainder in step (2) is set in drying to constant weight；
(5) the drying level-one extract remainder in step (4) is added in Soxhlet extractor together with second level extractant and is carried out
Extraction is separated by solid-liquid separation, obtains second level extract liquor and second level extract remainder；
(6) by the method recycling design of the second level extract liquor rotary evaporation in step (5) for being recycled, solvent recovery
Steaming excess afterwards is asphaltene；
(7) the second level extract remainder in step (5) set to drying to constant weight；
(8) the drying second level extract remainder in step (7) is added in Soxhlet extractor together with three-level extractant and is carried out
Extraction is separated by solid-liquid separation, obtains three-level extract liquor and three-level extract remainder；
(9) by the method recycling design of the three-level extract liquor rotary evaporation in step (8) for being recycled, solvent recovery
Steaming excess afterwards is preasphaltene；
(10) asphaltene of step (6) is uniformly mixed with the preasphaltene of step (9), obtains mixture, and will mixing
Object, which is put into progress thermal polycondensation preparation in fixed bed reactors, can spin pitch.
Further, in step (1), the coal tar heavy duty component is by coal tar through 250-300 DEG C, and vacuum degree is
Residue after 0.08-0.09MPa vacuum distillation, wherein being 10%-15% heavy oil, weight ratio 30%- comprising weight ratio
45% asphalitine.
Further, in step (2), the mass ratio of the coal tar heavy duty component and level-one extractant is 1:2-1:6, extraction
Taking temperature is 80-95 DEG C, extraction time 12-15h.
Further, in step (2), the level-one extractant is one of pentane, n-hexane, normal heptane or several
The mixture of kind.
Further, in step (4) and (7), the drying and processing condition of extract remainder is that 2-4h is first placed in ventilating kitchen, so
Afterwards in vacuum degree 0.08-0.09MPa, drying temperature is dry 2-8h at 100-180 DEG C.
Further, in step (5), the mass ratio of the dry level-one extract remainder and second level extractant is 1:2-1:6,
Extraction temperature is 110-125 DEG C, extraction time 12-15h.
Further, in step (5), the second level extractant is the mixed of one or more of benzene,toluene,xylene
Close object.
Further, in step (8), the mass ratio of the dry second level extract remainder and three-level extractant is 1:2-1:6,
Extraction temperature is 70-100 DEG C, extraction time 5-15h.
Further, in step (8), the three-level extractant is tetrahydrofuran.
Further, in step (10), the mass ratio of the preasphaltene of the asphaltene and step (9) of step (6) is 3:1-
1:2.The condition of thermal polycondensation are as follows: air mass flow 1-5mL/min/g, 1-10 DEG C of heating rate/min, final temperature are 360-450 DEG C,
Constant temperature time is 2-10h.
Further, in step (10), the evaluation criterion for spinning pitch spinnability of preparation is single hole melt spinning method, often
Secondary feeding quantity is that 5-30g can spin pitch, and spinning temperature is higher than 30-50 DEG C of softening point temperature, spinning pressure 0.3-1MPa, spinneret
Mouth diameter is 0.3 μm, speed of wrap 200m/min.
For the pitch prepared in accordance with the present invention that spins with excellent spinning properties, when melt-spun is streamline wide area type structure, H/C
Atom is relatively low (0.53-0.56), and aromaticity is higher (0.76-0.80), and softening point is higher (201 DEG C -230 DEG C), melting range it is narrow (≤
20 DEG C), rheological property is excellent after melting, good spinnability (single hole melt spinning length > 4500m)；Pitch can be spun through melt spinning,
The monofilament tensile strength of asphalt-based carbon fiber is 550-980MPa after pre-oxidation and carbonization, and single wire fracture elongation is 2.05-
2.4%.
The invention has the following advantages over the prior art:
It is mainly to remove the coal tar pitch of quinoline insolubles and ash content as raw material that existing coal base, which can spin pitch, and main component is
Asphaltene is prepared by thermal polycondensation, obtained to spin pitch there are higher low molecular compound amounts, and softening point is inclined
It is low, range of molecular weight distributions is wide, be to be easy to happen fracture of wire, and spun fibre strength is low in melt spinning in this way.The present invention with
Coal tar heavy duty group is divided into raw material, has carried out effective cutting to wherein asphaltene and preasphaltene using different solvents, by adjusting
The molecular weight distribution of asphaltene and preasphaltene, mixed proportion are prepared for lower low molecular compound content, and softening point is high, divides
The coal-based carbon fibrous raw material of son amount narrow distribution range spins pitch, and preparation process is simple, easy and safe to operate, is produced into
This is low, and raw material availability is high, and the utilization rate of tar heavy constituent greatly improved；Extractant of the invention can recycle,
With good economy.
Specific embodiment
Embodiment 1
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 250 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 825g.
50g coal tar heavy duty component and 100g normal heptane are added in Soxhlet extractor step 2, are heated to 80 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 15h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is positive heptane soluble species, and the residue after solvent recovery is placed in ventilating kitchen the 3h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 5g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 90g toluene, is heated to 125
DEG C, extract liquor S2 and extract remainder D2 are obtained after extracting 12h, is then recycled obtained extract liquor S2 with Rotary Evaporators, solvent
Residue after the recovery is xylene solubles.Xylene solubles are first placed into 2h in ventilating kitchen, it is dry then to put it into vacuum
In dry case, setting vacuum degree is that 0.09MPa obtains asphaltene, quality 10g after being heated to 100 DEG C of dry 8h.Extract remainder is set
It dries to constant weight in baking oven, it is added in Soxhlet extractor with 70g tetrahydrofuran, 70 DEG C is heated to, is extracted after extracting 15h
Liquid S3 and extract remainder D3 are taken, then recycles obtained extract liquor S3 with Rotary Evaporators, the residue after solvent recovery is four
Hydrogen furans soluble matter.Tetrahydrofuran soluble matter is first placed into 2h in ventilating kitchen, then puts it into vacuum oven, is arranged
Vacuum degree is 0.08MPa, after being heated to 110 DEG C of dry 5h, obtains preasphaltene, quality 25g.Extract remainder sets interior baking in baking oven
It does as residue.
Step 3 mixes 10g asphaltene with 5g preasphaltene, and gained mixture first places 4h in ventilating kitchen, then will
Mixture is put into electric drying oven with forced convection, after being heated to 110 DEG C of dry 8h, obtains uniformly mixed mixture.By mixture
It is put into fixed bed reactors, is continually fed into flow and is the air of 15mL/min, and be heated to the heating rate of 1 DEG C/min
380 DEG C, natural cooling after thermal polycondensation 10h, obtaining softening melting range is 230-247 DEG C, and ash content is 0.018% to spin pitch.It can
Pitch is spun through 265 DEG C of spinning temperature, spinning pressure 0.6MPa, spinning nozzle diameter is 0.3 μm, is melted under speed of wrap 200m/min
Melt spinning, fiber precursor is made.
Embodiment 2
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 300 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 750g.
50g coal tar heavy duty component and 150g pentane are added in Soxhlet extractor step 2, are heated to 80 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 12h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is pentane soluble matter, and the residue after solvent recovery is placed in ventilating kitchen the 4h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 5.01g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 135g dimethylbenzene, is added
Heat obtains extract liquor S2 and extract remainder D2 after extracting 14h to 120 DEG C, then returns obtained extract liquor S2 Rotary Evaporators
It receives, the residue after solvent recovery is xylene soluble part.Xylene soluble part is first placed into 3h in ventilating kitchen, then by it
It is put into vacuum oven, setting vacuum degree is that 0.09MPa obtains asphaltene, quality is after being heated to 150 DEG C of dry 8h
13g.Extract remainder is set in baking oven and dries to constant weight, it is added in Soxhlet extractor with 150g tetrahydrofuran, is heated to 80 DEG C, extraction
Extract liquor S3 and extract remainder D3 are obtained after taking 14h, is then recycled obtained extract liquor S3 with Rotary Evaporators, after solvent recovery
Residue be tetrahydrofuran soluble matter.Tetrahydrofuran soluble matter is first placed into 4h in ventilating kitchen, then puts it into vacuum
In drying box, setting vacuum degree is that 0.08MPa obtains preasphaltene, quality 24g after being heated to 120 DEG C of dry 10h.Raffinate
It is residue that object, which sets interior drying in baking oven,.
Step 3 mixes 10g asphaltene with 10g preasphaltene, and gained mixture first places 3h in ventilating kitchen, then
Mixture is put into electric drying oven with forced convection, after being heated to 130 DEG C of dry 6h, obtains uniformly mixed mixture.It will mixing
Object is put into fixed bed reactors, is continually fed into the air that flow is 40mL/min, is heated to the heating rate of 2 DEG C/min
400 DEG C, natural cooling after thermal polycondensation 6h, obtaining softening melting range is 224-240 DEG C, and ash content is 0.021% to spin pitch.It can spin
For pitch through 274 DEG C of spinning temperature, spinning pressure 0.5MPa, spinning nozzle diameter is 0.3 μm, is melted under speed of wrap 200m/min
Fiber precursor is made in spinning.
Embodiment 3
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 280 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 775g.
50g coal tar heavy duty component and 200g n-hexane are added in Soxhlet extractor step 2, are heated to 90 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 12h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is positive hexane solubles, and the residue after solvent recovery is placed in ventilating kitchen the 3h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 5.12g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 180g benzene, is heated to
120 DEG C, extract liquor S2 and extract remainder D2 are obtained after extracting 15h, then recycles obtained extract liquor S2 with Rotary Evaporators, it is molten
Agent residue after the recovery is benzene soluble matter.Benzene soluble matter is first placed into 12h in ventilating kitchen, then puts it into vacuum drying
In case, setting vacuum degree is that 0.09MPa obtains asphaltene, quality 12g after being heated to 180 DEG C of dry 2h.Extract remainder sets baking
It dries to constant weight in case, it is added in Soxhlet extractor with 130g tetrahydrofuran, 100 DEG C is heated to, is extracted after extracting 15h
Liquid S3 and extract remainder D3 are taken, then recycles obtained extract liquor S3 with Rotary Evaporators, the residue after solvent recovery is four
Hydrogen furans soluble matter.Tetrahydrofuran soluble matter is first placed into 4h in ventilating kitchen, then puts it into vacuum oven, is arranged
Vacuum degree is 0.08MPa, after being heated to 110 DEG C of dry 8h, obtains preasphaltene, quality 23g.Extract remainder sets interior baking in baking oven
It does as residue.
Step 3 mixes 10g asphaltene with 15g preasphaltene, and gained mixture first places 2h in ventilating kitchen, then
Mixture is put into electric drying oven with forced convection, after being heated to 160 DEG C of dry 2h, obtains uniformly mixed mixture.It will mixing
Object is put into fixed bed reactors, is continually fed into the air that flow is 75mL/min, is heated to the heating rate of 5 DEG C/min
450 DEG C, natural cooling after thermal polycondensation 2h, obtaining softening melting range is 202-220 DEG C, and ash content is that 0.03% can spin pitch.Drip can be spun
For blueness through 242 DEG C of spinning temperature, spinning pressure 0.4MPa, spinning nozzle diameter is 0.3 μm, melts and spins under speed of wrap 200m/min
Fiber precursor is made in silk.
Embodiment 4
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 270 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 770g.
50g coal tar heavy duty component and 250g n-hexane are added in Soxhlet extractor step 2, are heated to 95 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 13h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is positive hexane solubles, and the residue after solvent recovery is placed in ventilating kitchen the 4h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 5.15g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 270g benzene, is heated to
125 DEG C, extract liquor S2 and extract remainder D2 are obtained after extracting 12h, then recycles obtained extract liquor S2 with Rotary Evaporators, it is molten
Agent residue after the recovery is benzene soluble matter.Benzene soluble matter is first placed into 12h in ventilating kitchen, then puts it into vacuum drying
In case, setting vacuum degree is that 0.09MPa obtains asphaltene, quality 13g after being heated to 140 DEG C of dry 12h.Extract remainder sets baking
It dries to constant weight in case, it is added in Soxhlet extractor with 190g tetrahydrofuran, 70 DEG C is heated to, is extracted after extracting 14h
Liquid S3 and extract remainder D3 are taken, then recycles obtained extract liquor S3 with Rotary Evaporators, the residue after solvent recovery is four
Hydrogen furans soluble matter.Tetrahydrofuran soluble matter is first placed into 8h in ventilating kitchen, then puts it into vacuum oven, is arranged
Vacuum degree is 0.08MPa, after being heated to 160 DEG C of dry 4h, obtains preasphaltene, quality 22g.Extract remainder sets interior baking in baking oven
It does as residue.
Step 3 mixes 13g asphaltene with 4.3g preasphaltene, and gained mixture first places 4h in ventilating kitchen, then
Mixture is put into electric drying oven with forced convection, after being heated to 180 DEG C of dry 2h, obtains uniformly mixed mixture.It will mixing
Object is put into fixed bed reactors, is continually fed into the air that flow is 104mL/min, is heated to the heating rate of 10 DEG C/min
400 DEG C, natural cooling after thermal polycondensation 8h, obtaining softening melting range is 223-232 DEG C, and ash content is that 0.01% can spin pitch.Drip can be spun
For blueness through 263 DEG C of spinning temperature, spinning pressure 1.0MPa, spinning nozzle diameter is 0.3 μm, melts and spins under speed of wrap 200m/min
Fiber precursor is made in silk.
Embodiment 5
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 290 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 780g.
50g coal tar heavy duty component and 300g pentane are added in Soxhlet extractor step 2, are heated to 85 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 14h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is pentane soluble matter, and the residue after solvent recovery is placed in ventilating kitchen the 3h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 5.2g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 225g dimethylbenzene, heating
To 130 DEG C, extract liquor S2 and extract remainder D2 are obtained after extracting 14h, then recycles obtained extract liquor S2 with Rotary Evaporators,
Residue after solvent recovery is xylene soluble part.Xylene soluble part is first placed into 3h in ventilating kitchen, is then put
Enter in vacuum oven, setting vacuum degree is that 0.09MPa obtains asphaltene, quality 14g after being heated to 130 DEG C of dry 6h.
Extract remainder is set in baking oven and dries to constant weight, it is added in Soxhlet extractor with 155g tetrahydrofuran, is heated to 90 DEG C, extraction
Extract liquor S3 and extract remainder D3 are obtained after 14h, are then recycled obtained extract liquor S3 with Rotary Evaporators, after solvent recovery
Residue is tetrahydrofuran soluble matter.Tetrahydrofuran soluble matter is first placed into 2h in ventilating kitchen, it is dry then to put it into vacuum
In dry case, setting vacuum degree is that 0.08MPa obtains preasphaltene, quality 25g after being heated to 120 DEG C of dry 6h.Extract remainder
Setting interior drying in baking oven is residue.
Step 3 mixes 5g asphaltene with 10g preasphaltene, and gained mixture first places 4h in ventilating kitchen, then will
Mixture is put into electric drying oven with forced convection, after being heated to 110 DEG C of dry 8h, obtains uniformly mixed mixture.By mixture
It is put into fixed bed reactors, is continually fed into the air that flow is 60mL/min, is heated to 400 with the heating rate of 4 DEG C/min
DEG C, natural cooling after thermal polycondensation 4h, obtaining softening melting range is 209-229 DEG C, and ash content can spin pitch for 0.018%.Pitch can be spun
Through 239 DEG C of spinning temperature, spinning pressure 0.3MPa, spinning nozzle diameter is 0.3 μm, melts and spins under speed of wrap 200m/min
Fiber precursor is made in silk.
Embodiment 6
Coal tar is evaporated under reduced pressure in 1500 grams of quality reaction kettle, after being heated to 250 DEG C (vacuum degree after 2h by step 1
For 0.08MPa), surplus material is taken out from the autoclave, as coal tar heavy duty component, quality 830g.
50g coal tar heavy duty component and 300g normal heptane are added in Soxhlet extractor step 2, are heated to 90 DEG C, extraction
Extract liquor S1 and extract remainder D1 are obtained after 14h, are then recycled obtained extract liquor S1 with Rotary Evaporators, after solvent recovery
Residue is positive heptane soluble species, and the residue after solvent recovery is placed in ventilating kitchen the 2h that divulges information, obtains heavy oil, weighed
Obtaining heavy oil is 6g.Extract remainder D1 sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 265g toluene, is heated to
125 DEG C, extract liquor S2 and extract remainder D2 are obtained after extracting 15h, then recycles obtained extract liquor S2 with Rotary Evaporators, it is molten
Agent residue after the recovery is xylene solubles.Xylene solubles are first placed into 4h in ventilating kitchen, then put it into vacuum
In drying box, setting vacuum degree is that 0.09MPa obtains asphaltene, quality 12g after being heated to 180 DEG C of dry 3h.Extract remainder
It sets in baking oven and dries to constant weight, it is added in Soxhlet extractor with 230g tetrahydrofuran, 100 DEG C is heated to, is obtained after extracting 15h
To extract liquor S3 and extract remainder D3, then obtained extract liquor S3 is recycled with Rotary Evaporators, the residue after solvent recovery
For tetrahydrofuran soluble matter.Tetrahydrofuran soluble matter is first placed into 3h in ventilating kitchen, is then put it into vacuum oven,
Setting vacuum degree is that 0.08MPa obtains preasphaltene, quality 26g after being heated to 140 DEG C of dry 15h.Extract remainder sets baking oven
In it is interior drying be residue.
Step 3 mixes 10g asphaltene with 15g preasphaltene, and gained mixture first places 4h in ventilating kitchen, then
Mixture is put into electric drying oven with forced convection, after being heated to 150 DEG C of dry 5h, obtains uniformly mixed mixture.It will mixing
Object is put into fixed bed reactors, is continually fed into the air that flow is 120mL/min, is heated to the heating rate of 3 DEG C/min
450 DEG C, natural cooling after thermal polycondensation 5h, obtaining softening melting range is 201-220 DEG C, and ash content is that 0.022% can spin pitch.Drip can be spun
For blueness through 238 DEG C of spinning temperature, spinning pressure 0.7MPa, spinning nozzle diameter is 0.3 μm, melts and spins under speed of wrap 200m/min
Fiber precursor is made in silk.
The technical indicator of pitch can be spun made from each embodiment of table 1
The above description is only a preferred embodiment of the present invention, the present invention that the above embodiments are only used to help understand
Method and its core concept, it is to be understood that, to those skilled in the art, in the premise for not departing from the principle of the invention
Under, it can be with several improvements and modifications are made to the present invention.Protection scope of the present invention is limited by the accompanying claims.
Claims (12)
1. a kind of coal tar prepares the method that can spin pitch, it is characterised in that include the following steps:
(1) coal tar is distilled through high-temperature pressure-reduction in a kettle, surplus materials is coal tar heavy duty component；
(2) coal tar heavy duty component is added in Soxhlet extractor together with level-one extractant and is extracted, be separated by solid-liquid separation, obtain
Level-one extract liquor and level-one extract remainder；
(3) by the method recycling design of the level-one extract liquor rotary evaporation in step (2) for being recycled, after solvent recovery
Steaming excess is heavy oil；
(4) the level-one extract remainder in step (2) is set in drying to constant weight；
(5) the drying level-one extract remainder in step (4) is added in Soxhlet extractor together with second level extractant and is extracted,
It is separated by solid-liquid separation, obtains second level extract liquor and second level extract remainder；
(6) by the method recycling design of the second level extract liquor rotary evaporation in step (5) for being recycled, after solvent recovery
Steaming excess is asphaltene；
(7) the second level extract remainder in step (5) set to drying to constant weight；
(8) the drying second level extract remainder in step (7) is added in Soxhlet extractor together with three-level extractant and is extracted,
It is separated by solid-liquid separation, obtains three-level extract liquor and three-level extract remainder；
(9) by the method recycling design of the three-level extract liquor rotary evaporation in step (8) for being recycled, after solvent recovery
Steaming excess is preasphaltene；
(10) asphaltene of step (6) is uniformly mixed with the preasphaltene of step (9), obtains mixture, and mixture is put
Pitch can be spun by entering to carry out thermal polycondensation preparation in fixed bed reactors.
2. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that described in step (1)
Coal tar heavy duty component is to include weight ratio for 10%-15% heavy oil, and weight ratio is 30%-45% asphalitine.
3. a kind of coal tar as claimed in claim 2 prepares the method that can spin pitch, it is characterised in that coal tar heavy duty component by
Coal tar is through 250-300 oC, vacuum degree is the residue after 0.08-0.09MPa vacuum distillation.
4. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that the coal tar recombination
Dividing with the mass ratio of level-one extractant is 1:2-1:6, extraction temperature 80-95oC, extraction time are 12-15 h.
5. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that further, step
(2) in, the level-one extractant is the mixture of one or more of pentane, n-hexane, normal heptane.
6. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that in step (4) and (7),
The drying and processing condition of extract remainder is that 2-4 h is first placed in ventilating kitchen, then in vacuum degree 0.08-0.09 MPa, dry temperature
Spend 100-180oUnder C, dry 2-8 h.
7. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that further, step
(5) in, the mass ratio of the dry level-one extract remainder and second level extractant is 1:2-1:6, extraction temperature 110-125oC,
Extraction time is 12-15 h.
8. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that described in step (5)
Second level extractant is the mixture of one or more of benzene,toluene,xylene.
9. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that described in step (8)
The mass ratio of dry second level extract remainder and three-level extractant is 1:2-6, extraction temperature 70-100oC, extraction time 5-15
h。
10. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that described in step (8)
Three-level extractant is tetrahydrofuran.
11. a kind of coal tar as described in claim 1 prepares the method that can spin pitch, it is characterised in that further, step
(10) in, the mass ratio of the preasphaltene of the asphaltene and step (9) of step (6) is 3:1-1:2, the condition of thermal polycondensation are as follows: empty
Throughput is 1-5 mL/min/g, heating rate 1-10oC/min, final temperature 360-450oC, constant temperature time are 2-10 h.
12. as prepared by any one of claim 1-11 institute's method spins pitch, it is characterised in that it is former that peucinous H/C can be spun
Son is 0.53-0.56, aromaticity 0.76-0.80, softening point 201oC-230oC。
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| CN110578188A (en) * | 2019-08-12 | 2019-12-17 | 中国科学院山西煤炭化学研究所 | Method for preparing spinnable asphalt by co-thermal polycondensation of acid anhydride modified coal asphalt and kerosene co-refining residue |
| CN111004641A (en) * | 2019-12-27 | 2020-04-14 | 西安郎格飞博科技有限公司 | Spinnable asphalt and preparation method thereof |
| CN111925818A (en) * | 2020-08-14 | 2020-11-13 | 辽宁信德新材料科技股份有限公司 | Carbon fiber spinnable asphalt and preparation method and application thereof |
| CN112625722A (en) * | 2020-11-14 | 2021-04-09 | 北京化工大学 | Method for preparing spinnable asphalt by combining raw materials and application of spinnable asphalt in preparation of carbon fibers |
| EP4045703A4 (en) * | 2019-10-17 | 2024-04-17 | Tangold Inc | Fabrication of carbon fibers with high mechanical properties |
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| CN112625722B (en) * | 2020-11-14 | 2022-10-28 | 北京化工大学 | Method for preparing spinnable asphalt by combining raw materials and application of spinnable asphalt in preparation of carbon fibers |
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