CN107163970A - A kind of method that FCC slurry alkylation modification sedimentation separation prepares mesophase pitch - Google Patents
A kind of method that FCC slurry alkylation modification sedimentation separation prepares mesophase pitch Download PDFInfo
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- CN107163970A CN107163970A CN201710580221.4A CN201710580221A CN107163970A CN 107163970 A CN107163970 A CN 107163970A CN 201710580221 A CN201710580221 A CN 201710580221A CN 107163970 A CN107163970 A CN 107163970A
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 29
- 230000029936 alkylation Effects 0.000 title claims abstract description 24
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 24
- 230000004048 modification Effects 0.000 title claims abstract description 10
- 238000012986 modification Methods 0.000 title claims abstract description 10
- 238000004062 sedimentation Methods 0.000 title claims description 16
- 238000000926 separation method Methods 0.000 title claims description 11
- 239000002002 slurry Substances 0.000 title description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002994 raw material Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 230000003197 catalytic effect Effects 0.000 claims abstract description 11
- 239000000654 additive Substances 0.000 claims abstract description 10
- 230000000996 additive effect Effects 0.000 claims abstract description 10
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 7
- 239000003208 petroleum Substances 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 3
- 238000010926 purge Methods 0.000 claims description 12
- 229920002125 Sokalan® Polymers 0.000 claims description 8
- 239000004584 polyacrylic acid Substances 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 4
- 230000001195 anabolic effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000001816 cooling Methods 0.000 claims 1
- 238000009987 spinning Methods 0.000 abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 7
- 238000003825 pressing Methods 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- 230000002269 spontaneous effect Effects 0.000 abstract description 2
- 238000011112 process operation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 18
- 230000016507 interphase Effects 0.000 description 16
- 239000000203 mixture Substances 0.000 description 9
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000011295 pitch Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 description 4
- 229920000049 Carbon (fiber) Polymers 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000004917 carbon fiber Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 4
- 238000006068 polycondensation reaction Methods 0.000 description 4
- 241000772415 Neovison vison Species 0.000 description 3
- 150000001491 aromatic compounds Chemical class 0.000 description 3
- 239000010620 bay oil Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000006073 displacement reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000002715 modification method Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Natural products IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005899 aromatization reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 125000000753 cycloalkyl group Chemical group 0.000 description 1
- 230000020335 dealkylation Effects 0.000 description 1
- 238000006900 dealkylation reaction Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- HVTICUPFWKNHNG-UHFFFAOYSA-N iodoethane Chemical compound CCI HVTICUPFWKNHNG-UHFFFAOYSA-N 0.000 description 1
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000011331 needle coke Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
Classifications
-
- 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
Abstract
The invention provides a kind of high-purity, the preparation method of the spinnability petroleum base mesophase pitch of low softening point, this method is the catalytic cracked oil pulp by naphthene base crude through vacuum distillation, cut of its boiling point between 380~540 DEG C is cut as raw material, alkylation modification additive is added, under 380~450 DEG C, nitrogen first pressing 5MPa, 1~8h of spontaneous pressure reaction, then 260~350 DEG C are cooled to, 0.2~1.5h is purged with high pure nitrogen under normal pressure, obtains modified oil.Modified oil continues to react 2 12h, obtains middle phase precursor under 400~480 DEG C, pressure 4MPa.Phase precursor settles 0.5~3.5h at 280~360 DEG C in the middle of afterwards under normal pressure, stops reaction, is cooled to two layers of product point in normal temperature, reactor, and lower floor is prepared high-quality mesophase pitch.Present invention process operation is relatively simple, production cost is low, and obtained mesophase pitch anisotropic structure content is high (＞ 98%), and softening point is low (230~250 DEG C), carbon residue height (73~78%), spinning property is good.
Description
Technical field
Pass through alkylation modification-sedimentation separation combination process the present invention relates to a kind of catalytic cracked oil pulp of naphthene base crude
The method for preparing mesophase pitch, belongs to mink cell focus processing and new carbon prepares crossing domain.
Background technology
Mesophase pitch (mesophase pitch, abbreviation MP) is with pitch, mink cell focus, coal tar, high molecular polymer
And other aromatic compounds to be raw material react through thermal polycondensation be made or using aromatic compound be raw material through catalyzing and condensing
The mixture of flat plate-like condensed-nuclei aromatics composition, it is the advanced function material such as carbon fiber, needle coke, electrode material and Carbon foam to be recognized
The outstanding parent of material, these functional materials will be played in fields such as national defense industry, Aero-Space, hard-core technology, daily lifes
Great function.Oil refining process can produce the accessory substance that some are rich in aromatic hydrocarbons, the FCC oil that catalytic cracking (FCC) technique is produced
Slurry has higher C/H atomic ratios, is the desirable feedstock for preparing high-quality carbonaceous mesophase pitch.Compared to preparing carbon both at home and abroad at present
For the pure aromatics material such as primary raw material-polyacrylonitrile of fiber, produced in the petroleum refining process such as mink cell focus, asphalt
Accessory substance is cheap, abundance, therefore the preparation technology of petroleum base mesophase pitch is developed at present carbon materials both at home and abroad
Expect the focus and emphasis of area research.
The raw material mix and preparation technology of mesophase pitch are to determine the property such as interphase structure of polarized light and molecular structure
Key factor.Alkylation modification method refers to connects alkyl side chain on raw material condensed-nuclei aromatics molecule, the structure group of feed change molecule
Into so as to adjust carbonization reaction speed, the content of alkyl substituent, is finally reached raising interphase point in the middle phase molecule of change
Sub- mobility, the effect for improving interphase performance.Korai etc. is compared the interphase that coal tar asphalt is prepared with A240 pitches
Compared with, it is found that interphase molecular melting prepared by A240 pitches is good, this be due in its molecule containing more alkyl side chain and
Cycloalkane structure, molecular structure determines product property, thus interphase prepared by A240 pitches has preferable anisotropic optical
Structure.A kind of higher mesophase pitch of condensation degree is alkylated modified with reduction by Eser etc. with iodomethane and iodoethane, point
The hydrogenated bitumen containing more methyl and ethyl has not been obtained, and hydrogenated bitumen, which continues to carbonize, prepares interphase, and he has found interphase
The anisotropic structure content and molecular volume of pitch change with the difference of methyl and ethyl introduction volume, compare without alkyl
The mesophase pitch that change processing is obtained, after alkylation modification, anisotropic structure content is improved, and interphase molecular volume increases
Greatly.In addition, Korai etc. is contrasted mesophase pitch prepared by naphthalene and methyl naphthalene, it is believed that methyl naphthalene mesophase pitch optics
The reason for structure and preferable crystal structure is to remain part methyl structure in middle phase molecule.Then, Kwang etc. is in C9 bases
Between the molecular structure of asphalt phase studied, the soft of interphase can be reduced by demonstrating the presence of more methyl in middle phase molecule
Change point, increase crystal characteristic size.Greinke, which have studied light oil and be prepared after Friedel-Crafts after mesophase pitch, to be drawn
Conclusion, raw material take off small molecule that alkyl effect produces it is main be condensed to be formed during interphase in the charing later stage play a role, can
To reduce system viscosity, solvent action is played.Mochida etc. after quinoline insolubles in pitch (QI) alkylation pretreatment to preparing
The high Carbon Materials of degree of graphitization are gone out.It follows that alkylation modification method is also that a kind of middle phasic property can be improved
Effective ways.
Sedimentation separation method refers to separate two-phase by the isotropic phase density variation alternate with anisotropy, respectively
Met to the same sex on reactor top, and anisotropy phase can then be deposited in reactor lower part, then by physics cutting method, it is real
Now in charing system isotropic phase and anisotropy phase separation, anisotropy can be effectively improved by sedimentation method for separating
The content of structure.Spain CSIC researcher is separated using heat filtering method to petroleum base mesophase pitch, still
Preferable separating effect is not obtained, researcher proposes two separated by sedimentation in petroleum base mesophase pitch afterwards
Phase, and this method is optimized, the mesophase pitch that interphase content reaches 97vol.% is successfully obtained, the production
Product, which are easy to spin, obtains the carbon fiber with reasonable mechanical performance.Sedimentation separation method is simple to equipment requirement, is that one kind is easy to real
Existing phase disengagement method.It follows that using alkylation modification additive raw material is alkylated it is modified and to product or in
Between product carry out sedimentation separation be improve mesophase pitch quality effective means.
The distillate molecular weight distribution of raw material FCC slurry is wide, structure composition is complicated, only passes through the simple technological operation of a step
It is difficult to reach the purpose for preparing high modulus carbon fiber presoma mesophase pitch, therefore, two kinds or more of techniques is answered
Conjunction is to prepare the effective and feasible method of high-quality mesophase pitch.The present invention is by alkylation modification and two kinds of processes of sedimentation separation
It is compound to prepare mesophase pitch, raising product anisotropic structure content can be reached, softening point is reduced, spinning properties are improved
Purpose.
The content of the invention
It is an object of the invention to provide one kind with naphthene base crude catalytic cracked oil pulp mid-boiling point between 380~540 DEG C
Cut be raw material, the method for preparing mesophase pitch by alkylation modification-sedimentation separation combination process, to solve petroleum base
The problems such as mesophase pitch softening point is high, spinning properties are poor.The method technique is simpler, and production cost is low, obtained centre
Asphalt phase anisotropic structure content is high, and softening point is low, has large watershed type optical texture under polarisation, and spinning properties are good, are
Produce the excellent presoma of high modulus carbon fiber.
The method that a kind of FCC slurry alkylation modification-sedimentation separation of the present invention prepares mesophase pitch, its feature
It is to comprise the following steps：(1) by naphthene base crude catalytic cracked oil pulp through vacuum distillation, its boiling point is cut at 380~540 DEG C
Between cut be used as raw material；(2) a certain amount of alkylation modification additive is added, in 380~450 DEG C, initial nitrogen pressure
For under 5MPa, spontaneous pressure reacts 1~8h；(3) and then 260~350 DEG C are cooled to, under normal pressure with high pure nitrogen purging 0.2~
1.5h, obtains modified oil；(4) modified oil continues to react 2-12h, obtains interphase forerunner under 400~480 DEG C, pressure 4MPa
Body；(5) phase precursor is at 280~360 DEG C in the middle of after, 0.5~3.5h of heat sink drop under normal pressure, stops reaction, is cooled to normal temperature,
Two layers of product point in reactor, lower floor is prepared high-quality mesophase pitch.
In the step (2), alkylation additive is polyacrylic acid, alkylation additive and the mass ratio of raw material addition
For 0.05~~0.2:1；Alkylated reaction temperature is 400~440 DEG C, and the reaction time is 2~4h.
300~330 DEG C are cooled in the step (3), high pure nitrogen purges 0.5~1h；Purge high-purity used in reactor
The flow of nitrogen is 80~150mL/ (hg).
Reaction temperature is 420~450 DEG C in the step (4), and the reaction time is 4~10h；The softening of middle phase precursor
Point is 210~250 DEG C.
Hot settling temperature is 310~350 DEG C in the step (5), and the hot sedimentation time is 1~2h.
The present invention contains a small amount of using the vacuum distillate of naphthene base crude catalytic cracked oil pulp as raw material, in raw molecule
Alkyl side chain.During thermal polycondensation, dealkylation occurs for the alkyl side chain in raw molecule, produces free radical, promotes
Small molecule polycondensation forms macromolecular compound, is conducive to the formation of mesophase pitch.But taken when raw material contains excessive alkyl
During for base, a large amount of free radicals are produced when reaching feedstock cracking temperature, in system so that condensation reaction rate is accelerated, molecular weight is fast
Speed increase, system viscosity increase, mobility is deteriorated, and it is preferably orderly that the macromolecular aromatic compound resulted in has little time progress
Arrangement, so cause generation mesophase pitch molecular structure it is poor, thus alkylation additive selection and addition for
The formation of high-quality mesophase pitch is particularly important.The present invention is alkylation additive from polyacrylic acid, in certain process conditions
Under, modification is alkylated to raw material, the alkyl side chain content in appropriate increase raw material can reach improvement raw material mix composition
Purpose.The modified oil obtained after alkylation modification proceeds thermal polycondensation reaction and obtains middle phase precursor, interphase
Presoma includes isotropic structure and anisotropic structure, is that molecular weight distribution is wider, molecular structure composition is inhomogenous multiple
Hybrid compound, the present invention is separated to middle phase precursor using sedimentation method for separating, according to there is density contrast between two-phase,
Anisotropy is mutually deposited on reactor bottom, and isotropic phase is then on reactor top, by layered shaping, has just obtained high each
The mesophase pitch of anisotropy structural content.
Compared with the prior art the method for the present invention has advantages below：
1st, distillate of the raw material that the present invention is used for FCC slurry mid-boiling point between 380~540 DEG C, rich in aromatization
Compound, while without solid impurities such as the catalyst for having an impact the formation of interphase liquid crystal structure and development, improving interphase drip
Blue or green spinning properties；
2nd, alkylation additive polyacrylic acid can be effectively improved raw material mix composition, be formed with beneficial to mesophase structure shape
Into the modified oil with development, and polyacrylic acid consumption is few, has saved cost；
3rd, can effectively to solve mesophase pitch product each using the technique that alkylation modification-sedimentation separation is combined by the present invention
Anisotropy structural content is low, softening point is high and constitutes inhomogenous problem, improves the spinning properties of product.
Embodiment
The catalytic cracked oil pulp provided by the present invention with naphthene base crude is further discussed below through subtracting with reference to embodiment
Cut of the boiling point that pressure distillation is obtained between 380~540 DEG C is the method that raw material prepares mesophase pitch.
Embodiment 1：
By naphthene base crude catalytic cracked oil pulp the vacuum distillate 300g and 15g of Bohai Bay Oil (raw material addition
5wt%) polyacrylic acid is added to volume in 500ml stainless steel autoclaves；It is passed through empty in high pure nitrogen purging displacement kettle
Gas, continues to be filled with nitrogen to 5MPa first pressing, starts stirring, rotating speed is 500r/min, is warming up to 380 DEG C, from booster reaction 5h, so
Release pressure is cooled to 300 DEG C to normal pressure afterwards, purges 0.5h for 100mL/ (hg) high pure nitrogen using flow, is changed
Property oil；440 DEG C are continuously heating to, rotating speed 500r/min boosts to 4MPa, constant temperature and pressure reaction 6h, it is 221 to obtain softening point certainly
DEG C middle phase precursor；Be cooled to afterwards under 320 DEG C, normal pressure and settle 2h, product point two layers in reactor, lower floor be it is each to
The mesophase pitch that it is large watershed type optical texture under 98%, polarisation that anisotropic approach content, which is, its softening point is 237 DEG C, and H/C is former
Son is than being 0.52, and carbon residue is 75.2%, and when spinning temperature is 335 DEG C, tensile strength is up to 2.72GPa.
The optical texture and anisotropic structure content of mesophase pitch are soft by petrographic microscope and rock graphical analysis
Part is obtained；Softening point is determined using conventional needling method；The C of product, H element content use EP companies PE-2400SeriesHCHN
Elemental analyser is determined；Carbon residue determines (SH/T0170-92) using traditional electric furnace process；Spinning properties use domestic single screw rod spinning
Machine is measured.
Embodiment 2：
By naphthene base crude catalytic cracked oil pulp the vacuum distillate 260g and 52g of Bohai Bay Oil (raw material addition
20wt%) polyacrylic acid is added to volume in 500ml stainless steel autoclaves；It is passed through empty in high pure nitrogen purging displacement kettle
Gas, continues to be filled with nitrogen to 5MPa first pressing, starts stirring, rotating speed is 500r/min, is warming up to 450 DEG C, from booster reaction 1.5h,
Then release pressure is cooled to 320 DEG C to normal pressure, purges 0.3h for 100mL/ (hg) high pure nitrogen using flow, obtains
Modified oil；460 DEG C are continuously heating to, rotating speed 500r/min boosts to 4MPa, constant temperature and pressure reaction 4h, obtaining softening point is certainly
233 DEG C of middle phase precursor；It is cooled to afterwards under 320 DEG C, normal pressure and settles 2h, product divides two layers in reactor, lower floor is
The mesophase pitch that it is large watershed type optical texture under 98%, polarisation that anisotropic structure content, which is, its softening point is 243 DEG C,
H/C atomic ratios are 0.49, and carbon residue is 74.5%, and when spinning temperature is 338 DEG C, tensile strength is up to 2.69GPa.
Embodiment 3：
By naphthene base crude catalytic cracked oil pulp the vacuum distillate 300g and 24g of Bohai Bay Oil (raw material addition
8wt%) polyacrylic acid is added to volume in 500ml stainless steel autoclaves；It is passed through empty in high pure nitrogen purging displacement kettle
Gas, continues to be filled with nitrogen to 5MPa first pressing, starts stirring, rotating speed is 500r/min, is warming up to 430 DEG C, from booster reaction 3h, so
Release pressure is cooled to 300 DEG C to normal pressure afterwards, purges 0.5h for 100mL/ (hg) high pure nitrogen using flow, is changed
Property oil；440 DEG C are continuously heating to, rotating speed 500r/min boosts to 4MPa, constant temperature and pressure reaction 6h, it is 227 to obtain softening point certainly
DEG C middle phase precursor；Be cooled to afterwards under 320 DEG C, normal pressure and settle 2h, product point two layers in reactor, lower floor be it is each to
The mesophase pitch that it is large watershed type optical texture under 99%, polarisation that anisotropic approach content, which is, its softening point is 240 DEG C, and H/C is former
Son is than being 0.51, and carbon residue is 76.3%, and when spinning temperature is 338 DEG C, tensile strength is up to 2.85GPa.
Claims (6)
1. a kind of preparation method of the spinnability petroleum base mesophase pitch of high-purity, low softening point, it is characterised in that including with
Lower step：(1) by naphthene base crude catalytic cracked oil pulp through vacuum distillation, cut of its boiling point between 380~540 DEG C is cut
It is used as raw material；(2) a certain amount of alkylation modification additive is added, at 380~450 DEG C, under initial nitrogen pressure is 5MPa, from
1~8h of raw pressure reaction；(3) and then 260~350 DEG C are cooled to, purge 0.2~1.5h with high pure nitrogen under normal pressure, be modified
Oil；(4) modified oil continues to react 2-12h, obtains middle phase precursor under 400~480 DEG C, pressure 4MPa；(5) in after
Between phase precursor at 280~360 DEG C, 0.5~3.5h of heat sink drop under normal pressure, stop reaction, be cooled to product in normal temperature, reactor
Divide two layers, lower floor is prepared high-quality mesophase pitch.
2. the preparation method of mesophase pitch as claimed in claim 1, it is characterised in that：The preparation process is naphthene base crude
Cut of the catalytic cracked oil pulp mid-boiling point between 380~540 DEG C, by alkylation modification and the anabolic process of sedimentation separation.
3. the preparation method of mesophase pitch as claimed in claim 1, it is characterised in that：In the step (2), alkylation adds
Plus agent is polyacrylic acid, the mass ratio of alkylation additive and raw material addition for 0.05~~0.20:1；Alkylated reaction temperature
Spend for 400~440 DEG C, the reaction time is 2~4h.
4. the preparation method of mesophase pitch as claimed in claim 1, it is characterised in that：300 are cooled in the step (3)
~330 DEG C, high pure nitrogen purges 0.5~1h；The flow for purging high pure nitrogen used in reactor is 80~150mL/ (hg).
5. the preparation method of mesophase pitch as claimed in claim 1, it is characterised in that：Reaction temperature in the step (4)
For 420~450 DEG C, the reaction time is 4~10h；The softening point of middle phase precursor is 210~250 DEG C.
6. the preparation method of mesophase pitch as claimed in claim 1, it is characterised in that：Heat sink cooling in the step (5)
Spend for 310~350 DEG C, the hot sedimentation time is 1~2h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114959949A (en) * | 2022-04-27 | 2022-08-30 | 北京化工大学 | Fused ring aromatic carbon fiber and preparation method thereof |
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| CN106544758A (en) * | 2016-10-21 | 2017-03-29 | 中国石油大学(华东) | A kind of preparation method of high modulus pitch-based carbon fiber |
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- 2017-07-17 CN CN201710580221.4A patent/CN107163970A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106544758A (en) * | 2016-10-21 | 2017-03-29 | 中国石油大学(华东) | A kind of preparation method of high modulus pitch-based carbon fiber |
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| 向柠等: "煤焦油沥青添加废聚丙烯塑料制备改性中间相沥青", 《炭素技术》 * |
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| CN114959949A (en) * | 2022-04-27 | 2022-08-30 | 北京化工大学 | Fused ring aromatic carbon fiber and preparation method thereof |
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