CN112538362A - Method for improving rheological property of coal tar pitch - Google Patents
Method for improving rheological property of coal tar pitch Download PDFInfo
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- CN112538362A CN112538362A CN202011432801.7A CN202011432801A CN112538362A CN 112538362 A CN112538362 A CN 112538362A CN 202011432801 A CN202011432801 A CN 202011432801A CN 112538362 A CN112538362 A CN 112538362A
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- 238000000034 method Methods 0.000 title claims abstract description 45
- 239000011294 coal tar pitch Substances 0.000 title claims abstract description 28
- 239000011300 coal pitch Substances 0.000 claims abstract description 51
- 239000000852 hydrogen donor Substances 0.000 claims abstract description 29
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 26
- 238000004821 distillation Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 21
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000007789 sealing Methods 0.000 claims abstract description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 27
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 229910052717 sulfur Inorganic materials 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 239000011593 sulfur Substances 0.000 claims description 13
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 claims description 11
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 7
- 150000001454 anthracenes Chemical class 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 abstract description 12
- 230000003287 optical effect Effects 0.000 description 15
- 239000011302 mesophase pitch Substances 0.000 description 14
- 239000011280 coal tar Substances 0.000 description 11
- 239000011331 needle coke Substances 0.000 description 8
- 238000004939 coking Methods 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 238000005457 optimization Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000003245 coal Substances 0.000 description 3
- 230000003111 delayed effect Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000004005 microsphere Substances 0.000 description 3
- 229920000049 Carbon (fiber) Polymers 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000004917 carbon fiber Substances 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000011295 pitch Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 description 1
- 239000003830 anthracite Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 125000004855 decalinyl group Chemical group C1(CCCC2CCCCC12)* 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000002184 metal Chemical group 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 125000000147 tetrahydroquinolinyl group Chemical group N1(CCCC2=CC=CC=C12)* 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
- C10C3/023—Working-up pitch, asphalt, bitumen by chemical means reaction with inorganic compounds
-
- 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 invention relates to a method for improving rheological property of coal tar pitch. It comprises the following steps in sequence: (1) adding a hydrogen donor and coal tar pitch into a high-pressure kettle according to a certain mass ratio, fully mixing, and sealing the reaction kettle; (2) heating to raise the temperature of the materials in the kettle to 350-450 ℃, and keeping the constant temperature to perform hydrogenation reaction; then, when the temperature of the materials in the kettle is reduced to 200-320 ℃, pressure is released; recovering the residual hydrogen donor by reduced pressure distillation, and then cooling to room temperature; stirring in the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process; (3) and heating the treated coal pitch to 420 ℃ again, and keeping the constant temperature for 2-10 hours. The method can realize the regulation and control of the content of the heteroatoms in the coal pitch and improve the rheological property of the coal pitch.
Description
Technical Field
The invention relates to modification treatment and application of coal pitch, in particular to a method for improving rheological property of coal pitch.
Background
Coal tar is one of main byproducts in the coal coking process, and coal pitch is used as a tower bottom product after coal tar distillation, and accounts for 55-65% or even more of the coal tar in mass. China has abundant coal resources, the national coal tar yield in 2018 is 1806 ten thousand tons, the start rate of the deep processing industry of the coal tar is about 50 percent, the coal pitch yield is about 681.8 ten thousand tons, and nearly half of the capacity is left unused. In recent years, along with the improvement of the national requirement on environmental protection and the continuous emphasis of coal coking enterprises on the development of high-added-value application of coal pitch and other byproducts, the improvement of coal tar and pitch processing technology enables the coal pitch to have wide application prospects in the high-added-value fields of needle coke, mesophase carbon microspheres, pitch-based carbon fibers and the like. The coal tar pitch has the characteristics of high aromaticity and low H/C molar ratio, so that the softening point and viscosity of the coal tar pitch are high, the system viscosity of the coal tar pitch is rapidly increased in the process of further producing high-grade carbon materials such as mesophase pitch, needle coke, mesophase carbon microspheres and the like through a heat treatment process, the mesophase is difficult to develop, a wide-area optical texture is difficult to form, and the final product performance is low. Meanwhile, the content of heteroatoms such as N, S, O in the coal tar pitch is high, which not only influences the development process of optical texture of the product in the subsequent heat treatment process, but also has extremely important influence on the subsequent product performance, for example, the high-quality needle coke used for the production of ultra-high power electrodes at present puts forward higher requirements on the S content in the high-quality needle coke. Researches show that the higher the content of heteroatoms in the coal pitch is, the poorer the rheological property is, and the more adverse the application of the coal pitch in the high value-added field is. Therefore, the development of the treatment technology for removing the heteroatoms and improving the rheological property of the coal pitch has important significance for improving the utilization value of the coal pitch.
In the chinese patent CN209039405U, the fixed bed hydrogenation process is used to remove the heteroatoms such as sulfur, nitrogen, oxygen, metal, etc. in the coal tar, so as to obtain high-quality fuel oil. The method has excellent effect, but the process flow is relatively complex, and meanwhile, due to the fact that the viscosity of the coal tar is relatively high, the catalyst is easily deactivated by existing asphaltene, colloid and the like, and the method is not beneficial to reducing the production cost of enterprises.
In the Chinese patent CN107739627A, the nitrogen compound in the coal tar is removed by a method of mixing and reacting the coal tar with a multifunctional complexing agent, and the removal rate is over 75 percent. Chinese patent CN106947525A mentions a method of adsorptive heteroatom removal, but only nitrogen and sulfur heteroatoms are removed. Chinese patent CN111298800A proposes a hydrodesulfurization method. These patents are directed to heteroatom removal, but only one or two heteroatoms are removed, and the requirement for simultaneous removal of nitrogen, sulfur and oxygen is not met.
Oyabu researches the process of preparing mesophase pitch from coal tar pitch taking tetrahydroquinoline as a hydrogen donor by a reagent hydrogenation method, and finds that after the raw materials are hydrogenated, the softening point of a product prepared by thermal polycondensation is reduced, the alkyl structure is increased, the aromatic structure is reduced, the aromaticity is reduced, and the rheological property is increased. Li Ming et al in the preparation of mesophase pitch from petroleum pitch rich in aromatic components as a feedstock, hydrogenation was carried out using tetrahydronaphthalene as a hydrogen donor so that the hydrogen content in the mesophase pitch increased from 6.36wt% to 7.53wt% and the softening point decreased from 297 ℃ to 239 ℃. They also observed that during the hydrogenation reaction, the contents of HS and QI gradually decreased, while the contents of the two intermediate components (HI-TS and TI-QS) increased. This shows that as the hydrogenation process proceeds, the molecules of the intermediate product are more and more concentrated in the two intermediate components, and the rheological properties thereof increase. John and the like use anthracite as a raw material and prepare asphalt through hydrogenation, and compared with commercial coal tar asphalt, the prepared asphalt is found to have obviously reduced heteroatom content. The Zhang Yaong and the like use petroleum aromatic hydrocarbon-rich fraction as a raw material, use tetrahydronaphthalene as a hydrogen donor to treat the raw material, and find that the content of heteroatoms is reduced and the rheological property is improved compared with a product obtained by treating the raw material at the same temperature and pressure for the same time.
The prior methods disclosed above have a large amount of hydrogenation reagent and do not address the recycling of hydrogenation reagent, resulting in higher cost of coal tar pitch hydrogenation process.
Disclosure of Invention
The invention aims to provide a method for improving rheological property of coal tar pitch, which can regulate and control the content of heteroatoms in the coal tar pitch and improve the rheological property of the coal tar pitch.
The purpose of the invention is realized by the following technical scheme:
the method for improving rheological property of coal tar pitch is characterized by sequentially comprising the following steps of:
(1) adding a hydrogen donor and coal tar pitch into a high-pressure kettle according to a certain mass ratio, fully mixing, and sealing the reaction kettle;
(2) heating to raise the temperature of the materials in the kettle to 350-450 ℃, and keeping the constant temperature to perform hydrogenation reaction; then, when the temperature of the materials in the kettle is reduced to 200-320 ℃, pressure is released; recovering the residual hydrogen donor by reduced pressure distillation, and then cooling to room temperature; stirring in the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process;
(3) and heating the treated coal pitch to 420 ℃ again, and keeping the constant temperature for 2-10 hours to ensure that the coal pitch is polymerized and converted into mesophase pitch at the temperature of 420 ℃.
It is further clarified that the softening point of the coal pitch is higher than 50 ℃, and the coal pitch contains 0.8% by mass or more of nitrogen, 0.35% by mass or more of sulfur, and 0.9% by mass or more of oxygen.
More specifically, the hydrogen donor is preferably one or a mixture of several of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline, and hydrogenated anthracene oil.
For further optimization, the mass ratio of the hydrogen donor to the coal tar pitch is 1: (0.1 to 20).
As a further optimization, the hydrotreating time in the step (2) is 1-20 h, and the pressure is 0.5-20 MPa.
As a further optimization, the constant temperature time of the reduced pressure distillation in the step (2) is 1-20 h, and the pressure in the kettle is-0.1-0 MPa.
As a further optimization, the stirring maintaining speed is 20-1000 r/min.
In more detail, the method for improving rheological property of coal tar pitch is characterized by sequentially comprising the following steps:
(1) hydrogen donor and coal tar pitch are mixed according to the mass ratio of 1: (0.1-20) adding the mixture into an autoclave, closing the autoclave and keeping the autoclave sealed; wherein the softening point of the coal pitch is higher than 50 ℃, the mass content of nitrogen element is more than 0.8%, the mass content of sulfur element is more than 0.35%, and the mass content of oxygen element is more than 0.9%; the hydrogen donor is preferably one or a mixture of more of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline, hydrogenated anthracene oil and the like;
(2) adjusting the heating program of the autoclave to ensure that the materials in the autoclave are heated to 350-450 ℃ at a certain heating rate for hydrogenation reaction and kept at the constant temperature for 1-20 h, wherein the pressure in the reaction process is 0.5-20 MPa; then cooling to 200-320 ℃, and decompressing; when the temperature of the materials in the kettle is reduced to 150-300 ℃, recovering the residual hydrogen donor through reduced pressure distillation, wherein the pressure in the kettle is-0.1-0 MPa in the process of reduced pressure distillation, and keeping the temperature constant for 1-20 h; stirring the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process, wherein the stirring speed is 20-1000 r/min;
(3) and cooling the materials in the high-pressure kettle to room temperature, taking out, heating to 420 ℃ again, and keeping the constant temperature for 2-10 hours to ensure that the coal pitch is polymerized and converted into intermediate phase pitch at the temperature of 420 ℃, thus obtaining the final product.
The invention has the following beneficial effects:
the invention provides a method for improving rheological property of coal pitch, which adopts a solvent hydrogenation method to modify the coal pitch, and has simple process and strong operability; the method has the advantages that the method can simultaneously remove the heteroatoms such as nitrogen, sulfur, oxygen and the like in the coal pitch in one treatment process, and has obvious removal effect, in the coal pitch prepared by the method, the mass content of N element can be reduced to 0.4%, the mass content of S element can be reduced to 0.2%, and the content of O element can be obviously reduced; the coal pitch processed by the method has a wide-area or wide-area streamline optical texture, the molecular planarization degree is high, the rheological property is obviously improved, the softening point is reduced, the temperature of the lowest viscosity platform is reduced by 10-80 ℃, the application of the coal pitch in high added value fields such as carbon fiber, needle coke, mesophase carbon microsphere and the like is enhanced, and the application value of the coal pitch is improved; meanwhile, the invention also recycles the unreacted hydrogen donor solvent, which is beneficial to reducing the production cost.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments, and not a limitation on the scope of the present invention.
Example 1
A method for improving rheological property of coal tar pitch sequentially comprises the following steps:
(1) hydrogen donor and coal tar pitch are mixed according to the mass ratio of 1: 19 adding the mixture into an autoclave, closing the autoclave and keeping the autoclave sealed; wherein the softening point of the coal pitch is 92 ℃, the mass content of nitrogen element is 1.3%, the mass content of sulfur element is 0.6%, and the mass content of oxygen element is 2.3%; the hydrogen donor is tetrahydronaphthalene;
(2) adjusting the heating program of the high-pressure kettle to heat the materials in the kettle to 420 ℃ at room temperature for 3h, keeping the temperature of 420 ℃ for 8h to carry out hydrogenation reaction, wherein the pressure in the reaction process is 1 MPa; then opening the furnace body, cooling to 320 ℃ and releasing pressure; when the temperature of the materials in the kettle is reduced to 280 ℃, keeping the constant temperature for 10 hours, and recovering the residual hydrogen donor by a reduced pressure distillation method, wherein the pressure in the kettle is-0.1 MPa in the reduced pressure distillation process; stirring the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process at the stirring speed of 200 r/min;
(3) and cooling the materials in the high-pressure kettle to room temperature, taking out, heating to 420 ℃ again, and keeping the constant temperature for 2 hours to ensure that the coal pitch is polymerized and converted into mesophase pitch at the temperature of 420 ℃, thus obtaining the final product.
The coal pitch treated in example 1 was subjected to respective tests of softening point, element distribution, viscosity, and optical texture, and found that the softening point was reduced by 15 ℃ on average, the sulfur content was reduced from 0.6% to 0.28% by mass, the nitrogen content was reduced from 1.3% to 0.41% by mass, the oxygen content was reduced from 2.3% to 1.8% by mass, and the minimum viscosity appearance temperature was reduced from 154 ℃ to 132 ℃. Unlike the mesophase pitch directly heat-treated to prepare coal pitch having mosaic optical texture, the coal pitch obtained by the treatment in this example 1 is mesophase pitch having wide-area optical texture, and the needle coke prepared by further delayed coking has streamline optical texture.
Example 2
A method for improving rheological property of coal tar pitch sequentially comprises the following steps:
(1) hydrogen donor and coal tar pitch are mixed according to the mass ratio of 6: 5 adding the mixture into the high-pressure kettle, closing the high-pressure kettle and keeping the reaction kettle sealed; wherein the softening point of the coal pitch is 92 ℃, the mass content of nitrogen element is 1.3%, the mass content of sulfur element is 0.6%, and the mass content of oxygen element is 2.3%; the hydrogen donor is decahydronaphthalene;
(2) adjusting the heating program of the autoclave to heat the materials in the autoclave to 440 ℃ at room temperature for 3h, keeping the temperature at 440 ℃ for 8h to carry out hydrogenation reaction, wherein the pressure in the reaction process is 20 MPa; then opening the furnace body, cooling to 300 ℃ and releasing pressure; when the temperature of materials in the kettle is 300 ℃, recovering the residual hydrogen donor by a reduced pressure distillation method, wherein the pressure in the kettle is 0MPa in the reduced pressure distillation process, and keeping the constant temperature for 12 hours; stirring the reaction kettle in the hydrogenation and reduced pressure distillation processes at the stirring speed of 1000 r/min;
(3) and cooling the materials in the high-pressure kettle to room temperature, taking out, heating to 420 ℃ again, and keeping the constant temperature for 5 hours to ensure that the coal pitch is polymerized and converted into mesophase pitch at the temperature of 420 ℃, thus obtaining the final product.
The coal pitch treated in this example 2 was measured for softening point, element distribution, viscosity, and optical texture, and found to have an average softening point decrease of 20 ℃, a sulfur content decrease of 0.6% to 0.20% by mass, a nitrogen content decrease of 1.3% to 0.4% by mass, an oxygen content decrease of 2.3% to 1.5% by mass, and a minimum viscosity occurrence temperature decrease of 154 ℃ to 132 ℃. Unlike the mesophase pitch directly heat-treated to prepare coal pitch having mosaic optical texture, the coal pitch obtained by the treatment in this example is mesophase pitch having wide-area optical texture, and the needle coke prepared by further delayed coking has streamline optical texture.
Example 3
A method for improving rheological property of coal tar pitch sequentially comprises the following steps:
(1) hydrogen donor and coal tar pitch are mixed according to the mass ratio of 6: 5 adding the mixture into the high-pressure kettle, closing the high-pressure kettle and keeping the reaction kettle sealed; wherein the softening point of the coal pitch is 92 ℃, the mass content of nitrogen element is 1.3%, the mass content of sulfur element is 0.6%, and the mass content of oxygen element is 2.3%; the hydrogen donor is tetrahydroquinoline;
(2) adjusting the heating program of the autoclave to heat the materials in the autoclave to 450 ℃ after 3h at room temperature, keeping the temperature at 450 ℃ for 12h to carry out hydrogenation reaction, wherein the pressure in the reaction process is 0.5 MPa; then opening the furnace body, cooling to 200 ℃ and releasing pressure; when the temperature of the materials in the kettle is reduced to 150 ℃, recovering the residual hydrogen donor by a reduced pressure distillation method, wherein the pressure in the kettle is-0.1 MPa in the reduced pressure distillation process, and keeping the constant temperature for 12 hours; stirring the reaction kettle in the hydrogenation and reduced pressure distillation processes at the stirring speed of 1000 r/min;
(3) and cooling the materials in the high-pressure kettle to room temperature, taking out, heating to 420 ℃ again, and keeping the constant temperature for 10 hours to ensure that the coal pitch is polymerized and converted into mesophase pitch at the temperature of 420 ℃, thus obtaining the final product.
The coal pitch treated in this example 3 was measured for softening point, element distribution, viscosity, and optical texture, and found to have an average softening point decrease of 28 ℃, a sulfur content decrease of 0.6% to 0.20% by mass, a nitrogen content decrease of 1.3% to 0.42% by mass, an oxygen content decrease of 2.3% to 1.2% by mass, and a minimum viscosity occurrence temperature decrease of 154 ℃ to 119 ℃. Unlike the mesophase pitch prepared by directly performing heat treatment on coal pitch, which has a mosaic optical texture, the coal pitch obtained by the treatment in this embodiment is mesophase pitch with a wide-area optical texture, the softening point and the viscosity of which are significantly reduced, and needle coke prepared by further delayed coking has a streamlined optical texture.
Claims (7)
1. The method for improving rheological property of coal tar pitch is characterized by sequentially comprising the following steps of:
(1) adding a hydrogen donor and coal tar pitch into a high-pressure kettle according to a certain mass ratio, fully mixing, and sealing the reaction kettle;
(2) heating to raise the temperature of the materials in the kettle to 350-450 ℃, and keeping the constant temperature to perform hydrogenation reaction; then, when the temperature of the materials in the kettle is reduced to 200-320 ℃, pressure is released; recovering the residual hydrogen donor by reduced pressure distillation, and then cooling to room temperature; stirring in the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process;
(3) and heating the treated coal pitch to 420 ℃ again, and keeping the constant temperature for 2-10 hours.
2. The method for improving rheological properties of coal pitch according to claim 1, wherein: the softening point of the coal pitch is higher than 50 ℃, wherein the mass content of nitrogen element is more than 0.8%, the mass content of sulfur element is more than 0.35%, and the mass content of oxygen element is more than 0.9%; the hydrogen donor is one or a mixture of more of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline and hydrogenated anthracene oil.
3. The method for improving rheological properties of coal pitch according to claim 1 or 2, wherein: the mass ratio of the hydrogen donor to the coal tar pitch is 1: (0.1 to 20).
4. The method for improving rheological properties of coal pitch according to claim 1 or 2, wherein: the hydrotreating time in the step (2) is 1-20 h, and the pressure is 0.5-20 MPa.
5. The method for improving rheological properties of coal pitch according to claim 1 or 2, wherein: and (3) carrying out reduced pressure distillation in the step (2) for 1-20 h at a constant temperature, wherein the pressure in the kettle is-0.1-0 MPa.
6. The method for improving rheological properties of coal pitch according to claim 1 or 2, wherein: the stirring and maintaining speed is 20-1000 r/min.
7. The method for improving rheological properties of coal pitch according to claim 1, comprising the following steps in sequence:
(1) hydrogen donor and coal tar pitch are mixed according to the mass ratio of 1: (0.1-20) adding the mixture into an autoclave, closing the autoclave and keeping the autoclave sealed; wherein the softening point of the coal pitch is higher than 50 ℃, the mass content of nitrogen element is more than 0.8%, the mass content of sulfur element is more than 0.35%, and the mass content of oxygen element is more than 0.9%; the hydrogen donor is one or a mixture of more of tetrahydronaphthalene, decahydronaphthalene, tetrahydroquinoline and hydrogenated anthracene oil;
(2) adjusting the heating program of the autoclave to heat the materials in the autoclave to 350-450 ℃ for hydrogenation reaction and keeping the constant temperature for 1-20 h, wherein the pressure in the reaction process is 0.5-20 MPa; then cooling to 200-320 ℃, and decompressing; when the temperature of the materials in the kettle is reduced to 150-300 ℃, recovering the residual hydrogen donor through reduced pressure distillation, wherein the pressure in the kettle is-0.1-0 MPa in the process of reduced pressure distillation, and keeping the temperature constant for 1-20 h; stirring the reaction kettle in the hydrogenation reaction and the reduced pressure distillation process, wherein the stirring speed is 20-1000 r/min;
(3) and cooling the materials in the autoclave to room temperature, taking out, heating to 420 ℃ again, and keeping the constant temperature for 2-10 hours.
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| CN114381292A (en) * | 2022-02-10 | 2022-04-22 | 济宁碳素集团有限公司 | Preparation method of spinnable mesophase pitch |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114381292B (en) * | 2022-02-10 | 2024-02-06 | 济宁科能新型碳材料科技有限公司 | Preparation method of spinnable mesophase pitch |
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