CN106811235A - A kind of device and method of mink cell focus/residual oil/coal tar catalytic cracking polymerisation lighting - Google Patents
A kind of device and method of mink cell focus/residual oil/coal tar catalytic cracking polymerisation lighting Download PDFInfo
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- CN106811235A CN106811235A CN201611245229.7A CN201611245229A CN106811235A CN 106811235 A CN106811235 A CN 106811235A CN 201611245229 A CN201611245229 A CN 201611245229A CN 106811235 A CN106811235 A CN 106811235A
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- catalytic cracking
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
- C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
- C10G69/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step
- C10G69/126—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one polymerisation or alkylation step polymerisation, e.g. oligomerisation
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a kind of device and method of mink cell focus/residual oil/coal tar catalytic cracking polymerisation lighting, belong to oil refining, petrochemical industry, coal chemical technology.The method that mink cell focus/residual oil/coal tar is produced the method the high added value carbosphere and dipping agent bitumen of China's urgent need by the process of catalytic cracking and polymerization technology organic assembling, while by-product gasoline, diesel oil, light-end products can be produced with maximum, simplification of flowsheet, reduces overall energy consumption.
Description
Technical field
The invention belongs to refine oil, petrochemical industry, coal chemical technology, be related to a kind of mink cell focus/residual oil/coal tar lighting
Method, specifically by mink cell focus/residual oil/coal tar by catalytic cracking and the process of polymerization technology organic assembling
High added value carbosphere and the method for dipping agent bitumen that production China is badly in need of, while by-product gasoline, diesel oil.
Background technology
From Honda in 1973 etc. by since being separated pitch so as to find micron-sized carbonaceous mesophase spherules, by
In its excellent performance and wide application prospect, carbosphere has obtained the primary study of scientific research personnel.Carbosphere is by graphite
Lamella is constituted in the graphite-structure Disjunct distribution of glass phase, carbosphere due to the parallel structure piled up of synusia molecule, and
With it is spherical the characteristics of, sphere diameter is small and is evenly distributed, and these design features make it have high-ratio surface, excellent chemically stable
The performance such as property and heat endurance, becomes many new materials, can such as prepare high-intensity high-density C/C composites, height
A series of high performance carbon materials such as performance liquid chromatography pillar height specific surface active carbon material, lithium ion battery negative material.
The currently available Carbon Materials for making lithium ion battery negative mainly have graphite, pyrolytic carbon, carbon fiber, coke etc..It is multinomial
Result of study shows that the specific capacity of coke is relatively low.Though some pyrolytic carbons or carbon fiber are with specific capacity and cycle life higher,
It is relatively costly but preparation technology is usually relatively complex, and for those difficult graphitizations or not graphited pyrolytic carbon or carbon
For fiber, without discharge platform as graphite.
Then there is crystallinity high, good conductivity, the reversible appearance of discharge and recharge of material by the graphite obtained after carbon microspheres graphitization
Amount and efficiency for charge-discharge and the characteristic that operating voltage is all higher, charging/discharging voltage curve is relatively flat, are a kind of better performances
Lithium ion battery negative pole carbon material.Current substantial amounts of lithium ion battery has used carbon microspheres graphite-like carbon material as the negative of battery
Pole.The powerful battery preparation technology of high-performance is the key of new-energy automobile development, excellent negative material market demand
It is very big.
China's STUDY OF NEEDLE COKE TECHNOLOGY achieves important breakthrough in recent years, for production heavy caliber ultra-high power graphite electrode has been established well
A large amount of dipping agent bitumens are badly in need of for ultra-high power graphite electrode produces provided auxiliary raw material in basis, the country, and the country does not impregnate also at present
Agent pitch professional production factory.
Become weight with worldwide oil property, deteriorate, and sustained economic development requirement and environmental regulation
Increasingly strict, people are increasing to the demand of light clean fuel, these require existing oil Refining Technologies are carried out it is perfect
And improvement, satisfactory product is produced with minimum cost.
Catalytic cracking is that heavy oils reacts the light-end products such as production liquefied gas, gasoline and diesel oil in the presence of catalyst
Main process, occupy critical role in gasoline and diesel production.Particularly in China, the vapour of about 80% (mass fraction)
Oil and 1/3 diesel oil are all from the technique.It by the heavy oil conversion of substantial amounts of low value be society be badly in need of light Fuel and
Chemical products, are the topmost light materialization of heavy oil means of China.
Coal tar is resulting a kind of product liquid during the dry distillation of coal, and high temperature coal tar can be divided into by the temperature of destructive distillation
Oil, medium temperature coal tar and coalite tar, their composition and property have very big difference.In China due to individual enterprise's coal tar
Yield poorly, and produce the enterprise of coal tar and geographically disperse, tar resource never has and obtains fully for a long time
Utilize, except part high temperature coal-tar is used for the light fraction for extracting chemical products, a small amount of middle coalite tar for producing engine
Beyond fuel, remaining most of coal tar is all used as heavy oil and low-end product, causes the wasting of resources and environment dirty
Dye.With the development of Chinese large-sized Chemical Industry in recent years, fixed bed, In The Fluidized Bed Coal Gasification Technology and lignite destructive distillation upgrading
Technology has been applied in various production processes, and the yield of high temperature coal-tar is consequently increased, because of high temperature coal-tar asphalitine, glue
Matter is more, and up to the present, the processing and utilization of high temperature coal-tar is always a problem.
The technology of chemical products is produced to coal tar using the method for hydrogenation to have existed, and will using hydrogen addition technology
Coal tar processing also had research into the method for fuel oil in last century, but was limited to technical conditions at that time, technological operation bar
Part needs HTHP, there is no successfully.In recent years, influenceed and crude charging capacity and working ability by petroleum resources
Limitation, the yield of light-end products far can not meet the market demand, and this provides economic possibility for coal tar hydrorefining.And
The improvement of hydrofining technology constantly improve, catalyst activity, is also provided for engineering feasibility.Current coal tar hydrogenating
Method, wherein：
Chinese invention patent CN1464031A discloses a kind of method that coal tar hydrogenating produces diesel oil.The method description
Mainly coal tar first passes around fractionation, the heavy distillat for obtaining not as hydrotreating raw material, simply to coal tar in it is light
Matter cut carries out hydrotreating, and due to hydrocracking catalyst is not used, the diesel oil distillate that process is obtained can only be used as bavin
The blend component of oil product, and coal tar do not utilized completely, cause light-end products entirety yield to substantially reduce.
Chinese invention patent CN1464031A discloses a kind of coal tar hydrogenation process and catalyst.The patent requirements are developed
Special special-purpose catalyst, flow is common processing process, and only raw material modified, and its hydrogenation changes in addition
Contain molecular sieve in matter catalyst, the water to coal tar hydrogenating generation is very sensitive, because the presence of water vapour or water can make
Catalyst is destroyed, and which decreases the service life of catalyst, is seriously destroyed the performance of catalyst and is caused bed
Pressure drop rise, causes device to stop work.
United States Patent (USP) US4,855,037 discloses the catalyst and method of a kind of coal tar hydrogenating treatment.The method be by
Coal tar after hydrotreating is used for delayed coking.Hydrogenation technique is that occur as the pretreating process of delay coking of coal tar
, it is not directly produced the purpose product such as light-end products.And the method is mainly treatment mink cell focus, operating pressure is high, investment
It is larger.
Because decompression residuum viscosity is high, it is higher than great, heavy metal and sulfur content and colloid, asphalitine, be directly used in hydrogenation
Cracking or catalytic cracking unit do raw material, there is gasoline and diesel yield is low, and heat energy loss is big, equipment investment is high etc. it is unfavorable because
Element.
Patent CN1746265A discloses a kind of processing technology of poor-quality oil catalytic cracking.Inferior oil material is through catalytic cracking
The light diesel fuel cut Returning catalyticing cracking device for obtaining carries out freshening, and the heavy diesel fuel cut for obtaining carries out solvent extraction, extracts
Heavy aromatics as product, Returning catalyticing cracking device freshening of raffinating oil.The process is not enough filled to crude oil with poor quality lighting
Point, catalytic cracked oil pulp is not made full use of.
Patent CN1093395A discloses a kind of method that utilization high-content wax decompression residuum produces high quality common asphalt.
Decompression residuum is carried out solvent extraction by the method, obtains lube stock and road asphalt, while carbon residue heavy deasphalted oil high is obtained,
The carbon residue heavy deasphalted oil high is carried out into oxidation processes, high quality common asphalt can be obtained.The method is not to decompression slag
Oil carries out sufficiently effective utilization.
CN1382776A discloses the integrated processes of a kind of residual hydrocracking and RFCC.The method is by slag
Oil, slurry oil steaming thing, heavy catalytic cycle oil, optional distillate react institute together as the charging of hydrotreater
After thing steams petrol and diesel oil, hydrogenated residue enters catalytic cracking unit, the weight that catalytic cracking is obtained with optional vacuum gas oil (VGO)
Recycle oil returns to hydrogenation plant, can improve catalytic cracking unit gasoline and diesel yield.
CN101434865A discloses a kind of combined technical method.Heavy distillate enters the first hydroconversion reaction zone, generation
Oil enters the second hydrotreating reaction area, generation oil together through the isolated gas of high pressure and liquid with liquid after gas sweetening
Through the isolated gas of high pressure knockout drum and liquid, gas returns to the first hydrotreating reaction area, and mink cell focus enters catalytic cracking
Device obtains light oil and recycle oil, and recycle oil returns to catalytic cracking or hydrotreater.
CN102041095A discloses a kind of combined technical method.Residual oil raw material carries out hydrogenation reaction, reaction outflow first
Thing gas-liquid separation, gas phase is circulated for hydrogenation reaction, and liquid phase is not fractionated into being directly entered catalytic cracking unit；Catalytic cracking reaction
Effluent isolates dry gas, liquefied gas, catalytically cracked gasoline cut, diesel oil distillate Returning catalyticing cracking device, recycle oil and oil
Slurry returns to residual hydrogenation equipment.
There is yield of gasoline is low, and heat energy loss is big, and equipment investment is high etc. with catalytic cracking combined technique in above-mentioned hydrotreating
Unfavorable factor.
Therefore, this area is high, attached in the urgent need to finding a kind of utilization ratio of a new mink cell focus/residual oil/coal tar
A kind of value added method high, so that for comprehensive utilization of mink cell focus/residual oil/coal tar provides feasible scheme to improve resource
Utilization rate.
The content of the invention
It is light it is an object of the invention to provide a kind of process by catalytic cracking and polymerization technology organic assembling
Matterization processes the process of mink cell focus/residual oil/coal tar, high added value carbosphere and impregnating agent drip that production China is badly in need of
Green grass or young crops, while by-product gasoline, diesel oil, can produce light-end products with maximum, simplification of flowsheet reduces overall energy consumption.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of method of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting, the method includes following step
Suddenly：
(1) feedstock oil after preheating enters catalytic cracking unit, and cracking reaction is carried out in the presence of catalytic cracking catalyst,
It is changed into catalytically cracked gasoline after the oil gas condensation on catalytic cracking unit top, middle part produces catalytic cracking diesel oil, and bottom produces weight
Matter distillate；
(2) polymer reactor is entered after the heavy distillate of step (1) production and carbon black mixing, in N2Protection under carry out
Reaction, the gas reacted device top discharge that reaction is produced after terminating, the product liquid of production be discharged in stainless steel add it is molten
Agent and natural cooling；
(3) the mixed polymerisation liquid product of solvent is added to be separated through centrifuge, the solid product after separation is through water
Wash, purge, classification obtains carbosphere, the liquid product after separation is dipping agent bitumen.
The feedstock oil of technical solution of the present invention step (1) be mink cell focus, reduced crude, decompression residuum, wax tailings, in it is low
One kind or mixture in high temperature coal-tar.
The feedstock oil of technical solution of the present invention step (1) is preheated in heating furnace, the charging temperature 180~220 of heating furnace
DEG C, enter 0.2~0.35MPa of furnace pressure power；450~560 DEG C of the tapping temperature of heating furnace, the pressure 0.2 of coming out of the stove of heating furnace~
0.3MPa。
The catalytic cracking catalyst of technical solution of the present invention step (1) is selected from molecular sieve, heat-resistant inorganic oxide and clay
In at least one；It is preferred that：Molecular sieve is selected from the y-type zeolite with or without rare earth element, the super steady Y with or without rare earth element
Type zeolite, the silica-rich zeolite with five-membered ring structure, β zeolites, one or more in modenite, omega zeolite, with five yuan
The silica-rich zeolite of ring structure is ZSM-5 zeolite or ZRP zeolites；It is preferred that：Heat-resistant inorganic oxide is selected from aluminum oxide, silica, nothing
One or more in sizing sial, zirconium oxide, titanium oxide, boron oxide and alkaline earth oxide；It is preferred that：Clay is selected from kaolinite
Soil, halloysite, montmorillonite, diatomite, galapectite, saponite, tired de- soil, sepiolite, attapulgite, hydrotalcite and boron-moisten soil
In one or more.
The reaction condition of the catalytic cracking of technical solution of the present invention step (1) is：470~550 DEG C of reaction temperature, regeneration temperature
The mass ratio 3~18 of 600~800 DEG C of degree, catalyst and feedstock oil, 0.5~5 second reaction time, 0.1~0.5MPa of pressure.
Technical solution of the present invention step (2) carbon black is 1~50 with the mass ratio of heavy distillate：50~99, polymerisation
The reaction pressure of device is 15~30MPa, in N2Protection under be warmed up to 100~400 DEG C, the mixing time of temperature rise period is 1~2
Hour, 600~900 DEG C are warmed up to afterwards, continue to stir 1~2 hour.
The solvent that the product liquid of the polymer reactor described in technical solution of the present invention step (2) is added is that mixing C5 is molten
Agent, the content of pentane is 10~90wt% in C5.
The solid product washing of the centrifugal separator described in technical solution of the present invention step of the present invention (3) uses deionization
Water, electrical conductivity is less than 0.056us/cm, and purge gas are N2, the carbosphere particle diameter after classification is 8~25um, the yield of carbosphere
Height, can reach 50~60wt%, and needle penetration is 40~140 (0.1mm) when centrifuge separates 25 DEG C of liquid product dipping agent bitumen,
Softening point is 40~55 DEG C, ductility ＞ 150cm at 15 DEG C, can be used as the raw material of production needle coke.
A kind of device of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting, the device splits including catalysis
Makeup is put, and the output end of heating furnace is connected with catalytic cracking unit, and described catalytic cracking unit is connected with polymer reactor, is gathered
The top for closing reactor is connected with condenser, and the bottom of polymer reactor is connected with stainless steel, and the output end of stainless steel is led to
Centrifuge is crossed to be connected with water washing device, blow device and grading plant successively.Described catalytic cracking unit includes reaction-regeneration
System, fractionating system and absorption-systems stabilisation.
Beneficial effects of the present invention：
(1) present invention combines catalytic cracking and polymerization technology skill, simplification of flowsheet, reduces overall
Energy consumption, mink cell focus/residual oil/coal tar can be converted into the light-end products of high-quality to greatest extent, improve the yield of gasoline and diesel oil,
The heavy distillate that catalytic cracking is produced is the quality raw materials of polymerisation, and the carbosphere added value for reacting generation is high, economy effect
Benefit is good, and the commercial plant investment payback time is short.
(2) a certain amount of carbon black is added in the polymerization, is conducive to the carrying out of polymerisation, reduce the reaction time, always
Reaction time is no more than 4 hours, is conducive to the formation of carbosphere, makes the carbosphere particle diameter distribution of generation uniform.
(3) polymeric reaction product adds mixing C5 solvents, dissolves unreacted colloid, asphalitine, it is ensured that carbosphere
Yield and product quality, the yield of carbosphere can reach 40~60wt%, be not only easy to be well mixed with mixing C5 solvent agent, together
When ensure to produce the quality of dipping agent bitumen pitch, also solve topic between high, difficulty of transportation of pitch softening point etc..
Brief description of the drawings
Fig. 1 is a kind of process of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting of the invention
Process flow diagram.
Fig. 2 is the carbosphere grain-size graph that the embodiment of the present invention is prepared.
Wherein, 1- feedstock oils, 2- heating furnaces, feedstock oil after 3- heating, 4- catalytic cracking units, 5- catalytic cracking oil gas,
6- heavy distillates, 7- catalytic cracking diesel oils, 8- carbon blacks, 9- polymer reactor upper gas, 10- condensers, 11- catalytic cracking
Gasoline collecting tank, 12- catalytic cracked dry gas, 13- catalytically cracked gasolines, 14- nitrogen, 15- polymer reactors, 16- polymerisations
Product liquid, 17-C5 solvents, 18- stainless steels, 19- adds solvent post-polymerization product, 20- centrifuges, 21- impregnating agent
Pitch, 22- solid products, 23- water washing devices, 24- blow devices, 25- grading plants, 26- carbospheres.
Specific embodiment
With reference to embodiment, the present invention will be further described, but protection scope of the present invention not limited to this：
Such as Fig. 1, the device of mink cell focus/residual oil of the present invention/coal tar catalytic cracking-polymerisation lighting includes
Catalytic cracking unit, the output end of heating furnace is connected with catalytic cracking unit, described catalytic cracking unit and polymer reactor
Be connected, the top of polymer reactor is connected with condenser, and the bottom of polymer reactor is connected with stainless steel, stainless steel it is defeated
Go out end to be connected with water washing device, blow device and grading plant successively by centrifuge.Described catalytic cracking unit includes anti-
Should-regenerative system, fractionating system and absorption-systems stabilisation.
After being heated from the heated stove 2 of feedstock oil of pipeline 1, into catalytic cracking unit 4, what catalytic cracking unit was produced urges
Change cracking oil gas 5 and enter condenser 10, condensed liquid enters catalytically cracked gasoline collecting tank 11, dry gas 12 from tank deck out
Enter gas ductwork afterwards；The middle part of catalytic cracking unit 4 produces catalytic cracking diesel oil, and the bottom of catalytic cracking unit 4 produces heavy to evaporate
Oil 6, heavy distillate 6 and a certain amount of carbon black 8 is divided to enter polymer reactor 15 after mixing, under the protection of nitrogen 14, one
Temperature is gradually risen under the conditions of constant-pressure, after stirring certain hour, reaction temperature is increased to, after continuing to stir certain hour, instead
Should complete, the reacted device top discharge of the gas 9 that polymer reactor is produced, and by condenser after the mixing of catalytic cracking oil gas 5
10 condensations are changed into liquid, are used as catalytically cracked gasoline product, and the product liquid 16 of polymer reactor is discharged to stainless steel 18
In, add C5 solvents 17 and natural cooling；The mixed polymerisation liquid product 19 of solvent is added to be separated through centrifuge 20, point
Through water washing device 23, blow device 24, grading plant 25 obtains carbosphere 26, after centrifugation to solid product 22 after
Liquid product is dipping agent bitumen 21.
The process of a kind of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting, by feedstock oil (heavy
Oil, reduced crude, decompression residuum, wax tailings, in one kind in low high temperature coal-tar or mixture) heated in heating furnace,
200 DEG C of charging temperature, pressure 0.3MPa；510 DEG C of tapping temperature, come out of the stove pressure 0.25MPa, and the feedstock oil after heating enters hydrogenation
Cracking unit, the operating condition of catalytic cracking unit is shown in Table 2, and catalytic cracking unit uses molecular sieve catalyst, catalytic cracking dress
The catalytic cracking oil gas for putting generation enters condenser, and condensed liquid enters catalytically cracked gasoline collecting tank, and dry gas is from tank deck
Out enter gas ductwork afterwards；Catalytic cracking unit middle part produces catalytic cracking diesel oil, and catalytic cracking unit bottom produces heavy
Enter polymer reactor after distillate, heavy distillate and carbon black mixing, carbon black is 25 with the mass ratio of heavy distillate：75,
In N2Protection under, gradually rise temperature to 230 DEG C under the conditions of (gauge pressure) is 20MPa, after stirring 1.5 hours, be increased to anti-
650 DEG C of temperature is answered, after continuing to stir 1.5 hours, reaction is completed, the reacted device top discharge of the gas that polymer reactor is produced,
It is changed into liquid by condenser condensation after the catalytic cracking oil gas mixing produced with catalytic cracking unit, as catalytically cracked gasoline
Product is used, the product liquid of polymer reactor is discharged in stainless steel and adds C5 solvents and natural cooling, wherein pentane
Content is 55wt%；The mixed polymerisation liquid product of C5 solvents is added to be separated through centrifuge, the solid product after separation
Through electrical conductivity for the deionized water of 0.051us/cm is washed, N2Purging, classification, obtains carbosphere, and carbosphere particle diameter is 8~
25um, liquid product after separation is dipping agent bitumen, and needle penetration is 40~140 (0.1mm) during 25 DEG C of dipping agent bitumen, is softened
Point is 40~55 DEG C, ductility ＞ 150cm at 15 DEG C, can be used as the raw material of production needle coke.
The property of feedstock oil is shown in Table 1, and catalytic cracking unit operating condition is shown in Table 2, and product slates are shown in Table 3, dipping agent bitumen
Property be shown in Table 4, catalytically cracked gasoline and catalytic cracking diesel oil property are shown in Table 5, and carbosphere grain-size graph is shown in Fig. 2.
The raw material oil nature of table 1
| 1.06 | |
| S contents, m% | 6.01 |
| N content, m% | 0.78 |
| Carbon residue, m% | 24.74 |
| Metal (Ni+V), μ g/g | 487 |
| H/C | 1.43 |
| Saturation point, m% | 7.80 |
| Fragrance point, m% | 41.52 |
| Colloid, m% | 32.60 |
| Asphalitine, m% | 18.09 |
The catalytic cracking unit operating condition of table 2
| Embodiment weight % | |
| Catalytic cracking unit | |
| Reaction temperature, DEG C | 505 |
| Regeneration temperature, DEG C | 720 |
| Reaction time, second | 1.5 |
| Oil ratio | 8 |
The product slates of table 3
| Embodiment, wt% | |
| Carbosphere | 45.6 |
| Dipping agent bitumen (is free of C5 solvents) | 13.3 |
| Catalytic cracked dry gas | 2.4 |
| Catalytically cracked gasoline | 18.4 |
| Catalytic cracking dried firewood oil | 20.3 |
| It is total | 100 |
The dipping agent bitumen property of table 4
| Embodiment 1 | |
| Needle penetration (25 DEG C), 0.1mm | 87 |
| Ductility (15 DEG C), cm | >150 |
| Softening point, DEG C | 50 |
The catalytically cracked gasoline of table 5 and catalytic cracking diesel oil property
| Product | Gasoline | Diesel oil |
| 0.740 | 0.828 | |
| S, μ g/g | 15 | 35 |
| N, μ g/g | 5 | 24 |
| Condensation point, DEG C | -50 | |
| Cetane number | 50 | |
| RON | 93 | -- |
Claims (10)
1. the method for a kind of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting, it is characterised in that：The method bag
Include following steps：
(1) feedstock oil after preheating enters catalytic cracking unit, and cracking reaction is carried out in the presence of catalytic cracking catalyst, is catalyzed
It is changed into catalytically cracked gasoline after the oil gas condensation on cracking unit top, middle part produces catalytic cracking diesel oil, and bottom produces heavy to evaporate
Divide oil；
(2) polymer reactor is entered after the heavy distillate of step (1) production and carbon black mixing, in N2Protection under reacted,
The gas reacted device top discharge that reaction is produced after terminating, the product liquid of production be discharged in stainless steel add solvent and from
So cooling；
(3) the mixed polymerisation liquid product of solvent is added to be separated through centrifuge, the solid product after separation blows through washing
Sweep, be classified, obtain carbosphere, the liquid product after separation is dipping agent bitumen.
2. the method for mink cell focus/residual oil according to claim 1/coal tar catalytic cracking-polymerisation lighting, it is special
Levy and be：The feedstock oil of step (1) be mink cell focus, reduced crude, decompression residuum, wax tailings, in low high temperature coal-tar
A kind of or mixture.
3. the method for mink cell focus/residual oil according to claim 1/coal tar catalytic cracking-polymerisation lighting, it is special
Levy and be：The feedstock oil of step (1) is preheated in heating furnace, 180~220 DEG C of the charging temperature of heating furnace, enter furnace pressure power 0.2~
0.35MPa；450~560 DEG C of the tapping temperature of heating furnace, the 0.2~0.3MPa of pressure that comes out of the stove of heating furnace.
4. the method for mink cell focus/residual oil according to claim 1/coal tar catalytic cracking-polymerisation lighting, it is special
Levy and be：Step (1) catalytic cracking catalyst is selected from least one in molecular sieve, heat-resistant inorganic oxide and clay；It is preferred that：
Molecular sieve is selected from the y-type zeolite with or without rare earth element, the ultrastable with or without rare earth element, with five-membered ring
The silica-rich zeolite of structure, β zeolites, one or more in modenite, omega zeolite, the silica-rich zeolite with five-membered ring structure is
ZSM-5 zeolite or ZRP zeolites；It is preferred that：Heat-resistant inorganic oxide is selected from aluminum oxide, silica, amorphous silicon aluminium, zirconium oxide, oxygen
Change one or more in titanium, boron oxide and alkaline earth oxide；It is preferred that：Clay is selected from kaolin, halloysite, covers de-
One or more in soil, diatomite, galapectite, saponite, tired de- soil, sepiolite, attapulgite, hydrotalcite and boron-moisten soil.
5. the method for the mink cell focus/residual oil according to claim 1 or 4/coal tar catalytic cracking-polymerisation lighting,
It is characterized in that：The reaction condition of step (1) catalytic cracking is：470~550 DEG C of reaction temperature, 600~800 DEG C of regeneration temperature,
The mass ratio 3~18 of catalyst and feedstock oil, 0.5~5 second reaction time, 0.1~0.5MPa of pressure.
6. the method for the mink cell focus/residual oil according to claim 1 or 4/coal tar catalytic cracking-polymerisation lighting,
It is characterized in that：Step (2) carbon black is 1~50 with the mass ratio of heavy distillate：50~99, the reaction pressure of polymer reactor
It is 15~30MPa, in N2Protection under be warmed up to 100~400 DEG C, the mixing time of temperature rise period is 1~2 hour, Zhi Housheng
Temperature continues to stir 1~2 hour to 600~900 DEG C.
7. the method for the mink cell focus/residual oil according to claim 1 or 4/coal tar catalytic cracking-polymerisation lighting,
It is characterized in that：The solvent that the product liquid of the polymer reactor described in step (2) is added is mixing C5 solvents, pentane in C5
Content be 10~90wt%.
8. the method for the mink cell focus/residual oil according to claim 1 or 4/coal tar catalytic cracking-polymerisation lighting,
It is characterized in that：Carbosphere particle diameter after step (3) classification is 8~25 μm.
9. the device of a kind of mink cell focus/residual oil/coal tar catalytic cracking-polymerisation lighting, it is characterised in that：The device bag
Catalytic cracking unit is included, the output end of heating furnace is connected with catalytic cracking unit, described catalytic cracking unit and polymerisation
Device is connected, and the top of polymer reactor is connected with condenser, and the bottom of polymer reactor is connected with stainless steel, stainless steel
Output end is connected with water washing device, blow device and grading plant successively by centrifuge.
10. device according to claim 9, it is characterised in that：Described catalytic cracking unit includes reaction-regeneration system
System, fractionating system and absorption-systems stabilisation.
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Citations (2)
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|---|---|---|---|---|
| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4855037A (en) * | 1984-09-12 | 1989-08-08 | Nippon Kokan Kabushiki Kaisha | Hydrogenation catalyst for coal tar, a method of hydrogenation of coal tar with use of such catalyst, and a method of producing super needle coke from the hydrogenation product of coal tar |
| CN102225755A (en) * | 2011-05-26 | 2011-10-26 | 淄博矿业集团有限责任公司 | Preparation method of mesophase carbon microspheres from coal liquefaction residues |
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