CN104498077A - Method for preparing light oil from low-hydrogen-content oil with self-contained asphalten - Google Patents
Method for preparing light oil from low-hydrogen-content oil with self-contained asphalten Download PDFInfo
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- CN104498077A CN104498077A CN201410662918.2A CN201410662918A CN104498077A CN 104498077 A CN104498077 A CN 104498077A CN 201410662918 A CN201410662918 A CN 201410662918A CN 104498077 A CN104498077 A CN 104498077A
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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
- C10G7/00—Distillation of hydrocarbon oils
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Abstract
The invention provides a method for preparing light oil from low-hydrogen-content oil with self-contained asphalten. The method is suitable for processing of medium-low temperature coal tar. According to the invention, a deep evaporation method is adopted to isolate the medium-low temperature coal tar into distillate oil vapor V1 and liquid L1 under the condition of no occurrence of obvious coking, wherein the liquid L1 is mainly composed of macromolecular colloidal bituminous components; after cooling and molding, the liquid L1 used as soft coal or green coal can be used as fire coal to achieve green storage and usage of the liquid L1; and the distillate oil vapor V1 is condensed to obtain an oil product which can be used for preparing a clean oil product via a hydrogenation process. The method for preparing light oil from low-hydrogen-content oil with self-contained asphalten provided by the invention enables the product direction of the macromolecular colloidal bituminous components in medium-low temperature coal tar to jump out of the traditional range of coke, coal tar pitch, fuel oil, suspended-bed or bubbling-bed hydrogenation raw material to produce coal-like products; and the traditional concept of ultimate obtainment of light oil and residual oil through vapor-liqiud separation is converted into the concept of ultimate obtainment of light oil and solid through vapor-liqiud separation.
Description
Technical field
The present invention relates to a kind of method producing lightweight oil in self-contained bitum low hydrogen content oil; Particularly the present invention relates to a kind of method producing lightweight oil in self-contained bitum coal tar; More particularly the present invention relates to a kind of method producing lightweight oil in self-contained bitum middle coalite tar, adopt degree of depth gasification method, under the condition that obvious pyrogenic reaction does not occur, middle coalite tar is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition, liquid L1 is conduct " soft matchmaker " or coal green grass or young crops after cooling forming, can be used as coal-fired use, realize its environmental protection and store and use; Distillate steam V1 obtains clear gusoline through condensation gained oil product by hydrogenation process.The present invention is by the line of production of the macromolecular colloidal pitch shape component in middle coalite tar, jump out from the scope of traditional coke, coal-tar pitch, oil fuel, suspension bed or boiling bed hydrogenation raw material, the conversions concepts of traditional " vapor-liquid separation finally obtains light oil and residual oil " is the concept of " vapor-liquid separation finally obtains light oil and solid " by production class product of coal.
Background technology
In order to describe the problem, coalite tar heavy oil in routine or residual oil or the coal-tar pitch coal tar fraction of 500 DEG C (the such as normal boiling point higher than) are divided into light residue fraction and heavy resid component to treat by the present invention, are such as that the coal tar component of 500 ~ 540 DEG C is called the light residue fraction of coal tar, normal boiling point is called coal tar heavy duty residue fraction higher than the coal tar component of 540 DEG C by normal boiling point.Therefore, middle coalite tar degree of depth vaporization question essence of the present invention is exactly light for coal tar in conventional coal tar residue fraction vaporization is separated the problem of deviating from, namely improves coal tar heavy duty residue fraction purity simultaneously or improve the problem of its softening temperature.
At present, the processing scheme of the product whereabouts of the heavy resid component of middle coalite tar and the middle coalite tar of correspondence has following several, a small amount of bitum existence of middle coalite tar, causes the great uneconomical problem of various conventional processes:
1. produce and postpone coke, need to build coker, the component a large amount of (about more than 50%) increase investment, increase energy consumption, simultaneously making normal boiling point be 500 ~ 540 DEG C is converted into coke, industrial production shows, with northern Shensi coal-tar middle oil for raw material, coking yield about 14.5%, cooking gas yield about 5.0%, and coke quality is poor, use range is limited; Belong to uneconomic " oily zoom, gas " process;
2. oil fuel is produced, in order to reach the requirement of fuel oil viscosity, condensation point, the content of lightweight oil is wherein higher, and cause this constituent part low value to utilize, industrial production shows, with northern Shensi coal-tar middle oil for raw material, oil fuel yield about 10 ~ 15%, simultaneously because its combustionproperty is poor, seriously polluted, price is also lower, use range is limited, belongs to uneconomical utilization;
3. produce coal-tar pitch, due to reasons such as ash oontent are wherein high, coking value is low, product is difficult to sell;
4. as the raw material of hydrogenation process, belong to a kind of " for hydrogenation and hydrogenation " unreasonable selection, just to processing a small amount of bituminous matter being extremely difficult to hydrogenation, very easily causing catalyzer coking serious, use dead oil fixed bed reaction process instead suspension bed or boiling bed hydrogenation process, increase considerably process investment, increase catalyzer consumption, generate inferior heavy oil, reduce diesel yield, adding conventional gas and naphtha yield, is the practice of a kind of " losing more than gain ".
In order to overcome the shortcoming of above-mentioned prior art, the present invention is by the line of production of the macromolecular colloidal pitch shape component in middle coalite tar, jump out from the scope of traditional coke, coal-tar pitch, oil fuel, suspension bed or boiling bed hydrogenation raw material, the conversions concepts of traditional " vapor-liquid separation finally obtains light oil and residual oil " is the concept of " vapor-liquid separation finally obtains light oil and solid " by production class product of coal.
The present invention relates to a kind of method producing lightweight oil in self-contained bitum middle coalite tar, adopt degree of depth vaporization separation method, under the condition that obvious pyrogenic reaction does not occur, middle coalite tar is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition, liquid L1 is conduct " soft matchmaker " or coal green grass or young crops after cooling forming, can be used as coal-fired use, realize its environmental protection and store and use; Distillate steam V1 obtains clear gusoline through condensation gained oil product by hydrogenation process.
In producing with 500,000 tons/year of blue charcoal devices, coalite tar is processed as example, the normal boiling point that in fractionation 500,000 tons/year, coalite tar can obtain about 10 ~ 15% 5.0 ~ 7.5 ten thousand tons/year is higher than the coal tar heavy oil of 500 DEG C, the normal boiling point that this coal tar heavy oil contains 50 ~ 70% is 500 ~ 540 DEG C of coal tar fractions, even if even if isolate half also have 2.5 ~ 3.75 ten thousand tons/year by 50% its quantity of calculating, if be separated successfully, benefit is also huge.
In order to the extracting rate of the light residue fraction of coalite tar in improving, simultaneously in order to ensure that residual oil can flow out flasher or separation column in liquid form, during the present invention allows there is the degree of thermo-cracking in high the attending the meeting of the Heating temperature of coalite tar, but do not allow obvious pyrogenic reaction occurs.
Change a kind of angle to see, by the operational condition (working pressure of furnace outlet, service temperature) of the coke drum charging process furnace of the delayed coking process of middle coalite tar to the adjustment of reduction direction, cancel coke drum, and ensure the basic noncoking of coking fractional distillation column, namely the present invention is defined, therefore, the present invention is feasible.Clearly, the present invention is not coking.
Method of the present invention, the visbreaking working method seemed similar in appearance to the petroleum base vacuum residuum (major oil normal boiling point forms higher than 540 DEG C of hydrocarbon) of routine, but petroleum base vacuum residuum visbreaking converted products is oil product instead of solid phase prod, therefore, method of the present invention is significantly different from it.The operational condition difference of the course of processing greatly in addition, in order to be conducive to realizing viscosity breaking reaction, the visbreaking reaction of petroleum base vacuum residuum (major oil normal boiling point forms higher than 540 DEG C of hydrocarbon) operates usually under an increased pressure, instead of operates under the normal pressure being beneficial to deep vacuum distillation raising stock oil vaporization rate or reduced pressure.
Method of the present invention, the deep vacuum distillation method seemed similar in appearance to raising wax oil (major oil normal boiling point be 360 ~ 540 DEG C hydrocarbon composition) extracting rate of the petroleum base long residuum (major oil normal boiling point forms higher than 360 DEG C of hydrocarbon) of routine, but the product of the deep vacuum distillation method of the raising wax oil extracting rate of petroleum base long residuum is oil product instead of solid phase prod, , in order to suppress the better heat stability of heat scission reaction and petroleum base long residuum, usually there is not visbreaking reaction in the deep vacuum distillation process of petroleum base long residuum, therefore, method of the present invention is significantly different from it.
Cold oil due to the distillate steam V1 of middle coalite tar is suitable for as hydro-upgrading process raw material, therefore, present method can form combination process with coal tar fraction hydro-upgrading process, in this combination process, the light residue fraction hydrogenating materials of coal tar can be converted into hydrogenation wax oil component through deep hydrofinishing process, and hydrogenation wax oil component can be converted into diesel oil and more light constituent thereof through hydrocracking process.This is the second object of the present invention.
The method of the invention, is not only applicable to the processing of middle coalite tar, is equally applicable to coal-based oil containing heavy oil as the processing of coal-tar heavy oil, coal direct liquefaction oil, is suitable for containing the processing of more solid particulate as the oil shale oil of ash content yet.In the same way, the method for the invention is also applicable to the processing of the low hydrogen content mixing oil of asphaltenes.
The method of the invention has no report.
Therefore, the first object of the present invention is the method producing lightweight oil in a kind of self-contained bitum low hydrogen content oil of proposition.
The second object of the present invention is a kind of method proposing to produce lightweight oil in self-contained bitum coal tar.
The third object of the present invention is a kind of method proposing to produce lightweight oil in self-contained bitum middle coalite tar, adopt degree of depth gasification method, under the condition that obvious pyrogenic reaction does not occur, middle coalite tar is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition, liquid L1 conduct " soft matchmaker " or the use of coal green grass or young crops after cooling forming.
Summary of the invention
Produce the method for lightweight oil in a kind of self-contained bitum low hydrogen content oil of the present invention, it is characterized in that comprising with lower part:
At degree of depth vaporization separate part STEP1, under the condition that obvious pyrogenic reaction does not occur, the low hydrogen content hydrocarbon feed F01 of asphaltenes is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition.
The softening temperature of liquid L1 of the present invention is usually above 120 DEG C.
The present invention, at cooling forming part STEP2, liquid L1 becomes solid phase prod L1SP after cooling forming.
The present invention, at vaporised hydrocarbon recovery part STEP3, condensation obtains hydrocarbon ils HPF from the vapour phase comprising steam V1 of hydrocarbon feed F01.
The present invention, adding hydrogen partial STEP4, hydrocarbon ils HPF is converted into hydrogenation oil product through hydro-upgrading process HP at least partially, described hydro-upgrading process HP comprises the unifining process HT of hydrocarbon ils HPF, the hydrocracking process HC of the hydrofining wax oil HTVGO formed higher than 350 DEG C of hydrocarbon components primarily of normal boiling point that can also comprise that the hydrogenated oil HTP that is separated unifining process HT obtains.
The present invention, hydrocarbon feed F01, can be selected from one or more in following materials:
Hydrocarbon feed F01 of the present invention, can be selected from one or more in following materials:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. coal liquefaction gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. petroleum base wax oil thermal cracking tars;
9. petroleum based heavy fuel oils hot procedure gained heavy oil fraction product;
10. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils;
Described hot procedure comprises coking, catalytic cracking process, catalytic pyrolysis process, visbreaking process, thermal cracking process.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is the softening temperature of middle coalite tar, liquid phase L1: generally higher than 140 DEG C, should higher than 160 DEG C, especially higher than 180 DEG C.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and in liquid phase L1, normal boiling point is higher than the weight content of 540 DEG C of components: usually above 85%, generally higher than 90%, especially higher than 95 DEG C.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, service temperature: being generally 390 ~ 450 DEG C, being generally 400 ~ 440 DEG C, being preferably is 410 ~ 430 DEG C, is advisable with liquid phase L1 noncoking.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, service temperature: be generally 390 ~ 450 DEG C, generally higher than 400 ~ 440 DEG C, be 410 ~ 430 DEG C especially, working pressure: be usually less than 0.15MPaA, generally lower than 0.10MPaA, should lower than 0.07MPaA, be advisable with liquid phase L1 noncoking lower than 0.07MPaA especially.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the first operating method is:
Space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the second operating method is:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Leave the liquid phase L1 of flash zone T1S1, the water vapour stripping stage T1S3 vacuum flashing through being arranged in flash zone T1S1 bottom is deviate from light residue fraction and is separated into gas V11 and liquid L11, passes into stripped vapor T1SF at the bottom of separation column T1 tower; Gas V11 enters flash zone T1S1, and liquid L11 discharges separation column T1 as liquid product.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the third operating method is:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Gas phase V1 is by washing section T1SX and circulation cleaning liquid BLR counter current contact; The liquid B L that washing section T1SX bottom is flowed out is divided into two portions, and first part's circulation enters washing section T1SX top becomes circulation cleaning liquid BLR, and second section uses as liquid B LP and hydrocarbon feed F01 mixed cycle; The ratio of the weight rate BLPW of liquid B LP and the weight rate BLRW of circulation cleaning liquid BLR is K, K is 0.0005 to 0.01.
The present invention, after degree of depth vaporization separate part STEP1, water vapor Stripping section STU can be used, at water vapor Stripping section STU, to complete with stripping steam STUS from the liquid L1 of degree of depth vaporization separate part STEP1 at least partially and contact at least one times and be separated into vapour phase V2 and liquid phase L2, in liquid phase L1, residue fraction gasification enters in gas phase V2 at least partially, and the weight rate WL2 of liquid phase L2 is less than the weight rate WL1 of liquid phase L1.
The present invention, the working pressure of water vapor Stripping section STU: be usually less than 0.10MPaA, generally lower than 0.07MPaA, especially lower than 0.04MPaA.
The present invention, hydrocarbon feed F01, can be selected from one or more in following materials:
1. the hydrocarbon ils that gluey pitch shape component concentration is high;
2. the hydrocarbon ils that ash oontent is high;
3. the hydrocarbon ils that easily coking component concentration is high;
4. the hydrocarbon ils that high temperature easy reactive component content is high.
Embodiment
Below describe the present invention in detail.
Pressure of the present invention, refers to absolute pressure.
Concentration of component of the present invention, when not specializing, is weight concentration and mass concentration.
Conventional gas hydrocarbon of the present invention is the hydro carbons of gaseous state under referring to normal condition, comprises methane, ethane, propane, butane; The hydro carbons be in a liquid state under conventional liq hydrocarbon of the present invention refers to normal condition, comprises pentane and the higher hydro carbons of boiling point thereof; Impurity composition of the present invention refers to the hydrocracking thing of non-hydrocarbon component in stock oil as water, ammonia, hydrogen sulfide, hydrogenchloride etc.
In order to describe the problem, coalite tar heavy oil in routine or residual oil or the coal-tar pitch coal tar fraction of 500 DEG C (the such as normal boiling point higher than) are divided into light residue fraction and heavy resid component to treat by the present invention, are such as that the coal tar component of 500 ~ 540 DEG C is called the light residue fraction of coal tar, normal boiling point is called coal tar heavy duty residue fraction higher than the coal tar component of 540 DEG C by normal boiling point.Light residue fraction of the present invention and heavy resid component are a kind of concepts relatively.
Coal-based oil of the present invention, refers to the hydrocarbon ils from coal charge that the dry distillation of coal or coking of coal or the coal such as coal generating gas or DCL/Direct coal liquefaction hot procedure produce, comprises semi coking tar, middle temperature tar, high temperature tar, liquefied coal coil and mixing oil thereof.
Coal-based heavy oil of the present invention, refer to and compare as generally described from the coal-tar pitch of coal tar primarily of the cut of normal boiling point higher than the coal-based oil ingredient composition of 500 DEG C, usually contain a large amount of macromolecular substance as polycyclic aromatic hydrocarbons, colloid, bituminous matter etc., its hydrogen richness is lower, ash oontent is higher.
Coal-based heavy oil component of the present invention, refers to normal boiling point in coal-based oil higher than the hydrocarbon ils component of 500 DEG C, usually containing a large amount of macromolecular substance as polycyclic aromatic hydrocarbons, colloid, bituminous matter etc., its hydrogen richness is lower.
Coal tar of the present invention, refer to the coal tar from the process such as pyrolysis step of pyrolysis of coal or coking of coal or the dry distillation of coal or coal generating gas process or its cut, can be by product coalite tar or its cut of coal generating gas, also can be coal coking pyrolysis of coal process (comprising semi-coking, middle temperature coking, high-temperature coking process) by product coal tar or its cut, coal tar of the present invention can also be the mixing oil of above-mentioned coal tar.Coal tar of the present invention, comprises semi coking tar, middle temperature tar, high temperature tar, the mixing oil of different coal tar, the distillate of coal tar.
High-temperature coking belongs to coal high temperature pyrolysis process, and the outlet temperature of pyrolytic process is generally greater than 900 DEG C, usually between 1000 ~ 1400 DEG C.Described coal-tar heavy oil refers to the by product crude tar oil that coal high temperature pyrolysis produces coke and/or the production of town gas process.Coal-tar heavy oil is in primary distillation process, the following product of usual production: the products such as light oil (topping tar), carbolic oil, naphtalene oil, lightweight washing oil, heavy wash oil, lightweight carbolineum, heavy carbolineum, pitch, carbolic oil can be separated into crude phenols and dephenolize oil further, and naphtalene oil can be separated into thick naphthalene and de-naphtalene oil further.Coal-tar heavy oil lighting end of the present invention refers to: carbolineum, washing oil, naphtalene oil, de-naphtalene oil, carbolic oil, dephenolize oil, light oil and mixing oil thereof.
Because raw coal character and coking or gas-making process condition change all within the specific limits, coal tar oil properties also changes within the specific limits.Processing condition and the product requirement of coal tar primary distillation process also change within the specific limits, therefore the character of coal tar lighting end also changes within the specific limits.The character of coal tar lighting end, proportion is generally 0.92 ~ 1.25, normal boiling point is generally 60 ~ 500 DEG C and is generally 120 ~ 460 DEG C, usual metal content is 5 ~ 80PPm, sulphur content is 0.4 ~ 0.8%, nitrogen content is 0.6 ~ 1.4%, oxygen level is 0.4 ~ 9.0%, usual water-content is 0.2 ~ 5.0%, and carbon residue content is generally 0.5 ~ 13%.
The olefin(e) centent of usual coal tar lighting end is high, the high component also containing more easily reaction under mitigation condition of phenol content; therefore; the pre-hydrogenation process of coal tar lighting end of the present invention, usually uses the single dose of hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination.Coal tar heavy fractioning is coal-tar pitch cut particularly; its metal content is high, gum level is high, asphalt content is high; therefore; the pre-hydrogenation process of coal tar heavy fractioning of the present invention, usually uses the single dose of hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination
Produce in self-contained bitum low hydrogen content oil of the present invention lightweight oil process, it is the concept of a broad sense, at least comprise the heating evaporation sepn process of hydrocarbon feed F01, usually the fractionation by distillation process of hydrocarbon feed F01 is comprised, the unifining process HT of the light ends from hydrocarbon feed F01 can also be comprised, also can comprise the hydrocracking process of normal boiling point higher than 350 DEG C of components of unifining process HT hydrogenated oil HTY.
Degree of depth vaporization separate part STEP1 of the present invention, at least comprises a vaporization separating step, as required, can comprise multiple vaporization separating step, can comprise multiple heating steps simultaneously, can use well heater, flash tank, separation column.Degree of depth vaporization separate part STEP1 of the present invention, as required, can complete the distillate of dehydration, de-lighting end (such as carbolic oil, naphtalene oil, carbolineum) task need of production.
Liquid L1 of the present invention is usually after cooling forming process, and obtained formation solid is stacked, sale; Cooling forming process, in normally being formed with chain-driving in forming tank, cools with water and wind; According to Action Target, liquid phase L1 is as the high material of the aromatic carbon degree being rich in hydrocarbon matter, during its coking, coking yield is greater than 80%, cracked gas about 20%, oil product yield be low to moderate and be almost equal to zero, close with low-volatile coal character, can as the adulterant of solid coal fuel use such as pulverize after use with fine coal fusion, its storage accumulation problem can be solved.
Produce the method for lightweight oil in a kind of self-contained bitum low hydrogen content oil of the present invention, it is characterized in that comprising with lower part:
At degree of depth vaporization separate part STEP1, under the condition that obvious pyrogenic reaction does not occur, the low hydrogen content hydrocarbon feed F01 of asphaltenes is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition.
The softening temperature of liquid L1 of the present invention is usually above 120 DEG C.
The present invention, at cooling forming part STEP2, liquid L1 becomes solid phase prod L1SP after cooling forming.
The present invention, at vaporised hydrocarbon recovery part STEP3, condensation obtains hydrocarbon ils HPF from the vapour phase comprising steam V1 of hydrocarbon feed F01.
The present invention, adding hydrogen partial STEP4, hydrocarbon ils HPF is converted into hydrogenation oil product through hydro-upgrading process HP at least partially, described hydro-upgrading process HP comprises the unifining process HT of hydrocarbon ils HPF, the hydrocracking process HC of the hydrofining wax oil HTVGO formed higher than 350 DEG C of hydrocarbon components primarily of normal boiling point that can also comprise that the hydrogenated oil HTP that is separated unifining process HT obtains.
The present invention, hydrocarbon feed F01, can be selected from one or more in following materials:
Hydrocarbon feed F01 of the present invention, can be selected from one or more in following materials;
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. coal liquefaction gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. petroleum base wax oil thermal cracking tars;
9. petroleum based heavy fuel oils hot procedure gained heavy oil fraction product;
10. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils;
Described hot procedure comprises coking, catalytic cracking process, catalytic pyrolysis process, visbreaking process, thermal cracking process.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is the softening temperature of middle coalite tar, liquid phase L1: generally higher than 140 DEG C, should higher than 160 DEG C, especially higher than 180 DEG C.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and in liquid phase L1, normal boiling point is higher than the weight content of 540 DEG C of components: usually above 85%, generally higher than 90%, especially higher than 95 DEG C.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, service temperature: being generally 390 ~ 450 DEG C, being generally 400 ~ 440 DEG C, being preferably is 410 ~ 430 DEG C, is advisable with liquid phase L1 noncoking.
The present invention, at degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, service temperature: be generally 390 ~ 450 DEG C, generally higher than 400 ~ 440 DEG C, be 410 ~ 430 DEG C especially, working pressure: be usually less than 0.15MPaA, generally lower than 0.10MPaA, should lower than 0.07MPaA, be advisable with liquid phase L1 noncoking lower than 0.07MPaA especially.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the first operating method is:
Space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the second operating method is:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Leave the liquid phase L1 of flash zone T1S1, the water vapour stripping stage T1S3 vacuum flashing through being arranged in flash zone T1S1 bottom is deviate from light residue fraction and is separated into gas V11 and liquid L11, passes into stripped vapor T1SF at the bottom of separation column T1 tower; Gas V11 enters flash zone T1S1, and liquid L11 discharges separation column T1 as liquid product.
The present invention, at degree of depth vaporization separate part STEP1, use separation column T1, the third operating method is:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Gas phase V1 is by washing section T1SX and circulation cleaning liquid BLR counter current contact; The liquid B L that washing section T1SX bottom is flowed out is divided into two portions, and first part's circulation enters washing section T1SX top becomes circulation cleaning liquid BLR, and second section uses as liquid B LP and hydrocarbon feed F01 mixed cycle; The ratio of the weight rate BLPW of liquid B LP and the weight rate BLRW of circulation cleaning liquid BLR is K, K is 0.0005 to 0.01.
The present invention, after degree of depth vaporization separate part STEP1, water vapor Stripping section STU can be used, at water vapor Stripping section STU, to complete with stripping steam STUS from the liquid L1 of degree of depth vaporization separate part STEP1 at least partially and contact at least one times and be separated into vapour phase V2 and liquid phase L2, in liquid phase L1, residue fraction gasification enters in gas phase V2 at least partially, and the weight rate WL2 of liquid phase L2 is less than the weight rate WL1 of liquid phase L1.
The present invention, the working pressure of water vapor Stripping section STU: be usually less than 0.10MPaA, generally lower than 0.07MPaA, especially lower than 0.04MPaA.
The present invention, hydrocarbon feed F01, can be selected from one or more in following materials:
1. the hydrocarbon ils that gluey pitch shape component concentration is high;
2. the hydrocarbon ils that ash oontent is high;
3. the hydrocarbon ils that easily coking component concentration is high;
4. the hydrocarbon ils that high temperature easy reactive component content is high.
The invention has the advantages that: by the line of production of the macromolecular colloidal pitch shape component in middle coalite tar, from traditional coke, coal-tar pitch, oil fuel, jump out in the scope of suspension bed or boiling bed hydrogenation raw material, production class product of coal, by the concept that the conversions concepts of traditional " vapor-liquid separation finally obtains light oil and residual oil " is " vapor-liquid separation finally obtains light oil and solid ", achieve minimizing of middle coalite tar coal-tar pitch component product quantity and change solid with " class coal ", because the blue or green solid phase prod softening temperature of coal is high, oil content is few, volatility difference thus be easy to store, primarily of bituminous matter, macromole colloid forms therefore is easy to pulverize, form primarily of carbon therefore be suitable for doing fuel combustion.
Embodiment one
The middle coalite tar that the blue charcoal process of coal system produces in table 1, year amount of finish 500,000 tons/year, number 7920 when year goes into operation, quantity is 63132kg/h.In order to isolate light residue fraction to greatest extent, the bituminous matter in coal tar, ash content, particulate matter are concentrated on the blue or green thing of the coal obtaining high softening-point in heavy coal-tar pitch, adopt the present invention, operation steps is as follows simultaneously:
At degree of depth vaporization separate part STEP1, under the condition that obvious pyrogenic reaction does not occur, after raw material F01 heats temperature be 420 DEG C, under pressure is the condition of 0.10MPaA, point luxuriant through degree of depth vaporization is vapour phase V1 (59072kg/h, account for 93.57% of raw material F01) and the liquid phase L1 (4060/h, account for 6.43% of raw material F01) comprising residue fraction, and in liquid phase L1, normal boiling point is 80.42% higher than the weight content of 500 DEG C of components; Liquid phase L1 noncoking at this temperature;
At the first vaporization separate part STEP1, make normal boiling point in coal tar raw material enter in vapour phase V1 lower than 98.6% of the component of 500 DEG C, in vapour phase V1 normal boiling point lower than 500 DEG C, normal boiling point be the light residue fraction of coal tar of 500 ~ 540 DEG C and normal boiling point higher than the part by weight of the coal tar heavy duty residue fraction of 540 DEG C is 92.91%, 3.34%, 3.74%;
At degree of depth vaporization separate part STEP1, use separation column T1, the space up and down near the opening for feed of separation column T1 is flash zone T1S1, and the rectifying section T1S2 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
After degree of depth vaporization separate part STEP1, use water vapor Stripping section STU, at water vapor Stripping section STU, to complete with stripping steam STUS from the liquid L1 of degree of depth vaporization separate part STEP1 and once contact and be separated into vapour phase V2 and liquid phase L2, in this example, this step working pressure is 0.04MPaA; In this example, stripped vapor temperature is 430 DEG C, pressure is 0.1MPaA, flow is 486kg/h; Show water vapor Stripping section STU in stripping analog calculation, liquid phase L1 27.5% component complete vaporization.After stripping, the flow of oily L2 is 2944kg/h, accounts for 4.66% of coal tar raw material F01; After stripping, the temperature of oily L2 is 399 DEG C;
Space after stripping bottom the stripping tower T2 completing water vapor Stripping section STU between oily L2 storage area DL1 and water vapour stripping stage, be furnished with the refluxing opening L2SDC-N of cold scarce Posterior circle liquid phase L2SDC, after stripping oily L2 mix with circulation liquid phase L2SDC reduce temperature after become liquid phase L2SDCP, liquid phase L2SDCP to discharge bottom tower T2 to be cooled to about 200 ~ 250 DEG C by interchanger after pump pressurization becomes cold logistics L2SDCP1, the cold logistics L2SDCP1 of part is through reflux line, bottom tower T2, be mixed into liquid phase L2SDCP by refluxing opening L2SDC-N as liquid circulation liquid phase L2SDC and liquid phase L2 to discharge bottom tower T2, the cold logistics L2SDCP1 of part goes cooling forming step as liquid phase L2SDCP2, the temperature of liquid phase L2SDCP controls as being 280 ~ 300 DEG C,
Liquid phase L2SDCP2 enters cooling forming process, and obtained formation solid is stacked, sale; Cooling forming process, in being formed with chain-driving in forming tank, cools with water and wind.
In this example, the class coal solid yields of coal-tar middle oil raw material F01 be 4.66%, coal tar raw material F01 total vaporization rate be 95.34%, remove the water vapor of 4.2%, the vaporised fraction oil yield of coal tar raw material F01 is 91.14%; According to anhydrous butt coal tar conversion, the vaporised fraction oil yield of coal tar raw material F01 is 95.13%, and all the other clearly achieve target of the present invention.
Embodiment two
Based on embodiment one, at vaporizing oil recycling step, condensation, from the vapour phase V1 of degree of depth vaporization separate part STEP1 and the stripped oil vapour V2 from water vapor Stripping section STU, obtains hydrocarbon ils HPF.
At hydrogenation step, hydrocarbon ils HPF is converted into hydrogenation oil product through hydro-upgrading process HP, described hydro-upgrading process HP comprises the unifining process HT of hydrocarbon ils HPF, the hydrocracking process HC of the hydrofining wax oil HTVGO formed higher than 350 DEG C of hydrocarbon components primarily of normal boiling point also comprising that the hydrogenated oil HTP that is separated unifining process HT obtains.
This example defines the combination process of middle coalite tar deep drawing and vaporizing oil hydro-upgrading process.
Table 1 coal tar property analysis data
Claims (27)
1. produce a method for lightweight oil in self-contained bitum low hydrogen content oil, it is characterized in that comprising with lower part:
At degree of depth vaporization separate part STEP1, under the condition that obvious pyrogenic reaction does not occur, the low hydrogen content hydrocarbon feed F01 of asphaltenes is separated into distillate steam V1 and the liquid L1 primarily of macromolecular colloidal pitch shape component composition.
2. method according to claim 1, is characterized in that:
At degree of depth vaporization separate part STEP1, the softening temperature of liquid L1 is higher than 120 DEG C.
3. method according to claim 1, is characterized in that:
At cooling forming part STEP2, liquid L1 becomes solid phase prod L1SP after cooling forming.
4. method according to claim 1, is characterized in that:
At vaporised hydrocarbon recovery part STEP3, condensation obtains hydrocarbon ils HPF from the vapour phase comprising steam V1 of hydrocarbon feed F01.
5. method according to claim 4, is characterized in that:
Adding hydrogen partial STEP4, hydrocarbon ils HPF is converted into hydrogenation oil product through hydro-upgrading process HP at least partially, and described hydro-upgrading process HP comprises the unifining process HT of hydrocarbon ils HPF.
6. method according to claim 4, is characterized in that:
Adding hydrogen partial STEP5, hydrocarbon ils HPF is converted into hydrogenation oil product through hydro-upgrading process HP at least partially, described hydro-upgrading process HP comprises the unifining process HT of hydrocarbon ils HPF, the hydrocracking process HC of the hydrofining wax oil HTVGO formed higher than 350 DEG C of hydrocarbon components primarily of normal boiling point also comprising that the hydrogenated oil HTP that is separated unifining process HT obtains.
7. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
Hydrocarbon feed F01, is selected from one or more in following materials:
Hydrocarbon feed F01 of the present invention, can be selected from one or more in following materials:
1. coalite tar or its distillate or its hot procedure gained oil product;
2. coal-tar middle oil or its distillate or its hot procedure gained oil product;
3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;
4. coal liquefaction gained liquefied coal coil or its distillate or its hot procedure gained oil product; ;
5. shale oil or its distillate or its hot procedure gained oil product;
6. tar sand basic weight oil or its hot procedure gained oil product;
7. ethylene cracking tar;
8. petroleum base wax oil thermal cracking tars;
9. petroleum based heavy fuel oils hot procedure gained heavy oil fraction product;
10. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils;
Described hot procedure comprises coking, catalytic cracking process, catalytic pyrolysis process, visbreaking process, thermal cracking process.
8. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and the softening temperature of liquid phase L1 is higher than 140 DEG C.
9. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and the softening temperature of liquid phase L1 is higher than 160 DEG C.
10. the method according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and the softening temperature of liquid phase L1 is higher than 180 DEG C.
11. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, in liquid phase L1 normal boiling point higher than the weight content of 540 DEG C of components higher than 85%.
12. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, in liquid phase L1 normal boiling point higher than the weight content of 540 DEG C of components higher than 90%.
13. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, in liquid phase L1 normal boiling point higher than the weight content of 540 DEG C of components higher than 95 DEG C.
14. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and service temperature is 390 ~ 450 DEG C, is advisable with liquid phase L1 noncoking.
15. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and service temperature is 400 ~ 440 DEG C, is advisable with liquid phase L1 noncoking.
16. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and service temperature is 410 ~ 430 DEG C, is advisable with liquid phase L1 noncoking.
17. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and service temperature is 390 ~ 450 DEG C, and working pressure, lower than 0.15MPaA, is advisable with liquid phase L1 noncoking.
18. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, service temperature is 400 ~ 440 DEG C, working pressure, lower than 0.10MPaA, is advisable with liquid phase L1 noncoking.
19. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, hydrocarbon feed F01 is middle coalite tar, and service temperature is 410 ~ 430 DEG C, and working pressure, lower than 0.07MPaA, is advisable with liquid phase L1 noncoking.
20. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate.
21. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Leave the liquid phase L1 of flash zone T1S1, the water vapour stripping stage T1S3 vacuum flashing through being arranged in flash zone T1S1 bottom is deviate from light residue fraction and is separated into gas V11 and liquid L11, passes into stripped vapor T1SF at the bottom of separation column T1 tower; Gas V11 enters flash zone T1S1, and liquid L11 discharges separation column T1 as liquid product.
22. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
At degree of depth vaporization separate part STEP1, use separation column T1, space up and down near the opening for feed of separation column T1 is flash zone T1S1, and charging is separated into steam V1 and liquid L1 at this, and the rectifying section T1S2 separate vapour V1 of more than the flash zone T1S1 of separation column T1 obtains 2 or multiple distillate;
Gas phase V1 is by washing section T1SX and circulation cleaning liquid BLR counter current contact; The liquid B L that washing section T1SX bottom is flowed out is divided into two portions, and first part's circulation enters washing section T1SX top becomes circulation cleaning liquid BLR, and second section uses as liquid B LP and hydrocarbon feed F01 mixed cycle; The ratio of the weight rate BLPW of liquid B LP and the weight rate BLRW of circulation cleaning liquid BLR is K, K is 0.0005 to 0.01.
23. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
After degree of depth vaporization separate part STEP1, use water vapor Stripping section STU, at water vapor Stripping section STU, to complete with stripping steam STUS from the liquid L1 of degree of depth vaporization separate part STEP1 at least partially and contact at least one times and be separated into vapour phase V2 and liquid phase L2, in liquid phase L1, residue fraction gasification enters in gas phase V2 at least partially, and the weight rate WL2 of liquid phase L2 is less than the weight rate WL1 of liquid phase L1.
24. methods according to claim 23, is characterized in that:
The working pressure of water vapor Stripping section STU is lower than 0.10MPaA.
25. methods according to claim 23, is characterized in that:
The working pressure of water vapor Stripping section STU is lower than 0.07MPaA.
26. methods according to claim 23, is characterized in that:
The working pressure of water vapor Stripping section STU is lower than 0.04MPaA.
27. methods according to claim 1 or 2 or 3 or 4 or 5 or 6, is characterized in that:
Hydrocarbon feed F01, is selected from one or more in following materials:
1. the hydrocarbon ils that gluey pitch shape component concentration is high;
2. the hydrocarbon ils that ash oontent is high;
3. the hydrocarbon ils that easily coking component concentration is high;
4. the hydrocarbon ils that high temperature easy reactive component content is high.
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| CN105542826A (en) * | 2016-01-10 | 2016-05-04 | 何巨堂 | Method for extracting oil from solid particle and heavy hydrocarbon self-contained stream |
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