CN101892078A - Preparation method of coal-based naphtha with high potential aromatic content for catalytic reforming, product and application thereof - Google Patents
Preparation method of coal-based naphtha with high potential aromatic content for catalytic reforming, product and application thereof Download PDFInfo
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Abstract
The invention relates to a preparation method of coal-based naphtha with high aromatic potential content for catalytic reforming and application. The method comprises the following steps of: a) hydrogenation: mixing full cut fraction liquefied oil prepared from directly liquefying coal with hydrogen, delivering the mixture to an expanded bed hydro-treating reactor after the full cut fraction liquefied oil and the hydrogen are mixed, contacting the mixture with a hydro-treating catalyst to carry out hydrogenation reaction, and making material flow flowing out of an outlet of the expanded-bed hydro-treating reactor carry out separation and fractional distillation to obtain light distillates, mediate distillates and heavy distillates; and b) depth hydrogenation refining: mixing the light distillates and the mediate distillates obtained in the step a), mixing the mixture with the hydrogen, delivering the final mixture to a fixed bed depth hydrogenation refining reactor for contact with a hydrogenation refining catalyst to carry out a chemical reaction, and performing the separation and fractional distillation of a material flow flowing out of an outlet of the fixed bed depth hydrogenation refining reactor to obtain naphtha cut fraction with high aromatic potential content, which meets the feeding requirements on catalytic reforming. Thus, the service life of the catalyst is prolonged.
Description
Technical field
The present invention relates to a kind of method of further processing of the liquefaction oil that coal direct liquefaction is obtained.More particularly, the product and the application thereof that relate to the method for the high petroleum naphtha of aromatic hydrocarbon potential content that a kind of thick oil production that is obtained by coal direct liquefaction is suitable for the catalytic reforming charging, obtain by this method.
Background technology
Along with the raising day by day of China's rapid economy development and living standards of the people, also increasing to the demand of aromatic hydrocarbon.Be mainly reflected in chemical fibre production to the demand of aromatic hydrocarbon and high-octane rating motor spirit blend component aspects such as demand to aromatic hydrocarbon.Aromatic hydrocarbon mainly generates the cracking naphtha of oil and preparing ethylene by steam cracking by-product from the petroleum naphtha catalytic reforming.
The raw material of petroleum naphtha catalytic reforming mainly is virgin naphtha, hydrocracking petroleum naphtha.Virgin naphtha contains sulphur, nitrogen, metallic impurity toxic substances such as (as As, Cu, Pb etc.), and therefore, virgin naphtha must pass through pre-treatment could be as the acceptable material of catalytic reforming unit.
Arene underwater content is to estimate the important indicator of petroleum naphtha as reformer feed.The arene underwater content of virgin naphtha is relevant with the kind of crude oil, is about 32% as the aromatic hydrocarbon potential content of grand celebration virgin naphtha, and the arene underwater content of triumph virgin naphtha is about 49%.The arene underwater content of hydrocracking petroleum naphtha is relevant with the kind of hydrocracking raw material oil, arene underwater content to the narrow fraction (boiling point is 65～132 ℃) of grand celebration, triumph and isolated island vacuum gas oil hydrocracking gained, minimum with the Daqing oil of paraffinic base is 45%, Shengli Oil with intermediate base is 53% between two parties, and is up to 61% with the isolated island oil of cycloalkyl.
China's catalytic reforming unit has obtained bigger development in recent years, some refineries face the insufficient situation of reformer feed, and the raw material sources deficiency becomes a principal element of restriction China catalytic reforming technical development.The primary energy source structures shape of China coal direct liquefaction produce oil product and meet China's energy sustainable development strategy.The liquefaction oil of coal direct liquefaction production comprises lightweight liquefaction oil product and heavy liquefaction oil product, is the lightweight liquefaction oil very significant as the source that the raw material of catalytic reforming enlarges catalytic reforming raw material.But some character characteristics that kept the liquefaction feed coal by the liquefaction oil of coal direct liquefaction production, as nitrogen, oxygen heteroatom content height, liquefy oil product owing to contain impurity such as higher nitrogen, oxygen for lightweight, there is a spot of mechanical impurity, as tiny ickings etc., second-rate during as the catalytic reforming charging, therefore need further to handle.
European patent application EP 0203240 has been announced a kind of method that coal liquefaction craft improves naphtha yield of improving.This method is that the product that the coal oil mixture liquefaction that coal and suitable solvent are made into generates is divided into gas products, liquid product and solid phase prod, and further liquiefied product is divided into naphtha fraction, solvent cut and vacuum gas oil fraction; The mixture of part solvent cut and a part of vacuum gas oil fraction successively enters hydrotreating reactor, hydrocracking reactor, obtains naphtha fraction and solvent cut, thereby improves the productive rate of petroleum naphtha.This method has just improved the productive rate of petroleum naphtha, and the method for further handling for petroleum naphtha is not provided.
The open CN 1912062A of Chinese patent application has announced a kind of method of producing catalytic reforming raw material with the oil secondary processing of gasoline, at first secondary processing of gasoline is cut into light benzine cut, middle matter gasoline fraction and heavy gasoline cut; Middle matter gasoline fraction and hydrogen enter first hydrogenator together, under the Hydrobon catalyst effect, react, reaction effluent enters second hydrogenator without separating directly with after virgin naphtha mixes, under the effect of Hydrobon catalyst, react, the reaction effluent that generates cools off, separates, isolated liquid enters the distillation dehydration tower, obtains petroleum naphtha after removing impurity.This method mainly is that the alkene in the secondary processing of gasoline is saturated, and removes impurity such as sulphur nitrogen, and can be catalytic reforming provides sulphur, nitrogen content all qualified raw material, but the arene underwater content of raw material is often not high.
Compare with petroleum base petroleum naphtha (virgin naphtha and hydrocracking petroleum naphtha), coal-based petroleum naphtha has the characteristics of himself, the arene underwater content height of coal-based petroleum naphtha, it is the good raw material of catalytic reforming, but simultaneously its sulphur, nitrogen content are very high, usually all more than 1000 μ g/g, thereby be underproof catalytic reforming raw material.And above-mentioned disclosed patented technology does not all mention how coal-based petroleum naphtha could being converted into the acceptable material that is used for catalytic reforming.
Therefore, in order to overcome above-mentioned defective, need provide a kind of and be applicable to, so that the petroleum naphtha of the high aromatic hydrocarbon potential content that will be obtained by this method is produced the raw material of aromatic hydrocarbons as catalytic reforming from the method for the petroleum naphtha of the high aromatic hydrocarbon potential content of thick liquefaction Oil Production of coal direct liquefaction.
Summary of the invention
The objective of the invention is to provide on the basis of existing technology a kind of petroleum naphtha of the high aromatic hydrocarbon potential content of thick liquefaction Oil Production that obtains by coal direct liquefaction, so that produce the raw material of aromatic hydrocarbons as catalytic reforming.
For this reason, the invention provides a kind of production method that is used for the coal-based naphtha with high potential aromatic content of catalytic reforming, may further comprise the steps:
A) hydrogenation step: the full distillate oil that DCL/Direct coal liquefaction is produced mixes with hydrogen, it enters the expanded bed hydrotreating reactor from the expanded bed bottom after mixing together, contact so that hydrogenation reaction to take place with hydrotreating catalyst, with the logistics that flows out the outlet of expanded bed hydrotreating reactor through separating, after the fractionation, obtaining light ends oil, middle matter cut and heavy distillate; And
B) deep hydrofinishing step: after the light ends oil that step a) is obtained, middle matter distillate mix, mix with hydrogen again, enter fixed bed deep hydrofinishing reactor then together, contact with Hydrobon catalyst, so that chemical reaction to take place, with the logistics that flows out fixed bed deep hydrofinishing reactor outlet through separating, after the fractionation, obtaining meeting the naphtha fraction of the high aromatic hydrocarbon potential content of catalytic reforming charging requirement.
Preferably, the hydrogen of step a) constitutes by fresh hydrogen with from the recycle hydrogen of hydrotreating reactor system, and the hydrogen of step b) constitutes by fresh hydrogen with from the recycle hydrogen of deep hydrofinishing reactor assembly.More preferably, the hydrogen of step a) is mainly the recycle hydrogen from the hydrotreating reactor system; The hydrogen of step b) also is mainly the recycle hydrogen from the deep hydrofinishing reactor assembly.
More preferably, in the step a) from the recycle hydrogen of hydrotreating reactor system hydrogen concentration be 90～95%.The hydrogen concentration from the recycle hydrogen of hydrotreating reactor system in the step b) is 92～96%.
Preferably, the petroleum naphtha that is used for catalytic reforming raw material is derived from the liquefaction oil that coal direct liquefaction is produced, but not oil.
Preferably, the reaction conditions of the hydrotreating reactor of step a) is: hydrogen dividing potential drop 6.0～30.0MPa, 300～430 ℃ of temperature of reaction, liquid hourly space velocity 0.6～3h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and full cut liquefaction oil: 1Nm
3/ m
3And the reaction conditions of the deep hydrofinishing reactor of step b) is: hydrogen dividing potential drop 6.0～20.0MPa, 300～460 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and light ends oil, middle matter distillate: 1Nm
3/ m
3
More preferably, the reaction conditions of the hydrotreating reactor of step a) is: hydrogen dividing potential drop 10.0～20.0MPa, 330～400 ℃ of temperature of reaction, liquid hourly space velocity 0.5～3h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and full cut liquefaction oil: 1Nm
3/ m
3And the reaction conditions of the deep hydrofinishing reactor of step b) is: hydrogen dividing potential drop 10.0～18.0MPa, 350～420 ℃ of temperature of reaction, liquid hourly space velocity 0.6～3h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and light ends oil, middle matter distillate: 1Nm
3/ m
3
Preferably, the employed hydrotreating catalyst of expanded bed hydrotreating reactor of step a) is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, and VIII family metal is selected from Co or Ni; The employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, VIII family metal is selected from Co or Ni, and wherein the deep hydrofinishing reactor has comprised 2～4 beds.
Preferably, the ratio of expansion of the employed hydrotreating catalyst of expanded bed hydrotreating reactor of step a) is 20～40%, and more preferably the ratio of expansion of catalyzer is 25～35%, and the ratio of expansion of most preferred catalysts is about 30%.
More preferably, the employed hydrotreating catalyst of expanded bed hydrotreating reactor of step a) is selected from the HTS catalyst series of French AXENS production, the RS-1000 catalyzer that catalyzer branch office of Sinopec Group produces.
Most preferably, the employed hydrotreating catalyst of expanded bed hydrotreating reactor of step a) is the HTS-358 that French AXENS produces, and is Ni-Mo type supported catalyst.Another kind of preferred hydrotreating catalyst is the RS-1000 catalyzer that catalyzer branch office of Sinopec Group produces.
More preferably, the employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) comprises 2～3 beds, the employed deep hydrofinishing catalyzer of deep hydrofinishing reactor (25) of step b) is selected from RN catalyst series, FF catalyst series, the FH catalyst series that catalyzer branch office of Sinopec Group produces, the DZ series that Daqing petrochemical company research institute produces is as RN-1, RN-2, RNC-2, RN-10B, RN-22, RN-32, RN-32V, DZ-1, DZ-1A, DZ-10D, DZ-10G catalyzer.
Most preferably, the employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) comprises 3 beds, and the employed deep hydrofinishing catalyzer of deep hydrofinishing reactor (25) of step b) is selected from catalyzer RN-2, RNC-2 and the RN-32 that catalyzer branch office of Sinopec Group produces.
Preferably, in the step a), comprise that temperature in that the full fraction oil-hydrogen mixture of liquefaction light oil and liquefaction distillate enters the expanded bed hydrotreating reactor, can be between 250～300 ℃ according to the charge proportion between liquefaction light oil, liquefaction distillate and the hydrogen and different; Obtain temperature that hydrogenation products flows out the outlet of expanded bed hydrotreating reactor in the step a) according to the charge proportion between liquefaction light oil, liquefaction distillate and the hydrogen and different, can be between 300～390 ℃.
Preferably, in the step b), the temperature in that hydrogen and the mixture of light ends oil, middle matter distillate enter fixed bed hydrogenation refining reaction device can be between 300～380 ℃ according to the charge proportion between light ends oil and middle matter distillate and the hydrogen and different; Obtain temperature that hydrogenation products flows out the outlet of fixed bed hydrogenation refining reaction device in the step b) according to the charge proportion between light ends oil and middle matter distillate and the hydrogen and different, can be between 330～400 ℃.
Another aspect of the present invention provides a kind of coal-based naphtha with high potential aromatic content that is obtained by method of the present invention.
Preferably, wherein the aromatic hydrocarbon potential content of petroleum naphtha is 60～80wt%.
Another aspect of the present invention provides a kind of coal-based naphtha with high potential aromatic content that is obtained by method of the present invention to be used as the application of catalytic reforming raw material.
Preferably, the petroleum naphtha of this coal-based high aromatic hydrocarbon potential content is produced the raw material of the blend component of aromatic hydrocarbons or high-octane rating motor spirit as catalytic reforming.
Because the expanded bed hydrotreating reactor has been adopted in the hydrotreatment of the liquefaction oil product of the step a) of the inventive method, makes that catalyst in reactor is activity stabilized between whole on-stream period, the temperature of reactor unanimity.
Expanded bed reactor is adopted in hydrotreatment in the step a) of the present invention, and adopt the type reactor to have following advantage: one, the catalyst bed layer resistance can not increase.Because liquefaction light oil by DCL/Direct coal liquefaction production, the liquefaction distillate enters reactor from the expanded bed bottom, make the liquefaction distillate of producing by DCL/Direct coal liquefaction bring mechanical impurity in the hydrogenation system into such as trickle non-oil products such as pulverized coal particle can make it pass whole expanded bed beds by means of the fluidic effect in operational process, and can as fixed bed catalyst, not make mechanical impurity accumulate in the surface of the beds of oil product inlet, effectively avoided the obstruction of beds, like this in whole operation process, it is constant that the resistance of beds can keep, and can not influence running period owing to bed resistance increases as fixed-bed reactor; Two, adopted expanded bed reactor, made uniformity of temperature profile in the reactor, the reaction in the reactor is very even; Three, cancel cold hydrogen system, made reaction heat be fully used, reached purpose of energy saving; Four, cancelled forced circulation system in the expanded bed hydrotreating reactor that adopts in the present T-star technology, make catalyzer wherein no longer be subjected to the impact that pump circulation liquid flows, thereby prolonged catalyst life, and reduced requirement for the catalyst strength aspect, saved a compressor simultaneously, reduced facility investment and occupation of land, reduced cost, and made the entire equipment layout compacter.
Method provided by the invention is that the thick liquefaction oil with coal direct liquefaction production is a raw material, the petroleum naphtha of the extra-high-speed aromatic hydrocarbon potential content that the production catalytic reforming is used, the petroleum naphtha aromatic hydrocarbon potential content that obtains is greater than 70%, usually petroleum naphtha aromatic hydrocarbon potential content is between 70%～80%, especially be used to produce aromatic hydrocarbons as catalytic reforming raw material, as benzene,toluene,xylene, perhaps be used to produce the raw material of the blend component of high-octane rating motor spirit.
Description of drawings
Fig. 1 is the synoptic diagram of the method for the special naphtha with high potential aromatic content of production provided by the invention.
Embodiment
The specific embodiment of the present invention below is provided.Those skilled in the art should understand that wherein embodiment only is for illustrative purposes, should not be regarded as limiting by any way the scope of the invention defined by the claims.
In a specific embodiment of the present invention, a kind of method of producing the high petroleum naphtha of aromatic hydrocarbon potential content from the thick liquefaction oil of coal direct liquefaction is provided, this petroleum naphtha can be used as the charging of catalytic reforming.
This method comprises hydrotreatment and two steps of deep hydrofinishing of thick liquefaction oil:
Step a): hydrotreatment;
The purpose of hydrotreatment is that alkene is saturated, two rings are above aromatic hydrocarbon fractional saturation, part remove impurity such as oxygen in the liquefaction oil, nitrogen, sulphur, provide strong solvent for the coal direct liquefaction unit on the one hand, supply raw materials for follow-up deep hydrofinishing process on the other hand.
Expanded bed reactor is adopted in hydrotreatment provided by the invention, adopts the type reactor to have following advantage:
The catalyst bed layer resistance can not increase;
Because the liquefaction light oil of charging, liquefaction distillate enter reactor from the expanded bed bottom, make and to bring mechanical impurity in the hydrotreating reactor into such as trickle non-oil products such as pulverized coal particle can make it be dispersed in whole expanded bed catalyzer inside by means of the fluidic effect in operational process by liquefaction light oil, the liquefaction distillate of charging, and can as fixed bed catalyst, not make mechanical impurity accumulate in the surface of the beds of oil product inlet, effectively avoided the obstruction of beds;
In whole operation process, it is constant that activity of such catalysts can keep like this, can not influence running period owing to bed resistance increases as fixed-bed reactor;
Reactive system of the present invention has been cancelled cold hydrogen system, makes reaction heat be fully used, and has reached purpose of energy saving;
Expanded bed hydrotreating reactor of the present invention has been cancelled the pump circulation that adopts in the present T-star technology, make catalyzer wherein no longer be subjected to the impact that pump circulation liquid flows, thereby prolonged catalyst life, and saved a compressor, facility investment and occupation of land have been reduced, reduced cost, and made the entire equipment layout compacter.
Because the catalyzer that uses in the expanded bed hydrotreating reactor no longer is subjected to the impact of pump circulation liquid stream, thereby has reduced the requirement of its intensity aspect, increased the choice of useful catalyst, reduced the cost of catalyzer.
In the hydrotreatment process, alkene is saturated, the reaction ratio of deoxidation and desulfurization is easier to carry out, and the above aromatic hydrocarbons of two rings is saturated and the reaction of denitrogenation difficulty relatively.In this process, the saturated degree of the two above aromatic hydrocarbons of ring is subjected to coal direct liquefaction to strong solvent hydrogen supply performance limitations, therefore reaction conditions of the present invention and catalyzer will be taken into account the denitrification activity of the saturated and liquefied coal coil of the above aromatic hydrocarbon of two rings, the degree of saturation that should satisfy the above aromatic hydrocarbon of two rings reaches certain proportion, with this understanding the nitrogen content in the liquefied coal coil is reduced to minimum level again.
The principal reaction condition of the hydrotreating reactor of step a) provided by the invention is: hydrogen dividing potential drop 6.0～30.0MPa, 300～430 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1,, the gas-liquid volume charge ratio 900～1200 of hydrogen and full cut liquefaction oil: 1Nm
3/ m
3
The employed hydrotreating catalyst of expanded bed reactor of the present invention is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, and metal component is group vib or VIII family metal component; Wherein the group vib metal is selected from W or Mo, and VIII family metal is selected from Co or Ni.
The employed hydrotreating catalyst of described expanded bed hydrotreating reactor (5) of step a) is selected from the HTS catalyst series of French AXENS production, the RS-1000 catalyzer that catalyzer branch office of Sinopec Group produces, especially the HTS-358 catalyzer (it is a kind of Ni-Mo type supported catalyst) that French AXENS produces, and the RS-1000 catalyzer of catalyzer branch office of Sinopec Group production.
Step b): deep hydrofinishing
The purpose of step b)-deep hydrofinishing is that the raw material that step a)-hydrotreatment is produced is carried out further making with extra care, and to reduce remaining impurities in the raw material, obtains meeting the qualified naphtha product of catalytic reforming charging requirement; The raw material of this step is the light ends oil of step a)-hydrotreatment production and the mixing oil product of middle matter distillate.
In the present invention, the step b) deep hydrofinishing adopts fixed-bed reactor, in this reactor, has comprised 2～4 beds.
The principal reaction condition of deep hydrofinishing reactor provided by the invention is: hydrogen dividing potential drop 6.0～20.0MPa, 300～460 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and light ends oil, middle matter distillate: 1Nm
3/ m
3
The employed deep hydrofinishing catalyzer of this step is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, and metal component is group vib or VIII family metal component; Wherein the group vib metal is selected from W or Mo, and VIII family metal is selected from Co or Ni.
The employed deep hydrofinishing catalyzer of this step is selected from the DZ series that RN series fraction oil Hydrobon catalyst, FF catalyst series, FH catalyst series, Daqing petrochemical company research institute that catalyzer branch office of Sinopec Group produces produce, as RN-1, RN-2, RNC-2, RN-10B, RN-22, RN-32, RN-32V, DZ-1, DZ-1A, DZ-10D, DZ-10G catalyzer.Especially RNC-2 catalyzer.
The light ends oil that is not suitable as the DCL/Direct coal liquefaction solvent, the middle matter distillate that the deep hydrofinishing of the present invention by step b) obtains step a) carries out the foreign matter content of further saturated go forward side by side wherein sulphur of one-step removal, nitrogen, oxygen, make the final logistics that flows out fixed bed deep hydrofinishing reactor outlet through separating, after the fractionation, having obtained meeting the naphtha fraction of the high aromatic hydrocarbon potential content of catalytic reforming charging requirement.
In an embodiment, a kind of production method that is used for the coal-based naphtha with high potential aromatic content of catalytic reforming is provided, may further comprise the steps:
A) hydrogenation step: the full distillate oil that DCL/Direct coal liquefaction is produced mixes with hydrogen, the expanded bed hydrotreating reactor that it enters from the expanded bed bottom after mixing together, contact so that hydrogenation reaction to take place with hydrotreating catalyst, with the logistics that flows out the outlet of expanded bed hydrotreating reactor through separating, after the fractionation, obtaining light ends oil, middle matter cut and heavy distillate; And
B) deep hydrofinishing step: after the light ends oil that step a) is obtained, middle matter distillate mix, mix with hydrogen again, enter fixed bed deep hydrofinishing reactor then together, contact with Hydrobon catalyst, series of chemical takes place, with the logistics that flows out described fixed bed deep hydrofinishing reactor outlet through separating, after the fractionation, obtaining meeting the naphtha fraction of the high aromatic hydrocarbon potential content of catalytic reforming charging requirement.
In a preferred embodiment, the petroleum naphtha that is used for catalytic reforming raw material of the inventive method is derived from the liquefaction oil that coal direct liquefaction is produced, but not oil.
In a preferred embodiment, the hydrogen of step a) constitutes by fresh hydrogen with from the recycle hydrogen of hydrotreating reactor system, and the hydrogen of step b) constitutes by fresh hydrogen with from the recycle hydrogen of deep hydrofinishing reactor assembly.
One more preferably in the embodiment, the hydrogen of step a) is mainly the recycle hydrogen from the hydrotreating reactor system; The hydrogen of step b) also is mainly the recycle hydrogen from the deep hydrofinishing reactor assembly.
One more preferably in the embodiment, the hydrogen concentration from the recycle hydrogen of hydrotreating reactor system in the step a) is 90～95%, more preferably 92%.The hydrogen concentration from the recycle hydrogen of hydrotreating reactor system in the step b) is 92～96%, more preferably 95%.
In a preferred embodiment, the reaction conditions of the hydrotreating reactor of the step a) of the inventive method is: hydrogen dividing potential drop 6.0～30.0MPa, 300～430 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and full cut liquefaction oil: 1Nm
3/ m
3And the reaction conditions of the deep hydrofinishing reactor of step b) is: hydrogen dividing potential drop 6.0～20.0MPa, 300～460 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and light ends oil and middle matter distillate: 1Nm
3/ m
3
One more preferably in the embodiment, the reaction conditions of the hydrotreating reactor of step a) is: hydrogen dividing potential drop 10.0～20.0MPa, 330～400 ℃ of temperature of reaction, liquid hourly space velocity 0.5～3h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and full cut liquefaction oil: 1Nm
3/ m
3And the reaction conditions of the deep hydrofinishing reactor of step b) is: hydrogen dividing potential drop 10.0～18.0MPa, 350～420 ℃ of temperature of reaction, liquid hourly space velocity 0.6～3h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and light ends oil and middle matter distillate: 1Nm
3/ m
3
In a preferred embodiment, the employed hydrotreating catalyst of expanded bed hydrotreating reactor of the step a) of the inventive method is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, and VIII family metal is selected from Co or Ni; The employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, VIII family metal is selected from Co or Ni, and wherein the deep hydrofinishing reactor has comprised 2～4 beds.
In a preferred embodiment, the ratio of expansion of the employed hydrotreating catalyst of expanded bed hydrotreating reactor of the step a) of the inventive method is 20～40%, more preferably the ratio of expansion of catalyzer is 25～35%, and the ratio of expansion of most preferred catalysts is about 30%.
In a preferred embodiment, the employed hydrotreating catalyst of expanded bed hydrotreating reactor of step a) is selected from the HTS catalyst series of French AXENS production, the RS-1000 catalyzer that catalyzer branch office of Sinopec Group produces; The employed deep hydrofinishing catalyzer of step b) is selected from RN catalyst series, FF catalyst series, the FH catalyst series that catalyzer branch office of Sinopec Group produces, the DZ series that Daqing petrochemical company research institute produces is as RN-1, RN-2, RNC-2, RN-10B, RN-22, RN-32, RN-32V, DZ-1, DZ-1A, DZ-10D, DZ-10G catalyzer.
One more preferably in the embodiment, the employed deep hydrofinishing catalyzer of described deep hydrofinishing reactor of the step b) of the inventive method comprises 2～3 beds.The employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) is selected from catalyzer RN-2, RNC-2 and the RN-32 that catalyzer branch office of Sinopec Group produces.
In a further preferred implementation, the employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) comprises 3 beds, and the employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) is selected from catalyzer RN-2, RNC-2 and the RN-32 that catalyzer branch office of Sinopec Group produces.In a most preferred embodiment, the employed deep hydrofinishing catalyzer of the deep hydrofinishing reactor of step b) is the RNC-2 catalyzer that catalyzer branch office of Sinopec Group produces.
In a preferred embodiment, in the step a), the temperature in that liquefaction light oil, liquefaction cut oil-hydrogen mixture enter the expanded bed hydrotreating reactor is according to the charge proportion between liquefaction light oil, liquefaction distillate and the hydrogen and different, can be at 250～300 ℃, especially about 280 ℃; Obtain temperature that hydrogenation products flows out the outlet of expanded bed hydrotreating reactor in the step a) according to the charge proportion between liquefaction light oil, liquefaction distillate and the hydrogen and different, can be between 300～390 ℃, especially about 380 ℃.
In a preferred embodiment, in the step b), the temperature in that the mixture of hydrogen and light ends oil and middle matter distillate enters fixed bed hydrogenation refining reaction device is according to the charge proportion between light ends oil and middle matter distillate and the hydrogen and different, can be between 300～380 ℃, especially about 320 ℃; Obtain temperature that hydrogenation products flows out the outlet of fixed bed hydrogenation refining reaction device in the step b) according to the charge proportion between light ends oil and middle matter distillate and the hydrogen and different, can be between 330～400 ℃, especially about 350 ℃.
In the another embodiment of the present invention, provide a kind of coal-based naphtha with high potential aromatic content that obtains by method of the present invention.Wherein the aromatic hydrocarbon potential content of petroleum naphtha is 60～80wt%.
In the another embodiment of the present invention, provide a kind of coal-based naphtha with high potential aromatic content that obtains by method of the present invention to be used as the application of catalytic reforming raw material.The petroleum naphtha of this coal-based high aromatic hydrocarbon potential content especially is suitable as the raw material that catalytic reforming is produced the blend component of aromatic hydrocarbons or high-octane rating motor spirit.
In a preferred embodiment, the inventive method or the petroleum naphtha of described coal-based high aromatic hydrocarbon potential content produce the raw material of aromatic hydrocarbons as catalytic reforming.
Method provided by the invention is that the thick liquefaction oil with coal direct liquefaction production is a raw material, the petroleum naphtha of the extra-high-speed aromatic hydrocarbon potential content that the production catalytic reforming is used, the petroleum naphtha aromatic hydrocarbon potential content that obtains is greater than 70%, usually petroleum naphtha aromatic hydrocarbon potential content is between 70%～80%, especially be used to produce aromatic hydrocarbons as catalytic reforming raw material, as benzene,toluene,xylene, perhaps be used to produce the raw material of the blend component of high-octane rating motor spirit.
Below in conjunction with Fig. 1 and embodiment, the concrete work flow of the method for the special naphtha with high potential aromatic content of production provided by the invention is described in detail as follows, it only is for the present invention being given further instruction, therefore not limiting present method.
Fig. 1 is the synoptic diagram of the method for the high petroleum naphtha of a kind of aromatic hydrocarbon potential content that is suitable for the catalytic reforming charging from the thick oil production of coal direct liquefaction provided by the invention, omitted equipment component among the figure, for example process furnace, pump, interchanger, air cooler, tower, valve, storage tank etc.
After the thick oil of the lightweight oil that coal direct liquefaction is obtained and the mixed liquefied full fraction of mink cell focus enters first pump 2 and boosts via first pipeline 1, after mixing and heat from the fresh hydrogen of second pipeline 3 with from the recycle hydrogen of the 3rd pipeline 4, together enter the bottom of expansion hydrotreating reactor 5, the inlet temperature of expansion hydrotreating reactor 5 is 250～300 ℃, the catalyzer rate of expansion is 20～40%, generally 25～35%, preferably about 30%.The hydrogen dividing potential drop of expansion hydrotreating reactor 5 inside is 6.0～30.0MPa, and temperature of reaction is 300～430 ℃, and the liquid hourly space velocity of the thick oil of the mixed liquefied full fraction of charging is 0.2～4h
-1
The reaction mass that is come out by the top of expansion hydrotreating reactor 5 enters first high-pressure separator 10 through the 4th pipeline 9 and carries out gas and liquid separation; Deliver to the hydrogenation reaction system recycle after sending first centrifugal compressor 11 to boost the isolated gas, the liquid of first high-pressure separator, 10 bottoms enters first light pressure separator 13 through the 5th pipeline 12 to be continued to separate.
The gas on first light pressure separator, 13 tops is drawn through the 6th pipeline 14, and the liquid of bottom enters first separation column 16 through the 7th pipeline 15 to be separated; The lighting end at first separation column, 16 tops is drawn through the 8th pipeline 17, lighting end enters first separating tank 18 after cooling, the gas on first separating tank, 18 tops is drawn through the 9th pipeline 19, the lighting end liquid of first separating tank, 18 bottoms is drawn through the tenth pipeline 20, after the intermediate oil 21 of drawing with first separation column, 16 middle parts is mixed together, as the raw material of step b) deep hydrofinishing; The liquid of first separation column, 16 bottoms is drawn through the 12 pipeline 22, be delivered to coal direct liquefaction device (not shown) and use as strong solvent.
To draw through the 11 pipeline 21 from the mixing oil product (middle matter cut) of first separation column, 16 centre exits, and after second pump 23 boosts, after mixing and heat, together enter the top of deep hydrofinishing reactor 25 from the fresh hydrogen of second pipeline 3 with from the recycle hydrogen of the 15 pipeline 24.Deep hydrofinishing reactor 25 is the syllogic fixed-bed reactor.
The reaction mass that is come out by deep hydrofinishing reactor 25 bottoms enters second high-pressure separator 27 through the 16 pipeline 26 and carries out gas and liquid separation, isolated gas is delivered to the recycle of deep hydrofinishing reactive system after sending second centrifugal compressor 28 to boost, and the liquid of second high-pressure separator, 27 bottoms enters second light pressure separator 30 through the 17 pipeline 29 to be continued to separate.The gas on second light pressure separator, 30 tops is drawn through the 18 pipeline 31.
The liquid of second light pressure separator, 30 bottoms enters after-fractionating tower 33 through the 20 pipeline 32 to be separated.
The liquid at after-fractionating tower 33 middle parts is drawn as the kerosene product through the 21 pipeline 34 and is sent.
The liquid of after-fractionating tower 33 bottoms is drawn as diesel oil through the 22 pipeline 35 and is sent.
The lighting end at after-fractionating tower 33 tops is drawn after cooling through the 23 pipeline 36 and is entered second separating tank 37.
The gas on second separating tank, 37 tops is drawn through the 25 pipeline 38.The naphtha product 39 of second separating tank, 37 bottoms is drawn through the 26 pipeline 38, as the raw material of catalytic reforming.
Method provided by the invention is that the thick liquefaction oil with coal direct liquefaction is a raw material, produce the petroleum naphtha of the high aromatic hydrocarbon potential content that is suitable for the catalytic reforming charging, the sulphur content of the petroleum naphtha that obtains, nitrogen content are all less than 0.5 μ g/g, the aromatic hydrocarbon potential content of petroleum naphtha is usually greater than 70wt%, even can reach about 80wt%.Low, the aromatic hydrocarbon potential content height of sulphur, nitrogen impurity content in the product that the method for the petroleum naphtha that the aromatic hydrocarbon potential content that is suitable for the catalytic reforming charging through above-mentioned thick oil production by coal direct liquefaction of the present invention is high obtains is the fine catalytic reforming raw material.Carry out to prepare after catalytic reforming is handled the blend component of benzene,toluene,xylene and high-octane rating motor spirit by the high petroleum naphtha of aromatic hydrocarbon potential content of method preparation of the present invention.
The thick liquefaction oil properties of employed coal direct liquefaction is listed in the table 1 in the present embodiment; Hydrotreating step reaction conditions a) is listed in the table 2; List in table 3, the table 4 respectively through lighting end, middle runnings oil properties that hydrotreating step a) obtains; Employed raw material oil properties is listed in the table 5 in the deep hydrofinishing step b); The reaction conditions of deep hydrofinishing step b) is listed in the table 6, and the character of the petroleum naphtha of being produced through the deep hydrofinishing step b) is listed in the table 7.
Table 1 is used for hydrotreating step stock oil character a)
| Analysis project | Analytical results |
| Density (20 ℃), g/cm 3 | 0.9156? |
| O，wt％? | 1.81? |
| S，μg/g? | 650? |
| N，μg/g? | 2246? |
| Boiling range (ASTM D-86), ℃ | ? |
| Initial boiling point/5% | 117/146? |
| 10％/30％? | 165/214? |
| 50％/70％? | 239/263? |
| 90%/do | 300/347? |
Table 2 hydrotreating step reaction conditions a)
| Processing parameter | Numerical value |
| Reaction pressure, MPa (a) | 13.7? |
| Temperature of reaction, ℃ | 380? |
| The catalyst volume air speed *，h -1 | 1.5? |
| The beds rate of expansion, % | 30? |
| Ratio of mixture (the v: v) of liquefaction light oil, liquefaction distillate | 30∶1? |
| Charge ratio (the v: v) of hydrogen and (liquefaction light oil, liquefaction distillate) | (900～1200)∶1? |
| The catalyzer that uses | HTS-358 catalyzer (AXENS) |
| Enter the temperature in of hydrotreating reactor, ℃ | 280? |
| Enter the inlet pressure of hydrotreating reactor, MPa | 13.5? |
| Flow out the temperature out of hydrotreating reactor, ℃ | 380? |
| Flow out the inlet pressure of hydrotreating reactor, MPa | 13.45? |
*Catalyst volume air speed (h
-1)=liquid feeding volume/(the catalyst volume unit time)
The lighting end product property that table 3 a) obtains through hydrotreating step
| Analysis project | Analytical results |
| Density (20 ℃), g/cm 3 | 0.7571? |
| ?C，wt％? | 85.54? |
| ?H，wt％? | 14.14? |
| ?O，wt％? | 0.31? |
| ?S，μg/g? | 4? |
| ?N，μg/g? | 81? |
| Boiling range (ASTM D-86), ℃ | ? |
| Initial boiling point/5% | 78/92? |
| ?10％/30％? | 94/99? |
| ?50％/70％? | 106/114? |
| 90%/do | 131/170? |
The middle runnings product property that table 4 a) obtains through hydrotreating step
| Analysis project | Analytical results |
| Density (20 ℃), g/cm 3 | 0.9161? |
| C，wt％? | 88.16? |
| H，wt％? | 11.39? |
| O，wt％? | 0.39? |
| S，μg/g? | 47? |
| N，μg/g? | 506? |
| Boiling range (ASTM D-86), ℃ | ? |
| Initial boiling point/5% | 189/214? |
| 10％/30％? | 225/251? |
| 50％/70％? | 268/287? |
| 90%/do | 316/345? |
Table 5 is used for the stock oil character of deep hydrofinishing step b)
| Analysis project | Analytical results |
| Density (20 ℃), g/cm 3 | 0.8855? |
| C，wt％? | 87.49? |
| H，wt％? | 11.81? |
| O，wt％? | 0.58? |
| S，μg/g? | 98? |
| N，μg/g? | 1155? |
| Boiling range (ASTM D-86), ℃ | ? |
| Initial boiling point/5% | 105/116? |
| 10％/30％? | 138/193? |
| 50％/70％? | 221/247? |
| 90%/do | 288/333? |
The reaction conditions of table 6 deep hydrofinishing step b)
| Processing parameter | Numerical value |
| Reaction pressure, MPa | 13.7? |
| Temperature of reaction, ℃ | 365? |
| The ratio of mixture of lightweight oil, middle matter oil (v: v) | 75∶25? |
| Charge ratio (the v: v) of hydrogen and (lightweight oil, middle matter oil) | (900～1200)∶1? |
| The catalyst volume air speed *，h -1 | 0.8? |
| The catalyzer that uses | RNC-2 catalyzer (catalyzer branch office of China Petrochemical Industry) |
| Enter the temperature in of beds, ℃ | 320? |
| Enter the inlet pressure of beds, MPa | 8.0? |
| The temperature out of outflow catalyst bed, ℃ | 350? |
| The inlet pressure of outflow catalyst bed, MPa | 7.8? |
*Catalyst volume air speed (h
-1)=liquid feeding volume/(the catalyst volume unit time)
The naphtha product character that table 7 obtains through the deep hydrofinishing step b)
| Analysis project | Analytical results |
| Density (20 ℃), g/cm 3 | 0.7606? |
| ?C，wt％? | 85.54? |
| ?H，wt％? | 14.46? |
| ?O，wt％? | 0? |
| ?S，μg/g? | ＜0.5? |
| ?N，μg/g? | ＜0.3? |
| Arene underwater content, wt% | 74.7? |
| Boiling range (ASTM D-86), ℃ | ? |
| Initial boiling point/5% | 85/96? |
| ?10％/30％? | 99/103? |
| ?50％/70％? | 107/118? |
| 90%/do | 133/161? |
As can be seen from Table 1, oxygen, the nitrogen content of the thick liquefaction oil that is obtained by coal direct liquefaction are very high.The data of table 3～4 show, the thick liquefaction oil product that is obtained by coal direct liquefaction is after the hydrotreatment of step a), and wherein oxygen level and nitrogen content reduce significantly, have reached the purpose of hydrotreatment.The data of table 8 show that after handling through the deep hydrofinishing of step b), the sulphur content in the petroleum naphtha, nitrogen content are all less than 0.5 μ g/g, and the aromatic hydrocarbon potential content of petroleum naphtha is the raw material that the fine catalytic reforming is used to prepare aromatic hydrocarbons greater than 70%.
By the thick liquefaction oil with coal direct liquefaction provided by the invention is raw material, production is suitable for the sulphur content, nitrogen content of the petroleum naphtha that method obtained of petroleum naphtha of high aromatic hydrocarbon potential content of catalytic reforming charging all less than 0.5 μ g/g, the aromatic hydrocarbon potential content of petroleum naphtha is greater than 70wt%, usually at 70～80wt%, even can reach about 80wt%.Low, the aromatic hydrocarbon potential content height of sulphur, nitrogen impurity content in the product that the method for the petroleum naphtha that the aromatic hydrocarbon potential content that is suitable for the catalytic reforming charging through above-mentioned thick oil production by coal direct liquefaction of the present invention is high obtains is the fine catalytic reforming raw material.The high petroleum naphtha of aromatic hydrocarbon potential content by method preparation of the present invention carries out can preparing as the aromatic hydrocarbons of benzene,toluene,xylene and the blend component of high-grade gasoline after catalytic reforming is handled.
Below be the explanation of the Reference numeral among Fig. 1:
1 first pipeline;
2 first pumps;
3 second pipelines; Fresh hydrogen;
4 the 3rd pipelines; Recycle hydrogen;
9 the 4th pipelines;
10 first high-pressure separator; High pressure separates;
11 first centrifugal compressors;
12 the 5th pipelines;
13 first light pressure separators; Low pressure is separated;
14 the 6th pipelines;
15 the 7th pipelines;
16 first separation columns; Fractionation;
17 the 8th pipelines; Light ends oil;
18 first separating tanks;
19 the 9th pipelines;
20 the tenth pipelines;
21 the 11 pipelines; Intermediate oil; Middle matter cut;
22 the 12 pipelines; Heavy distillate;
23 second pumps;
24 the 15 pipelines;
25 (fixed bed) deep hydrofinishing reactor;
26 the 16 pipelines;
27 second high-pressure separator; High pressure separates
28 second centrifugal compressors;
29 the 17 pipelines;
30 second light pressure separators; Low pressure is separated
31 the 18 pipelines;
32 the 20 pipelines;
33 after-fractionating towers; Fractionation
34 the 21 pipelines; The kerosene product;
35 the 22 pipelines; Diesel oil;
36 the 23 pipelines;
37 second separating tanks; Naphtha product;
38 the 25 pipelines;
39 naphtha fractions.
The above is the preferred embodiments of the present invention only, and it is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of being done, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. a production method that is used for the coal-based naphtha with high potential aromatic content of catalytic reforming is characterized in that, this method may further comprise the steps:
A) hydrogenation step: the full cut liquefaction oil that DCL/Direct coal liquefaction is produced mixes with hydrogen (3,4), enter expanded bed hydrotreating reactor (5) after the mixing together from the expanded bed bottom, contact so that hydrogenation reaction to take place with hydrotreating catalyst, the logistics that will flow out described expanded bed hydrotreating reactor (5) outlet obtains light ends oil (17), middle matter cut (21) and heavy distillate (22) after separating (10,13), fractionation (16); And
B) deep hydrofinishing step: the described light ends oil (17) that step a) is obtained, after matter distillate (21) mixes in described, mix with hydrogen (3,24) again, enter fixed bed deep hydrofinishing reactor (25) then together, contact so that chemical reaction to take place with Hydrobon catalyst, the logistics that will flow out described fixed bed deep hydrofinishing reactor (5) outlet obtains meeting the naphtha fraction (39) of the high aromatic hydrocarbon potential content of catalytic reforming charging requirement after separating (27,30), fractionation (33).
2. method according to claim 1 is characterized in that, the petroleum naphtha that is used for catalytic reforming raw material is derived from the liquefaction oil that coal direct liquefaction is produced.
3. method according to claim 1 is characterized in that, the reaction conditions of the described expanded bed hydrotreating reactor (5) of step a) is: hydrogen dividing potential drop 6.0～30.0MPa, 300～430 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and described full cut liquefaction oil: 1Nm
3/ m
3And the reaction conditions of the described deep hydrofinishing reactor (25) of step b) is: hydrogen dividing potential drop 6.0～20.0MPa, 300～460 ℃ of temperature of reaction, liquid hourly space velocity 0.2～4h
-1, the gas-liquid volume charge ratio 900～1200 of hydrogen and described light ends oil (17), described middle matter distillate (21): 1Nm
3/ m
3
4. according to each described method of claim 1～3, it is characterized in that, the employed hydrotreating catalyst of described expanded bed hydrotreating reactor (5) of step a) is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, and VIII family metal is selected from Co or Ni; The employed deep hydrofinishing catalyzer of described deep hydrofinishing reactor (25) of step b) is a carrier with unformed aluminum oxide or silicon oxide, loaded metal component on it, metal component is group vib or VIII family metal component, wherein the group vib metal is selected from W or Mo, VIII family metal is selected from Co or Ni, and wherein said deep hydrofinishing reactor (25) has comprised 2～4 beds.
5. according to each described method of claim 1～3, it is characterized in that the ratio of expansion of the employed hydrotreating catalyst of described expanded bed hydrotreating reactor (5) of step a) is 20～40%, is preferably 25～35%, most preferably is about 30%.
6. method according to claim 4, it is characterized in that the employed hydrotreating catalyst of described expanded bed hydrotreating reactor (5) of step a) is selected from the HTS catalyst series of French AXENS production, the RS-1000 catalyzer that catalyzer branch office of Sinopec Group produces.
7. method according to claim 4, it is characterized in that, the employed deep hydrofinishing catalyzer of described deep hydrofinishing reactor (25) of step b) comprises 2～3 beds, and the employed deep hydrofinishing catalyzer of described deep hydrofinishing reactor (25) of step b) is selected from the DZ catalyst series that RN series fraction oil Hydrobon catalyst, FF catalyst series, FH catalyst series, Daqing petrochemical company research institute that catalyzer branch office of Sinopec Group produces produce.
8. the coal-based naphtha with high potential aromatic content that obtains according to each described method of claim 1～7.
9. coal-based naphtha with high potential aromatic content according to claim 8, the aromatic hydrocarbon potential content of wherein said petroleum naphtha is 60～80wt%.
10. that obtain according to each described method of claim 1～7 or claim 8 or 9 described coal-based naphtha with high potential aromatic content are used as the application of catalytic reforming raw material.
11. application according to claim 10, the aromatic hydrocarbon potential content of wherein said petroleum naphtha is 60～80wt%.
12., it is characterized in that the petroleum naphtha of described coal-based high aromatic hydrocarbon potential content is used to produce the blend component of aromatic hydrocarbons or high-octane rating motor spirit as catalytic reforming raw material according to claim 10 or 11 described application.
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| CN 201110007174 CN102051224B (en) | 2010-06-24 | 2011-01-13 | Production method of coal-based high-aromatic-hydrocarbon-potential-content naphtha for catalytic reforming, product and application thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051228A (en) * | 2011-01-28 | 2011-05-11 | 赵丽 | Method for producing aromatic hydrocarbon by catalytically reforming hydrogenation naphtha |
| CN102051229A (en) * | 2011-01-28 | 2011-05-11 | 赵丽 | Process for producing aromatic hydrocarbons by large-scale continuous reforming |
| CN102533331A (en) * | 2011-11-29 | 2012-07-04 | 神华集团有限责任公司 | Method for processing direct coal liquefaction oil |
| CN103965961A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Hydrogenization reforming system, hydrogenization reforming process, and aromatic products of coal liquefaction full distillate |
| CN111349460A (en) * | 2020-03-17 | 2020-06-30 | 中国神华煤制油化工有限公司 | Low freezing point diesel oil and its preparation method and device |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010042700A1 (en) * | 2000-04-17 | 2001-11-22 | Swan, George A. | Naphtha and cycle oil conversion process |
| CN1162516C (en) * | 2002-02-07 | 2004-08-18 | 中国石油化工股份有限公司 | Process for greatly preparing hihg-quality diesel oil or jet fuel from liquefied coil oil |
| CN100497547C (en) * | 2005-10-24 | 2009-06-10 | 中国石油化工股份有限公司 | Hydrocracking method |
-
2010
- 2010-06-24 CN CN2010102180091A patent/CN101892078A/en active Pending
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102051228A (en) * | 2011-01-28 | 2011-05-11 | 赵丽 | Method for producing aromatic hydrocarbon by catalytically reforming hydrogenation naphtha |
| CN102051229A (en) * | 2011-01-28 | 2011-05-11 | 赵丽 | Process for producing aromatic hydrocarbons by large-scale continuous reforming |
| CN102533331A (en) * | 2011-11-29 | 2012-07-04 | 神华集团有限责任公司 | Method for processing direct coal liquefaction oil |
| CN103965961A (en) * | 2014-04-29 | 2014-08-06 | 神华集团有限责任公司 | Hydrogenization reforming system, hydrogenization reforming process, and aromatic products of coal liquefaction full distillate |
| CN111349460A (en) * | 2020-03-17 | 2020-06-30 | 中国神华煤制油化工有限公司 | Low freezing point diesel oil and its preparation method and device |
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|---|---|
| CN102051224A (en) | 2011-05-11 |
| CN102051224B (en) | 2013-09-25 |
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