CN110964560A

CN110964560A - Method for combining poor-quality hydrocarbon hydrogenation thermal cracking reaction section with post-positioned hydrofining reaction section

Info

Publication number: CN110964560A
Application number: CN201811200084.8A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2018-09-29
Filing date: 2018-09-29
Publication date: 2020-04-07

Abstract

A method for combining an inferior hydrocarbon hydrogenation thermal cracking reaction section with a post-hydrogenation refining reaction section is characterized in that based on the rule that the product of the inferior hydrocarbon hydrogenation thermal cracking reaction process R10 contains olefin, after the hydrogenation thermal cracking reaction section R10 of the inferior hydrocarbon such as coal tar heavy oil with high contents of metal, polycyclic aromatic hydrocarbon, colloid and asphaltene, the post-hydrogenation refining reaction section R20 operated in series is arranged to obtain a reaction product R20P, so that a hydrogenation product with lower olefin content and higher stability is obtained, and the hydrogenation product with lower olefin content and lower thermal reaction activity is separated from R20P to obtain an asphalt component with low olefin content and low thermal reaction activity and used as high-quality needle coke raw material asphalt; typically R20 requires the use of a highly active dispersed catalyst and or a hydrogen donating hydrocarbon; generally the average operating temperature of R20 is substantially lower than the average operating temperature of the hydrocracking reaction zone R10; the olefin hydrogenation saturation reaction section of the hot high-molecular gas of the product R20P can also be arranged to reduce the olefin content of the hydrocarbon in the hot high-molecular gas.

Description

Method for combining poor-quality hydrocarbon hydrogenation thermal cracking reaction section with post-positioned hydrofining reaction section

Technical Field

The invention relates to a method for combining an inferior hydrocarbon hydrocracking reaction section and a post-hydrofining reaction section, based on the rule that the product of the inferior hydrocarbon hydrocracking reaction process R10 contains olefin, after the hydrocracking reaction section R10 of the coal tar heavy oil with high content of inferior hydrocarbon such as metal, polycyclic aromatic hydrocarbon, colloid and asphaltene, the post-hydrofining reaction section R20 operated in series is arranged to obtain a reaction product R20P, so that a hydrogenation product with lower olefin content and higher stability is obtained, and the hydrogenation product with lower olefin content and lower thermal reaction activity is separated from R20P to obtain an asphalt component with low olefin content and low thermal reaction activity which is used as high-quality needle coke raw material asphalt; typically R20 requires the use of a highly active dispersed catalyst and or a hydrogen donating hydrocarbon; generally the average operating temperature of R20 is substantially lower than the average operating temperature of the hydrocracking reaction zone R10; the olefin hydrogenation saturation reaction section of the hot high-molecular gas of the product R20P can also be arranged to reduce the olefin content of the hydrocarbon in the hot high-molecular gas.

Background

The high-power and ultrahigh-power graphite electrode made of needle coke has the outstanding advantages of small resistivity, small thermal expansion coefficient, strong thermal shock resistance, high mechanical strength, good oxidation resistance and the like, and compared with the common electrode steel-making, the high-power and ultrahigh-power graphite electrode can shorten the smelting time of electric furnace steel-making by 50-70%, reduce the power consumption by 20-50% and increase the production capacity by 1.3 times. Therefore, high quality needle coke is a high value functional carbon material.

The needle coke is prepared by adopting a liquid-phase carbonization technology, and the coking raw materials are gradually pyrolyzed and polycondensed in the liquid-phase carbonization process to form mesophase spherules. The mesophase globules are fully grown, fused and oriented, and finally cured into a carbon product with a fibrous structure, namely needle coke. The production process of the needle coke comprises 3 parts of raw material pretreatment, delayed coking and calcination.

The coal-based needle coke refers to needle coke prepared from materials obtained by taking coal as a resource, and the invention refers to needle coke prepared from oil products based on coal tar.

A document for recording the raw material properties, processing method and product performance index information of coal-based needle coke is disclosed in publication A01: ①, publication name of coal tar chemical engineering, pages 262 to 268, book code for ② retrieval, ISBN code, 7-5024-.

As the raw oil for producing needle coke, in which active components influence the formation process of mesophase and as a result, the pitch contains a small amount of highly active reactive components (including olefin components), the crosslinking reaction proceeds smoothly, and oriented crosslinking and condensation are present, and anisotropic mosaic structure and fibrous structure are easily obtained. If the highly reactive component present in the pitch controls the crosslinking, it is non-oriented crosslinking and an isotropic carbon and fine mosaic structure is obtained. The latter situation often occurs when low temperature dry distilled coal tar is used as a raw material for liquid phase carbonization, because the coal tar contains more olefins, and the thermal cracking reaction process (including the hydro-thermal cracking reaction process) of the hydrocarbon generally produces the olefins. Generally, the hydrocracking reaction of the high temperature coal tar containing the colloidal pitch component also produces a certain amount of olefin components having a broad distribution of carbon atoms, and the hydrocarbon components having conventional boiling points in the range of the light pitch of the needle coke feedstock typically contain the hydrocracked product olefins.

The invention relates to a series hydro-upgrading method in a hydro-thermal cracking reaction process of high-temperature coal tar containing a colloidal asphalt component, which focuses on the following main problems: how to reduce the olefin content of the asphaltene component in the final reaction product and reduce its thermal reactivity.

The idea of the invention is: a method for combining an inferior hydrocarbon hydrogenation thermal cracking reaction section with a post-hydrogenation refining reaction section is characterized in that based on the rule that the product of the inferior hydrocarbon hydrogenation thermal cracking reaction process R10 contains olefin, after the hydrogenation thermal cracking reaction section R10 of the inferior hydrocarbon such as coal tar heavy oil with high contents of metal, polycyclic aromatic hydrocarbon, colloid and asphaltene, the post-hydrogenation refining reaction section R20 operated in series is arranged to obtain a reaction product R20P, so that a hydrogenation product with lower olefin content and higher stability is obtained, and the hydrogenation product with lower olefin content and lower thermal reaction activity is separated from R20P to obtain an asphalt component with low olefin content and low thermal reaction activity and used as high-quality needle coke raw material asphalt; typically R20 requires the use of a highly active dispersed catalyst and or a hydrogen donating hydrocarbon; generally the average operating temperature of R20 is substantially lower than the average operating temperature of the hydrocracking reaction zone R10; the gas-phase hydrogenation olefin saturation reaction section R70 of the hot high-molecular gas of the product R20P can also be arranged to reduce the olefin content of the hydrocarbon in the hot high-molecular gas; the invention has the advantages of simple series flow and low investment.

For flexible adjustment operation, the upper space of the hydrogenation reactor of the post-hydrogenation refining reaction section R20 is provided with a system consisting of a liquid collector, a liquid guide pipeline, a circulating pump and a liquid conveying pipeline, and an intermediate liquid-phase product or a final liquid-phase product can be injected into the upstream hydrogenation reaction space for circulating operation.

The invention is also suitable for the poor hydrocarbon hydrogenation thermal cracking reaction process needing to be provided with the post-positioned hydrogenation refining reaction section.

The invention has a distinct characteristic that based on a clear 'reaction section' concept, a temperature regulation and control means between reaction sections is arranged according to the difference of the dominant reaction targets of the reaction process or according to the fluctuation interval of the reaction temperature of the reaction process, thereby being obviously different from the reaction temperature distribution mode that the average reaction temperature gradually rises in the overall reaction process of a plurality of suspension bed reactors and/or boiling bed reactors in the prior art.

There are many methods related to the hydrogenation of coal tar containing coal pitch to produce needle coke raw material, but none of them proposes the technical scheme of the present invention, and the following are several related patent methods or patent application methods:

① Chinese patent ZL201110167634.2 relates to a process for preparing needle coke raw material by using medium and low temperature tar and high temperature asphalt, which relates to a process for producing needle coke raw material by hydrogenation of coal tar containing coal asphalt, but does not provide a technical scheme similar to the invention;

② Chinese patent ZL201110167667.7 relates to a process for preparing needle coke raw material by using medium and low temperature tar, which relates to the process of producing needle coke raw material by hydrogenation of coal tar containing coal pitch, but does not provide a technical scheme similar to the invention;

③ patent ZL201110171211.8 centrifugal method of coal tar purification and coal tar preparation needle coke raw material process, relate to the process of producing needle coke raw material of coal tar hydrogenation containing coal pitch, but does not propose the technical scheme similar to this invention;

④ Chinese patent ZL201110284485.8 relates to a process for preparing needle coke raw material by coal tar pitch, which relates to a process for producing needle coke raw material by coal tar containing coal pitch through hydrogenation, but does not provide a technical scheme similar to the invention;

⑤ Chinese patent ZL201110339693.3 is a process for preparing needle coke raw material by utilizing coal tar and heavy phase circulation, which relates to the process of producing needle coke raw material by hydrogenation of coal tar containing coal pitch, but does not provide a technical scheme similar to the invention;

⑥ Chinese patent ZL201110339694.8 is a process for preparing needle coke raw material by combining coal tar pitch with heavy phase circulation, which relates to the process of producing needle coke raw material by hydrogenation of coal tar containing coal pitch, but does not provide a technical scheme similar to the invention;

⑦ Chinese patent ZL201310231391.3 relates to a process for producing needle coke, which relates to a process for producing needle coke raw materials by hydrogenation of coal tar containing coal pitch, but does not provide a technical scheme similar to the invention;

⑧ Chinese patent ZL 201310231394.7 relates to a process for producing needle coke raw material by hydrogenation of coal tar containing coal pitch, but does not provide a technical scheme similar to the invention;

⑨ patent ZL201610902143.0 relates to a method and a system for producing light fuel and needle coke by coal tar, which relates to a process for producing needle coke raw materials by coal tar suspension bed hydrogenation containing coal pitch, but does not provide a technical scheme similar to the invention;

⑩ patent ZL 201610902769.1 discloses a method and a system for producing light fuel and needle coke in a maximized mode by coal tar, and relates to a process for producing needle coke raw materials by coal tar-containing pitch through coal tar suspension bed hydrogenation.

There are many methods for producing light fuel oil by hydrogenation of coal tar containing coal pitch, but none of them proposes the technical scheme of the invention, and the following are several related patent methods or patent application methods:

① A method for converting heavy oil of coal tar by hydrogenation in suspension bed hydrogenation reactor comprises using all coal tar components (including fraction with conventional boiling point lower than 370 deg.C and fraction with conventional boiling point higher than 370 deg.C) as raw material for hydrocracking, and performing hydrocracking reaction in suspension bed or bubbling bed hydrocracking reactor, wherein the hydrocarbon components with conventional boiling point lower than 330 deg.C are introduced into hydrocracking reaction, which has harmful process defects;

② chinese patent ZL201010217358.1 describes a coal tar heavy oil hydrogenation lightening method using a suspension bed hydrogenation reactor, which comprises coal tar raw material pretreatment and distillation separation, coal tar heavy fraction suspension bed hydrocracking and light distillate conventional upgrading process.zl 201010217358.1 is characterized in that a suspension bed or bubbling bed hydrocracking reactor is used to perform a hydrocracking reaction process R1 by using a fraction of coal tar at a temperature higher than 370 ℃, most (about 80%) of heavy oil (pitch) with a reaction product higher than 370 ℃ is directly recycled back to be cracked, a small part (about 20%) of the heavy oil (pitch) is subjected to solid-liquid separation, and the solid catalyst is separated and then recycled back to be cracked, so that large molecular pitch in coal tar is cracked into small molecular light oil products as much as possible, the separated catalyst is thrown out, and the purpose of the external throwing is to remove a small amount of high molecular polymer and deactivated catalyst generated in the cracking process;

③ Chinese patent ZL201210022921.9 provides a hydrogenation and lightening method of heavy oil with low hydrogen content using hydrogen supply hydrocarbon, for all fractions of coal tar higher than 330 ℃, the coal tar heavy oil with conventional boiling point higher than 450 ℃ directly enters an expansion bed (such as suspension bed or fluidized bed) hydrogenation and thermal cracking reaction zone HPU21, meanwhile, the coal tar distillate with conventional boiling point of 330-450 ℃ is used as precursor of hydrogen supply solvent oil to pass through a hydrogenation modification reaction zone HPU1 to produce hydrogen supply hydrocarbon material flow SHS mainly composed of hydrocarbon components with conventional boiling point of 330-450 ℃, and then the SHS is introduced into the hydrogenation and thermal cracking reaction zone HPU21, which obviously improves KL ratio of hydrogen supply hydrocarbon weight to fresh raw material F10X weight in the SHS flow reaction zone, thereby having obvious effects of reducing condensation speed, improving liquid product yield in coal tar heavy oil hydrogenation conversion process, improving product quality, reducing reaction temperature rise, enhancing device operation stability and safety, and no hydrogenation and refining reaction zone R20 is arranged in the method;

④ chinese patent ZL200810166719.7 describes a combined hydro-conversion method of coal tar fractions with different boiling ranges, a first hydrocarbon fraction containing a coal tar light fraction with a conventional boiling point lower than 390 ℃ is converted in a first hydro-refining reaction part, the first hydro-refining reaction effluent and a second hydrocarbon fraction containing a coal tar heavy fraction with a conventional boiling point higher than 370 ℃ are converted in a second hydro-refining reaction part, the second hydro-refining reaction effluent is separated and a product is recovered, chinese patent ZL200810166719.7 performs combined hydro-conversion on the coal tar fractions with different boiling ranges to form a more suitable hydro-refining reaction temperature distribution, which has the advantages of improving product quality, stabilizing operation, prolonging operation period and the like, and is particularly suitable for small-scale classified combined hydro-conversion of medium and high temperature coal tar wide fractions.

⑤ CN105623724A discloses a hydro-thermal cracking method for producing low carbon number single six-membered ring hydrocarbon from high aromatic hydrocarbon, which can economically produce C in a large amount by using medium and low temperature coal tar₆～C₁₀The cyclohexane hydrocarbon or benzene hydrocarbon is catalytically reformed and aromatic extracted to obtain benzene hydrocarbon. For the coal tar hydrogenation thermal cracking reaction process R10, the process recovers a first hydrogenation reaction effluent R10P to obtain a material flow containing first hydrogenation product oil, the first hydrogenation product oil hydrocarbon with the normal boiling point higher than 350 ℃ usually returns to the first hydrogenation reaction process R10 to contact with a first hydrogenation catalyst R10C, at least a part of the first hydrogenation product oil hydrocarbon with the normal boiling point of 260-350 ℃ returns to the first hydrogenation reaction process R10 to contact with a first hydrogenation catalyst R10C, and the normal easy-heating condensed hydrocarbon component with the extremely high boiling point in the first hydrogenation reaction effluent R10P does not return to the first hydrogenation reaction process R10; the process is not equipped with a post-positioned hydrofinishing reaction section R20.

The method of the invention is not reported.

The method of the invention is suitable for newly-built devices and can also be used for reforming the existing devices.

The invention aims to provide a method for combining an inferior hydrocarbon hydrocracking reaction section with a post-hydrofining reaction section.

Disclosure of Invention

The invention relates to a method for combining an inferior hydrocarbon hydrocracking reaction section and a post-hydrofining reaction section, which is characterized by comprising the following steps:

(1) in a first hydrogenation reaction process R10, under the condition that hydrogen and liquid-phase hydrocarbon exist and diluted hydrocarbon or mixed-phase material with hydrogen-supplying hydrocarbon or solid particle catalyst possibly exists, the poor-quality hydrocarbon HDS is subjected to a first hydrogenation reaction R10R to obtain a first hydrogenation reaction product BASE-R10P; the first hydrogenation product BASE-R10P contains at least a portion of olefins;

poor quality hydrocarbons HDS, which are high aromatic hydrocarbon feeds comprising a hydrocarbon component HD with a conventional boiling point above 450 ℃;

poor quality hydrocarbons HDS, comprising a conventional liquid hydrocarbon feedstock HDSL, possibly comprising a solid particulate feedstock HDSs;

a first hydrogenation reaction R10R comprising a desulfurization reaction of at least a portion of the hydrocarbon feedstock, a thermal cracking reaction to produce free radicals, a thermal cracking free radical hydrogenation stabilization reaction;

a first hydrogenation reaction R10R, comprising a hydrofinishing reaction of at least a portion of the hydrocarbon component HD of the hydrocarbon feedstock HDSL, a hydrocracking reaction of at least a portion of the hydrocarbon component HD of the hydrocarbon feedstock HDSL, possibly a hydrogenation reaction of at least a portion of the possibly present solid feed HDSS; the hydrofining reaction of the first hydrogenation reaction R10R comprises a hydrosaturation reaction of unsaturated hydrocarbons or a hydrogenolytic reaction with hydrocarbons containing impurities;

a first hydrogenation process R10, using an upflow hydrogenation reactor R10E, possibly with a hydrogenation catalyst R10C; when a hydrogenation catalyst is used in the first hydrogenation process R10, the catalyst enters and is discharged from the reaction space of the used upflow hydrogenation reactor R10E;

there may be a portion of the first hydrogenation product BASE-R10P deposited or otherwise residing or circulating within the interior space of the hydrogenation reactor R10E;

the first hydrogenation reaction product BASE-R10P is a mixed phase material containing hydrogen, impurity components, conventional gaseous hydrocarbon, and conventional liquid hydrocarbon, and optionally solid particles, and at least comprising gas phase and liquid phase;

a material based on the first hydrogenation reaction product BASE-R10P is used as a first hydrogenation reaction effluent R10P;

the first hydrogenation reaction effluent R10P is used for discharging a first hydrogenation reaction product BASE-R10P, which is a mixed phase material containing at least a gas phase and a liquid phase and containing hydrogen, impurity components, conventional gas hydrocarbon and conventional liquid hydrocarbon and possibly solid particles;

the first hydrogenation reaction effluent R10P appears in the form of 1-path or 2-path or multi-path material R10PX, and the compositions and phase states of different R10PX streams are the same or different;

a first hydrogenation reaction process R10, which may comprise 2 or more sub-hydrogenation reaction zones R101, R102, etc. operating in series, wherein, the stream containing at least a part of normal liquid hydrocarbon based on the reaction effluent of the upstream sub-hydrogenation reaction zone enters the downstream adjacent sub-hydrogenation reaction zone, the first sub-hydrogenation reaction zone R101 of the first hydrogenation reaction process R10 obtains a reaction effluent R101P, the stream R101PX containing at least a part of hydrogenation product oil R101P0 based on the reaction effluent R101P enters the second sub-hydrogenation reaction zone R102 of the first hydrogenation reaction process R10, and the reaction effluent of the last sub-hydrogenation reaction zone is used as the first hydrogenation reaction effluent R10P;

a stream comprising at least a portion of conventional liquid hydrocarbons based on the first hydrogenation effluent R10P, used as a feedstock R20-FEED containing an olefinic component of liquid phase hydrocarbons for the second hydrogenation process R20;

FEED R20-fed, a high aromatic hydrocarbon FEED comprising a hydrocarbon component HDH having a conventional boiling point above 450 ℃;

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

(2) in the second hydrogenation reaction process R20, under the condition that hydrogen, liquid-phase hydrocarbon and hydrogenation catalyst exist and diluted hydrocarbon or a mixed phase material of hydrogen-supplying hydrocarbon possibly exists, the raw material R20-FEED is subjected to a second hydrogenation reaction R20R to obtain a second hydrogenation reaction product BASE-R20P; the olefin concentration of the hydrocarbons in the second hydrogenation product BASE-R20P is lower than that of the hydrocarbons in the first hydrogenation product BASE-R10P;

a second hydrogenation reaction R20R, an olefin hydrosaturation reaction involving at least a portion of the hydrocarbon components HDH in the feedstock R20-FEED, a hydrofinishing reaction involving at least a portion of the hydrocarbon components in the feedstock R20-FEED, and possibly a hydrocracking reaction involving at least a portion of the hydrocarbon components in the feedstock R20-FEED; the hydrofining reaction of the second hydrogenation reaction R20R comprises a hydrosaturation reaction of unsaturated hydrocarbons or a hydrogenolytic reaction with hydrocarbons containing impurities;

in the second hydrogenation reaction process R20, an upflow hydrogenation reactor R20E is used, a hydrogenation catalyst R20C is used, and a catalyst enters and is discharged from the reaction space of the upflow hydrogenation reactor R20E;

there may be a portion of the second hydrogenation product BASE-R20P deposited or otherwise residing or circulating within the interior space of the hydrogenation reactor R20E;

the second hydrogenation reaction product BASE-R20P is a mixed phase material containing at least gas phase and liquid phase, which contains hydrogen, impurity components, conventional gaseous hydrocarbon, and conventional liquid hydrocarbon, and may contain solid particles;

a material based on the second hydrogenation reaction product BASE-R20P is used as a second hydrogenation reaction effluent R20P;

the second hydrogenation reaction effluent R20P is used for discharging a second hydrogenation reaction product BASE-R20P, which is a mixed phase material containing at least a gas phase and a liquid phase and containing hydrogen, impurity components, conventional gas hydrocarbon and conventional liquid hydrocarbon and possibly solid particles;

the second hydrogenation reaction effluent R20P appears in the form of 1 or 2 or more paths of materials R20PX, and the compositions and phase states of different R20PX streams are the same or different;

the reaction space of the second hydrogenation reaction process R20 may comprise 2 or more sub-hydrogenation reaction zones which are operated in series, in this case, a stream containing at least a part of conventional liquid hydrocarbons based on the reaction effluent of the upstream sub-hydrogenation reaction zone enters a downstream adjacent sub-hydrogenation reaction zone, the first sub-hydrogenation reaction zone R201 of the second hydrogenation reaction process R20 obtains a reaction effluent R201P, the stream R201PX containing at least a part of hydrogenation product oil R201P0 based on the reaction effluent R201P enters the second sub-hydrogenation reaction zone R202 of the second hydrogenation reaction process R20, and the reaction effluent of the last sub-hydrogenation reaction zone is used as a second hydrogenation reaction effluent R20P;

(3) in the recovery process SR, the second hydrogenation effluent R20P is recovered to obtain a hydrogen-rich gas SRV consisting substantially of hydrogen in volume and a liquid stream SRL consisting substantially of normal liquid hydrocarbons, possibly containing solid particles, at least a portion of the hydrogen-rich gas SRV being returned to the hydrogenation process for recycling.

In the invention, the first hydrogenation reaction process R10 may include a front reaction section R10A of the first hydrogenation reaction process R10 and a rear reaction section R10B of the first hydrogenation reaction process R10, and is characterized in that:

a first hydrogenation reaction process R10 comprising a front reaction section R10A of a first hydrogenation reaction process R10 and a rear reaction section R10B of the first hydrogenation reaction process R10 which are operated in series;

① in the front reaction section R10A of the first hydrogenation process R10, under the condition that hydrogen and liquid phase hydrocarbon exist and diluted hydrocarbon or mixed phase material with hydrogen supply hydrocarbon or solid particle catalyst exists, the poor quality hydrocarbon HDS carries out the first front hydrogenation reaction R10AR containing shallow saturation reaction of hydrogenation aromatic hydrocarbon to obtain a first front hydrogenation reaction product BASE-R10 AP;

a first front hydrogenation reaction R10AR comprising at least part of the hydrofinishing reaction R10A-HD-HTR of the hydrocarbon fraction HD of the liquid hydrocarbon feedstock HDSL, the hydrofinishing reaction R10A-HD-HTR comprising at least part of the hydrosaturation reaction R10A-HD-HDAR of the polycyclic aromatic hydrocarbons, possibly comprising the hydrosaturation reaction of other unsaturated hydrocarbons or the hydrogenolysis reaction of hydrocarbons containing impurities;

in the first front hydrogenation reaction process R10A, at least part of hydrogenation carbon residue removal reaction of HDS occurs, and the carbon residue value of hydrocarbons in the first front hydrogenation reaction product BASE-R10AP is lower than that of the inferior hydrocarbon HDS;

a first front hydrogenation reaction R10AR which is carried out under the condition of liquid phase reaction as the main, wherein the partial hydrogenation saturation reaction R10A-HD-HDAR of polycyclic aromatic hydrocarbon generated by at least a part of hydrocarbon components HD reduces the aromatic carbon rate of at least a part of hydrocarbon components HD and converts the aromatic carbon rate into hydrocarbon components HDH, the aromatic ring of at least a part of polycyclic aromatic hydrocarbon components HDA is saturated to form methylene bridge bond, and the aromatic carbon rate of the hydrocarbon in a first front hydrogenation reaction product BASE-R10AP is lower than that of the inferior hydrocarbon HDS;

a first front hydrogenation reaction R10AR, using an upflow hydrogenation reactor R10AE, possibly using a hydrogenation catalyst R10 AC; when the hydrogenation catalyst R10AC is used in the first front hydrogenation reaction process R10A, the catalyst enters and is discharged from the reaction space of the used upflow hydrogenation reactor R10 AE;

there may be a portion of the first front hydrogenation product BASE-R10AP deposited or otherwise residing or circulating within the interior space of the hydrogenation reactor R10 AE;

the first front hydrogenation product BASE-R10AP, which is a material containing hydrogen, conventional liquid hydrocarbons and possibly solid particles;

a first front hydrogenation product BASE-R10A-based material was used as the first front hydrogenation effluent R10 AP;

r10AP is used to discharge BASE-R10AP as a feed containing hydrogen, conventional liquid hydrocarbons and possibly solid particulates;

r10AP, appearing in the form of 1-path or 2-path or multi-path material R10APX, wherein the compositions and the phase states of different R10APX streams are the same or different;

the stream R10AP-XO-TOR10B based on R10AP and containing hydrocarbon oil in R10AP enters the first hydrogenation reaction process R10B at the back part;

stream R10AP-XO-TOR10B, a high aromatic hydrocarbon feed comprising the hydrocarbon component HDH having a conventional boiling point above 450 ℃;

stream R10AP-XO-TOR10B, possibly comprising solid particulate feedstock R10AP-XO-TOR10 BS;

② in the rear reaction section R10B of the first hydrogenation process R10, the stream R10AP-XO-TOR10B is subjected to a first rear hydrogenation reaction R10BR containing a hydrocracking reaction in the presence of hydrogen, liquid phase hydrocarbons and possibly diluent hydrocarbons or a mixed phase feed with the hydrogen-donating hydrocarbons or with a solid particulate catalyst to obtain a first rear hydrogenation reaction product BASE-R10 BP;

stream R10AP-XO-TOR10B comprising conventional liquid hydrocarbon feedstock R10AP-XO-TOR10BL, possibly comprising solid particulate feedstock R10AP-XO-TOR10 BS;

a first, rear hydrogenation reaction R10BR, comprising the hydrocracking reaction of at least a portion of the hydrocarbon components HDH of the conventional liquid hydrocarbon feedstock R10AP-XO-TOR10BL, and possibly the hydrofinishing reaction of at least a portion of the hydrocarbon components HDH of the conventional liquid hydrocarbon feedstock R10AP-XO-TOR10 BL; the hydrofinishing reaction of the first rear hydrogenation reaction R10BR comprises a hydrosaturation reaction of unsaturated hydrocarbons or a hydrogenolytic reaction with hydrocarbons containing impurities;

a reaction section R10B at the back of the first hydrogenation reaction process R10, an upflow hydrogenation reactor R10BE is used, and a hydrogenation catalyst R10BC is possibly used; when a hydrogenation catalyst R10BC is used in a reaction section R10B at the rear part of the first hydrogenation reaction process R10, a catalyst enters and is discharged from a reaction space of an up-flow hydrogenation reactor R10 BE;

there may be a portion of the first rear hydrogenation reaction product BASE-R10BP deposited or otherwise residing or circulating within the interior space of the hydrogenation reactor R10 BE;

a first rear hydrogenation effluent R10BP for discharging a first rear hydrogenation product BASE-R10BP, which is a mixed phase material containing at least a gas phase and a liquid phase and containing hydrogen, impurity components, conventional gaseous hydrocarbons, and conventional liquid hydrocarbons and possibly solid particles;

the first rear hydrogenation reaction effluent R10BP, which is in the form of 1 or 2 or more paths of material R10BPX, and the composition and phase state of different R10BPX streams are the same or different;

a material based on the first rear hydrogenation reaction product BASE-R10BP was used as the first hydrogenation reaction product BASE-R10P;

a material based on the first hydrogenation product BASE-R10P was used as the first hydrogenation effluent R10P.

In the present invention, the first hydrogenation reaction process R10 may include a reaction space of a front reaction section R10A of the first hydrogenation reaction process R10, a rear reaction section R10B of the first hydrogenation reaction process R10, and a rear reaction section R10B of the first hydrogenation reaction process R10, which is divided into 2 or more sub-hydrogenation reaction zones operated in series, and a cracked intermediate liquid product of the rear reaction section R10B of the first hydrogenation reaction process R10 is returned to the front reaction section R10A of the first hydrogenation reaction process R10 to contact with the first hydrogenation catalyst R10AC for at least a part of hydrogenation saturation reaction, and is characterized in that:

the reaction space of the reaction section R10B at the back part of the first hydrogenation reaction process R10 is divided into sub-hydrogenation reaction zones according to the following principle: every 1 starting point of the cycle of the cracking intermediate liquid product, a boundary point of 1 sub-hydrogenation reaction zone is formed, so that N starting points of the cycle of the cracking intermediate liquid product exist, N boundary points of the sub-hydrogenation reaction zones are formed, and "M ═ N + 1" sub-hydrogenation reaction zones R10BX exist, and X ═ 1 to (N + 1); n is more than or equal to 2;

the reaction space of the rear reaction section R10B of the first hydrogenation reaction process R10 is divided into 2 or more sub-hydrogenation reaction zones which are operated in series, and a cracking intermediate liquid product circulating material flow R10BXMP-LR obtained in the thermal high-pressure separation process R10B XMP-THPS of at least 1 sub-hydrogenation reaction zone before the last 1 sub-hydrogenation reaction zone R10BM returns to the front reaction section R10A of the first hydrogenation reaction process R10 to be contacted with a first hydrogenation catalyst R10AC to generate at least partial hydrogenation saturation reaction;

a stream of conventional liquid hydrocarbon product comprising an upstream sub-hydrogenation reaction zone in a rear reaction section R10B of the first hydrogenation reaction process R10 enters an adjacent downstream sub-hydrogenation reaction zone operating in series;

According to the invention, (1) in the first hydrogenation process R10, the poor quality hydrocarbon HDS can be selected from one or more of the following materials:

① low temperature coal tar or distillate oil thereof or oil obtained from thermal processing process thereof, wherein the thermal processing process is distillation process or thermal cracking process or coking process or catalytic cracking process;

② the medium temperature coal tar or distillate oil thereof or oil obtained from the thermal processing process thereof, the thermal processing process is distillation process or thermal cracking process or coking process or catalytic cracking process;

③ high temperature coal tar or distillate oil thereof or oil obtained from thermal processing process thereof, the thermal processing process is distillation process or thermal cracking process or coking process or catalytic cracking process;

④ the process of preparing oil by directly liquefying coal by hydrogenation or the process of thermal processing comprises the process of preparing oil by directly liquefying coal by hydrogenation using hydrogen-supplying solvent oil, the process of co-refining oil and coal, and the process of coal hydrothermally dissolving, wherein the thermal processing process is a distillation process or a thermal cracking process or a coking process or a catalytic cracking process;

⑤ petroleum-based heavy oil or distillate oil thereof or oil obtained from thermal processing process thereof, wherein the thermal processing process is distillation process, thermal cracking process, coking process, catalytic cracking process or catalytic cracking process;

⑥ shale oil or its distillate or oil obtained from its thermal processing, wherein the thermal processing is distillation, thermal cracking, coking, catalytic cracking, or catalytic cracking;

⑦ petroleum sand-based heavy oil or distillate oil thereof or oil obtained by thermal processing, wherein the thermal processing is distillation process, thermal cracking process, coking process, catalytic cracking process or catalytic cracking process;

⑧ other hydrocarbon oils having a gum weight content of greater than 15% or and an asphaltene weight content of greater than 5.0%.

In the invention, (1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS can be 5-95%;

(2) in the second hydrogenation process R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P may be less than 75% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

In the invention, (1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS can be 10-65%;

(2) in the second hydrogenation process R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P may be less than 65% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

In the invention, (1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS can be 10-35%;

(2) in the second hydrogenation process R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P may be less than 35% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

In the invention, (1) in the first hydrogenation process R10, a suspension bed hydrogenation reactor or a boiling bed hydrogenation reactor or a combined hydrogenation reactor of a suspension bed and a boiling bed or a moving bed hydrogenation reactor can be used;

(2) the second hydrogenation reaction process R20 may use a suspension bed hydrogenation reactor or a boiling bed hydrogenation reactor or a combined suspension bed and boiling bed hydrogenation reactor or a moving bed hydrogenation reactor.

In the invention, (3) H of hydrogen-rich gas SRV in the process of recovering SR₂Volume concentration: typically greater than 75%, typically greater than 85%.

The invention, (1) the inferior hydrocarbon HDS comes from coal tar, mainly by the conventional boiling point is higher than 330 degrees C hydrocarbon component HD composition;

in the first hydrogenation reaction process R10, a suspension bed hydrogenation reactor is used, and the used hydrogenation catalyst R10C can be a composite coal tar hydrogenation catalyst which comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the catalyst R10C is less than 2 wt%; R10C powdery particles with the particle diameter of 1-100 mu m;

the operating conditions of the first hydrogenation reaction process R10 may be: the temperature is 300-480 ℃, the pressure is 6.0-30.0 MPa, the volume ratio of hydrogen to raw oil is 0.01: 1-4000: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-8.0 percent of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.1-10.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.05-3.0 percent;

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the operating conditions of the second hydrogenation reaction process R20 can be as follows: the temperature is 280-440 ℃, the pressure is 6.0-30.0 MPa, the volume ratio of hydrogen to raw oil is 300: 1-4000: 1, and hydrogenation catalysis is carried outThe adding weight of the reagent R20C is 0.001-8.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.1-10.0 hr^-1；

The average reaction temperature of the second hydrogenation reaction process R20 is at least 10 ℃ lower than the average reaction temperature of the first hydrogenation reaction process R10.

In the present invention, the operating conditions may be:

(1) the low-quality hydrocarbon HDS is derived from coal tar and mainly consists of a hydrocarbon component HD with the conventional boiling point higher than 330 ℃;

in the first hydrogenation process R10, the hydrogenation catalyst R10C at least contains Mo element, and the main working form of Mo in the first hydrogenation process R10 is M₀S₂In the method, the hydrogenation catalyst R10C is powdery particles with the particle size of 1-100 mu m;

the operating conditions of the first hydrogenation reaction process R10 are: the temperature is 360-460 ℃, the pressure is 12.0-22.0 MPa, the volume ratio of hydrogen to raw oil is 50: 1-600: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-5.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.2-2.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.25 to 2.5 percent;

(2) the operating conditions of the second hydrogenation process R20 are as follows: the temperature is 300-410 ℃, the pressure is 12.0-22.0 MPa, the volume ratio of hydrogen to raw oil is 300: 1-2000: 1, the adding weight of the hydrogenation catalyst R10C is 0.01-5.0 percent of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.2-5.0 hr^-1；

The average reaction temperature of the second hydrogenation reaction process R20 is at least 20 ℃ lower than the average reaction temperature of the first hydrogenation reaction process R10.

In the present invention, the operating conditions may be:

in the first hydrogenation process R10, the hydrogenation catalyst R10C at least contains Mo element, and the main working form of Mo in the first hydrogenation process R10 is M₀S₂In the method, the hydrogenation catalyst R10C is powdery particles with the particle size of 0.0001-100 mu m;

of the first hydrogenation process R10The operating conditions were: the temperature is 350-460 ℃, the pressure is 17.0-23.0 MPa, the volume ratio of hydrogen to raw oil is 50: 1-2000: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-5.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.2-2.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.25 to 2.5 percent;

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the operating conditions of the second hydrogenation reaction process R20 are as follows: the temperature is 300-420 ℃, the pressure is 17.0-23.0 MPa, the volume ratio of hydrogen to raw oil is 500: 1-1200: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-3.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.3-2.0 hr^-1；

The average reaction temperature of the second hydrogenation reaction process R20 is at least 25 ℃ lower than the average reaction temperature of the first hydrogenation reaction process R10.

In the present invention, the operation targets may be:

(1) the low-quality hydrocarbon HDS is derived from coal tar, wherein the content of colloid asphaltene is 10-90%, the content of carbon residue is 0.01-25%, and the content of metal is 2-2000 PPm;

① in the front reaction section R10A of the first hydrogenation reaction process R10, the inferior hydrocarbon HDS carries out the first front hydrogenation reaction R10AR which mainly comprises the shallow saturation reaction of hydrogenation aromatic hydrocarbon, the hydrogenation removal rate of colloid asphaltene is more than 5%, and the hydrogenation removal rate of carbon residue is more than 5%;

② in the reaction section R10B at the back of the first hydrogenation reaction process R10, the chemical hydrogen consumption of the poor quality hydrocarbon HDS is higher than 1.0%, and the hydrogenation thermal cracking conversion rate of the poor quality hydrocarbon HDS is more than 10%.

In the present invention, the operation targets may be:

(1) the low-quality hydrocarbon HDS is derived from high-temperature coal tar, and the content of colloid asphaltene is 10-90%, the content of carbon residue is 0.01-25%, and the content of metal is 2-2000 PPm;

① in the front reaction section R10A of the first hydrogenation reaction process R10, the first front hydrogenation reaction R10AR which is mainly the light saturation reaction of hydrogenation aromatic hydrocarbon is carried out on the inferior hydrocarbon HDS, the hydrogenation removal rate of colloid asphaltene is 2% -5%, and the hydrogenation removal rate of carbon residue is 5% -35%;

② in the reaction section R10B at the back of the first hydrogenation reaction process R10, the chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.2% -2.5%, and the hydro-thermal cracking conversion rate of the inferior hydrocarbon HDS is 10% -35%.

In the invention, (2) in the second hydrogenation reaction process R20, a thermal high-pressure separation process R20MP-THPS can be set;

r20MP-THPS is arranged in the upper space of the hydrogenation reactor R20XE, and the collected liquid R20MP-THPS-LR is returned to the first hydrogenation process R10 by a system consisting of a liquid collector, a liquid guide pipeline, a circulating pump and a liquid delivery pipeline.

In the second hydrogenation reaction process R20, a sub-hydrogenation reaction zone operated in series exists, and a thermal high-pressure separation process R20MP-THPS can be arranged in the sub-hydrogenation reaction zone;

the thermal high-pressure separation process R20MP-THPS is completed in an independent thermal high-pressure separator R20 MP-THPS-E;

separating the intermediate reaction effluent or the final reaction effluent of the second hydrogenation process R20 in a hot high-pressure separator R20MP-THPS-E to obtain a hot high-pressure liquid R20MP-THPS-L containing dissolved hydrogen and conventional liquid hydrocarbons with conventional boiling points higher than 350 ℃ and a net product stream R20MP-THPS-PP, wherein the R20MP-THPS-L may contain solid particles;

at least one part of the thermal high-separation liquid R20MP-THPS-L returns to the first hydrogenation reaction process R10;

the net product stream R20MP-THPS-PP enters the downstream adjacent sub-hydrogenation reaction zone.

According to the invention, (2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the cracked liquid product recycle stream R20ZP-LR obtained in the thermal high-pressure separation process R20ZP-THPS of the last 1 sub-hydrogenation reaction zone R20M can return to the first hydrogenation reaction process R10 to contact with the first hydrogenation catalyst R10C to carry out at least part of hydrogenation saturation reaction.

In the invention, generally, (3) SR is separated in the recovery process, and a thermal high-pressure separation process THPS is arranged;

separating the second hydrogenation reaction effluent R20P to obtain a hot high-component gas THPS-V containing hydrogen, impurity hydrogenation products, conventional gas hydrocarbon and conventional liquid hydrocarbon with the conventional boiling point lower than 350 ℃ and a hot high-component liquid THPS-L containing dissolved hydrogen and conventional liquid hydrocarbon with the conventional boiling point higher than 350 ℃ in the THPS in the hot high-pressure separation process, wherein the THPS-L may contain solid particles;

recovering the hot high-molecular gas THPS-V to obtain hydrogen-rich gas SRV mainly comprising hydrogen and liquid stream SRL mainly comprising conventional liquid hydrocarbon and possibly containing solid particles, and returning at least part of the hydrogen-rich gas SRV to the hydrogenation reaction process for recycling.

recovering the hot high-temperature liquid THPS-L to obtain hydrocracked distillate oil R20P-ML mainly comprising hydrocarbon components with the conventional boiling point of 250-530 ℃, and allowing at least part of the hydrocracked distillate oil R20P-ML to enter a hydrogenation reaction process R10 or R20.

recovering the hot high-temperature liquid THPS-L to obtain hydrocracked tail oil R20P-DO which mainly comprises hydrocarbon components with the conventional boiling point higher than 530 ℃, wherein at least part of the hydrocracked tail oil R20P-DO does not enter the hydrogenation reaction process.

In the present invention, generally, the catalyst-containing hydrocarbon feed RKKC obtained based on the second hydrogenation reaction effluent R20P is recycled back to the first hydrogenation reaction process R10 to be mixed with the feedstock or intermediate or final product of the first hydrogenation reaction process R10;

the catalyst containing hydrocarbon feed RKKC may be selected from one or more of the following:

① a portion of the hot high-pressure oil obtained during the hot high-pressure separation of the second hydrogenation effluent R20P, is used as the catalyst-containing hydrocarbon feed RKKC;

② a portion of the catalyst-containing hydrocarbon feed discharged from the distillation column during the fractional distillation of the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feed RKKC;

③ a portion of the catalyst-containing distilled condensed oil discharged from the distillation column during the fractionation of the second hydrogenation effluent R20P is used as the catalyst-containing hydrocarbon feed RKKC;

④ a portion of the catalyst-containing distillation bottoms discharged from the distillation column during the fractional distillation of the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feed RKKC;

⑤ at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke feedstock, the catalyst-containing hydrocarbon feed obtained in the separation process of extracting needle coke feedstock from coal-containing pitch feed based on the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feed RKKC;

⑥ at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke feedstock, the catalyst-containing heavy pitch hydrocarbon feedstock obtained in the separation process of extracting needle coke feedstock from coal-containing pitch feedstock based on the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feedstock RKKC;

⑦ at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke feedstock, the catalyst-containing light pitch hydrocarbon feedstock obtained in the separation process of extracting needle coke feedstock from coal-containing pitch feedstock based on the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feedstock RKKC;

⑧ at least a part of the pitch component of the second hydrogenation effluent R20P is used as needle coke feedstock and the catalyst-containing medium pitch hydrocarbon feedstock obtained in the separation process of extracting needle coke feedstock from coal-containing pitch feedstock based on the second hydrogenation effluent R20P is used as catalyst-containing hydrocarbon feedstock RKKC.

In the invention, generally, the separated hydrocarbon material RKKC containing the catalyst is recycled to the second hydrogenation reaction process R20 to be mixed with the raw material or intermediate product or final product of the second hydrogenation reaction process R20;

① at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke raw material, the catalyst-containing hydrocarbon material obtained in the separation process of the needle coke raw material extracted from the coal-containing pitch material based on the second hydrogenation effluent R20P by the solvent separation method is used as the catalyst-containing hydrocarbon material RKKC;

② at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke raw material, the catalyst-containing heavy pitch hydrocarbon material obtained in the separation process of extracting needle coke raw material from coal-containing pitch material based on the second hydrogenation effluent R20P by solvent separation method is used as catalyst-containing hydrocarbon material RKKC;

③ at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke raw material, the catalyst-containing light pitch hydrocarbon material obtained in the separation process of extracting needle coke raw material from coal-containing pitch material based on the second hydrogenation effluent R20P by solvent separation method is used as catalyst-containing hydrocarbon material RKKC;

④ at least a part of the pitch component in the second hydrogenation effluent R20P is used as needle coke raw material, the catalyst-containing medium pitch hydrocarbon material obtained in the separation process of extracting needle coke raw material from coal-containing pitch material based on the second hydrogenation effluent R20P by solvent separation method is used as catalyst-containing hydrocarbon material RKKC;

the separation process using the solvent separation method to separate the light liquid phase and the heavy liquid phase may be selected from 1 of the following:

① solvent-settling process, including light liquid phase distillation or and heavy liquid phase distillation if present;

② solvent-centrifugation, including light liquid phase distillation or and possibly heavy liquid phase distillation;

③ solvent-filtration process, including light liquid phase distillation process or and heavy liquid phase distillation process if present;

④ solvent-flocculation method, including light liquid phase distillation process or and heavy liquid phase distillation process if present;

⑤ solvent-extraction process, including light liquid phase distillation process or and heavy liquid phase distillation process if present;

⑥ supercritical extraction method, comprises light liquid phase distillation or heavy liquid phase distillation.

According to the invention, the olefin hydrogenation saturation reaction section of the hot high-molecular gas of the product R20P can be arranged to reduce the olefin content of the hydrocarbons in the hot high-molecular gas.

In the present invention, (1) in the first hydrogenation reaction process R10, a stream containing at least a part of conventional liquid hydrocarbons based on the first hydrogenation reaction effluent R10P is used as a feedstock R20-fed containing an olefin component of liquid-phase hydrocarbons of the second hydrogenation reaction process R20;

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

the mode of operation of the stream comprising at least a portion of conventional liquid hydrocarbons based on the first hydrogenation effluent R10P as FEED R20-fed comprising olefin components of liquid phase hydrocarbons for the second hydrogenation process R20 may be selected from 1 or more of the following:

① the first hydrogenation effluent R10P is used as the raw material R20-FEED containing olefin components and enters the second hydrogenation process R20;

② the first hydrogenation effluent R10P is used as the raw material R20-FEED containing olefin components, and enters the second hydrogenation process R20 after being mixed with the cooling material;

③ the first hydrogenation reaction effluent R10P enters a thermal high-pressure separation process R10P-HS to be separated into thermal high-molecular oil R10P-HSO and thermal high-molecular gas R10P-HSV, at least one part of the thermal high-molecular oil R10P-HSO is used as raw material R20-FEED containing olefin components, and the thermal high-molecular oil enters a second hydrogenation reaction process R20;

④ the first hydrogenation reaction effluent R10P enters a thermal high-pressure separation process R10P-HS to be separated into thermal high-molecular oil R10P-HSO and thermal high-molecular gas R10P-HSV, at least one part of the thermal high-molecular oil R10P-HSO is used as a raw material R20-FEED containing olefin components, and the mixture is mixed with a cooling material and then enters a second hydrogenation reaction process R20;

⑤ the first hydrogenation reaction effluent R10P enters a thermal high-pressure separation process R10P-HS to be separated into thermal high-molecular oil R10P-HSO and thermal high-molecular gas R10P-HSV, at least a part of the thermal high-molecular oil R10P-HSO is depressurized, and liquid R10P-HSOA obtained after degassing is used as raw material R20-FEED containing olefin components to enter a second hydrogenation reaction process R20;

⑥ the first hydrogenation effluent R10P enters into a thermal high-pressure separation process R10P-HS to be separated into thermal high-molecular oil R10P-HSO and thermal high-molecular gas R10P-HSV, at least a part of the thermal high-molecular oil R10P-HSO is depressurized, liquid R10P-HSOA obtained after degassing is used as raw material R20-FEED containing olefin components, and the raw material R20-FEED is mixed with cooling material and then enters into a second hydrogenation process R20.

Detailed Description

The present invention is described in detail below.

The pressure in the present invention refers to absolute pressure.

The conventional boiling point of the invention refers to the vapor-liquid equilibrium temperature of a substance at one atmospheric pressure.

The conventional boiling range as referred to herein refers to the conventional boiling range of the distillate fraction.

The specific gravity of the present invention refers to the ratio of the density of a liquid at ordinary pressure and 15.6 ℃ to the density of a liquid at ordinary pressure and 15.6 ℃ unless otherwise specified.

The compositions or concentrations or amounts or yield values of the components described herein are weight basis values unless otherwise specified.

The conventional gaseous hydrocarbon refers to hydrocarbon which is gaseous under conventional conditions, and comprises methane, ethane, propane and butane.

The conventional liquid hydrocarbon refers to hydrocarbon which is liquid under conventional conditions, and includes pentane and hydrocarbon with higher boiling point.

The impurity elements in the invention refer to non-hydrogen, non-carbon and non-metal components in the raw oil, such as oxygen, sulfur, nitrogen, chlorine and the like.

The impurity component in the invention refers to the hydrogenation conversion product of non-hydrocarbon component in the raw oil, such as water, ammonia, hydrogen sulfide, hydrogen chloride and the like.

The naphtha component of the present invention refers to conventional liquid hydrocarbons having a conventional boiling point of less than 200 ℃.

The conventional boiling point of the hydrocarbon contained in the diesel component is usually 155-375 ℃, and the conventional boiling point is usually 200-350 ℃.

The normal boiling point of the hydrocarbon contained in the wax oil component is generally 350-575 ℃ and generally 370-530 ℃.

The heavy oil component of the present invention contains hydrocarbons having a conventional boiling point generally greater than 350 c, generally greater than 450 c, specifically greater than 530 c, and more specifically greater than 575 c.

The atmospheric resid component of the present invention, typically an atmospheric fractionation tower bottoms, contains hydrocarbons having a conventional boiling point typically greater than 330 c, typically greater than 350 c, and particularly greater than 370 c.

The vacuum residue component of the present invention, typically a vacuum fractionation tower bottoms, typically contains hydrocarbons having a conventional boiling point generally greater than 450 c, typically greater than 530 c, and particularly greater than 575 c.

The medium hydrocarbon refers to hydrocarbon with a conventional boiling point of 230-400 ℃.

The heavy hydrocarbon refers to hydrocarbon with a conventional boiling point higher than 350 ℃.

The gas-liquid volume ratio or the hydrogen-oil volume ratio in the hydrogenation reaction process refers to the ratio of the volume flow of the hydrogen in the standard state to the volume flow of the specified oil material flow at normal pressure and 20 ℃.

The said low carbon number single six-membered ring hydrocarbon in the present invention refers to C₆～C₉The benzene-series hydrocarbon or cyclohexane-series hydrocarbon has a normal boiling point of usually 70 to 180 ℃, and is suitable for being used as raw material naphtha for preparing aromatic hydrocarbon by catalytic reforming.

The aromatic hydrocarbon with a double ring structure in the invention refers to hydrocarbons containing two ring structures, wherein at least one ring belongs to aromatic rings, such as naphthalene, tetrahydronaphthalene and hydrocarbons with side chains.

The tricyclic aromatic hydrocarbon refers to a hydrocarbon containing three ring structures, at least one of which belongs to an aromatic ring, such as fluorene, dibenzofuran, dibenzothiophene, carbazole, dibenzopyridine, anthracene, phenanthrene, and side chain hydrocarbons thereof or partially hydrogenated saturated products thereof.

The polycyclic aromatic hydrocarbon of the present invention is a hydrocarbon having four or more ring structures, at least one of which belongs to an aromatic ring.

The high aromatic hydrocarbon refers to a hydrocarbon material with high aromatic carbon rate, generally refers to a hydrocarbon material with the aromatic carbon rate higher than 40%, and particularly refers to an oil product with high aromatic concentration containing tricyclic aromatic hydrocarbon or polycyclic aromatic hydrocarbon, such as coal tar distillate, coal hydrogenation direct liquefaction oil distillate or hydrogenation modified oil based on the coal tar distillate and the coal hydrogenation direct liquefaction oil distillate, wherein the main product of such a high aromatic hydrocarbon hydrogenation thermal cracking process can be low-carbon single six-membered ring hydrocarbon.

The aromatic ring number of the polycyclic aromatic hydrocarbon is more than or equal to 3.

Coal tar is described below.

The coal tar of the invention refers to coal tar or fractions thereof from the pyrolysis steps of coal pyrolysis, coal carbonization or coal gas production, and the like, and can be coal tar or fractions thereof at low temperature, which are byproducts of coal gas production, or coal tar or fractions thereof, which are byproducts of coal coking and coal pyrolysis (including low-temperature coking, medium-temperature coking and high-temperature coking), can be mixed oil of the coal tar, and can be extracted oil, such as deasphalted coal tar or fractions thereof, obtained by extracting the coal tar with a light hydrocarbon solvent.

The high-temperature coking belongs to the high-temperature pyrolysis process of coal, and the final temperature of the pyrolysis process is generally more than 900 ℃ and is usually between 1000 and 1400 ℃. The high-temperature coal tar refers to the byproduct crude tar produced in the process of preparing coke and/or urban coal gas by high-temperature pyrolysis of coal. High temperature coal tar in a primary distillation process typically produces the following products: light oil (topping tar), phenol oil, naphthalene oil, light wash oil, heavy wash oil, light anthracene oil, heavy anthracene oil, asphalt and other products, wherein the phenol oil can be further separated into crude phenol and dephenolized oil, and the naphthalene oil can be further separated into crude naphthalene and dephenolized oil. The high-temperature coal tar light fraction refers to: anthracene oil, wash oil, naphthalene oil, decalin oil, phenol oil, dephenolized oil, light oil, and mixtures thereof.

Because the properties of raw coal and the coking or gas-making process conditions are changed within a certain range, the properties of coal tar are also changed within a certain range. The technological conditions and product requirements of the primary distillation process of the coal tar are also changed within a certain range, so that the properties of the light fraction of the coal tar are also changed within a certain range. The specific gravity of the coal tar light fraction is usually 0.92-1.25, the conventional boiling point is usually 60-500 ℃ and is usually 120-460 ℃, the metal content is usually 5-80 PPm, the sulfur content is 0.4-0.8%, the nitrogen content is 0.6-1.4%, the oxygen content is 0.4-9.0%, the water content is usually 0.2-5.0%, and the carbon residue content is usually 0.5-13%.

The medium-low temperature coal tar is a coal tar product from coal pyrolysis or coal gas production or other processes, can be low-temperature coal tar from a low-temperature coking process (the carbonization temperature is lower than 700 ℃) or medium-temperature coal tar (the carbonization temperature is between 700 and 950 ℃) from a medium-temperature coking process or mixed oil of the medium-temperature coal tar and the medium-temperature coal tar, and generally contains a coal tar heavy oil component. As the properties of raw coal and the coking or gas-making process conditions are changed within a certain range, the properties of medium and low temperature coal tar are also changed within a certain range. The medium and low temperature coal tar of the invention has a specific gravity of 0.89-1.15, and usually has a metal content of 5-200 PPm, a sulfur content of 0.1-0.7% and a nitrogen content of 0.6-1.6%. The medium-low temperature coal tar of the invention sometimes has an inorganic water content of 0.2% to 5.0% and sometimes has an organic oxygen content of usually 2.5% to 18%, particularly 3.5% to 10%, more particularly 5% to 10%.

The coal tar generally comprises a mixture of hydrocarbon components with a conventional boiling range of 120-450 ℃ and hydrocarbon components with a conventional boiling range higher than 450 ℃, a light fraction FD1 with a conventional boiling range of 120-260 ℃ contains bicyclic aromatic hydrocarbon fractions, a middle fraction FD2 with a conventional boiling range of 260-370 ℃ contains bicyclic aromatic hydrocarbon fractions and tricyclic aromatic hydrocarbon fractions, a heavy fraction FD3 with a conventional boiling range of 370-450 ℃ contains bicyclic to tetracyclic aromatic hydrocarbon fractions, and a residual fraction FD4 with a conventional boiling range higher than 450 ℃ is a coal pitch fraction.

The coal tar light distillate oil refers to the coal tar distillate oil with the conventional boiling point of 60-480 ℃ and 60-450 ℃ generally, and can be subjected to hydrogenation modification by adopting a fixed bed hydrogenation technology.

The coal tar heavy distillate oil refers to medium-low temperature coal tar distillate with the conventional boiling point usually higher than 370 ℃ and usually higher than 400 ℃, the hydro-thermal cracking process of the coal tar heavy distillate oil refers to a process for producing the coal tar distillate with the molecular weight lower than that of a cracking raw material by at least part of hydro-cracking reaction, the process usually comprises parallel hydro-demetallization, hydro-refining and hydro-thermal cracking reaction, and the proper reactor form is an up-flow expanded bed such as a suspension bed reactor or an ebullated bed reactor.

The residual oil fraction FD4 is usually difficult to realize long-period and high-yield hydrogenation and lightening by adopting a conventional fixed bed technology, so that the conversion is realized by adopting an upflow expansion bed such as a suspension bed or a boiling bed hydrogenation technology, in order to prevent the agglomeration of colloidal asphaltenes from causing unnecessary coking reaction, solvent hydrocarbons with good mutual solubility with the coal residue oil fraction are usually required to be dissolved and dispersed to form a dilute solution of the colloidal asphaltenes, and the solvent hydrocarbons can be heavy fraction FD3 with the conventional boiling range of 370-450 ℃, can also be partially saturated conversion products of hydrogenated aromatic hydrocarbons of the heavy fraction FD3 and the residual oil fraction FD4, and can also be partially saturated conversion products of hydrogenated aromatic hydrocarbons of the middle fraction FD 2. The conversion product of the middle fraction FD2, which is partially saturated with hydrogenated aromatic hydrocarbon, belongs to an excellent hydrogen supply solvent and is rich in hydrogen supply hydrocarbon.

The high aromatic carbon rate inferior hydrocarbon HDS can be 1 kind of wide-cut high aromatic hydrocarbon, and can also be 2 or more kinds of high aromatic hydrocarbons with different boiling ranges; the hydrogenation reaction process carried out in the first hydrogenation reaction process R10 can process 1 kind of inferior hydrocarbon HDS, and can also process 2 or more kinds of inferior hydrocarbon HDS with different boiling ranges; when 2 or more high aromatic hydrocarbons with different boiling ranges are processed in the first hydrogenation reaction process R10, the first hydrogenation reaction process can be 2-path or multi-path feeding, catalyst bed layers or reaction spaces through which raw materials of different paths flow can be the same or different, and can be a parallel hydrogenation relationship, or a series hydrogenation process relationship in which raw materials firstly and secondly enter a plurality of reaction zones respectively, or a relationship in which raw materials are firstly hydrogenated in parallel and secondly hydrogenated products are converged and then hydrogenated jointly, or other more complex combination relationships.

According to the present invention, the coal tar is usually subjected to a process of filtering off solid particles before being subjected to hydrotreating or before being subjected to fractionation.

The coal tar generally contains high-value compounds such as phenol, naphthalene, anthracene and the like, and the high-value compounds can be extracted before entering the hydrogenation process.

The process flow range of the hydrocarbon raw material HDS comprises a separation and fractionation process of a first hydrogenation reaction process R10, a second hydrogenation reaction process R20 and a second hydrogenation reaction effluent R20P, and also can comprise a separation process for preparing a needle coke raw material, a coking process for producing needle coke, a calcination process of the needle coke and other subsequent related processes or an upstream initial coal tar process.

Generally, the coal tar light fraction, such as the fraction with a conventional boiling point lower than 350 ℃, has high olefin content, high phenol content, high colloid content and more components which are easy to react under mild conditions, so that the pre-hydrogenation process of the coal tar light fraction generally uses a series combination or a mixed combination of a single agent or double agents or multiple agents of a hydrogenation protective agent, an olefin hydrogenation saturant, a hydrogenation deoxidizer, a hydrogenation carbon residue removing agent, a hydrogenation desulfurizing agent and the like, and a down-flow fixed bed hydrogenation reactor is generally used.

In the deep hydrogenation modification process of the coal tar light fraction, or the material flow distillate oil obtained by separating the second hydrogenation reaction effluent R20P, the hydrogenation upgrading reaction is carried out to obtain the hydrogenation upgrading reaction product, and the series combination or the mixed combination of single agent, double agent or multiple agents of a hydrodesulfurization agent, a hydrodenitrogenation agent, an aromatic hydrocarbon hydrogenation saturant, a naphthene hydrogenation ring-opening catalyst, a hydroisomerization catalyst, a hydrocracking catalyst and the like is usually used, and a downflow fixed bed hydrogenation reactor is usually used.

The production process of coal tar and coal-based needle coke is described in detail below.

Coal tar is a product of coal coking, coal gas making, coal pyrolysis or other coal thermal processing processes, and because the properties of raw coal change within a certain range, the coking, gas making, pyrolysis or other coal thermal processing process conditions change within a certain range, the properties of coal tar also change within a certain range. The coal tar of the invention has a specific gravity of 0.89-1.30, and generally has a metal content of 5-1200 PPm, a sulfur content of 0.1-1.2%, a nitrogen content of 0.1-1.8% and an aromatic hydrocarbon content of 50-99%. The coal tar of the present invention sometimes has an inorganic water content of 0.2% to 5.0%, and sometimes has an organic oxygen content of 0.05% to 12%, particularly 0.5% to 10%. The coal tar of the invention generally has an ash content of 0.005-5.00%.

The needle coke with excellent performance can be prepared by using coal tar pitch with proper composition and property or adding other blending materials.

A document for recording the data about the raw material properties, the processing method and the product performance index information of the coal-based needle coke is disclosed in the publication A02: ① with the names of the publications in delayed coking process and engineering, pages 57-64 and pages 351-372, ② searches for the codes of ISBN, 978-7-80229-456-1, Chinese edition library CIP data core (2007), No. 168082, ③ master code, Dianthus superbus and ④ publication in China petrochemical press.

A document for recording the data about the properties of raw materials, processing methods and performance index information of coal-based needle coke is disclosed in A03: ① publication name, modern coal chemical engineering technical handbook, pages 1408 to 1411, ② retrieval uses a book code, ISBN code, 978-7-122-09636-4, Chinese edition library CIP data core (2010) No. 197010, ③ master code, Hendede, ④ publication and chemical industry Press.

As raw oil for producing needle coke, the composition factors influencing the formation of the intermediate phase mainly comprise:

① active ingredient

If the asphalt contains a small amount of highly reactive components, the crosslinking reaction proceeds smoothly, and the oriented crosslinking and condensation are caused, so that an anisotropic mosaic structure and a fibrous structure are easily obtained. If the highly reactive component present in the pitch controls the crosslinking, it is non-oriented crosslinking and an isotropic carbon and fine mosaic structure is obtained. The latter situation often occurs when low-temperature dry distillation coal tar is used as a raw material for liquid-phase carbonization;

② quinoline insolubles

The quinoline insolubles referred to herein are primary quinoline insolubles such as free carbon and carbon black. Their presence results in a decrease in the activation energy of the reaction and an increase in the reaction rate constant. The presence of primary quinoline insolubles, while beneficial to the nucleation process, is not beneficial to the growth and coalescence of globules. When their mass fraction exceeds 5%, the pellets have a diameter of only a few micrometers and have an onion-type structure. This structure is not easily graphitized.

③ oxygen, sulfur, nitrogen and heterocyclic compounds thereof

It has been reported that the presence of more than 7% oxygen in the pitch results in complete suppression of mesophase conversion, and non-graphitizing coke is produced. The sulfur is added into the asphalt to promote the rapid conversion of the intermediate phase, and when the addition amount exceeds 7 percent, the intermediate phase molecules are widely crosslinked, and finally the non-graphitizable glassy carbon is generated. In addition, sulfur can also cause crystal expansion. The heterocyclic compound containing oxygen, sulfur and nitrogen has high thermal reactivity, participates in the primary generation of mesophase spherule and is enriched in the mesophase spherule, so that a fine grain mosaic structure is generated.

④ metal element

The asphalt mainly contains Na, K, Mg, Ca, Fe, Cu, Al, V, Ni and the like, which can activate asphalt molecules, accelerate the generation and fusion of mesophase spherule to form a mosaic structure and increase the thermal collision coefficient of the needle coke.

The raw material pretreatment process of the coal-based needle coke mainly aims at removing Quinoline Insoluble (QI) in coal tar pitch. The composition of the coal tar pitch has an influence on the formation of the mesophase, for example, active components, quinoline insolubles, metal elements, heterocyclic compounds, and nitrogen, sulfur, oxygen, etc. The main component of the coal tar pitch is aromatic hydrocarbon, but the coal tar pitch contains a certain amount of quinoline insoluble substances, wherein the quinoline insoluble substances include amorphous carbon generated by heating and condensing certain high molecular resin-shaped substances during distillation of coal tar, and coal dust and coke powder brought out from a coke oven chamber along with coal gas. They adhere around the mesophase, hindering the growth and coalescence of the spherical crystals. The needle coke having a good fiber structure cannot be obtained after the coking. Therefore, it is necessary to remove the crude Quinoline Insolubles (QI) that hinder the growth of the spherules and then to conduct the compositional modulation to obtain a raw material that meets the production requirements of needle coke, which is a necessary step for producing needle coke from coal tar pitch. The pretreatment process of the coal-based needle coke raw material mainly comprises a filtration method, a centrifugal separation method, a solvent method and a vacuum distillation method. The solvent method is further classified into a solvent-settling method, a solvent-centrifugation method, a solvent-filtration method, a solvent-flocculation method, a solvent-extraction method, a supercritical extraction method, and the like.

The needle coke production process UT1 based on coal tar pitch without removing quinoline insoluble substances generally comprises a raw material pretreatment process UT1, a delayed coking process UT20 and a calcination process UT 30. The suspension bed hydrogenation modification process R10 of the material R10F containing high-temperature coal pitch by using a hydrogenation catalyst R10C obtains a suspension bed hydrogenation product R10P containing R10C, and the suspension bed hydrogenation product R10P is separated to obtain an oil material R10P-HS-VS containing an asphalt component of the suspension bed hydrogenation modification product containing R10C; according to a conventional solvent method separation method, in a solvent method separation process UT1, oil R10P-HS-VS containing asphalt components of a suspension bed hydrogenation modified product is separated into light asphalt UT1-10-L containing R10C and solvent and heavy asphalt UT1-10-H containing R10C and solvent; the light asphalt UT1-10-L is separated into solvent UT1-10-L-S and needle coke raw material light asphalt tower bottom oil UT1-10-L-MIXP containing R10C in the fractionation process UT1-20, the separation result of the distillation method is that the needle coke raw material light asphalt tower bottom oil UT1-10-L-MIXP contains a large amount of R10C, so that the quality of needle coke is reduced, even needle coke cannot be obtained, meanwhile, the needle coke raw material light asphalt tower bottom oil UT1-10-L-MIXP containing R10C carries a large amount of catalysts R10C, and the fresh catalyst consumption of R10 is greatly increased.

The needle coke production process UT based on coal tar pitch without quinoline insoluble removal generally comprises a raw material pretreatment process UT1, a delayed coking process UT2 and a calcination process UT 3.

In the pretreatment process of the coal-based needle coke by the raw material solvent method, a mixed solvent prepared from aromatic hydrocarbon and aliphatic hydrocarbon is usually used as an extracting agent, and quinoline insoluble substances in the raw material coal pitch are removed through settling separation. There are many methods disclosed for the pretreatment of pitch to obtain needle coke feedstock refined pitch and heavy pitch, and any suitable method can be used in the present invention, typical methods are the following:

① A method for producing coal tar pitch needle coke, which comprises using a mixed solvent of aromatic hydrocarbon and aliphatic hydrocarbon at a ratio of 1: 0.6-1: 1.2 as an extractant;

② A production method and a system of coal-series needle coke of Chinese patent ZL200910198177.6 are characterized in that in the specified process conditions of the pretreatment process of the solvent method, the mass ratio of the coal tar pitch to the solvent is 1: 0.6-1: 2.0, the solvent is formed by mixing aliphatic hydrocarbon and aromatic hydrocarbon, the mass ratio of the aliphatic hydrocarbon to the aromatic hydrocarbon is 1: 0.6-1.4, the initial boiling point of the solvent under normal pressure is more than or equal to 150 ℃, the distillate w/w before 310 ℃ is more than or equal to 95%, the aliphatic hydrocarbon is a petroleum hydrocarbon solvent, the aromatic hydrocarbon is one fraction in the processing process of tar or is formed by mixing several fractions in the processing process of tar, and the distillate w/w of the aromatic hydrocarbon under normal pressure and at the temperature of 235-250 ℃ is 50-85%;

③ Chinese patent ZL201110284485.8 is a process for preparing needle coke raw material by using coal tar pitch, in the specified process conditions of the pretreatment process of the solvent method, pitch and solvent are fully mixed, and insoluble substances in the mixed solution are removed by a physical separation method, wherein the physical separation is centrifugal separation, the viscosity of the mixed solution subjected to centrifugal separation is 40-90 mpa · s, the solvent is a mixture of coal-series light oil and coal-series aromatic oil or a mixture of BTX and coal-series aromatic oil, the mass ratio of the coal-series light oil or the BTX to the coal-series aromatic oil is 20: 80-95: 5, and the mass ratio of the solvent to the pitch is 0.5-10;

④ Chinese patent ZL201110339693.3 is a process for preparing needle coke raw material by utilizing coal tar and heavy phase circulation, and comprises the following steps in the process conditions of the pretreatment process of the coal tar by a solvent method:

step 1, fully mixing coal tar with a first solvent, and removing first solvent insoluble substances in the mixture by adopting a physical separation method to obtain a first clarified liquid;

the first solvent is coal-series light oil, and the mass ratio of the first solvent to the coal tar is 0.05-10;

step 2, separating and removing the first solvent in the first clarified liquid, and hydrogenating the residual components after the first solvent is removed to obtain refined asphalt;

step 3, fully mixing the first solvent insoluble substance obtained in the step 1 with a second solvent, and removing the second solvent insoluble substance in the mixture by a physical separation method to obtain a second clear liquid;

the second solvent is coal-series medium oil, the mass ratio of the coal-series medium oil to the coal-series light oil is 1: 0.1-1: 2, and the mass ratio of the second solvent to the first solvent insoluble substances is 0.5-50;

step 4, separating and removing the second solvent in the second clarified liquid to obtain a refined heavy component;

step 5, mixing the refined asphalt and the refined heavy component to obtain a raw material for preparing the needle coke;

⑤ patent ZL 201310231391.3A process for producing needle coke, wherein the solvent is a mixture of coal-series light oil and coal-series aromatic oil or a mixture of BTX and coal-series aromatic oil under the specified process conditions of the pretreatment process by a solvent method, the mass ratio of the coal-series light oil or the mixture of BTX and coal-series aromatic oil is 0.25-19, the mass ratio of the solvent to the asphalt is 0.5-10, the coal-series light oil is one or more of gas light oil, tar light oil and naphtha light oil, and the coal-series aromatic oil is one or more of washing oil, absorption oil, cresol oil and anthracene oil;

⑥, the chinese patent application No. 201711084211.8, which is a process for producing needle coke by compounding and blending raw materials including wash oil, anthracene oil and asphalt in medium-low temperature coal tar, is characterized in that in the specified process conditions of the pretreatment process by a solvent method, an extraction agent adopted by solvent extraction is a mixture of aromatic hydrocarbon and alkane according to a mass ratio of 1.2-1.8: 1, wherein the aromatic hydrocarbon is one or more of toluene, furfural and N-methylpyrrolidone, and the alkane is any one of N-hexane, N-heptane and cyclohexane;

⑦ Chinese patent application No. 201711084214.1 discloses a process for producing coal-based needle coke from medium-low temperature coal tar pitch, wherein in the specified process conditions of the pretreatment process by a solvent method, an extracting agent is composed of aromatic hydrocarbon and alkane, the mass ratio of the aromatic hydrocarbon to the alkane is 1: 1-5: 1, wherein the aromatic hydrocarbon is any one of toluene, xylene and wash oil, and the alkane is any one of n-hexane, n-heptane and cyclohexane;

⑧ Chinese patent application No. 201810300971.6 needle coke industrial production raw material pretreatment solvent extraction system and method, in the process condition of the pretreatment process of the solvent method, a mixed extraction agent of aromatic hydrocarbon and aliphatic hydrocarbon is used, the aromatic hydrocarbon is wash oil, dephenolized phenol oil or a mixture of the wash oil and the dephenolized phenol oil, and the aliphatic hydrocarbon is aviation kerosene.

There are many disclosed methods for preparing needle coke from coal tar pitch, and any suitable method can be used in the present invention, and the following 2 methods are typical:

① Chinese patent ZL200510136737.7 describes a process for preparing needle coke by using coal tar soft pitch as a raw material, which is characterized in that the inlet temperature of a coking heating furnace is 320 ℃, the outlet temperature is 420-520 ℃, the raw material enters a coking tower, the temperature is increased from 420 ℃ to 440-450 ℃ at the rate of 5 ℃ per hour, then the raw material is fed at a constant temperature for 2-4 hours, then the temperature is rapidly increased to 460-470 ℃, the raw material is fed at a constant temperature for 4-6 hours, then the temperature is rapidly increased to 490-520 ℃, and the total feeding time is 4-36 hours.

② patent ZL201510015130.7 describes a process for co-production of needle coke, mesophase carbon microspheres and high-quality asphalt, wherein mesophase carbon microspheres are produced by mixing heavy phase asphalt produced by raw material asphalt pretreatment and raw material asphalt, and the by-product asphalt for producing the mesophase carbon microspheres is mixed with refined asphalt obtained by raw material asphalt pretreatment to serve as a needle coke raw material, and comprises the processes of raw material asphalt pretreatment, polymerization reaction, separation and drying of polymerization products, by-product asphalt processing, coking and calcining.

In the raw material solvent method pretreatment process of coal-based needle coke, a mixed solvent prepared from aromatic hydrocarbon and aliphatic hydrocarbon is usually used as an extracting agent, and quinoline insoluble substances in raw material coal pitch are removed through sedimentation separation. Although the solvent method for pretreating raw materials of coal-based needle coke is complex in process and large in investment, the method is used in large quantities because of high yield of refined pitch, good quality of needle coke and stable operation, and is used by the Ministry of heat energy of Mitsubishi chemical industry, China midge Steel group, Anshan mountain.

The coal-based needle coke raw oil refers to raw hydrocarbon oil for preparing needle coke based on coal tar, and can be distilled distillate oil obtained by fractionating coal tar, light components obtained by separating coal pitch, namely the light pitch, and can be hydro-modified oil products of hydrocarbon oil based on coal tar.

The conventional boiling range of the suitable coal-based needle coke raw oil is usually 330-530 ℃, namely the conventional boiling range mainly comprises 3-ring aromatic hydrocarbon, 4-ring aromatic hydrocarbon and 5-ring aromatic hydrocarbon, preferably mainly comprises 3-ring aromatic hydrocarbon and 4-ring aromatic hydrocarbon, and the higher the aromaticity of the hydrocarbon component is, the better the aromaticity is, the better the needle coke yield in the coking process is.

The coal-based needle coke raw oil of the invention generally refers to raw hydrocarbon oil from high-temperature coal tar for preparing needle coke, and can be distillate oil obtained by fractionating high-temperature coal tar, light component obtained by separating high-temperature coal tar coal pitch, namely the light pitch, and can be oil products or isolates thereof after hydrogenation modification of hydrocarbon oil based on high-temperature coal tar.

The raw material for producing needle coke is usually refined pitch (light pitch) obtained by pretreating coal pitch, and the index of the raw material for producing needle coke is generally shown in Table 1.

Table 1 shows technical specifications of needle coke feedstocks.

TABLE 1 technical indices of needle coke feedstock

Item	General index	Good index
			Aromatic hydrocarbon content,% (mass fraction) is not less than	60
Conradson carbon residue, the percentage (mass fraction) is less than or equal to	10
			Ash content%	0.3	0.05
Sulfur content, percent (mass fraction) is less than or equal to	0.6	0.50
			Density, (g/cm)³) ≥		1.02
Quinoline insoluble substance QI is less than or equal to		1.0
			Vanadium, PPm (weight) is less than or equal to		50
Nickel, PPm (weight) is less than or equal to		50
			Correlation coefficient BMCI ≥		120

In the delayed coking process of coal-based needle coke, the raw materials are converted into gas, gasoline, kerosene, diesel oil, wax oil and coke. The technological process and equipment for delayed coking of needle coke are basically the same as those for delayed coking of ordinary petroleum coke, and the main equipment includes heating furnace, coke tower and fractionating tower, but some necessary measures are taken in individual equipment, coking condition and operation, such as controlling temp. raising speed of feeding material, pressure of coking tower, gas injection quantity and regulating circulation ratio to make the oil material maintain a relatively stable state in the coking tower, fully utilizing the plastic flow of intermediate phase material and ordering of molecular arrangement, at the same time making the gas phase product produce shearing force to create the condition of so-called "gas flow coke-drawing" so as to finally form needle coke with streamlined structure. The needle coke produced in the delayed coking process contains high moisture and volatile components, is called green coke, and can be used as a raw material of a high-power and ultrahigh-power graphite electrode only by carrying out high-temperature calcination treatment under the condition of air isolation.

During the calcination process of the coal-based needle coke, the structure and the element composition of the needle coke are changed in a series, so that the physical and chemical properties of the needle coke are improved. The purpose of calcination is to remove moisture and volatiles from the green coke and to improve the carbon content, density, strength, conductivity and chemical stability of the coke. Needle coke calcination is usually carried out in rotary kilns or rotary kilns, where raw coke enters from one end of the kiln and contacts with the exhaust gas of high-temperature calcination, at the outlet end there is a gas-fired oil burner, and the temperature of the calcination zone can be as high as 1500 ℃. The residence time and the heating speed of the coke in the kiln are determined by the rotation speed of the kiln body, the true density of the calcined needle coke is an important evaluation index of the calcination effect, and the calcined needle coke with the true density of more than 2.130 g/cc belongs to needle coke with good quality.

Table 2 shows the technical indexes of coal-based needle coke in the national standard GB/T32158-2015 of the people's republic of China.

As can be seen from Table 2, the increase in ash content from 0.3 mass percent to 0.4 mass percent will result in a reduction in the needle coke product grade from premium to premium, and therefore, in the upgrading of coal tar pitch, the introduction of extraneous ash material such as inorganic solid particles is minimized. That is, the method has great economic significance for effectively reducing the ash content in the coal-based needle coke raw oil by adopting a proper method.

In the calcining process of the coal-based needle coke, the release of sulfur needs higher temperature to break C-S chemical bonds, and generally, the sulfur can be released in a large amount in a high-temperature range of 1200-1500 ℃, so that the sulfur content of a calcined needle coke product of high-sulfur needle coke (green coke) produced by high-sulfur-content raw material coal pitch is high, the expansion coefficient of a high-power and ultrahigh-power graphite electrode prepared by the high-sulfur needle coke product is higher, and the crystal expansion phenomenon exceeding the use upper limit is generated, so that the use function is greatly influenced, and as can be seen from table 2, the sulfur content is increased from 0.4 percent (mass fraction) to 0.5 percent (mass fraction), so that the product grade of the needle coke is reduced from primary grade to secondary grade, and the price is greatly reduced. Therefore, the method has great economic significance for effectively reducing the sulfur content in the coal-based needle coke raw oil by adopting a proper method.

TABLE 2 technical indices of coal-based needle coke (GB/T32158-

At present, the industrial method for preparing needle coke raw oil based on high-temperature coal tar pitch comprises a flash evaporation method and a solvent method, and the main aim is to control the quinoline insoluble content of the needle coke raw oil. The flash evaporation method cuts a section of raw material suitable for producing needle coke from coal tar pitch through vacuum distillation, and separates out residues (including quinoline insoluble QI). The solvent method uses aliphatic hydrocarbon and aromatic hydrocarbon to prepare a mixed solvent according to a certain proportion, the boiling point of the mixed solvent is generally lower than that of the coal pitch to be treated so as to facilitate the distillation separation operation in the later period, the coal pitch is treated by the mixed solvent to remove quinoline insoluble substances, and the method has the advantages of high yield of needle coke raw materials (fine materials), good quality of needle coke products and the defects of complex process, high control requirement of operation parameters and higher investment cost.

Neither the flash evaporation method nor the solvent method belongs to a physical separation method without changing the molecular structure, so that the sulfur content of the coal-based needle coke raw oil is difficult to be greatly reduced, and the medium pitch molecules with a slightly larger molecular weight and a proper structure cannot be converted into the light pitch suitable for the small coal-based needle coke raw oil, so that the sulfur content limits the source of high-temperature coal tar for producing high-quality needle coke, and the utilization rate of the high-boiling-point medium pitch of the high-temperature coal tar with low sulfur content, low metal content, low ash content and low quinoline insoluble content cannot be improved.

Table 3 shows the properties of a typical high quality oil-based needle coke feedstock. ,

TABLE 3 typical Properties of high-quality oil-based needle coke feedstock

Item	Catalytic cracking clarified oil	No. 1 thermal cracking tar	No. 1 thermal cracking tar
				Aromatic hydrocarbon content,% (volume fraction) is not less than	61.7	89.8	66.1
Conradson carbon residue, the percentage (mass fraction) is less than or equal to	0.48	0.07	0.56
				Sulfur content, percent (mass fraction) is less than or equal to	5.7	9.4	8.6

The properties of a typical high-quality oil-based needle coke raw material are shown in Table 3, and the catalytic cracking clarified oil is taken as an example, the aromatic content of the catalytic cracking clarified oil is only 61.7 percent and is far lower than the aromatic content of the high-quality coal-based needle coke raw material, which shows that the needle coke raw material with better comprehensive performance can be prepared by reducing the content of impurities (sulfur and nitrogen) as much as possible under the condition of ensuring that the saturation depth of aromatic hydrocarbon is proper and low through a hydrogenation impurity removal (desulfurization and denitrification) reaction process.

By combining the analysis, the invention provides a moderate hydro-upgrading method of high-temperature coal tar or high-temperature coal tar pitch, which reduces the sulfur content or and the metal content or the ash content or the quinoline insoluble content or increases the oil content suitable for producing high-quality coal-based needle coke through a hydro-upgrading reaction process R10, thereby widening the initial raw material range of the high-quality raw oil of the coal-based needle coke or improving the yield of the high-quality raw oil of the coal-based needle coke obtained from the suitable high-temperature coal tar, and simultaneously obtaining the hydro-upgraded heavy pitch. Compared with unhydrogenated initial oil with the same boiling range, the hydro-modified heavy asphalt has high hydrogen content, low viscosity and enhanced liquidity, so that the hydro-modified heavy asphalt can be used as a blending material of other coal asphalt, such as fuel oil, liquid asphalt and the like prepared by blending the hydro-modified heavy asphalt with coal asphalt of medium-temperature coal tar obtained by medium-temperature pyrolysis of long-flame coal, thereby improving the asphalt value and market price of the hydro-modified heavy asphalt.

Because high-temperature coal tar or high-temperature coal tar coal pitch contains more colloid, asphaltene and solid particles, the appropriate operation mode of the hydrogenation modification reaction process R10 is a suspension bed hydrogenation process.

In order to flexibly control the sulfur content and the nitrogen content of the needle coke delayed coking raw material light asphalt, the invention can carry out moderate hydrogenation refining on the suspension bed distillate oil product or and the light asphalt to carry out moderate hydrogenation desulfurization reaction and hydrogenation denitrification reaction, and the project investment can be greatly reduced by completing the tasks in a combined process mode. And the high-temperature coal tar fractionation process or the hydro-upgrading reaction process of distillate oil obtained in the fractionation process of a suspension bed hydrogenation product R10P can be combined together.

The invention can jointly process medium-temperature coal tar distillate or medium-temperature coal tar pitch with proper components and properties, such as the coal pitch of medium-temperature coal tar generated in the fast pyrolysis process of a long-flame coal fluidized bed.

There are many medium-low temperature coal tar suspension bed hydrogenation process methods and high-temperature coal tar suspension bed hydrogenation process methods, and the following are typical 2 methods:

① patent ZL 201010217358.1A coal tar suspension bed hydrogenation method of heterogeneous catalyst, including coal tar raw material pretreatment and distillation separation, coal tar heavy fraction suspension bed hydrocracking and light distillate oil conventional upgrading process, wherein the suspension bed hydrogenation reaction temperature is 320-480 ℃, the reaction pressure is 8-19 MPa, the volume space velocity is 0.3-3.0 h < -1 >, the hydrogen oil volume ratio is 500-2000, the catalyst is a powdery particle coal tar suspension bed hydrogenation catalyst containing molybdenum, nickel, cobalt, tungsten or iron single metal active component or composite multi-metal active component, the addition amount is that the weight ratio of the active component metal amount and the coal tar raw material is 0.1: 100-4: 100, most of the tail oil containing the catalyst after the hydrogenation reaction product is separated out light oil is directly circulated to the suspension bed reactor, after a small part of the tail oil is subjected to catalyst removal treatment, the suspension bed reactor is further lightened, the heavy oil is completely or maximally circulated, the purpose of producing light oil and catalyst recycling at maximum amount from coal tar is realized, and the utilization efficiency of raw material and catalyst is greatly improved.

② Chinese patent ZL201210022921.9 discloses a hydrogenation and lightening method of heavy oil with low hydrogen content using hydrogen-supplying hydrocarbon, wherein the hydrogen-supplying hydrocarbon material flow rich in hydrogen-supplying hydrocarbon is used in the hydrogenation and lightening process of heavy oil such as coal pitch, which has the effects of inhibiting the condensation and coking speed, improving the yield of liquid products in the coal tar heavy oil hydrogenation and transformation process, improving the product quality, reducing the reaction temperature rise and enhancing the operation stability and safety of the device.

Chinese patent ZL201010217358.1, chinese patent ZL201210022921.9 and similar patent processes are mostly targeted methods for producing light distillate to the maximum extent, and therefore, matched catalysts, process conditions and equipment have been developed. The method of the present invention can realize a suitable deep hydrogenation process based on the prior art, and can realize high selectivity for hydrodesulfurization as much as possible, so that the present invention is feasible.

In order to prevent the deposition of high-temperature coal pitch in the reaction system or thermal polycondensation, a diluent or a hydrogen donor is added as necessary during the reaction (to the reaction raw material, the reaction intermediate, the reaction final product) to dilute the coal pitch.

The basic idea of the invention is: a combined method of high aromatic hydrocarbon suspension bed hydrogenation and solvent method needle coke raw material extraction process is characterized in that under the condition of existence of diluted hydrocarbon or and hydrogen-supplying hydrocarbon, a high-temperature coal tar suspension bed hydrogenation modification reaction process R10 is used for reducing sulfur content or and reducing metal content or and reducing ash content or and reducing quinoline insoluble content, and a product R10 in the reaction process R10P is separated to obtain coal-based needle coke raw material oil with proper sulfur content or metal content or ash content or quinoline insoluble content, so that high-quality coal-based needle coke is prepared.

Since the operation goal of the hydro-upgrading reaction process R10 is to obtain hydrocarbons with high aromatic degree and low sulfur content, the ideal hydrogenation depth is a moderate hydrogenation, and the optimized operation conditions (such as catalyst type, catalyst amount, reaction pressure, reaction temperature, reaction time, hydrogen/oil volume ratio, and reactor operation mode) need to be selected according to the material properties (such as sulfur content and colloid asphaltene content) of the specific suspension bed hydrogenation process R10 and the desired product properties (such as sulfur content, colloid asphaltene content and quinoline insoluble content) and reaction depth (such as heavy asphalt cracking rate) of the suspension bed hydrogenation process R10.

Because high-temperature coal tar or high-temperature coal tar coal pitch contains more colloid and asphaltene and only contains a small amount of light distillate oil with low viscosity, the suitable operation mode of the hydrogenation modification reaction process R10 is a suspension bed hydrogenation process.

Since the operation goal of the hydro-upgrading reaction process R10 is to obtain an upgraded fraction with proper properties and a boiling range of 330-530 ℃, in order to reduce the energy consumption for separating other materials added, the added diluted hydrocarbon or hydrogen donor hydrocarbon preferably mainly comprises the conventional hydrocarbon with a boiling point lower than 330 ℃; in order to reduce the flow range of the recycled materials and reduce the investment and energy consumption, the invention recommends a short-flow circulating process, because the operation target of the hydro-upgrading reaction process R10 is to expect to obtain an upgraded fraction with a boiling range of 330-530 ℃ and the larger the boiling point difference is, the better the energy consumption is for reducing the separation of other materials added.

As a method for optimizing the operation, in order to improve and reduce undesired chemical reactions (excessive hydrogenation saturation reaction, excessive thermal cracking reaction, excessive thermal condensation reaction), it is necessary to shorten the reaction time, that is, to shorten the thermal action time, and therefore, it is necessary to use a highly efficient catalyst (highly active catalyst with high degree of dispersion) and to use a process technique for improving the catalyst efficiency (discharging reaction products that suppress the catalyst activity).

The method of the invention can produce high-quality high-valence carbon materials with high value, such as needle coke, and simultaneously obtain coking distillate oil in the coking process of producing the needle coke, and can carry out combined hydrogenation modification together with the distillate oil obtained in the fractionation process of high-temperature coal tar or the fractionation process of a suspension bed hydrogenation product R10P.

In order to flexibly adjust the sulfur content or the nitrogen content of the delayed coking raw material for producing the needle coke, at least a part of light asphalt or component oil thereof can be introduced into a fixed bed hydrogenation modification process R600 to carry out hydrogenation modification with proper hydrogenation depth for carrying out hydrogenation desulfurization reaction and hydrogenation denitrification reaction, and then the product of the hydrogenation modification process R600 is separated to obtain the hydrogenation modification raw material R600-KP for producing the needle coke.

The following describes the poor quality hydrocarbon hydrocracking reaction process for the poor quality hydrocarbons.

The hydrogenation reaction space, which refers to a process fluid flow space where the hydrogenation reaction takes place, may be a reaction inner space such as a hollow cylinder reactor zone, a gas stripping hydrogen mixing zone, a liquid collecting cup upper space region, etc., and may be a reactor outer space such as a pipe inner space, a valve inner space, a mixer inner space, a pump inner space, etc.

According to the upflow hydrogenation reactor, the macroscopic flow leading direction of a process medium in a reaction space or a hydrogenation catalyst bed layer is from bottom to top.

The upflow type expanded bed reactor is a vertical upflow type reactor, and belongs to an expanded bed reactor when a catalyst is used; the vertical type means that the central axis of the reactor is vertical to the ground in a working state after installation; the upflow means that the material main body flows in the reaction process from bottom to top to pass through the reaction space or the catalyst bed layer or flow in the same direction with the upward catalyst; the expanded bed means that a catalyst bed layer is in an expanded state in a working state, the expansion ratio of the catalyst bed layer is defined as the ratio KBED of the maximum height CWH of the working state when a reaction material passes through the catalyst bed layer and the height CUH of an empty bed standing state of the catalyst bed layer, generally, when the KBED is lower than 1.10, the bed is called a micro-expanded bed, when the KBED is between 1.25 and 1.55, the bed is called an ebullated bed, and a suspended bed is considered as the most extreme form of the expanded bed.

The back-mixed flow expanded bed reactor refers to an operation mode of using a reaction zone or a main reaction zone of the expanded bed reactor, wherein liquid flow back-mixing or circulating liquid exists; the return flow or the circulating liquid refers to at least one part of liquid phase XK-L in the intermediate product XK or the final product XK at the flow point K as a circulating liquid flow XK-LR to return to an upstream reaction zone of the flow point K, and the reaction product of the circulating liquid flow XK-LR flows through the point K and exists in XK. The mode of forming the back flow can be any suitable mode, such as arranging a built-in inner circulation tube, a built-in outer circulation tube, a built-in liquid collecting cup, a flow guide tube, a circulating pump, an external circulating tube and the like.

The invention discloses a liquid product circulating upflow type expanded bed hydrogenation reactor system, which is characterized in that a liquid product returns to an upstream reaction space for circular processing or liquid product circulation exists in an operation mode of a reaction zone or a main reaction zone of an expanded bed reactor; the liquid product circulation in the hydrogenation reactor refers to that at least a part of the liquid phase XK-L in the intermediate product XK or the final product XK at the flow point K is used as a circulating liquid flow XK-LR to return to a reaction area upstream of the flow XK, and the circulating liquid flow XK-LR passes through the point K and exists in XK. The way of forming the circulation of the liquid product can be any suitable way, but a gas-liquid separation zone must be arranged in the head space in the reactor to obtain the circulating liquid and other products, namely a built-in liquid collecting cup, a diversion pipe and a circulating booster, wherein the circulating booster is usually a circulating pump and can be arranged inside or outside the reactor.

The liquid collecting cup or the liquid collector arranged in the reactor refers to a container which is arranged in the reactor and is used for collecting liquid, the upper part or the upper part of the container is usually provided with an opening on the side surface, and a guide pipe is arranged on the bottom part or the lower part of the container for conveying or discharging the collected liquid; the top liquid collector of the expanded bed reactor is usually arranged in a liquid removal area of gas-liquid materials to obtain liquid and gas-liquid mixed phase material flow containing a small amount of bubbles or obtain liquid and gas, and at least part of liquid phase products are pressurized by a circulating pump and then return to a reaction space for circular processing. Typical examples are the heavy OIL ebullated bed hydrogenation reactor, the HTI coal hydrogenation direct liquefaction reactor, the Shenhua coal hydrogenation direct liquefaction reactor used in the H-OIL process.

The suspended bed reactor of the invention can be in any suitable structural form, can be an empty cylinder suspended bed reactor to form piston flow or back mixing flow with internal circulation, can be an internal circulation guide cylinder to form internal circulation flow or internal external circulation flow, can be a back mixing flow pattern using an external circulation pipe to make liquid in an upper reaction space flow into external circulation flow of a lower reaction space former, and can be a back mixing flow pattern using a top product separation system, a liquid collection system and a guide system to form forced internal circulation flow through a circulation pressurization system.

The thermal high separator is a gas-liquid separation device for separating intermediate products or final products of hydrogenation reaction, and can be provided with a hydrogen gas stripping function to reduce the content of low-boiling-point components in separated liquid.

The two-stage or multi-stage hydrogenation method of the invention refers to a hydrogenation method comprising two reaction stages or a plurality of reaction stages.

The hydrogenation reaction stage refers to a flow path section from the beginning of a hydrogenation reaction process of a hydrocarbon raw material to the gas-liquid separation of a hydrogenation product of the hydrocarbon raw material to obtain at least one liquid-phase product consisting of at least one part of generated oil, and comprises the hydrogenation reaction process of the hydrogenation reaction stage and the gas-liquid separation process of at least one part of the hydrogenation reaction product of the hydrogenation reaction stage. Therefore, the first-stage hydrogenation method refers to a flow mode that the processing process of the initial hydrocarbon raw material only comprises one hydrogenation reaction step and a gas-liquid separation process of a product of the hydrogenation reaction step, wherein 1 or 2 or more hydrogenation reactors which are operated in series can be used according to the requirement of the hydrogenation reaction step, so that the number and the form of the reactors are not the basis for determining the reaction level, and the reaction step consisting of one or a plurality of series reactors and the product separator are combined together to form the hydrogenation reaction level in the sense of completion.

The secondary hydrogenation method of the invention refers to a flow mode that the processing process of the initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and is formed by two different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps, wherein at least a part of a flow formed by the oil generated by the primary hydrogenation enters the secondary hydrogenation reaction process.

The three-stage hydrogenation method refers to a flow mode that the processing process of an initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and is formed by three different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps, wherein at least one part of a material flow formed by the oil generated by the first-stage hydrogenation enters a second-stage hydrogenation reaction process, and at least one part of a material flow formed by the oil generated by the second-stage hydrogenation enters a third-stage hydrogenation reaction process. The flow structure of the hydrogenation method with more stages can be analogized according to the principle. The multistage hydrogenation method refers to a flow mode that the processing process of the initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and consists of three or more different hydrogenation reaction processes and hydrogenation product gas-liquid separation processes.

The three-stage hydrogenation method refers to a flow mode that the processing process of the initial hydrocarbon raw material comprises a liquid material processing flow which is operated in series and comprises three different hydrogenation reaction steps and a gas-liquid separation process of products of the corresponding hydrogenation reaction steps.

The invention relates to a method similar to a two-stage hydrogenation method, which is a method similar to the two-stage hydrogenation method, and is regarded as the two-stage hydrogenation method when the ratio of the flow of a back-mixing liquid phase of a rear-stage upper feeding back-mixing flow expansion bed reactor to the flow of a liquid phase in an upper feeding tends to be infinite.

The reaction product BASE-R10P of the upflow hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F is at least a gas-liquid two-phase material flow, and in most cases, the material flow belongs to a gas-liquid-solid three-phase material flow. The hydrogenation reaction effluent R10P is used for discharging a hydrogenation reaction product BASE-R10P, appears in the form of 1-path or 2-path or multi-path materials, and is a gas phase or liquid phase or gas-liquid mixed phase or gas-liquid-solid three-phase material flow.

The solvent hydrocarbon ADSC refers to hydrogen donor hydrocarbon or hydrogen donor hydrocarbon precursor, and serves as hydrogen donor hydrocarbon or hydrogen transfer hydrocarbon or viscosity reduction hydrocarbon or diluent in the upflow hydrogenation process (hydrogenation modification reaction process and hydrogenation thermal cracking reaction process) of heavy oil.

The hydrogen donor refers to hydrocarbon components with hydrogen donor function in the coal hydrogenation direct liquefaction reaction process, the heavy oil hydrogenation reaction process and the kerosene co-refining hydrogenation reaction process, and the hydrogen donor comprises partially saturated bicyclic aromatic hydrocarbon and partially saturated polycyclic aromatic hydrocarbon. The hydrogen supply hydrocarbon releases active hydrogen to stabilize the hydrogenation of thermal cracking free radicals, and reduces the concentration of the thermal cracking free radicals in the reaction space, thereby having the function of inhibiting thermal cracking and reducing the thermal cracking rate of heavy hydrocarbons, for example, in the front reaction section R10A of the heavy oil hydrocracking reaction process R10 where a large amount of thermal cracking reactions occur, the hydrogen supply hydrocarbon with sufficient amount has the function of inhibiting thermal condensation coking, and has positive influence on the production process; in the rear reaction section R10B in which the number of thermal cracking reactions is greatly reduced, the same amount of hydrogen-supplying hydrocarbons contains a part of excess hydrogen-supplying hydrocarbons, which have negative effects of inhibiting thermal cracking of heavy hydrocarbons and reducing the thermal cracking rate of heavy hydrocarbons.

The hydrogen donor precursor herein refers to a hydrocarbon component which can be converted into a hydrogen donor after hydrogenation or a converted product after hydrogen donor hydrocarbons lose part of hydrogen.

The hydrogen transfer hydrocarbon refers to hydrocarbon components with hydrogen transfer function in a coal hydrogenation direct liquefaction reaction process, a heavy oil hydrogenation reaction process and a kerosene co-refining hydrogenation reaction process, such as polycyclic aromatic hydrocarbon.

The parts of the present invention are described in detail below.

The following describes a hydrogen donating hydrocarbon (or hydrogen donating hydrocarbon component) DS, a hydrogen donating hydrocarbon precursor DS-BF, a hydrogen donating solvent SHS, a hydrogen losing and donating solvent (or hydrogen donating hydrocarbon precursor, or hydrogen donating hydrocarbon to be reactivated) MFS, a hydrogenation stabilization reaction process MR for conducting a reactivation process of the hydrogen losing and donating solvent MFS or the hydrogen donating hydrocarbon precursor DS-BF.

The hydrogen-supplying hydrocarbon component DS herein refers to a hydrocarbon component having a hydrogen-supplying function in a heavy oil thermal cracking reaction process (including a heavy oil hydrocracking reaction process), a coal hydrogenation direct liquefaction reaction process, and a kerosene co-refining hydrogenation reaction process, and the hydrogen-supplying hydrocarbon includes a partially saturated bicyclic aromatic hydrocarbon and a partially saturated polycyclic aromatic hydrocarbon (generally, a tricyclic hydrocarbon and a tetracyclic hydrocarbon are preferable). In the hydrogen supply hydrocarbon, the hydrogen supply speed of a dihydro body is higher than that of a tetrahydro body, and the hydrogen supply speed of the dihydro body of tricyclic aromatic hydrocarbon is higher or lower than that of the dihydro body of bicyclic aromatic hydrocarbon; tests have demonstrated that polycyclic aromatic hydrocarbons, although not having a hydrogen donating ability, have the ability to transfer hydrogen. The relative hydrogen supply rates at 400 ℃ for the following components were as follows:

for the hydrogen donor solvents SHS used in industry, which are usually mixed hydrocarbons containing the hydrogen donor hydrocarbon component DS or and the hydrogen donor hydrocarbon precursor hydrocarbon component DS-BF, common sources of hydrogen donor solvents SHS are:

① hydrocarbon fraction with the conventional boiling point of 220-480 ℃ of low-temperature coal tar;

② hydrocarbon fraction with the conventional boiling point of 220-480 ℃ of medium-temperature coal tar;

③ hydrocarbon fraction with the conventional boiling point of 220-480 ℃ of the high-temperature coal tar;

④ hydrocarbon fraction with the conventional boiling point of 220-480 ℃ of pulverized coal pyrolysis tar;

⑤ hydrocarbon fraction of ethylene tar at 220-480 ℃;

⑥ heavy oil is used as basic hydrocarbon fraction of 220-480 ℃ obtained in the heavy oil thermal processing process, wherein the thermal processing process is a heavy oil catalytic cracking process or a heavy oil catalytic cracking process;

⑦ hydrocarbon fractions with the temperature of 220-480 ℃ obtained in the process of direct liquefaction reaction by coal hydrogenation;

⑧ hydrocarbon fraction with normal boiling point of 450-570 ℃;

⑨ other hydrocarbons rich in the hydrogen-donating hydrocarbon component DS or mixed hydrocarbons with the hydrogen-donating hydrocarbon precursor hydrocarbon component DS-BF.

Taking the hydrocracking reaction process of heavy oil as an example, in the hydrocracking reaction process of hydrocarbons, the hydro-stabilization process of obtaining active hydrogen from hydrocarbon thermal cracking radicals is carried out, the hydrocarbon thermal cracking radicals belong to hydrogen-capturing agents, and meanwhile, the hydrocarbon components with excellent hydrogen-donating capability release active hydrogen atoms (called hydrogen loss) to become hydrocarbons with higher aromatic carbon rate and poorer hydrogen-donating capability; because the hydrogen supply hydrocarbon has special composition and higher price, for reducing the cost, for the occasion that a large amount of hydrogen supply hydrocarbon needs to exist, in order to reduce the consumption of the externally supplied hydrogen supply hydrocarbon, the DS-BF of the hydrogen loss and supply hydrocarbon (or a hydrogen supply hydrocarbon precursor or the hydrogen supply hydrocarbon to be reactivated) is generally required to be recovered in a certain way to obtain the MFS of the hydrogen loss and supply solvent, and the hydrogen supply capacity of the MFS of the hydrogen loss and supply solvent is recovered through the MR in the hydrogenation stable reaction process and then recycled; it is apparent that the hydrogen-losing hydrogen-donating solvent MFS is also a mixed hydrocarbon in general and is usually mixed with the product having the same boiling point in the heavy oil hydrogenation process, so that if the product having the same boiling point in the heavy oil hydrogenation process belongs to the hydrogen-donating hydrocarbon component DS or the hydrogen-donating hydrocarbon precursor component DS-BF, the amount of the hydrogen-donating solvent may be increased, and if the product having the same boiling point in the heavy oil hydrogenation process does not belong to the hydrogen-donating hydrocarbon component DS or the hydrogen-donating hydrocarbon precursor component DS-BF, the concentration of the hydrogen-donating hydrocarbon in the hydrogen-donating solvent may be decreased, and for a stable production system in which the hydrogen-donating solvent circulates, a recycled material in which the hydrocarbon component is substantially stable is formed.

Because the hydrogen supply solvent can rapidly provide active hydrogen and rapidly transfer the active hydrogen (for example, the active hydrogen on the surface of the catalyst is rapidly transferred so as to improve the efficiency of the catalyst for generating the active hydrogen and improve the utilization rate of the active hydrogen) in the hydrogenation and thermal cracking reaction process of the heavy oil, the utilization efficiency of the active hydrogen can be improved if the hydrogen supply hydrocarbon component DS can transfer more active hydrogen in a reasonable flow manner (for example, through more hydrocarbon hydrogenation reaction processes) in the circulation process of the hydrogen supply solvent, thereby forming the efficient use method of the active hydrogen.

The beneficial effect of the hydrogen donor hydrocarbon component DS in the hydro-thermal cracking reaction process of the hydrocarbons is mainly shown as follows:

① in the process of converting into hydrogen loss solvent, the molecular is uniformly dispersed in the whole reaction space, and provides active hydrogen for the free radical in the liquid phase reaction space, which has hydrogen supply ability, hydrogen supply agent and coking inhibitor function, and the distribution uniformity can not be realized by the present nanometer catalyst with the smallest granularity;

② the whole process of providing active hydrogen for hydrocarbon belongs to hydrogen transfer between hydrocarbon molecules, basically does not generate reaction heat, and has the function of reducing the reaction heat in the hydrogenation process of the target hydrocarbon oil;

③ can reduce the temperature of the hydrocarbon thermal cracking reaction, and has the function of a dynamic coking inhibitor;

④ has molecule inducing function, and can reduce the cleavage energy of molecular hydrogen and accelerate the dissociation speed of molecular hydrogen;

⑤ rapidly transferring active hydrogen (such as rapidly transferring active hydrogen out of the surface of the catalyst to improve the efficiency of the catalyst in generating active hydrogen and the utilization rate of active hydrogen);

⑥ under proper conditions and under the action of hydrogenation catalyst, it can convert the state of hydrogen-supplying hydrocarbon and its precursor for several times to act as active hydrogen transfer agent for several times.

① can induce thermal cracking reaction, reduce thermal cracking reaction temperature, and reduce thermal condensation reaction amount, thereby improving operation stability and prolonging operation period;

② can shorten the reaction time, reduce the amount of thermal condensation reaction, thereby improving the operation stability and prolonging the operation period;

③ can reduce the total temperature rise of the reaction;

④ can increase the retention rate of pyrolysis molecules, reduce the yield of thermal condensation compounds such as coke, and reduce the yield of gas, i.e. increase the yield of light oil products and save the energy consumption of solid-liquid separation;

⑤ can improve the operation stability, prolong the operation period and improve the catalyst efficiency;

⑥ can increase the overall thermal cracking conversion of heavy oil.

The hydrogenation reaction zone MR targeted for the production of hydrogen-donating hydrocarbons is described in detail below.

According to the invention, the stream SHS containing the hydrogen-donating hydrocarbon DS which is recycled is a stream or a separated stream of a hydrogen-donating hydrocarbon precursor stream SHSBF which is rich in bicyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons and is obtained by converting MRP (MRP) obtained as a hydrogenation reaction effluent in a hydrogenation reaction zone MR which aims at preparing the hydrogen-donating hydrocarbons; the hydrogenation reaction zone MR, which is targeted for the production of hydrogen-donating hydrocarbons, can be operated under any suitable conditions.

The hydrogenation stabilizing reaction process MR can adopt a granular catalyst bed layer (a down-flow fixed bed, an up-flow fixed bed and an up-flow micro-expansion bed) reaction mode, and the temperature is generally 280-440 ℃, the pressure is generally 6.0-20.0 MPa, and the volume space velocity of the hydrogenation catalyst MR-CAT is generally 0.05-10.0 hr^-1And the volume ratio of the hydrogen to the raw oil is 30: 1-3000: 1.

The hydrogenation stabilizing reaction process MR can adopt a moving bed or fluidized bed hydrogenation reaction mode using a particle catalyst, and the temperature is generally 280-440 ℃, the pressure is 6.0-20.0 MPa, and the volume space velocity of the hydrogenation catalyst MR-CAT is 0.05-10.0 hr^-1Reaction strip with hydrogen/raw oil volume ratio of 100: 1-1200: 1And (4) operating under the condition of one piece.

The hydrogenation stabilizing reaction process MR can even adopt a suspension bed hydrogenation reaction mode, and generally operates under the reaction conditions that the temperature is 280-440 ℃, the pressure is 6.0-20.0 MPa, the added hydrogenation catalyst is preferably an oil-soluble catalyst or a water-soluble catalyst with high dispersity, and the volume ratio of hydrogen to raw oil is 100: 1-1200: 1.

The aromatic hydrogenation partial saturation reaction in the hydrogenation reaction zone MR aimed at hydrogen supply hydrocarbon preparation of the present invention refers to a hydrogen-consuming reaction process in the presence of hydrogen and a suitable hydrogenation catalyst MR-CAT (catalyst having aromatic hydrogenation partial saturation function) for the occurrence of a hydrocarbon material SHSBF rich in bicyclic aromatic hydrocarbons and/or polycyclic aromatic hydrocarbons, wherein the minimum reaction depth has the minimum industrial significance: the hydrogenation reaction depth is determined according to the aromatic hydrocarbon component structure in the SHSBF and the expected aromatic hydrocarbon partial saturation degree, the higher the hydrogen supply hydrocarbon weight concentration value SHN in the hydrocarbon fraction with the conventional boiling point of 250-530 ℃ in the effluent MRP of the hydrogenation reaction is, the better the SHN is, the SHN is usually more than 6 wt%, and generally more than 10 wt%.

The hydrogenation reaction zone MR targeted for hydrogen supply hydrocarbon preparation has wide variation range of operation conditions due to different properties of raw materials (metal content, oxygen content, olefin content, sulfur content, nitrogen content, aromatic hydrocarbon content, distillation range and specific gravity) and different hydrogenation reaction (hydrodeoxygenation, hydrodesulfurization, hydrodenitrogenation and hydrogenation partial saturation) depths, and is determined according to specific process conditions.

For the reaction mode of the granular catalyst bed layer (downflow fixed bed, upflow micro-expansion bed), the hydrogenation reaction zone MR targeted for preparing the hydrogen-supplied hydrocarbon, the hydrogenation catalyst MR-CAT used can be one or the combination and the mixed loading of two or more kinds of hydrogenation refining catalysts, can be a special catalyst for specific raw materials, and can also be a hydrogenation refining catalyst which is used in the proper petroleum refining heavy diesel oil type or wax oil type hydrogenation refining process and has the functions of hydrogenation demetallization, hydrogenation deoxidation, hydrogenation desulfurization, hydrogenation denitrification, hydrogenation saturation and the like, and the combination thereof. The catalyst for the aromatic hydrocarbon hydrogenation partial saturation reaction process of producing the coal liquefaction solvent oil by using the coal liquefaction crude oil and the deep hydrofining catalyst of the coal tar light fraction can be generally used.

The hydrogenation reaction zone MR which aims at preparing hydrogen-supplying hydrocarbon uses a hydrogenation catalyst MR-CAT which at least comprises an aromatic hydrocarbon hydrogenation saturation catalyst, usually also comprises a hydrogenation demetalization catalyst and an olefin hydrogenation saturation catalyst (the position of the process is usually positioned before the bed layer of the aromatic hydrocarbon hydrogenation saturation catalyst).

Any make-up sulphur may be added to the hydrogenation reaction zone MR targeted for hydrogen-donating hydrocarbon production, as required, to ensure the minimum hydrogen sulphide concentration necessary in the reaction section, such as 500ppm (v) or 1000ppm (v), to ensure that the hydrogen sulphide partial pressure necessary for the catalyst does not fall below the minimum necessary value. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or carbon disulfide or dimethyl disulfide which generates hydrogen sulfide after contacting with high-temperature hydrogen.

The hydrogen supply solvent is used in the upflow hydrogenation reaction process of the material containing the coal tar pitch, so that free radicals can be rapidly eliminated, the hydrogen content of a thermal cracking product can be improved, and the thermal cracking reaction can be inhibited, namely the thermal cracking conversion rate is reduced; while the enhanced residuum quality of the upflow hydroprocessing reaction process of the coal tar pitch-containing material allows for further hydropyrothermal cracking (such as cyclic hydropyrocracking) to increase the overall thermal cracking conversion. As for the overall effect of the primary thermal cracking of the material containing the coal tar pitch and the secondary thermal cracking of the primary thermal cracking tail oil of the material containing the coal tar pitch, the hydrogen supply solvent can be used for effectively improving the overall hydrogenation thermal cracking conversion rate and effectively reducing the yield of the externally thrown solid tail oil.

For the invention, the main purpose of the upflow hydrogenation process of the material containing the coal tar pitch is to perform thermal cracking desulfurization or hydrodesulfurization and hydrodemetallation to a proper depth, and simultaneously perform hydrodemetallation to a certain degree, hydrogenation aromatic hydrocarbon partial saturation reaction of high boiling point hydrocarbon components to a certain degree, hydrogenation thermal cracking reaction, thermal cracking reaction and hydrogenation stabilization reaction of thermal cracking free radicals to produce a suspension bed hydrogenation product with low sulfur content, low metal content and more needle coke suitable components, therefore, the suspension bed hydrogenation product may need to be fractionated first, then the obtained hydrogenated coal tar pitch is separated into primary hydrogenation refined pitch and primary hydrogenation heavy pitch, and then the primary hydrogenation heavy pitch is returned to the suspension bed hydrogenation modification process for secondary processing, thereby improving the beneficial overall thermal cracking conversion rate. As for the overall effects of the primary hydrocracking of the coal tar pitch and the secondary hydrocracking of the tail oil of the primary hydrocracking of the coal tar pitch, the hydrogen supply solvent can effectively improve the overall hydrocracking conversion rate, effectively reduce the yield of the externally thrown solid tail oil and further improve the economical efficiency of the process.

The medium-low temperature coal tar is a coal tar product from coal pyrolysis or coal gas production or other processes, can be low-temperature coal tar from a low-temperature coking process (the carbonization temperature is lower than 700 ℃) or medium-temperature coal tar (the carbonization temperature is between 700 and 950 ℃) from a medium-temperature coking process or mixed oil of the medium-temperature coal tar and the medium-temperature coal tar, and generally contains a coal tar heavy oil component. As the properties of raw coal and the coking or gas-making process conditions are changed within a certain range, the properties of medium and low temperature coal tar are also changed within a certain range. The medium and low temperature coal tar of the invention has a specific gravity of 0.89-1.15, and usually has a metal content of 5-200 PPm, a sulfur content of 0.1-0.7% and a nitrogen content of 0.6-1.6%. The medium-low temperature coal tar of the invention sometimes has an inorganic water content of 0.2% to 5.0% and sometimes has an organic oxygen content of usually 2.5% to 11%, particularly 3.5% to 10%, more particularly 5% to 10%.

The high-temperature coal tar refers to high-temperature coal tar generated in the high-temperature coal coking process, and naphthalene in the high-temperature coal tar is usually recovered before the high-temperature coal tar enters a hydrogenation device due to the high price of the naphthalene component.

The invention can jointly process medium-temperature coal tar distillate or medium-temperature coal tar pitch with proper components and properties, such as the coal pitch of the medium-temperature coal tar generated in the fast pyrolysis process of the long-flame coal fluidized bed, and the composition and the properties of the medium-temperature coal tar are slightly different from those of the high-temperature coal tar.

The basic attributes of a suitable catalyst for the upflow hydro-upgrading process R10 for coal-containing tar oil R10F are described in detail below.

As mentioned above, the main purpose of the upflow hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F is to perform thermal cracking desulfurization or hydrodesulfurization and hydrodemetallization at a suitable depth, and simultaneously perform hydrodemetallization reaction to a certain extent, and simultaneously perform hydrogenation aromatics partial saturation reaction, hydrogenation thermal cracking reaction, thermal cracking reaction and hydrogenation stabilization reaction of thermal cracking radicals to a certain extent for high boiling hydrocarbon components, so as to produce a suspension bed hydrogenation product with low sulfur content, low metal content and more suitable components for needle coke, and therefore, naturally put forward the following requirements for the catalyst:

① adopts high-activity catalyst to reduce the use ratio, thereby reducing the carrying capacity in the refined asphalt;

② high dispersity, i.e. small particle size, increases the external surface area of unit weight of catalyst, reduces the use ratio, thereby reducing the carrying amount in refined asphalt;

③ the coking rate on the surface of the catalyst is low, and the coke is not deposited in the coke as much as possible;

④ the difference between the specific gravity of the catalyst and the specific gravity of the coal tar pitch is enough to ensure the sedimentation separation;

⑤ the ability to promote thermal cracking reactions is minimized.

The upflow hydrocracking reaction process CR of the inferior heavy hydrocarbon CRF of the present invention, which may be a hydrocracked product vacuum residue THC-VR of the coal tar pitch component, is described in detail below.

The upflow hydrocracking process CR for poor quality heavy hydrocarbon CRF generally includes thermal cracking reactions that generate thermally cracked radicals, hydrogenation stabilization reactions for the thermally cracked radicals, and generally also includes hydrofinishing reactions such as hydrogenation saturation reactions or partial hydrogenation saturation reactions for aromatics.

The inferior heavy hydrocarbon CRF upflow hydrogenation modification process CR of the present invention is described in detail below, with the implication that partial hydrogenation saturation of aromatics is the desired dominant reaction in the overall hydrogenation reaction.

The inferior heavy hydrocarbon CRF of the present invention, typically inferior heavy hydrocarbon, generally has the following meanings: under the condition of not using a hydrogen supply solvent and under the same other operating conditions (reaction pressure, reaction temperature, catalyst composition, addition amount, existence amount, retention time, hydrogen-oil volume ratio and reactor operating mode), the coking tendency of the inferior heavy hydrocarbon CRF in the hydrocracking reaction process is more serious than that of the fraction with the same boiling range in the coal-containing asphalt hydrocarbon oil R10F, namely the coking rate is higher or the coking conversion rate is lower than that of the hydrocracking reaction process; typically, the carbon residue values for hydrocarbons having a normal boiling point above 530 ℃ in poor quality heavy hydrocarbon CRF are higher than the carbon residue values for hydrocarbons having a normal boiling point above 530 ℃ in coal-containing bitumen hydrocarbon oil R10F.

Compared with the conventional hydrogenation thermal cracking reaction process, the up-flow hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF mainly aims to ensure that the inferior heavy hydrocarbon CRF has more hydrogenation saturation reactions and sufficient thermal cracking free radical hydrogenation stable reactions under the condition of the existence of a catalyst and a possibly existing hydrogen supply solvent, effectively reduce the carbon residue value of the inferior heavy hydrocarbon CRF and ensure that the hydrocarbons with the conventional boiling point higher than 530 ℃ become the raw materials of the hydrogenation thermal cracking reaction process with proper hydrogenation thermal cracking degree.

In the combined process of the present invention, the first reaction task of the up-flow hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF of the present invention is to perform hydrogenation carbon residue removal reaction of the inferior heavy hydrocarbon, i.e. hydrogenation saturation reaction of heavy aromatics, colloids and asphaltenes, and of course, hydrogenation refining reaction (including demetallization hydrogenation hydrogenolysis reaction, olefin hydrogenation saturation reaction, hydrogenation impurity removal (oxygen, sulfur and nitrogen) reaction, hydrogenation aromatic hydrocarbon saturation or partial saturation reaction, hydrogenation carbon residue removal reaction) or hydrocracking reaction can occur at the same time. Typical feedstock for the upflow hydro-upgrading reaction process CR of heavy hydrocarbon CRF of poor quality is the product residue of the upflow hydro-upgrading reaction process R10 of coal-containing asphaltic hydrocarbon oil R10F, which is typically enriched in the bottoms of a vacuum fractionator during product fractionation, such residue THC-VR typically containing added catalyst conversions such as molybdenum sulfide and the like, R10 product metal sulfides from coal-containing asphaltic hydrocarbon oil R10FL, and coke that may accumulate.

When poor quality heavy hydrocarbon CRF comprises hydrocarbons R10-VR with conventional boiling points above 530 ℃ from R10 product R10P from an upflow hydro-upgrading process of coal-containing bitumen hydrocarbon oil R10F, the carbon residue content of the heavy oil fraction R10-VR is generally higher than the carbon residue content of the same boiling range fraction of the feedstock R10F, or the liquid phase in the up-flow hydro-upgrading reaction process R10 of the hydrocarbon material is suitable for being used as a dispersion solution of colloid, asphaltene and liquid-phase coke in the hydro-thermal cracking reaction process of the poor quality heavy hydrocarbon CRF, therefore, the invention introduces the heavy hydrocarbon in the CR reaction product in the upflow hydrogenation modification reaction process of poor quality heavy hydrocarbon CRF into the second half of the upflow hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F for moderate hydrogenation thermal cracking reaction, the thermal cracking depth of hydrocarbon heavy hydrocarbon CRF of poor quality can be controlled simultaneously to prevent the production of a second liquid phase (bitumen phase) due to the yield of thermal condensate such as asphaltenes exceeding a limit caused by an excessively high thermal cracking rate.

In the up-flow hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF, when the supply of active hydrogen is not timely, the thermal cracking free radicals of colloid and asphaltene can produce condensation reaction to produce molecules or structure groups with larger molecular weight, and the final result of repeated dehydrogenation and condensation reaction is the generation of coke, which is, of course, a negative reaction needing to be inhibited or reduced.

The reactor form of the up-flow hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF can be any suitable form, and can be one or the combination of a plurality of suspended bed reactors and combined bed reactors of boiling beds and suspended beds.

The reactor used in the up-flow hydrogenation modification reaction process CR of the poor quality heavy hydrocarbon CRF can be 1 or 2 or more, the working mode of the reactor can be any suitable form, and the reactor is usually an up-flow type expanded bed reactor or an up-flow type expanded bed reactor with liquid product circulation, and the whole reaction area of a single up-flow type expanded bed reactor can be artificially divided into 2 or more reaction areas. The control mode of the inlet temperature of any reaction zone of the upflow type expanded bed reactor can be the regulation of the temperature or the flow rate of hydrogen, and can be the regulation of the temperature or the flow rate of oil products.

The reactor used in the up-flow hydrogenation modification reaction process CR of poor quality heavy hydrocarbon CRF may have volume ratio of liquid phase to gas phase (or vapor phase) in the reaction space, which may be the case of liquid phase being the main, and "actual volume of liquid phase/(actual volume of liquid phase + actual volume of gas phase)" in the reaction space is defined as the liquid phase fraction KL of the reaction space, and the fraction KL is usually greater than 0.5, generally greater than 0.65, even greater than 0.80, so as to form a practically enhanced liquid phase hydrogenation mode, and in order to keep the hydrogen partial pressure of the reaction space sufficiently high, it may be necessary to add hydrogen 2 or more times at different height positions of the reactor.

To adjust the reaction feed properties, or to control the liquid phase properties of the reaction process, a portion of the liquid feedstock R10F may be introduced into the upflow, hydro-modification reaction process CR of poor quality heavy hydrocarbon CRF.

To adjust the reaction feed properties, or to control the liquid phase properties of the reaction process, the intermediate liquid product of the upflow hydro-upgrading reaction process R10, e.g., a portion of the liquid product of the front reaction section, or the final liquid product, e.g., a portion of the liquid product of the back reaction section, of the coal tar pitch-containing hydrocarbon oil R10F may be introduced directly into the upflow hydro-upgrading reaction process CR of heavy hydrocarbon CRF of poor quality at high temperature and pressure.

In order to shorten the path of residual oil components in the upflow type hydrogenation modification reaction product R10P of the coal-containing asphalt hydrocarbon oil R10F entering the upflow type hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF, when distillate oil (hydrocarbon with the conventional boiling point lower than 530 ℃) contained in the liquid phase of the reaction product R10P is rich in a hydrogen donor or a hydrogen donor precursor, part of the liquid phase of the reaction product R10P can be directly introduced into the upflow type hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF, and at the moment, a tail oil high-pressure conveying short path is formed; when the liquid phase of the reaction product R10P contains distillate oil (hydrocarbons with conventional boiling point lower than 530 ℃) containing only a small amount of hydrogen donor or hydrogen donor precursor, it is usually necessary to obtain residual oil or mixed oil of residual oil and heavy wax oil in the produced oil separation and recovery system of the reaction product R10P, and the residual oil or mixed oil is introduced into the upflow type hydrogenation modification reaction process CR as poor heavy hydrocarbon, and at this time, a conventional long tail oil conveying path is formed.

An important object of the present invention is to reuse (recycle, serial recycle) the hydrogen donor solvent component in the reaction product CRP as required, so that the heavy oil component in the reaction product CRP can be subjected to combined hydrocracking in the upflow hydrocracking reaction process R10 (such as a rear reaction stage) of the coal-containing bituminous hydrocarbon oil R10F.

The coal tar pitch-containing hydrocarbon oil R10F refers to a hydrocarbon oil material containing coal tar pitch HDS; the coal tar pitch HDS generally has a hydrocarbon boiling point of > 370 ℃, generally > 400 ℃, in particular > 450 ℃, and contains hydrocarbon components such as colloids, asphaltenes, possibly solid particles, having a conventional boiling point of > 530 ℃.

The upflow type hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F refers to an upflow type expanded bed hydrogenation thermal cracking reaction process, such as a suspension bed hydrogenation thermal cracking reaction process, a suspension bed and fluidized bed combined hydrogenation thermal cracking reaction process and the like.

In the upflow expanded bed hydrocracking reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F, hydrodesulfurization reaction, hydrocracking reaction and thermal cracking free radical hydrogenation stabilization reaction of at least part of coal asphalt components HDS are carried out, and at least part of hydrocarbon products with lower sulfur content and lower boiling point are generated; the upflow hydro-upgrading reaction process R10 of the coal-containing tar oil R10F usually does not need to achieve the complete lightening of the single-pass reaction, and usually has a reasonably high single-pass conversion rate of 15% to 55%, so that a certain amount of unconverted coal tar components, such as 45% to 85% of unconverted coal tar components, exist in the hydro-upgrading reaction product R10P, and a hydro-thermal cracking product residual oil THC-VR is formed.

If from the perspective of component structure, the hydrogenated and thermally cracked product residual oil THC-VR is itself a residue of un-lightened macromolecules or a converted matter or a concentrated matter of macromolecules of a thermal condensate in the coal tar pitch component, compared with the same boiling range fraction of the coal tar pitch component HDS of a hydrogenated and thermally cracked precursor thereof, the colloid content, the asphaltene content and the carbon residue content in the hydrogenated and thermally cracked product residual oil THC-VR should not be significantly increased, such as the increase range is limited to be below 5-20%; in fact, it is desirable that the hydrocracked product residue, THC-VR, is itself a residue of unreduced macromolecules or a concentrate of macromolecules of the thermal condensate in the coal tar pitch component, typically having a reduced colloid content, asphaltene content, carbon residue content, such as at least 10% to 25% compared to the same boiling range fraction of the coal tar pitch component HDS, which is a hydrothermally cracked precursor thereof. According to experimental studies, such results limit the hydroconversion of the coal tar pitch HDS to typically 5% to 55%, typically 15% to 45%, and most preferably 20% to 35%.

In order to improve the comprehensive processing efficiency of the device, the hydro-thermal cracking reaction process R10 is preferably used for optimizing the single-pass conversion rate of the coal tar pitch component HDS in the coal tar pitch-containing hydrocarbon oil R10F; the excessive increase of the conversion per pass of the coal tar pitch component HDS in the coal tar pitch-containing hydrocarbon oil R10F inevitably increases the thermal condensation reaction of the super-macromolecules in the coal tar pitch component HDS, increases the quantity of the thermal condensation product colloid, asphaltene and liquid phase coke, increases the gas yield, increases the hydrogenation saturation depth of the hydrocarbons with the conventional boiling point lower than 370 ℃ to form the low-aromaticity hydrocarbons with low dissolving and dispersing capacity to the coal tar pitch, and generates the extraction action to concentrate the coal tar pitch, so that the increase of the quantity of the colloid, the asphaltene and the liquid phase coke and the reduction of the quantity of the suitable solvent oil of the colloid, the asphaltene and the liquid phase coke develop to the super-saturation degree or the critical saturation degree, which can cause the precipitation of the colloid, the asphaltene and the liquid phase coke from a stable colloid solution system to form a super-saturated asphalt phase, namely a second liquid phase, and cause the rapid coking in containers such as a reactor and the like, forcing the plant to shut down.

In fact, the scheme of the invention aims to produce high-quality needle coke raw oil, so that the single-pass conversion rate of the coal asphalt component HDS in the coal-containing asphalt hydrocarbon oil R10F is too high to increase the yield of light distillate oil and reduce the quantity of the target asphalt component, which is basically contradictory and inappropriate to the aim of the invention.

In fact, the scheme of the invention aims to produce more high-quality needle coke raw oil, so that under the condition that the single-pass conversion rate of the coal tar pitch component HDS in the coal tar pitch-containing hydrocarbon oil R10F is the same, and under the condition that the desulfurization rate and the thermal cracking rate are the same, the lower the hydrogenation amplitude is, the better the hydrogenation amplitude is, on one hand, the hydrogen consumption cost can be reduced, and on the other hand, the dehydrogenation task of the delayed coking thermal cracking reaction process for producing the needle coke in the later period can be reduced, so that in general, the higher the selectivity of the desulfurization reaction in the upflow expanded bed hydrogenation thermal cracking reaction process R10 is, the better the high-selectivity desulfurization reaction catalyst is, and the condition of important optimization operation is formed. The present invention preferably uses molybdenum-based catalysts, in particular nano-scale molybdenum-based catalysts.

On the premise of the fact that the increase of the conversion per pass of the coal-containing asphalt hydrocarbon oil R10F inevitably increases the amount of the thermal condensate colloid, the asphaltene and the liquid-phase coke, the method of avoiding the precipitation of the colloid, the asphaltene and the liquid-phase coke inevitably reduces the conversion per pass of the coal-containing asphalt hydrocarbon oil R10F or introduces external solvent oil. When the residual components after separating naphthalene and phenol from high-temperature coal tar are used as raw material oil in an upflow expanded bed hydrocracking reaction process R10, the weight ratio of light fraction (hydrocarbons with the conventional boiling point lower than 370 ℃) to coal tar pitch (hydrocarbons with the conventional boiling point higher than 370 ℃) is usually in the range of 35: 55-40: 50, namely 0.64: 1-0.8: 1, and the adjustment of the conversion per pass of the coal tar pitch-containing hydrocarbon oil R10F is free and passive within a certain range, so that the 'solvent oil (or hydrogen donor) for introducing appropriate external colloid, asphaltene and liquid phase coke and the use method thereof' become an important technical problem in relation to the feasibility, stability and economy of long-term operation of the upflow expanded bed hydrocracking reaction process R10 of the coal tar pitch-containing hydrocarbon oil R10F, and an important object of the invention is that the appropriate colloid for introducing external, Under the condition of solvent oil (or hydrogen donor) of asphaltene and liquid-phase coke, the existing solvent oil use method is improved to reduce the using amount or use cost of the solvent oil (or hydrogen donor), so that the reasonable reduction of the scale of R10 and a product separation system can obviously save investment, reduce hydrogen consumption and energy consumption, and improve the economy of R10.

The diluent KWS in the present invention refers to hydrocarbons entering the upflow hydro-upgrading reaction process R10, which can reduce the viscosity of the overall reaction liquid phase, or reduce the asphalt concentration, or increase the hydrogen supply capacity (coke inhibition) or reduce the reaction temperature, and it is preferable that the introduction of the diluent KWS does not adversely affect or affect the needle coke feedstock fraction, and therefore, the diluent KWS is preferably hydrocarbons having a normal boiling point of less than 320 ℃ and appearing as liquid as possible in the upflow hydro-upgrading reaction process R10, that is, the diluent KWS is preferably hydrocarbons having a normal boiling point of 250 to 320 ℃.

The diluent KWS can be an external supply stream, can be hydrocarbons with a proper boiling range, such as normal hydrocarbons with a boiling point of 250-320 ℃, obtained by separating a reaction product R10P in an upflow hydro-upgrading reaction process R10, and can be hydrocarbons rich in hydrogen-supplying hydrocarbons.

The upflow hydro-upgrading reaction process R10 of the coal-containing bituminous hydrocarbon oil R10F of the present invention is described in detail below.

The coal tar pitch hydrogenation reaction which may be performed by the upflow hydrogenation upgrading reaction process R10 of the coal tar pitch-containing hydrocarbon oil R10F of the present invention is described below.

In the upflow hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F, at least part of coal-containing asphalt hydrocarbon oil R10FL undergoes desulfurization reaction or hydrodesulfurization reaction, thermal cracking reaction and thermal cracking free radical hydrogenation stabilization reaction to generate at least part of hydrocarbon products with lower sulfur content and hydrocarbon products with lower boiling point; the upflow hydro-upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F usually cannot or is not expected to realize the total lightening of a single-pass reaction, namely, a reasonably high thermal cracking single-pass conversion rate is usually existed, so that a certain amount of unconverted coal asphalt exists in a hydro-upgrading reaction product R10P; the unconverted coal tar pitch is separated into refined pitch (light pitch) and heavy pitch in the pitch refining part, and the heavy pitch is used as tail oil; in order to reduce the amount of the discharged tail oil, the hydrocracking reaction process of the tail oil may need to be arranged to produce low-boiling products, and in order to simplify the overall flow and reduce the investment and energy consumption, the hydrocracking reaction process of the tail oil and the up-flow hydrogenation upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F may form a combined process, i.e., all the processes are combined or part of the processes are combined.

Although the upflow hydrogenation upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F is aimed at the desulfurization reaction or hydrodesulfurization reaction, thermal cracking reaction, and thermal cracking radical hydrogenation stabilization reaction of macromolecular hydrocarbons, since the hydrogenation catalyst generally used in the upflow hydrogenation upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F has a hydrofining function itself, and active hydrogen present can also induce the hydrofining reaction of hydrocarbon molecules, some hydrofining reactions (hydrodemetallization reaction, hydrodeoxygenation reaction, hydrodenitrogenation reaction, hydroaromatics partial saturation reaction, and olefins hydrogenation saturation reaction) must also occur in the upflow hydrogenation upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F.

In the upflow hydro-upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F, when the supply of active hydrogen is not timely, thermal cracking radicals of colloid and asphaltene undergo condensation reaction to produce molecules or structural groups with higher molecular weight, and the final result of repeated dehydrogenation and condensation reaction is the generation of coke, which is, of course, a negative reaction that needs to be suppressed or reduced.

The main application object of the invention is an up-flow hydrogenation upgrading reaction process R10 of coal-containing asphalt hydrocarbon oil R10F, the number of used reactors can be 1 or 2 or more, and the number of commonly used reactors is 2-4; the reactor operation mode of the upflow type hydro-upgrading reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F can be in any suitable form, and is generally an upflow type expanded bed reactor or an upflow type expanded bed reactor with liquid product circulation, and the whole reaction zone of a single upflow type expanded bed reactor can be artificially divided into 2 or more reaction zones. The control mode of the inlet temperature of any reaction zone of the upflow type expanded bed reactor can be adjusting the temperature or the flow rate of hydrogen, adjusting the temperature or the flow rate of oil products, and certainly, the introduction of a heat exchanger can also be used for heat exchange and cooling.

The upflow hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F uses a reactor, the volume ratio of liquid phase and gas phase (or vapor phase) in the reaction space of which can be the case of mainly liquid phase, and defines the 'actual volume of liquid phase/(actual volume of liquid phase + actual volume of gas phase') in the reaction space as the liquid phase fraction KL of the reaction space, the fraction KL is usually more than 0.45, usually more than 0.55, even more than 0.70, so as to form a practically enhanced liquid phase hydrogenation mode, and in order to keep the hydrogen partial pressure of the reaction space high enough, 2 times or more hydrogen addition at different heights of the reactor may be needed.

When the latter half reaction process R10B of the upflow type hydrogenation modification reaction process R10 of the coal-containing bituminous hydrocarbon oil R10F is combined with the heavy oil component CRPVR in the reaction product CRP of the upflow type hydrogenation modification reaction process CR of the inferior heavy hydrocarbon CRF, the residence time of the latter half reaction process R10B usually firstly meets the requirement of controlling the hydrocracking rate of the heavy oil component CRPVR, and the hydrocracking rate upper limit of the heavy oil component CRPVR is usually set to prevent the conversion rate per pass from being too high.

The reactor form of the upflow type hydrogenation modification reaction process R10 of the coal-containing asphalt hydrocarbon oil R10F can be any suitable form, and has various known forms, such as an upflow fixed bed reactor, an upflow type micro-expansion bed reactor, an upflow type moving bed reactor, an upflow type online replacement bed reactor, a fluidized bed reactor, a suspension bed reactor, a combined bed reactor of the fluidized bed and the suspension bed and the combination of specific forms thereof, and most of the coal-containing asphalt hydrocarbon oil R10F has industrial application cases, and forms relatively fixed technical characteristics.

The colloidal asphalt-like component contained in the petroleum-based residual oil is a dispersed phase generally existing in a supermolecular structure, analysis data shows that the colloidal asphalt-like component dispersed phase is a stable structure group with the molecular weight as high as thousands to tens of thousands or even hundreds of thousands, and the group contains a large number of polycyclic aromatic hydrocarbon units and contains elements such as metal, sulfur, nitrogen and the like, the main task of the lightening process is to dissociate, hydrogenate and saturate the macromolecules into small molecules which are ten times, hundred times or even thousands times less than the original carbon, obviously, the thermal cracking task of the process is dominant, which cannot be realized by only depending on hydrodemetallization, hydrodesulfurization, hydrodenitrogenation and hydroaromatic saturation, and the pre-hydrogenation processes such as hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, hydroaromatic saturation and the like of the petroleum-based residual oil are substantially the hydrofining process prepared for the subsequent hydrocracking reaction, otherwise, the hydrocracking catalyst active center in the conventional downflow fixed bed reactor is quickly covered due to metal deposition and quick coking, so that the operation period is too short, and the lowest economic operation period required by the industrial process cannot be maintained; even if the conventional processes of hydrodemetallization, hydrodesulfurization, hydrodenitrogenation, hydroaromatic saturation and the like in the downflow fixed bed reactor are used, the higher conversion rate cannot be achieved, because the problem of rapid and large-amount coking inevitably generated in the high-temperature thermal cracking process is difficult to overcome, which is determined by the thermodynamic property of the process; in order to overcome the defects of the fixed bed reactor system, the reactor forms are various forms such as an upflow fixed bed, an upflow micro-expansion bed, an upflow on-line replacement bed, an upflow strong expansion bed, namely a boiling bed, an upflow limit expansion bed, namely a suspension bed boiling and a downflow on-line replacement bed.

In the hydrocracking process of petroleum-based residual oil, the conversion rate of cracking the fraction with the conventional boiling point of more than 530 ℃ into the fraction with the conventional boiling point of less than 530 ℃ is usually 40-80 percent or even higher, in order to achieve such high cracking rate and improve the reaction speed, the high-temperature condition necessary for thermal cracking with stronger degree is inevitably used, the rapid coking of the catalyst active center is inevitable, in order to remove and replace the catalyst with the rapidly reduced activity caused by metal deposition and coking in the reactor bed layer, the technical personnel develop an up-flow type expansion bed reactor with the larger expansion ratio of the boiling bed layer and the suspension bed layer, and combine the subsequent hot high-pressure separator and the reactor into a combined device, greatly simplify the transfer system of the residual oil with high viscosity, easy foaming and easy solidification between the devices (between the reactor and the hot high fraction), improve the reliability of the system, and reduce the production cost of the petroleum-based residual oil, The safety and the heat insulation performance improve the uniformity of the temperature of the materials in the reactor and save the occupied area; the method has the advantages that the high conversion rate of residue oil boiling bed hydrocracking and suspension bed hydrocracking can not be achieved by a fixed bed reactor, endothermic cracking reaction and exothermic hydrogenation reaction are mixed to be beneficial to the utilization of reaction heat and the reduction of reaction temperature rise, and a large amount of thermal state reaction generated oil or intermediate reaction generated oil is recycled to directly heat raw oil so as to reduce the preheating temperature of the raw oil; in the unfavorable aspect, the expansion ratio of the catalyst bed layer is larger, compared with a fixed bed reactor, the complexity of the system is increased, the stability of the operation is reduced, and the engineering investment is greatly increased; the loss of the catalyst due to reasons other than coking is increased due to increased abrasion and collision of the catalyst; the quality of the product containing a portion of the fresh feed low conversion product is necessarily poor because of the severe back mixing of the catalyst and liquid phases present in the bed.

The residue OIL boiling bed hydrocracking industrialization technology comprises an H-OIL technology and an LC-FINING technology, in order to optimize and stably control the boiling state of a catalyst, a circulating OIL circulating pump system is arranged, a collector of circulating OIL is arranged above a catalyst bed layer in a reactor, namely, a high-temperature high-pressure separator which provides circulating OIL for a circulating pump and needs to be arranged at a high-elevation position is combined with a boiling bed reactor, the structure of the high-temperature high-pressure separator is simplified, but in order not to influence the fluidization state of the boiling bed, the arrangement position, the size and the form of the collector of the circulating OIL need to be carefully designed; usually, a collector of circulating oil is arranged right below a spherical seal head at the upper part of a reactor, a collector liquid guide pipe of the circulating oil is arranged in the reactor, and the liquid guide pipe has a certain rectification effect on the gas, liquid and solid multi-phase flow of a suspension bed or a boiling bed layer, so that the heat preservation and heat tracing problem of the liquid guide pipe is solved, and the adverse effect of the fluid flow in a flow guide pipe on the equipment stability of the reactor is weakened or eliminated; a hydrogenation reaction system of residue oil boiling bed, a catalyst intermittent discharge system and a catalyst intermittent feeding system are required to be arranged, and the system is complex, large in investment and complex in operation; another disadvantage of the residue ebullated-bed hydrogenation system is that part of the product is highly hydrogenated and saturated hydrocarbons, so the liquid phase of the product has poor ability to dissolve residual colloids and asphaltenes, and therefore, the conversion rate is low and the yield of tail oil is high, which limits the economy of the process to a certain extent; another disadvantage of the residue ebullated-bed hydrogenation system is that it is not possible to process inferior heavy residues with too high a content of carbon residue and too high a content of metals, because too high a content of metals makes the consumption of demetallization catalysts too large and makes the catalyst cost too large, and too high a content of carbon residue makes the conversion rate of the reaction process too low or rapid coking causes rapid shutdown, which limits the scope of application of the process.

The upflow fluidized bed hydrogenation technology has the technical key points that a catalyst bed layer is violently expanded by the upward flow of reaction materials (mainly liquid phase), the expansion rate of the catalyst bed layer is generally between 25 and 45 percent, and the catalyst bed layer can form the capability of damaging catalyst agglomeration and a wide area channel for freely discharging small particle impurities at the cost of losing the advantages of high activity, high interception rate and uniform material hydrogenation conversion depth of part of fixed bed hydrogenation catalysts, so that heavy oil with higher metal content and higher residual carbon content can be processed, the product quality of the heavy oil is reduced too much compared with the fixed bed technology, but the product quality of the heavy oil is better than that of a suspended bed; because the expansion power of the fluidized bed is mainly derived from carrying of liquid phase materials, a large amount of hydrogen is not suitable to be used in the process so as to prevent the volume efficiency of the liquid phase of the reactor from being too low, therefore, the exothermic effect in the reaction process cannot be too high, the fluidized bed hydrogenation technology is more suitable for processing paraffin-based or paraffin intermediate-base petroleum-based heavy oil, the macroscopic heat effect after the heat absorption amount of the thermal cracking reaction and the exothermic amount of free radical hydrogenation are offset is smaller, the total temperature rise of the reactor is lower, and the hydrogen consumption of the raw oil in unit weight is usually 1.4% -2.3%. However, even so, the deactivation rate of the catalyst is still too high, for which reason the average activity of the catalyst is maintained by periodically withdrawing part of the old catalyst with low activity and then supplementing part of the new catalyst with high activity, thus resulting in the high cost of consumption of the highly active hydrogenation catalyst, which is expensive, and in fact, it is not economical to process petroleum-based low-quality residues. Meanwhile, due to the characteristics of thermal reaction, the quality of hydrogenation tail oil is poor at high conversion rate, and only the hydrogenation tail oil can be used as fuel oil to vaporize the raw material, so that the conversion rate of the light weight of the raw material hydrogenated by the fluidized bed is usually 60-75 percent, namely the conversion rate is low. The granular catalyst used in the boiling bed hydrogenation technology is basically the same as the conventional fixed bed granular (preferably spherical) hydrofining catalyst, still belongs to a high-activity granular catalyst rich in a large number of internal pore channels and high internal surface area, and cannot meet the requirements of diffusion and hydro-conversion of low-quality residual oil macromolecules, the conventional boiling point is higher than 530 ℃ and has a huge molecular size and strong polarity, or the pore channels of the catalyst are blocked to lose activity, or the catalyst is adsorbed on the active center of the inner wall for a long time to generate a shielding effect, and under the condition of lacking active hydrogen, because the hydrogenation solid is difficult to desorb and desorb, a thermal condensation dominant reaction is generated, and the pore channels are blocked. The excessive catalyst deactivation speed results in unacceptable hydrogenation catalyst consumption cost, and more importantly, the great amount of reaction heat released by the great amount of saturated aromatic hydrogen consumption makes the boiling bed hydrogenation technology have no safety, the high temperature induced fast coking of colloid asphaltene also forms great amount of coking in the bottom distribution disc and central liquid circulation pipe of the reactor, and the equipment is forced to stop fast. If the upflow boiling bed hydrogenation technology is selected to process the inferior residual oil with high metal content and high carbon residue content, the results are necessarily that a large amount of coke is generated in the reactor, the operation period is too short, the reaction temperature cannot be controlled, namely unsafe, and the catalyst deactivation cost is surprisingly high, and the effects are proved by the industrial operation results of the trial-produced inferior heavy oil boiling bed hydrogenation device.

The development of residual oil suspension bed hydrocracking technology is based on the coal hydrogenation direct liquefaction technology of 20 th century 40 s, and is a process of residual oil thermal cracking reaction and thermal cracking free radical hydrogenation stable reaction which are caused under high temperature and high pressure by leading reaction under the condition of coexistence of hydrogen and fully dispersed catalyst or additive. In the hydrocracking reaction process of the suspension bed, the dispersed catalyst or additive is fine-particle powder which is suspended in reactants and can effectively inhibit the generation of coke. The residual oil suspension bed hydrogenation technology has almost no limit to the content of mechanical impurities of the raw materials, and can process asphalt and oil sand.

Typical residual oil suspension bed hydrocracking technologies with industrial operation performance include CANMET residual oil suspension bed hydrocracking process in Canada and EST residual oil suspension bed hydrocracking process in Eini, Italy. Other residual oil suspension bed hydrocracking technologies include BPVCC technology route from British oil company, BPVCC technology from British oil company, HDHPLUS technology from Venezuela national oil company (PDVSA), Uniflex technology from UOP in the United states, VRSH technology from Chevron in the United states, and the like.

In order to overcome the defects of the particle catalyst hydrogenation technology, the suspension bed hydrogenation technology thoroughly abandons the mode of using a huge amount of inner surfaces of particle catalysts as hydrogenation reaction sites, and the technical key points are that the outer surfaces of high-dispersity particle catalysts are used as the hydrogenation reaction sites, so that the problem of a diffusion path for colloid asphaltene to reach the hydrogenation reaction sites is thoroughly solved, the colloid asphaltene can be used for treating inferior heavy oil with higher metal content and higher carbon residue content, and certainly, the inferior heavy oil with extremely high metal content and extremely high carbon residue content is preferably treated by a coking process such as a delayed coking process; the bed expansion rate of the reaction space of the suspension bed hydrogenation reactor reaches the maximum value, and the addition amount of the solid catalyst is usually lower than 10 percent (based on the weight of the raw oil), thereby forming the advantages of 'having coke carrier capacity' and 'discharging free channel of suspended particle impurities'. However, in fact, the suspension bed hydrogenation reactor does not have the bed concept, the reaction space completely loses the advantages of high activity, high interception rate and uniform material hydrogenation conversion depth of the fixed bed hydrogenation catalyst, and the fixed bed hydrogenation catalyst has the dual characteristics of high liquid phase back mixing and high liquid phase short circuit, so that the product quality is greatly reduced compared with the fixed bed technology, and the suspension bed hydrogenation technology can only be used as a pretreatment process of poor oil, but cannot produce high-quality products.

The reaction efficiency of the catalyst surface of the suspension bed hydrogenation reactor strongly depends on the renewal frequency of the catalyst surface and the stable replacement rate of the reaction space, so the renewal means and the replacement means of the catalyst surface are important technical means which can not be lost and can improve the catalyst efficiency, and the existing reactor of the industrial heavy oil suspension bed hydrogenation device adopts a bubbling bed without a circulating pump, which is a huge technical defect, and the result is that: the internal back-mixing liquid phase quantity is uncontrollable, the internal back-mixing catalyst quantity (catalyst deposition quantity) is uncontrollable, the suitable particle size range of the catalyst is too narrow to be controlled, the liquid phase retention time is uncontrollable, the uncontrollable performance is stronger along with the enlargement of the diameter of the reactor, and the effects are proved by the industrial operation result of the trial production poor-quality heavy oil suspended bed hydrogenation device. The present invention recommends the use of a suspended bed reactor with liquid product circulation in order to achieve the desired renewal frequency of the catalyst surface and a stable rate of replacement of the reaction space.

The reaction efficiency of the catalyst surface of the suspension bed hydrogenation reactor is also influenced by the adsorption and occupation of polar impurities in the gas phase in the reactor, and a large amount of polar impurities such as H are generated in the coal tar hydrogenation process and the tar and coal co-refining process₂O、NH₃、CO、CO₂The catalyst can be strongly adsorbed on the surface of the catalyst to form a shielding effect, so that the CHEVRON company of the international well-known oil product technology supplier provides a scheme for arranging a gas-liquid separator in the middle of a reactor to discharge impurity gas in time and introduces high-purity hydrogen at the lower part of a subsequent suspension bed hydrogenation reactor, but the arrangement of the independent gas-liquid separator has large investment, difficult liquid level control and large operation risk; therefore, the project recommends that a 'gas short-flow' technology can be adopted, under the condition of not adding a gas-liquid separator, gas-liquid mixed phase materials containing gas are introduced into the space at the top of the suspension bed reactor for gas-liquid separation, gas phase is directly discharged, most of liquid phase enters the liquid phase reaction space through a circulating pipe, high-purity hydrogen material flow is introduced into the lower part of a subsequent suspension bed hydrogenation reactor, a gas phase environment with extremely low impurities is formed, meanwhile, the condition of high hydrogen volume concentration is formed, conditions are created for fully exerting the activity of the catalyst, and the method is favorable for reducing the total pressure of the device, improving the conversion rate per pass, reducing the thermal cracking gas-making reaction and reducing the thermal condensation reaction; the scheme for timely discharging the impurity gas also has the advantages of timely discharging the low-boiling-point hydrocarbon components and reducing the thermal cracking rate, and is favorable for improving the liquid yield and reducing the hydrogen consumption.

A typical heavy oil lightening reaction which occurs inside a suspension bed hydrogenation reactor for poor-quality heavy oil is essentially a series process of performing double bond hydrogenation of liquid-phase macromolecules into single bonds, cracking of the single bonds into free radicals and stable free radical hydrogenation in a liquid phase, a large number of free radicals are generated in the whole aggregation-state liquid phase at a high thermal cracking temperature (400-480 ℃) and are relatively uniformly distributed in the whole liquid phase space, the free radical hydrogenation is stabilized at the fastest speed for preventing thermal condensation, obviously, the purpose cannot be achieved by virtue of active hydrogen on the surface of a catalyst (because the probability of liquid-phase hydrocarbon molecules contacted by the catalyst is too low, the moving process of the active hydrogen can also be combined into inactive hydrogen molecules), preferably, the active hydrogen and the free radicals uniformly exist adjacently, and are synchronously released when the free radicals are generated, so as to realize high-efficiency active hydrogen supply. The timely addition of the hydrogen donor with proper boiling point can just over-meet the requirement, prevent thermal condensation and improve the retention rate of light products, and the effects are proved by the successful long-term operation results of the Shenhua coal hydrogenation direct liquefaction device which runs for 8 years and uses the hydrogen donor. For the heavy fraction with huge molecular size and strong polarity, which has the conventional boiling point higher than 530 ℃, if active hydrogen can not be provided timely, a large amount of thermal cracking free radicals of colloid and asphaltene can condense condensates larger than the cracking precursors thereof, so that the yield of hydrogenated thermal cracking distillate oil (hydrocarbons with the conventional boiling point lower than 530 ℃) is reduced, and even thermal condensates such as coke or coke precursors which are dissolved and carried by the liquid phase in the reaction process are generated to cause rapid shutdown of the device, and the effects are proved by a large number of experimental results. The invention uses the operation mode of sufficient hydrogen donor, aims to provide the raw material residual oil with more rigorous thermal cracking conversion rate or processing property by timely providing sufficient active hydrogen to inhibit coking, enlarges the application range of the process and improves the operation stability and the economical efficiency of the process.

Possible uses of the hot high pressure separation process or the warm high pressure separation process of the present invention are described in detail below with respect to the XHBM process.

In the gas stripping process XHBM, the countercurrent contact separation times of the liquid hydrocarbon W material and the stripping hydrogen XBH are as follows: generally 1 to 8 times, usually 2 to 4 times; the quantity of the stripping hydrogen XBH is determined according to the requirement of the separation target of the XHBM component in the stripping process; the operating pressure of the XHBM of the stripping process, typically slightly below that of its feed; the operation temperature of the gas stripping process XHBM is determined according to the requirement of the gas stripping process XHBM component separation target, and is usually 180-480 ℃, and is usually 250-440 ℃.

The working mode of the upflow reactor can be selected as follows:

① suspension bed hydrogenation reactor;

② ebullated bed hydrogenation reactor, which discharges the catalyst with reduced activity from the bottom of the bed in a batch mode, and replenishes fresh catalyst from the upper part of the bed in a batch mode to maintain the catalyst inventory in the bed;

③ combined hydrogenation reactor of suspension bed and boiling bed

④ micro-expanded bed.

The flow form or type of the upflow hydro-upgrading reaction process R10 of the coal-tar pitch-containing hydrocarbon oil R10F is described in detail below.

The reaction separation section of the present invention refers to a process including a hydro-upgrading reaction process (or referred to as a reaction section) of the coal tar pitch-containing hydrocarbon oil R10F and a separation process (or referred to as a separation section) of heavy oil hydrocarbon components and lower boiling point hydrocarbon components in the hydro-upgrading reaction product; the process for separating the heavy oil hydrocarbon component from the lower boiling point hydrocarbon component may be a process for separating the residual oil from the wax oil component (usually including a vacuum fractionation process), a process for separating the heavy wax oil component from the light wax oil component (usually including a vacuum fractionation process), or a process for separating the diesel oil from the wax oil component (which may or may not include a vacuum fractionation process).

The reaction separation process of the present invention comprises a first hydro-upgrading reaction process of the coal tar pitch-containing hydrocarbon oil R10F and a first separation process of heavy oil hydrocarbon components and lower boiling point hydrocarbon components of the first hydro-upgrading reaction product, and may include a recycling process in which unconverted residual oil or modified oil thereof discharged from the first separation process (usually including a vacuum fractionation process) is recycled to the first hydro-upgrading reaction process for recycling hydro-upgrading.

The existing suspension bed hydrogenation modification or hydrogenation thermal cracking reaction separation methods of heavy oil or residual oil belong to a reaction separation process mostly, wherein the residual oil suspension bed hydrogenation cracking reaction separation method with industrial operation performance comprises a Canadian CANMET residual oil suspension bed hydrogenation thermal cracking process (which is later integrated into Uniflex technology of UOP company in America) and an EST residual oil suspension bed hydrogenation thermal cracking process of Italy Eny company. Other residual oil suspension bed hydrocracking reaction separation methods include BPVCC technology of British oil company, HDHPLUS technology of Venezuela national oil company (PDVSA), VRSH technology of Chevron in the United states and the like.

If a thermal cracking system of the circulating heavy oil containing solid particles and unconverted residual oil components is arranged, in a first reaction section, in order to prevent the circulating residual oil which is carried by raw oil and is difficult to thermally crack, thermal condensation coke or coke precursors from being excessively accumulated to form high-concentration asphaltene to deteriorate the liquid phase property of the first reaction section (increase the carbon residue value, increase the viscosity value and reduce the average hydrogen content), in order to prevent sulfide solids, other ashes, catalyst solid particles and other solids generated by metals carried by the raw oil from being excessively accumulated to form high-concentration solid-containing circulating residual oil, a certain ratio of vacuum residue discharged by the first separation section is required to be discharged; compared with the fresh residual oil UR10F, the discharged vacuum residual oil of the first separation section has higher solid particle carrying rate, higher asphaltene concentration and more difficult hydrocracking cracking of the asphaltene.

The primary hydrogenated coal pitch hydrogenated by the suspension bed is separated into primary hydrogenated refined pitch (light pitch) and primary hydrogenated heavy pitch, if the primary hydrogenated heavy pitch is recycled to the upflow type hydrogenation modification reaction process R10, the amount of the heavy pitch in the liquid phase of the upflow type hydrogenation modification reaction process R10 is greatly increased, and sufficient medium pitch and light fraction must be correspondingly present for dissolving and dispersing the primary hydrogenated heavy pitch, so that the size of the upflow type hydrogenation modification reaction process R10 is greatly increased and is uneconomical. Therefore, the invention uses the operation mode of two reaction separation sections, the heavy primary hydrogenated asphalt enters the second section hydrogenation modification reaction process to obtain the second section hydrogenation modified product, the second section hydrogenation modified product is separated to obtain the secondary hydrogenated asphalt, and the secondary hydrogenated coal asphalt is separated into the secondary hydrogenated refined asphalt (light asphalt) and the secondary hydrogenated heavy asphalt, usually, part or all of the secondary hydrogenated heavy asphalt can be discharged as the final discharged heavy asphalt, and part of the second section hydrogenated heavy asphalt can be recycled to enter the second section hydrogenation modification reaction process or the first section hydrogenation modification reaction process according to the needs. In order to suppress possible thermal condensation reactions, the second stage of the hydro-upgrading reaction employs a sufficient amount of hydrogen-donating solvent.

The invention can use a sectional type heavy oil suspension bed hydrogenation thermal cracking reaction separation method.

The two reaction separation processes comprise a first reaction separation section and a second reaction separation section which takes the discharged vacuum residue US10-VR-OUT of the first separation process US10 of the first reaction separation section UT1 as raw oil UR 20F. A second reaction separation process comprising a second hydrocracking reaction process of raw oil UR20F and a second separation process (usually comprising vacuum fractionation) of heavy oil components and lower boiling hydrocarbon components of the second hydrocracking reaction product, which may include a short circulation process for circulating the unconverted residual oil or modified oil thereof discharged from the second separation process (usually comprising vacuum fractionation) back to the second hydrocracking reaction process for cyclic hydrocracking, in order to prevent the accumulation of sulfide solids, ash, solid particles of catalyst, etc. generated by metals carried by raw oil UR20F, during the second hydrocracking reaction, the second separation process (usually including the second vacuum fractionation process) of the second reaction separation section must discharge discharged heavy oil containing solid particles, such as vacuum residue US20-VR-OUT, mainly composed of unconverted residue. In order to simplify the process, the gas phase material flow of the second reaction process can be recovered through the first reaction process or combined with the gas-containing material of the first reaction process, the gas phase material flow of the separation process of the second reaction product can be recovered through the gas-containing material of the separation process of the first reaction product, and the unconverted residual oil of the second reaction process can be recycled to the first reaction process to reduce the consumption of the catalyst, thereby forming the combined process.

The three reaction separation section processes comprise a first reaction separation section and a second reaction separation section, and also comprise a third reaction separation section which takes the discharged vacuum residue US20-VR-OUT of a second section separation process US20 of the second reaction separation section UT20 as raw oil UR 30F. A third reaction separation process, a third hydrocracking reaction process UR30 containing raw oil UR30F and a third separation process (usually including vacuum fractionation) for separating wax oil component and residual oil component of the third hydrocracking reaction product, which can include a short circulation process for circulating the unconverted residual oil or modified oil thereof discharged from the third separation process (usually including vacuum fractionation) back to the third hydrocracking reaction process UR30 for circulating hydrocracking, in order to prevent the accumulation of sulfide solids, ash, solid particles of catalyst, etc. generated by metals carried in raw oil UR30F, and solid particles existing in the third hydrocracking reaction process, the third separation process (usually including the third vacuum fractionation process) of the third reaction separation section must discharge discharged vacuum residue US30-VR-OUT containing solid particles and mainly composed of unconverted residue. In order to simplify the process, the gas phase material flow of the third section of reaction process can be recovered through the upstream reaction section reaction process or jointly with the gas-containing material of the upstream reaction section reaction process, the gas phase material flow of the third section of reaction product separation process can be jointly recovered through the gas-containing material of the upstream reaction section reaction product separation process, and the third section of unconverted residual oil can be recycled to the upstream reaction section reaction process to reduce the consumption of the catalyst, so that the combined process is formed.

The present invention, if necessary, can constitute a process comprising four or more reaction separation stages, and generally, satisfactory results can be obtained by using two reaction separation stages.

It may be necessary to first fractionate the hydrogenation product of the suspension bed, then separate the hydrogenated coal pitch into a first hydrorefined pitch and a first hydrogenated heavy pitch, and then return the first hydrogenated heavy pitch to the suspension bed hydrogenation upgrading process for secondary processing, thereby increasing the beneficial overall thermal cracking conversion rate. As for the overall effects of the primary hydrocracking of the coal tar pitch and the secondary hydrocracking of the tail oil of the primary hydrocracking of the coal tar pitch, the hydrogen supply solvent can effectively improve the overall hydrocracking conversion rate, effectively reduce the yield of the externally thrown solid tail oil and further improve the economical efficiency of the process.

In fact, the upflow hydro-upgrading reaction process R10 of the coal-containing tar oil R10F has about 8 key problems:

① prevent coking of furnaces containing coal tar pitch hydrocarbon oils R10F, which involves the problem of how to lower the furnace exit temperature, and also involves the problem of how to use coking inhibitors such as hydrogen donor solvents;

② inhibit thermal condensation of the initial thermal cracking process of the coal-containing bituminous hydrocarbon oil R10F, which relates to the problem of how to supply active hydrogen rapidly and also to the problem of how to use a hydrogen-supplying solvent;

③ preventing the solution system from generating a super saturated asphalt phase, namely a second liquid phase at the end of the thermal cracking reaction process, which relates to the problem of reasonably controlling the conversion per pass and also relates to the problem of timely discharging light saturated hydrocarbon to prevent the light saturated hydrocarbon from reducing the aromaticity of the solution;

④ the heavy asphalt component is properly modified to improve the hydrogen content, improve the use value and improve the process economy, which relates to the problem of optimizing the conversion per pass and also relates to the problem of how to use the hydrogen-supplying solvent;

⑤ reduces the cost of the cycle process of the tail oil hydrocracking and improves the process economy, which relates to the combination method of the tail oil modification and cycle hydrocracking reaction process and the fresh heavy oil suspension bed hydrocracking reaction process, and also relates to the problem of how to use the hydrogen supply solvent efficiently;

⑥ if hydrogen donor solvent is used, the method is adopted to shorten the circulation path and reduce the use cost;

⑦ if hydrogen donor solvent is used, the method is adopted to reduce the pollution degree to the needle coke raw material and improve the use efficiency;

⑧ upflow hydro-upgrading reaction process R10, under the operation target of controlling proper hydrodesulfurization conversion rate, hydrogenation thermal cracking conversion rate and prolonging operation period, how to reduce the concentration of colloid asphaltene in liquid phase solution and prevent the colloid asphaltene from separating out to become second liquid phase, which relates to the problem of how to form high-performance cycle solvent oil (strong coking resistance, rich hydrogen supply capacity and dissolving capacity to colloid asphaltene).

The present invention has been developed in response to the present teachings, and in particular, in response to the present teachings, a means for alleviating or eliminating some of the problems set forth above is provided.

The invention can be combined with any other suitable suspension bed hydro-thermal cracking process of the coal-containing asphalt hydrocarbon oil R10F to form a corresponding combined process, and the possible combined technologies are at least:

① in the process of hydrogenation of fresh coal-containing asphalt hydrocarbon oil R10F in a suspension bed, a liquid product circulation reactor is used to transfer the heat of the initial hydrogenation modification reaction to the raw oil, so as to reduce the preheating temperature to 360-400 ℃, prevent the furnace tube of the feeding heating furnace from coking, and also prevent coking by using a certain amount of hydrogen supply solvent;

② the catalyst with high dispersion and high activity such as molybdenum catalyst can be used, and hydrogen donor solvent can be used to rapidly provide active hydrogen and inhibit the thermal condensation of the initial hydro-upgrading process of raw oil, which is an essential active scheme and can significantly improve the properties of the first hydro-upgrading tail oil;

③ preventing the solution system from generating a super-saturated asphalt phase, i.e. a second liquid phase, in the last stage of the hydro-upgrading reaction process, which requires reasonably controlling the conversion per pass, e.g. 15-35%, using a liquid product circulating reactor to improve the aromaticity of the liquid phase hydrocarbon at the outlet of the reactor, and simultaneously adopting the reaction zone at the end of the reactor to inject stripping hydrogen to discharge light hydrocarbon with high saturation in time to prevent the reduction of the aromaticity of the solution and the reduction of the liquid yield due to over-circulating thermal cracking, and reducing the existence of excessive hydrogen supply solvent, thereby improving the thermal cracking rate and reducing the thermal cracking rate of the hydrogen supply solvent;

④ may require the use of highly aromatic wax oil, added to the reaction section of the second reaction section, to safely control the asphaltene concentration in the liquid phase within the reactor to a safe range and to safely carry unconverted asphaltenes out of the reactor;

⑤ can adopt batch feeding technique to reduce peak value of active hydrogen consumption;

⑥ the combination method of the tail oil circulation hydrogenation modification reaction process and the fresh material suspension bed hydrogenation thermal cracking reaction process can reduce the cost of the tail oil circulation hydrogenation modification reaction process and improve the process economy, because the secondary or even multiple serial circulation of the hydrogen supply solvent is formed, the hydrogen supply speed and the total hydrogen supply capacity of the hydrogenation area of the circulation path of the hydrogen supply solvent can be obviously improved, and the recycling efficiency is improved;

⑦ provides a highly efficient circulation path for diluting hydrocarbon or hydrogen donor solvent, which can shorten the length of the circulation path, reduce the investment and energy consumption of the circulation path, reduce the pollution degree of the hydrogen donor solvent, and effectively reduce the circulation cost;

⑧ the special reactivation step of the hydrogen donor solvent can be combined with the distillate oil hydrogenation upgrading step, the process integration level is further improved, and the investment and energy consumption of the overall process are reduced;

⑨ upflow hydrogenation modification reaction process R10 uses suspension bed hydrogenation reactor, preferably liquid product circulation suspension bed hydrogenation reactor;

⑩ the light oil is processed together with the catalytic cracking process or coking process of heavy oil in the whole process of heavy oil processing.

The invention can form various combined processes by changing the flow forms of each reaction section or separation section, by jointly processing other hydrocarbon-containing materials suitable for joint processing and by combining the subsequent processing methods of hydrocarbon oil in various thermal high-molecular gases.

In the present invention, diluent oil or a hydrogen donor solvent may be used in each reaction stage.

The oil product obtained in the second hydrogenation reaction process R20 of the invention may include naphtha (conventional boiling range 60-180 ℃ cut) R20P-Y-N01, first light diesel oil (conventional boiling range 180-220 ℃ cut) R20P-Y-N02, second light diesel oil (conventional boiling range 220-265 ℃ cut) R20P-Y-N03, heavy diesel oil (conventional boiling range 265-350 ℃ cut) R20P-Y-N04, light wax oil (conventional boiling range 350-480 ℃ cut) R20P-Y-N05, heavy wax oil (conventional boiling range 480-530 ℃ cut) R20P-Y-N06, residual oil (conventional boiling point higher than 530 ℃ hydrocarbon) R20P-Y-N07, the names are only name of one, and can also be called light oil (conventional boiling range 60-180 ℃ cut) R20-Y-N01, and first wash oil (conventional boiling range 180 ℃ R220-180 ℃ Y220-N02-Y-N01), the names are only name of one name of light oil (conventional boiling range 60-180 ℃ cut) R20-Y-N638, The second wash oil (the fraction with the conventional boiling range of 220-265 ℃) R20P-Y-N03, anthracene oil (the fraction with the conventional boiling range of 265-350 ℃) R20P-Y-N04, light asphalt (the fraction with the conventional boiling range of 350-480 ℃) R20P-Y-N05, medium asphalt (the fraction with the conventional boiling range of 480-530 ℃) R20P-Y-N06 and heavy asphalt (the hydrocarbon with the conventional boiling point higher than 530 ℃) R20P-Y-N07.

According to the naphtha (the fraction with the conventional boiling range of 60-180 ℃) R20P-Y-N01 in the product obtained by the method, deep hydrofining such as desulfurization and denitrification can be performed according to needs, benzene ring hydrogenation saturation reaction is expected to occur as little as possible, and the hydrofined naphtha (the fraction with the conventional boiling range of 60-180 ℃) can be used as a catalytic reforming raw material to prepare aromatic hydrocarbon.

The first light diesel oil (the fraction with the conventional boiling range of 180-220 ℃) R20P-Y-N02 or the hydrogenation stable oil thereof in the product obtained by the invention is not suitable for entering an upflow hydrogenation modification reaction process R10 andor R20 generally, because the boiling point is too low and the first light diesel oil is easy to vaporize and is difficult to serve as a liquid phase solvent component; if entering the upflow hydro-upgrading process R10 andor R20, the products of the further thermal cracking reaction are produced in large quantities of gas and are uneconomical; therefore, unless the value of the gas hydrocarbon is huge, the first light diesel oil (the fraction with the conventional boiling range of 180-220 ℃) R20P-Y-N02 is generally not suitable to enter an upflow hydro-upgrading reaction process R10 and/or R20 or a special hydro-thermal cracking process or a hydro-cracking process or other thermal cracking processes for processing, and can generally enter a hydrofining reaction process for desulfurization and denitrification to produce clean light diesel oil.

In the product obtained by the combined process of the invention, the second light diesel oil (the fraction with the conventional boiling range of 220-265 ℃) R20P-Y-N03 is hydrogenated and stabilized oil, which is hydrogen-supplying solvent oil with proper boiling point and excellent hydrogen-supplying capability required by an upflow type hydrogenation modification reaction process R10 andor R20, and in addition, for an upflow type hydrogenation modification reaction process R10 andor R20, the second light diesel oil or the hydrogenation stabilized oil thereof plays a role of a liquid phase basic solvent component in the front reaction process of an upflow type hydrogenation modification reaction process R10 andor R20, but most of the second light diesel oil or the second light diesel oil is vaporized in the rear reaction process of the upflow type hydrogenation modification reaction process R10 andor R20, and the residual resources exist in the up-flow type hydrogenation modification reaction process R10 andor R20, so the second light diesel oil (the fraction with the conventional boiling range of 220-265 ℃) R20-Y-N03 or the hydrogenation stabilized oil thereof, part of the light hydrogen-donating solvent oil is usually used as the light hydrogen-donating solvent oil for the upflow hydrogenation upgrading reaction process R10 andor R20, and part of the light hydrogen-donating solvent oil is used as the hydrogenation upgrading raw material for the hydrogenation upgrading reaction process to produce the final product.

The heavy diesel oil (fraction with the conventional boiling range of 265-350 ℃) R20P-Y-N04 in the product obtained by the combined process of coal hydrogenation direct liquefaction has hydrogenation-stabilized oil products, is hydrogen-supply solvent oil with proper boiling point and excellent hydrogen supply capability which is most needed in the upflow type hydrogenation modification reaction process R10 andor R20, and in addition, the heavy diesel oil or the hydrogenation-stabilized oil thereof plays a role of a liquid-phase basic solvent component in the whole flow of the upflow type hydrogenation modification reaction process R10 andor R20 in the upflow type hydrogenation modification reaction process R10 andor R20, and generally belongs to a main product of the upflow type hydrogenation modification reaction process R10R 20 due to the existence of residual resources in the upflow type hydrogenation modification reaction process R10 andR 20, so that the heavy diesel oil (fraction with the conventional boiling range of 265-350 ℃) R20P-Y-N04 or the hydrogenation-stabilized oil thereof is partially used as the heavy hydrogen-supply solvent oil used in the upflow type hydrogenation modification reaction process R10 andor R20, and part of the raw materials is used as hydrogenation upgrading raw materials for producing final products in the hydrogenation upgrading reaction process.

The light wax oil (the fraction with the conventional boiling range of 350-480 ℃) R20P-Y-N05 in the product obtained by the invention is not suitable for being returned to the secondary hydrogenation of R10 and/or R20 in the upflow hydrogenation modification reaction process as long as the impurity content meets the requirement of being used as a needle coke raw material. According to the combined process, the light wax oil (the fraction with the conventional boiling range of 350-480 ℃) R20P-Y-N05 or the hydrogenation stable oil product thereof in the product obtained by directly liquefying coal through hydrogenation can be returned to the R10 and/or R20 secondary hydrogenation in the upflow hydrogenation modification reaction process according to the needs.

Heavy wax oil (fraction with a conventional boiling range of 480-530 ℃) R20P-Y-N06 in the product obtained by the method is not suitable for returning to an upflow hydrogenation modification reaction process R10 and/or R20 for secondary hydrogenation as long as the impurity content meets the requirement of being used as a needle coke raw material. According to the combined process, the light wax oil (the fraction with the conventional boiling range of 350-480 ℃) R20P-Y-N05 or the hydrogenation stable oil product thereof in the product obtained by directly liquefying coal through hydrogenation can be returned to the R10 and/or R20 secondary hydrogenation in the upflow hydrogenation modification reaction process according to the needs. In general, heavy wax oil (a conventional fraction with a boiling range of 480-530 ℃) R20P-Y-N06 carries a small amount of solid particles and belongs to a material with high carbon residue content and serious hydrogen deficiency, and excessive thermal cracking generates thermal condensate and even forms coke.

Because the conventional boiling point residual oil (hydrocarbons with conventional boiling point higher than 530 ℃) R20P-Y-N07 in the product obtained by the invention is usually present in the heavy asphalt stream at the bottom of the vacuum tower, the discharge system is not recycled for processing, and of course, part of the residual oil can be recycled back to the upflow hydro-upgrading reaction process R10 andor R20 according to the needs.

As mentioned above, the main object of the present invention is to produce a hydroupgraded asphalt component suitable as a light asphalt as a raw material of needle coke, and therefore, in the separation and fractionation process of the product R20P of the upflow hydroupgrading reaction process R20, the cutting schemes of the different fractions having a normal boiling point higher than 350 ℃ can be adjusted as required, such as a light fraction separated into a normal boiling range of 350 to 400 ℃ and a bottoms oil mainly composed of a remaining fraction having a normal boiling point higher than 400 ℃, a light fraction separated into a normal boiling range of 350 to 450 ℃ and a bottoms oil mainly composed of a remaining fraction having a normal boiling point higher than 450 ℃, a bottoms oil separated into a normal boiling range of 350 to 500 ℃ and a bottoms oil mainly composed of a remaining fraction having a normal boiling point higher than 500 ℃, of course, a bottoms oil mainly composed of a remaining fraction having a normal boiling point higher than 350 ℃ can be directly obtained, the separation scheme needs to consider the feasibility and stability of the operation process of extracting the needle coke raw material, the fluidity of tower bottom oil and other related technical problems.

The stripping process 1HBM of the thermal high-pressure separation process S10 of the second hydrogenation reaction effluent R20P of the present invention is described in detail below.

In the stripping process 1HBM, the countercurrent contact separation times of liquid hydrocarbon R20P-L and stripping hydrogen 1BH are as follows: generally 1 to 8 times, usually 2 to 4 times; the quantity of stripping hydrogen 1BH is determined according to the requirement of a 1HBM component separation target in the stripping process; the operating pressure of the stripping process 1HBM is slightly lower than that of the second hydrogenation reaction process R20; the operating temperature of the 1HBM in the gas stripping process is determined according to the requirement of the separation target of the 1HBM component in the gas stripping process, and is usually 220-400 ℃, and is usually 280-380 ℃.

The hydro-upgrading reaction process R88 using a fixed bed hydrogenation reactor of the present invention is described in detail below.

The hydrogenation upgrading reaction process R88, the number of fixed bed reactors used can be 1 or 2 or more; the operation mode of the catalyst bed layer of the hydrogenation upgrading reaction process R88 can be in any suitable form, can be a combination of two or more different types of reactors, and can be a down-flow fixed bed reactor, an up-flow fixed bed reactor or an up-flow micro-expansion bed, and the operation mode of the catalyst bed layer is generally a down-flow fixed bed. The hydrogenation upgrading reaction process using the fixed bed hydrogenation reactor uses 1, 2 or more fixed bed catalyst beds, and the inlet temperature of the second and subsequent catalyst beds can be controlled by using cold hydrogen or cold oil.

The hydrogenation upgrading reaction process R88 of the fixed bed hydrogenation reactor uses hydrogenation upgrading catalysts which can be 1, 2 or a series combination of a plurality of types of hydrogenation upgrading catalysts, and the hydrogenation activity of the downstream hydrogenation upgrading catalyst is generally equal to or higher than that of the upstream hydrogenation upgrading catalyst along the flow direction of the reactant flow.

In the hydrogenation upgrading reaction process R88 of the fixed bed hydrogenation reactor, the volume ratio of the liquid phase to the gas phase (or vapor phase) in the catalyst bed of the reactor is defined as the liquid phase fraction KL, which may be greater than 0.75, even greater than 0.95, in order to keep the hydrogen partial pressure in the hydrogenation upgrading catalyst bed sufficiently high, and it may be necessary to add hydrogen at the inlet of each upgrading catalyst bed.

The characteristic parts of the present invention are described in detail below.

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

the reaction space of the second hydrogenation reaction process R20 may comprise 2 or more sub-hydrogenation reaction zones operated in series, in this case, the stream containing at least a part of normal liquid hydrocarbons based on the reaction effluent of the upstream sub-hydrogenation reaction zone enters the downstream adjacent sub-hydrogenation reaction zone, the first sub-hydrogenation reaction zone R201 of the second hydrogenation reaction process R20 obtains a reaction effluent R201P, the stream R201PX containing at least a part of hydrogenation product oil R201PO based on the reaction effluent R201P enters the second sub-hydrogenation reaction zone R202 of the second hydrogenation reaction process R20, and the reaction effluent of the last sub-hydrogenation reaction zone is used as the second hydrogenation reaction effluent R20P;

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the operating conditions of the second hydrogenation reaction process R20 can be as follows: the temperature is 280-440 ℃, the pressure is 6.0-30.0 MPa, and the volume ratio of hydrogen to raw oil is 300: 1-4000: 1The weight of the added hydrogenation catalyst R20C is 0.001-8.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.1-10.0 hr^-1；

In the present invention, the operating conditions may be:

first hydrogenation reactionThe operating conditions of process R10 were: the temperature is 350-460 ℃, the pressure is 17.0-23.0 MPa, the volume ratio of hydrogen to raw oil is 50: 1-2000: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-5.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.2-2.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.25 to 2.5 percent;

In the present invention, the operation targets may be:

① solvent-settling process comprising distillation of a light liquid phase or, if present, a heavy liquid phase,

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

The general control principle of the gas phase hydrogen sulfide concentration in the hydrogenation reaction process of the present invention is described in detail below.

Any make-up sulfur may be added to the hydrogenation process requiring make-up sulfur, as desired, but is typically added to the inlet of the most upstream hydrogenation process for use of sulfur in series to ensure the minimum hydrogen sulfide concentration necessary for the hydrogenation process, such as 500PPm by volume or 1000PPm by volume or 3000PPm by volume, to ensure that the hydrogen sulfide partial pressure necessary for the catalyst is not less than the minimum necessary. The supplementary sulfur may be hydrogen sulfide or a material which can be converted into hydrogen sulfide and has no adverse effect on the hydroconversion process, such as hydrogen sulfide-containing gas or oil, or carbon disulfide or dimethyl disulfide or sulfur (such as liquid sulfur) which generates hydrogen sulfide after being contacted with high-temperature hydrogen. When the amount of hydrogen sulfide in the gas phase of the hydrogenation reaction processes R20 and R70 meets the requirement, the sulfur supplementing agent can be not used.

The general principles of the high pressure separation process of the hydrogenation reaction effluent of the present invention are described in detail below.

The high-pressure separation process of the hydrogenation reaction effluent usually comprises a cold high-pressure separator, when the density of the hydrocarbon oil in the hydrogenation reaction effluent is high (for example, the density is close to the water density) or the viscosity is high or the hydrocarbon oil is difficult to separate by emulsification with water, a hot high-pressure separator with the operation temperature usually being 150-450 ℃ needs to be arranged, at the moment, the hydrogenation reaction effluent enters the hot high-pressure separator to be separated into hot high-pressure gas mainly comprising hydrogen in volume and hot high-pressure oil liquid mainly comprising conventional liquid hydrocarbon and possibly existing solids, the hot high-pressure gas enters the cold high-pressure separator with the operation temperature usually being 20-80 ℃ to be separated into cold high-pressure oil and cold high-pressure gas, and the following aims are achieved because a large amount of high-boiling-point components enter the hot high-pressure oil liquid: the cold high-fraction oil becomes less dense or less viscous or easily separated from water. The high-pressure separation process of the hydrogenation reaction effluent is provided with the hot high-pressure separator, and the high-pressure separation process also has the advantage of reducing heat loss because the hot high-pressure separation oil liquid can avoid the cooling process of using an air cooler or a water cooler for hot high-pressure separation gas. Meanwhile, part of the hot high-oil-content liquid can be returned to the upstream hydrogenation reaction process for recycling, so as to improve the overall raw material property of the hydrogenation reaction process receiving the circulating oil, or the circulating oil is subjected to circulating hydrogenation.

Before the hydrogenation reaction effluent or hot high-pressure gas enters the cold high-pressure separation part, the temperature is usually reduced (generally, heat exchange with the reaction part feed) to about 220-100 ℃ (the temperature should be higher than the crystallization temperature of the ammonium hydrosulfide in the gas phase of the hydrogenation reaction effluent), then washing water is usually injected into the reaction effluent to form a hydrogenation reaction effluent after water injection, the washing water is used for absorbing ammonia and other impurities such as hydrogen chloride and the like which may be generated, and the water solution after absorbing the ammonia necessarily absorbs the hydrogen sulfide. In the cold high-pressure separation part, the effluent of the hydrogenation reaction after water injection is separated into: a cold high-molecular gas mainly composed of hydrogen in volume, a cold high-molecular oil mainly composed of conventional liquid hydrocarbon and dissolved hydrogen, and a cold high-molecular water mainly composed of water and dissolved with ammonia and hydrogen sulfide. The cold high-moisture water generally contains 0.5-15% (w), preferably 1-8% (w) of ammonia. One purpose of the washing water injection is to absorb ammonia and hydrogen sulfide in the hydrogenation reaction effluent, prevent the formation of ammonia hydrosulfide or ammonia polysulfide crystals from blocking the heat exchanger channels, and increase the pressure drop of the system. The injection amount of the washing water is determined according to the following principle: on the one hand, the washing water is divided into vapor phase water and liquid phase water after being injected into the hydrogenation reaction effluent, and the liquid phase water amount is required to be more than zero, and is preferably 30 percent or more of the total amount of the washing water; in yet another aspect, the wash water is used to absorb ammonia from the hydrogenation effluent, to prevent the high partial gas from having too high an ammonia concentration, and to reduce catalyst activity, and generally the lower the ammonia volume concentration of the high partial gas, the better, the lower the ammonia volume concentration of the high partial gas, the more typically no greater than 200ppm (v), and most preferably no greater than 50ppm (v). The operating pressure of the cold high-pressure separator is the difference between the pressure of the hydrogenation reaction part and the actual pressure drop, and the difference between the operating pressure of the cold high-pressure separator and the hydrogenation reaction pressure is not too low or too high, generally 0.35-3.2 MPa, and generally 0.5-1.5 MPa. The hydrogen volume concentration value of the cold high-molecular gas should not be too low (leading to a rise in the operating pressure of the plant), and should generally be not less than 70% (v), preferably not less than 80% (v), and most preferably not less than 85% (v). At least one part of the cold high-molecular gas, which is 85-100 percent as mentioned above, is returned to the hydrogenation reaction part for recycling so as to provide the hydrogen amount and the hydrogen concentration which are necessary for the hydrogenation reaction part; in order to increase the investment efficiency of the plant, it is necessary to ensure that the recycle hydrogen concentration does not fall below the aforementioned lower limit, for which reason, depending on the specific feedstock properties, reaction conditions, product distribution, a portion of the cold high-molecular gas may be removed to remove methane and ethane produced by the reaction. For discharged cold high-molecular gas, conventional membrane separation process or pressure swing adsorption process or oil washing process can be adopted to realize the separation of hydrogen and non-hydrogen gas components, and the recovered hydrogen is used as new hydrogen.

Fresh hydrogen is fed into the hydrogenation section to replenish hydrogen consumed during the hydrogenation reaction, and the higher the concentration of fresh hydrogen, the better, the more preferably the concentration of fresh hydrogen is not lower than 95% (v), and the more preferably not lower than 99% (v). All of the fresh hydrogen may be introduced into any of the hydrogenation reaction sections.

Compared with the inferior hydrocarbon hydrogenation thermal cracking reaction method without a post-arranged hydrofining reaction section, the method has the advantages that:

① setting post-positioned hydrofining reaction section R20, reducing olefin content in product oil such as asphalt fraction, and reducing their thermal reaction activity;

② is provided with a post-hydrogenation refining reaction section R20, which is beneficial to fully playing the hydrogenation function of hydrogenation catalyst with proper and strong hydrogenation saturation function, such as micron-scale and nano-scale MoS2 or other high-efficiency compound catalysts, namely realizing the secondary use of high-activity hydrogenation catalyst, wherein the types and liquid phase concentrations of partial catalysts R20C existing in the post-hydrogenation refining reaction section R20 can be different from the types and liquid phase concentrations of catalysts R10C existing in the hydrocracking reaction process R10;

③ is provided with a post-positioned hydrofining reaction section R20, which is beneficial to reducing the operation temperature of the final hydrogenation product hot high-pressure separator and the concentration of the easy-to-heat condensation compound in the liquid phase, prolonging the operation period of the hot high-pressure separator, and reducing the coking amount of the wall surface of the R20P hot high-pressure separator;

④ is provided with a post-positioned hydrofining reaction section R20, and can also generate other hydrofining reactions such as aromatic hydrocarbon hydrogenation saturation reaction and the like under the condition of inhibiting thermal cracking reaction, so that the hydrogen content of heavy components is increased, namely the property of the circulating oil is improved, the conversion rate of asphaltene in the circulating oil to light substances is increased, and the thermal condensation conversion rate of asphaltene in the circulating oil is reduced, thereby processing the raw material R10F with worse quality;

⑤ is provided with a post-positioned hydrofining reaction section R20, which can form a clear concept of 'reaction stage or reaction section', namely 'hydrogenation thermal cracking section and post-positioned hydrofining reaction section', and further establish a concept of segmented reaction liquid phase product circulation according to the difference of the dominant reaction targets of the reaction process or according to the fluctuation interval of the reaction temperature of the reaction process;

⑥ setting post-positioned hydrofining reaction section, based on clear concept of 'reaction stage or reaction section', setting temperature control means between reaction stages according to different reaction targets of reaction process or fluctuation interval of reaction temperature in reaction process, thus being obviously different from the flow form of no heater such as heating furnace between multiple suspension bed reactors and/or boiling bed reactors in the prior art, under most conditions, a heat extractor is required to be arranged between the hydrocracking reaction process R10 and the post-positioned hydrofining reaction section R20 or a large amount of cooling materials are required to be injected to realize flexible adjustment of temperature difference between reaction stages;

⑦ setting post-positioned hydrofining reaction section, based on clear concept of 'reaction stage or reaction section', controlling or adjusting light oil volume ratio or reaction space liquid fraction in sections under the condition of ensuring reaction hydrogen partial pressure according to the difference of the leading reaction target of the reaction process or according to the difference of hydrogen consumption speed of the reaction process, the post-positioned hydrofining reaction section can adopt lower hydrogen-oil volume ratio or higher liquid-gas volume ratio, improve the space efficiency of the reactor, increase the liquid phase reaction time for olefin hydrogenation saturation reaction, thus it may need to use the upstream product gas-liquid separation process and the upstream method of leading out at least part of gas phase product without passing through the post-positioned hydrofining reaction section, and the following method can be used:

a. chinese patent application publication No. CN 107937023A, application No. 201610920699.2A a method for two-stage hydrogenation of hydrocarbon material by using a liquid collecting cup expansion bed reactor at the front section, in the headspace of an expansion bed reactor ARZE in a hydrocarbon material one-stage hydrogenation reaction process AR, a first-stage hydrogenation reaction product ARZP is separated into a collection liquid ARZP-L led out of a liquid collecting cup and a gas-containing product ARZP-M, at least one part of ARZP-L is used as a BR raw material in a second-stage hydrogenation process and is mixed with high-purity hydrogen to carry out a second-stage hydrogenation reaction BRR to be converted into a product BRP, a target hydrogenation reaction is carried out at high selectivity and high speed between a gas phase rich in hydrogen and impurities and a liquid phase rich in high-boiling-point hydrocarbon, and a thermal condensation reaction; ARP-M can be recovered together with BRP; CRP and BRP can be jointly recovered as a product obtained in a three-stage hydrogenation process CR of hydrocarbon liquid discharged from a BR reactor; the hydrogenation products at the rear section form various circulation flows when returning to different hydrogenation reaction processes at the upstream; high boiling point hydrogen-supplying hydrocarbon is preferably used in the latter stage hydrogenation process;

b. a method for preparing hydrocarbon material by two-stage hydrogenation includes such steps as mixing the first-stage hydrogenated product ARP with BRXE intermediate BRXE-8P in the back-mixed expanded bed reactor BRXE of two-stage hydrogenation process to obtain reflux liquid BRXEP-LR and gas-contained material BRXEPM, returning BRXEP-LR to BR upstream hydrogenation reaction region of BRXE-DBP, cyclically hydrogenating to convert it to BRXE-8P, and adding hydrogen in gas phase₂The high-selectivity and high-efficiency hydrogenation reaction is carried out under the conditions of high volume concentration and low impurity volume concentration and low concentration of low-boiling-point hydrocarbon and high concentration of high-boiling-point hydrocarbon in a liquid phase, and the thermal condensation of the high-boiling-point hydrocarbon and the secondary cracking of the low-boiling-point hydrocarbon are obviously inhibited; gas in BRXE-8 is stripped to remove low boiling point hydrocarbon in ARP liquid phase, and the low boiling point hydrocarbon enters gas phase to be discharged from BRXE; the BRP enters a three-stage hydrogenation process CR to construct a three-stage hydrogenation process;

c. chinese patent application publication No. CN 107955646A, application No. 201610920591.3A is a hydrogenation method of hydrocarbon material with a rear-section upper and lower double-feeding expansion bed reactor, wherein a collection liquid ARXP-L and a gas-liquid product ARXP-M are led out from a liquid collection cup by separating a material ARXP in the top space of an expansion bed reactor ARX in a first-section hydrogenation reaction process AR; in a two-stage hydrogenation reaction process BR using high-purity hydrogen, at least one part of ARXP-L enters a reaction space KA of an expansion bed reactor BRX to obtain a reaction product BSKP and the ARXP-M, the reaction product BSKP and the ARXP-M are mixed in the reaction space KB and enter a liquid removing area at the top of a back mixing flow expansion bed reactor BRZ of the BR to separate a reflux liquid BRXP-LR and a gas-liquid product BRXP-M, the BRXP-LR returns to a circulating conversion process of an upstream hydrogenation reaction area in the BR section, the hydrogenation product of the BRXP-LR or the BRXP-LR contacts with the hydrogenation product of the ARXP-L or the ARXP-L, and;

⑧, a large amount of hydrogen-supplying hydrocarbon is used, the hydro-upgrading of the hydrocarbon component BSAA with the conventional boiling point of 250-450 ℃ in the coal tar is fully utilized to generate oil, the ratio KSH of the weight of the hydrogen-supplying solvent of R10 to the weight of the coal asphalt component is effectively improved, the dispersion degree of the coal asphalt component HD can be effectively increased, the active hydrogen obtaining speed is improved, the condensation coking speed of the hydrocarbon component HD is reduced, and the improvement of the conversion rate of the lightweight asphalt is facilitated;

⑨ according to the requirement, the single-pass thermal cracking rate of R10 in the hydro-thermal cracking reaction process with proper depth can be flexibly selected, the yield of the asphalt component of the needle coke raw material is improved to the maximum extent, or the gas yield is reduced to the maximum extent, and the thermal condensation product yield of the heavy asphalt component is reduced;

⑩ hydrogenation thermal cracking reaction process R10, which can process coal tar heavy oil or coal tar of inferior quality, opens up an effective coal tar processing path for enlarging the raw material source of needle coke, namely, the existing resources are utilized to produce needle coke of superior quality in larger quantity;

can be applied to newly built devices or the reconstruction of existing devices.

Examples

Example one

The properties of the high temperature coal tar feedstock are shown in tables 4-9.

Table 4 shows the general property analysis of high temperature coal tar A.

Table 5 shows the yields of the respective narrow fractions of the high-temperature coal tar A.

Table 6 shows the properties of the < 180 ℃ cut from high-temperature coal tar A.

Table 7 shows narrow cut Properties 1 of high temperature coal tar A.

Table 8 shows narrow cut Properties 2 of high temperature coal tar A.

Table 9 shows the analysis of the properties of the pitch of high-temperature coal tar A.

As can be seen from Table 5, the yield of coal pitch of the high temperature coal tar A of > 450 ℃ was 44.31%.

The invention aims to perform hydro-upgrading on the coal tar BSK (the yield is 46 percent of the high-temperature coal tar A) at the bottom of a distillation tower of the high-temperature coal tar A at the temperature of more than 420 ℃, and perform suspension bed hydro-thermal cracking reaction on the coal tar of the high-temperature coal tar A diluted by a hydrogen supply solvent to perform upgrading, thereby producing high-quality needle coke raw materials, performing hydro-thermal cracking and hydro-modification on heavy pitch (increasing the hydrogen content, increasing the fluidity, reducing the viscosity and reducing the softening point), and simultaneously reducing the catalyst content in the heavy pitch as much as possible, namely converting part of primary heavy pitch components into micromolecular high-quality needle coke raw material components.

According to the invention, a method described in patent ZL201210022921.9, namely a method for performing hydrogenation and lightening of low-hydrogen heavy oil by using hydrogen-supplying hydrocarbon, namely performing a suspension bed (or bubbling bed or slurry bed) hydrocracking reaction of a heterogeneous catalyst on coal tar heavy fraction, wherein a hydrogen-supplying solvent is a hydrogen-supplying agent (the hydrogen content is 8.5-9.0%) obtained by hydrogenating a fixed bed of high-temperature tar fraction with a conventional boiling point of 260-320 ℃, and the weight flow rate of the hydrogen-supplying solvent is 0.65-0.75 times (calculated according to 0.7) of the weight flow rate of coal pitch, and the method comprises the following steps:

a. coal tar pitch, hydrogen donor solvent, molybdenum-based dispersed catalyst and vulcanizing agent slurry mixing step: uniformly mixing a certain amount of compounding oil (hydrogen supply solvent), powdery catalyst particles (a composite high-activity hydrogenation catalyst, the mass ratio of metal tungsten to metal molybdenum is 0.5: 100-3.5: 100) with the granularity of less than 5 mu m and a vulcanizing agent (liquid sulfur) together under the stirring condition of 80-200 ℃ to prepare catalyst oil slurry, controlling the solid concentration of the catalyst oil slurry within the range of 20-35%, and independently pressurizing the vulcanizing agent and then feeding the vulcanizing agent into a coal asphalt oil slurry feeding furnace;

b. a first hydrogenation reaction process R10;

mixing the catalyst oil slurry with the rest of mixed hydrocracking raw materials R10F of the suspension bed and circulating oil containing the catalyst (the recycling circulation amount of the catalyst is about 25% -35% of the addition amount) to form a mixture, boosting the pressure of the mixture by a raw material pump, mixing hydrogen, heating by a heating furnace, and then feeding the mixture into a hydrogenation reactor of the suspension bed (or a bubbling bed or a slurry bed) for hydrocracking reaction, wherein the addition amount of the catalyst accounts for 200-300 PPm of the raw material slurry of the hydrogenation reactor of the suspension bed calculated by the weight of the active metal component fluidized compound, and the reference is 250 PPm;

in the first hydrogenation reaction process R10, the suspension bed hydrogenation reaction temperature is 420-440 ℃, the reaction pressure is 16-19 MPa, and the volume space velocity is 0.45-0.5 h^-1The volume ratio of hydrogen to oil is 500-800, and the catalyst is a matched powdery particle coal tar hydrogenation catalyst of a composite metal active component;

c. a second hydrogenation process R20;

the temperature of the first hydrogenation reaction effluent R10P is 440 ℃, the temperature is reduced to 398 ℃ by using quenching hydrogen, and then the first hydrogenation reaction effluent enters a suspension bed hydrogenation reactor of a second hydrogenation reaction process R20 to carry out post-hydrogenation refining reaction;

in the second hydrogenation reaction process, the reaction temperature of R20 is 398-408 ℃, the reaction pressure is 16-19 MPa, and the volume space velocity is 1.8-2.0 h^-1The volume ratio of hydrogen to oil is 300-400; the olefin concentration of the hydrocarbons in the second hydrogenation product BASE-R20P is less than 65% of the olefin concentration of the hydrocarbons in the first hydrogenation product BASE-R10P; thereby preparing the needle coke raw food light component with higher thermal stability;

and the second hydrogenation reaction effluent R20P passes through a high-temperature separator and a low-temperature separator to obtain a liquid-solid phase high-low oil mixture flow and a hydrogen-rich gas part. Hydrogen-rich gas is used as recycle hydrogen. Fractionating the liquid-solid phase high-low fraction oil mixture by a fractionating tower to obtain light distillate oil with the temperature of less than 370-400 ℃, obtaining heavy oil (distillate oil with the temperature of more than 370-400 ℃) at the bottom of the tower, wherein a small part of normal bottom heavy oil can be directly circulated into a suspension bed hydrogenation reactor as circulating oil to further carry out hydrogenation and lightening reaction; most to all of the heavy oil at the bottom of the tower is used as maltene, and anthracene oil is possibly used for adjusting the softening point and the fluidity of the maltene according to requirements;

and (3) the light distillate oil with the conventional boiling point of less than 370-400 ℃ in the hydrogenation reaction product of the suspension bed enters a special hydrogenation upgrading process to produce products such as gas, liquefied gas, naphtha, diesel oil and the like.

d. In the asphalt pretreatment part UT1, oil material R10P-HS-VS containing asphalt components is separated into needle coke raw material refined asphalt UT1-LP and heavy asphalt UT1-HP, the concentration of quinoline insoluble substances of the needle coke raw material refined asphalt UT1-LP is lower than that of the heavy asphalt UT1-HP, and the average normal boiling point of the needle coke raw material refined asphalt UT1-LP is lower than that of the heavy asphalt UT 1-HP;

the working method of the asphalt pretreatment part UT1 is a solvent-settling method, and comprises a solvent extraction separation step UT1-10, a distillation step UT1-20 for extracting and separating discharged light liquid, and a distillation step UT1-30 for extracting and separating discharged heavy liquid;

in the step of solvent extraction separation UT1-10, oil material R10P-HS-VS containing asphalt component and solvent UT1-10-SF are continuously mixed, contacted, settled and separated, the solvent UT1-10-SF extracts light component in the oil material R10P-HS-VS containing asphalt component and forms light liquid phase, heavy component in the oil material R10P-HS-VS containing asphalt component forms heavy liquid phase, the light liquid phase and the heavy liquid phase are respectively discharged after settlement separation, and light asphalt UT1-10-L containing solvent of hydrogenation modified catalyst R10C and heavy UT1-10-H containing solvent of hydrogenation modified catalyst R10C are obtained;

in the step of distillation and separation of light asphalt UT1-10-L, UT1-10-L containing a solvent and a hydrogenation modified catalyst R10C is separated into solvent UT1-10-L-S, light asphalt distillate UT1-10-L-LP with low content of hydrogenation modified catalyst R10C and liquid material UT1-10-L-HP rich in hydrogenation modified catalyst R10C in UT 1-20;

returning the material based on the solvent UT1-10-L-S to the solvent extraction separation step UT1-10 for recycling, and when the loss of the solvent UT1-10-L-S is obvious, discontinuously supplementing the solvent UT 1-10-L-S;

the liquid material UT1-10-L-HP of the enriched hydro-upgrading catalyst R10C is completely returned to R10 to contact with R10F or a hydro-converted substance thereof, can be returned to the low-pressure raw material coal pitch of R10, and then enters the reaction process R10 for recycling;

a part of the liquid feed UT1-10-L-HP returning agent enriched with the hydro-upgrading catalyst R10C can be subjected to an extraction separation step of UT1-10 and oil material R10P-HS-VS containing asphalt components or UT 1-10-SF;

the total light asphalt distillate UT1-10-L-LP based on the low hydro-upgrading catalyst R10C content is used as refined asphalt UT1-LP and as raw material UT2-TF for producing needle coke, and the yield is 33% of high-temperature coal tar A and 72% of coal asphalt BSK.

In the distillation step UT1-30 of the heavy asphalt UT1-10-H, the heavy asphalt UT1-10-H containing the hydrogenation modification catalyst R10C and the solvent is separated into the solvent UT1-10-H-S and the heavy asphalt UT1-10-H-HP containing the hydrogenation modification catalyst R10C;

returning the materials based on the solvent UT1-10-H-S to the solvent extraction separation step UT1-10 for recycling;

part of the heavy bitumen UT1-10-H-HP containing the hydro-upgrading catalyst R10C may be returned to R10 to contact R10F or its hydroconverter;

UT1-10 can be partially contacted with oil material R10P-HS-VS containing asphalt components or UT1-10-SF in the step of extracting and separating heavy asphalt UT1-10-H-HP returning agent containing hydro-upgrading catalyst R10C;

35 to 100 percent of heavy asphalt UT1-10-H-HP containing a hydro-upgrading catalyst R10C is used as the heavy asphalt UT1-HP and is used as other coal asphalt materials.

The weight proportion SK100 of the quantity of the hydrogenation modification catalyst R10C in the liquid material UT1-10-L-HP to the quantity of the hydrogenation modification catalyst R10C in the light asphalt UT1-10-L is more than or equal to 0.98.

The weight ratio SK300 of the weight of the hydrocarbons in the liquid material UT1-10-L-HP to the weight of the hydrocarbons in the light asphalt UT1-10-L is less than or equal to 0.05.

The weight ratio SK500 of the hydrogenation modification catalyst R10C in the liquid material UT1-10-L-HP is more than or equal to 0.005.

The extraction solvent UT1-10-SF is mixed oil with the weight ratio of aliphatic hydrocarbon to aromatic hydrocarbon of 1.0: 1.0-1.0: 1.2, wherein the aliphatic hydrocarbon solvent is n-heptane or and aviation kerosene, and the aromatic hydrocarbon solvent is benzene or toluene or xylene or wash oil;

in the solvent extraction and separation step UT1-10, the extraction temperature is 60-80 ℃, the extraction time is 8-10 h, and the ratio of the weight flow of the solvent UT1-10-SF to the weight flow of the oil material R10P-HS-VS containing the asphalt component is 1.0-1.2.

For a suspension bed hydrogenation device with 30 ten thousand tons/year coal tar pitch processing capacity, the hydrogen supply agent flow is 21 ten thousand tons/year, the concentration of catalyst metal in the total slurry of the suspension bed hydrogenation feeding is controlled to be 250PPm, 125 tons/year of the catalyst (calculated by metal) is needed, and the recycling amount of the catalyst is about more than 30 percent of the addition amount, namely more than 37.5 tons/year.

The invention is beneficial to using micron-level or nanometer-level high-activity catalyst (molybdenum-based catalyst) with high dispersity, can reduce the R10 gas yield in the process of hydrogenation modification of the suspension bed, obviously improves the properties of the heavy asphalt of the hydrogenation product of the suspension bed, limits the quantity of the catalyst in the final heavy asphalt product, and reduces the introduction of pollutants as much as possible.

TABLE 4 analysis of general Properties of high temperature coal tar A

TABLE 5 yield of each narrow cut of high temperature coal tar A

Range of distillation range	Narrow fraction yield, m%	Cumulative yield m%
			＜180	1.85	1.85
180～210	3.34	5.19
			210～230	16.84	22.03
230～280	5.71	27.74
			280～330	6.60	34.34
330～360	4.66	39.00
			360～450	16.20	55.20
＞450	44.31	99.51
			Loss of power	0.49	100.00

TABLE 6 Properties of the < 180 ℃ cut of high-temperature coal tar A

TABLE 7 narrow cut Properties of high temperature coal tar A1

TABLE 8 narrow cut Properties of high temperature coal tar A2

TABLE 9 analysis of Properties of Tar Pitch of high temperature coal tar A

Claims

1. The method for combining the poor-quality hydrocarbon hydrocracking reaction section with the post-positioned hydrofining reaction section is characterized in that:

a first hydrogenation reaction process R10, which may comprise 2 or more sub-hydrogenation reaction zones R101, R102, etc. operating in series, wherein, the stream containing at least a part of normal liquid hydrocarbon based on the reaction effluent of the upstream sub-hydrogenation reaction zone enters the downstream adjacent sub-hydrogenation reaction zone, the first sub-hydrogenation reaction zone R101 of the first hydrogenation reaction process R10 obtains a reaction effluent R101P, the stream R101PX containing at least a part of hydrogenation product oil R101PO based on the reaction effluent R101P enters the second sub-hydrogenation reaction zone R102 of the first hydrogenation reaction process R10, and the reaction effluent of the last sub-hydrogenation reaction zone is used as the first hydrogenation reaction effluent R10P;

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

2. The method of claim 1, further comprising:

3. The method of claim 1, further comprising:

4. A method according to claim 1, 2 or 3, characterized in that:

(1) in the first hydrogenation process R10, the poor quality hydrocarbon HDS is selected from one or more of the following materials:

5. A method according to claim 1, 2 or 3, characterized in that:

(1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS is 5-95 percent;

(2) in the second hydrogenation R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P was less than 75% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

6. A method according to claim 1, 2 or 3, characterized in that:

(1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS is 10-65%;

(2) in the second hydrogenation R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P was less than 65% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

7. A method according to claim 1, 2 or 3, characterized in that:

(1) in the first hydrogenation reaction process R10, the hydrogenation thermal cracking rate of the hydrocarbons with the conventional boiling point higher than 450 ℃ in the inferior hydrocarbon HDS is 10-35 percent;

(2) in the second hydrogenation R20, the olefin concentration of hydrocarbons in the second hydrogenation product BASE-R20P was less than 35% of the olefin concentration of hydrocarbons in the first hydrogenation product BASE-R10P.

8. The method of claim 1, further comprising:

(1) a first hydrogenation reaction process R10, which is a suspension bed hydrogenation reactor or a boiling bed hydrogenation reactor or a combined type hydrogenation reactor of a suspension bed and a boiling bed or a moving bed hydrogenation reactor;

(2) in the second hydrogenation reaction process R20, a suspension bed hydrogenation reactor or a boiling bed hydrogenation reactor or a combined type of suspension bed and boiling bed hydrogenation reactor or a moving bed hydrogenation reactor is used.

9. The method of claim 1, further comprising:

(3) h of hydrogen-rich gas SRV in recovery process SR₂The volume concentration is more than 75%.

10. The method of claim 1, further comprising:

(3) h of hydrogen-rich gas SRV in recovery process SR₂Volume concentrationThe degree is more than 85%.

11. A method according to claim 1, 2 or 3, characterized in that:

in the first hydrogenation reaction process R10, a suspension bed hydrogenation reactor is used, and the used hydrogenation catalyst R10C is a composite coal tar hydrogenation catalyst and comprises a high-activity component and a low-activity component; the weight ratio of the high-activity component metal to the low-activity component metal is 1: 10 to 10: 1; the high-activity component is a water-soluble salt compound of molybdenum or a mixture thereof; the low-activity component is iron oxide ore or iron sulfide ore, wherein the iron content in the ore is not less than 40 wt%, and the water content of the catalyst R10C is less than 2 wt%; R10C powdery particles with the particle diameter of 1-100 mu m;

the operating conditions of the first hydrogenation reaction process R10 are: the temperature is 300-480 ℃, the pressure is 6.0-30.0 MPa, the volume ratio of hydrogen to raw oil is 0.01: 1-4000: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-8.0 percent of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.1-10.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.05-3.0 percent;

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the operating conditions of the second hydrogenation reaction process R20 are as follows: the temperature is 280-440 ℃, the pressure is 6.0-30.0 MPa, the volume ratio of hydrogen to raw oil is 300: 1-4000: 1, the adding weight of the hydrogenation catalyst R20C is 0.001-8.0 percent of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.1-10.0 hr^-1；

12. A method according to claim 1, 2 or 3, characterized in that:

in the first hydrogenation process R10,the hydrogenation catalyst R10C at least contains Mo element, and the main working form of Mo in the first hydrogenation reaction process R10 is M₀S₂In the method, the hydrogenation catalyst R10C is powdery particles with the particle size of 1-100 mu m;

13. A method according to claim 1, 2 or 3, characterized in that:

the operating conditions of the first hydrogenation reaction process R10 are: the temperature is 350-460 ℃, the pressure is 17.0-23.0 MPa, the volume ratio of hydrogen to raw oil is 50: 1-2000: 1, the adding weight of the hydrogenation catalyst R10C is 0.001-5.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.2-2.0 hr^-1(ii) a The chemical hydrogen consumption of the inferior hydrocarbon HDS is 0.25 to 2.5 percent;

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the operating conditions of the second hydrogenation reaction process R20 are as follows: the temperature is 300-420 ℃ and the pressure isThe force is 17.0-23.0 MPa, the volume ratio of hydrogen to raw oil is 500: 1-1200: 1, the weight of the added hydrogenation catalyst R10C is 0.001-3.0% of the weight of the inferior hydrocarbon HDS, and the volume space velocity is 0.3-2.0 hr^-1；

14. A method according to claim 2 or 3, characterized in that:

15. A method according to claim 2 or 3, characterized in that:

16. A method according to claim 1, 2 or 3, characterized in that:

(2) in the second hydrogenation reaction process R20, a thermal high-pressure separation process R20MP-THPS is arranged;

17. A method according to claim 1, 2 or 3, characterized in that:

(2) in the second hydrogenation process R20, there is a sub-hydrogenation reaction zone operated in series, and in the sub-hydrogenation reaction zone there is a thermal high-pressure separation process R20 MP-THPS;

18. The method of claim 1, further comprising:

(2) the second hydrogenation reaction process R20 uses a suspension bed hydrogenation reactor, and the cracked liquid product recycle stream R20ZP-LR obtained in the thermal high-pressure separation process R20ZP-THPS of the last 1 sub-hydrogenation reaction zone R20M returns to the first hydrogenation reaction process R10 to contact with the first hydrogenation catalyst R10C to generate at least partial hydrogenation saturation reaction.

19. The method of claim 1, further comprising:

(3) in the recovery process, SR is divided, and a thermal high-pressure separation process THPS is set;

20. The method of claim 1, further comprising:

21. The method of claim 1, further comprising:

22. The method of claim 1, further comprising:

the hydrocarbon material RKKC containing the catalyst is obtained based on the second hydrogenation reaction effluent R20P and is circularly returned to the first hydrogenation reaction process R10 to be mixed with the raw material or the intermediate product or the final product of the first hydrogenation reaction process R10;

a catalyst containing hydrocarbon feed RKKC selected from one or more of the following:

23. The method of claim 1, further comprising:

the separated hydrocarbon material RKKC containing the catalyst is circularly returned to the second hydrogenation reaction process R20 to be mixed with the raw material or intermediate product or final product of the second hydrogenation reaction process R20;

24. The method of claim 1, further comprising:

25. The method of claim 1, further comprising:

26. The method of claim 1, further comprising:

the olefin hydrogenation saturation reaction section of the hot high-molecular gas of the product R20P is arranged to reduce the olefin content of the hydrocarbon in the hot high-molecular gas.

27. The method of claim 1, further comprising:

(1) in the first hydrogenation reaction process R10, a stream comprising at least a portion of conventional liquid hydrocarbons based on the first hydrogenation reaction effluent R10P is used as a feedstock R20-FEED containing an olefinic component of liquid phase hydrocarbons of the second hydrogenation reaction process R20;

feedstock R20-fed, possibly comprising solid particulate feedstock R20-FEEDs;

the stream comprising at least a portion of the conventional liquid hydrocarbons based on the first hydrogenation effluent R10P is used as a feedstock R20-fed containing olefinic components of liquid-phase hydrocarbons for the second hydrogenation process R20 in a manner selected from 1 or more of the following: