CN111410991B

CN111410991B - Slurry bed hydrogenation reactor system and catalytic hydrogenation process based on reactor system

Info

Publication number: CN111410991B
Application number: CN202010428596.0A
Authority: CN
Inventors: 路阳
Original assignee: Shanghai Jianyuan Biotechnology Co ltd
Current assignee: Shandong Huibang New Material Co ltd
Priority date: 2020-05-20
Filing date: 2020-05-20
Publication date: 2022-04-12
Anticipated expiration: 2040-05-20
Also published as: CN111410991A

Abstract

The invention relates to the technical field of petrochemical industry, in particular to a slurry bed hydrogenation reactor system and a catalytic hydrogenation process based on the reactor system, wherein raw oil heavy oil is firstly subjected to a thermal cracking process in a slurry bed cracking reactor under the action of a solid catalyst, unconverted heavy oil and the solid catalyst are led out from a separation section at the upper part of the slurry bed cracking reactor, cracked oil gas and hydrogen gas generated by cracking are sent to the lower part of a slurry bed refining reactor through a leading-out pipe, the cracked oil gas and the hydrogen gas are mixed with a liquid phase at the top of the refining reactor through an ejector by utilizing self pressure to complete liquid phase self-circulation of the slurry bed refining reactor, the cracked oil gas is subjected to a hydrofining process in the slurry bed refining reactor under the action of a liquid catalyst, hydrogen supply solvent and active components of the liquid catalyst are led out from the separation section at the upper part of the slurry bed refining reactor, and refined oil gas and hydrogen gas generated by refining are led out from the top of the slurry bed refining reactor, the use cost of the solid catalyst and the liquid catalyst can be greatly reduced.

Description

Slurry bed hydrogenation reactor system and catalytic hydrogenation process based on reactor system

Technical Field

The invention relates to the technical field of petrochemical industry, in particular to a slurry bed hydrogenation reactor system and a catalytic hydrogenation process based on the reactor system.

Background

Along with continuous exploitation and consumption of petroleum resources, light crude oil resources are less and less in the world, the yield of heavy crude oil is continuously increased, particularly for the current situation of more coal and less oil resources in China, the crude oil resource reserves are seriously insufficient, and the heavy fraction content in the crude oil is high (generally accounting for 30% -50%). Heavy oil and poor oil are very important resources for the continuous development of the economy all over the world. In addition, with the popularization and application of the coal grading and quality-grading conversion technology, the total coal tar yield increases year by year, and according to preliminary estimation, the national coal tar yield is about 2000 ten thousand tons/year, and if the coal tar yield is not reasonably utilized, the survival pressure is brought to enterprises, and serious resource waste and environmental pollution are caused. Therefore, the hydrogenation of heavy oil, low-grade oil, coal tar, and the like to achieve light weight and cleanliness has become one of the trends in the development of fossil energy technology.

The slurry bed hydrogenation process is a hydrogenation process mainly based on hydrocracking reaction, wherein heavy/poor-quality raw materials are subjected to hydrogen and a catalyst, becomes a novel heavy oil upgrading process, and is one of the technologies which are considered to be most promising to realize the lightening and cleaning of the heavy and poor-quality raw materials at present.

The solid catalyst is mainly natural mineral containing active metal elements, industrial waste residue and artificially synthesized solid powder additive, and has the advantages of wide raw material source, simple process, low cost, need of ultrafine grinding, difficult dispersion, easy deposition, abrasion to equipment, high difficulty in subsequent tail oil treatment and the like.

The oil-soluble liquid catalyst has the advantages of good dispersibility, small addition amount, high activity and the like, does not cause the problems of deposition, abrasion and the like, and also has better coking inhibition effect. The disadvantages are high manufacturing cost, poor coke adsorption capacity and difficult separation and recovery from the tail oil.

The heavy oil slurry bed hydrogenation process mainly comprises the main reactions of thermal cracking, catalytic hydrogenation, demetalization and the like, and also comprises some side reactions of coking and condensation. Reaction temperature, reaction pressure and catalyst are the main factors affecting the heavy oil slurry bed reaction. The reaction temperature is increased, so that the thermal cracking reaction rate can be greatly increased, and the coking condensation reaction of oil products can be increased more easily. The reaction pressure, precisely the partial pressure of hydrogen, is increased, which is favorable for reducing coking condensation.

The catalyst types are as follows: at present, the catalyst is roughly classified into a supported solid catalyst and an unsupported liquid catalyst. The solid catalyst is prepared by loading active sulfide components (such as molybdenum sulfide, nickel sulfide, cobalt sulfide and the like) of metals for catalytic hydrogenation on a porous solid carrier. The liquid catalyst is a precursor containing active metal and capable of being decomposed under reaction conditions to generate nano-scale metal sulfide particles, and the nano-scale metal sulfide particles decomposed by the liquid catalyst play a role in a slurry bed reactor. The deactivation of solid catalysts using porous solids as carriers is mainly caused by the blockage of the channels by coke or metals. The activity of the nano metal sulfide catalyst without the solid carrier is basically not influenced by coking and metal impurities, and the nano metal sulfide catalyst has strong stability and can be recycled for many times.

When heavy and poor oil products with high metal content and high carbon residue value are processed, a solid catalyst with a large specific surface area is required to provide a huge specific surface area for adsorbing and containing coke and metal chelates generated by reaction, and the impurities are taken out of a reaction system, so that the impurities in a slurry bed reactor can be prevented from accumulating. The solid catalyst has low cost because its carrier is porous material such as low-cost active carbon, natural kaolin, amorphous aluminosilicate, etc.

In a reaction system using a liquid catalyst alone, in order to reduce the accumulation of coke and impurity metals in the reaction system, tail oil containing active metal sulfide components in a certain proportion needs to be discharged. The process of discharging tail oil outside will bring loss of active metal sulfide, and corresponding liquid catalyst needs to be supplemented to ensure the catalytic activity of the reaction system, which will result in higher use cost of the liquid catalyst.

The hydrogenation reactor has a large volume and a large weight, so that the investment ratio in a hydrogenation device is very large. The main material of the hydrogenation reactor is chromium molybdenum steel, the reaction condition of thermal cracking is generally more than 450 ℃, the allowable stress value of the chromium molybdenum steel is reduced rapidly after the temperature is more than 450 ℃, in order to reduce the operation temperature of the chromium molybdenum steel and improve the bearing capacity of the chromium molybdenum steel, a heat insulation lining needs to be arranged in the reactor, the arrangement of the heat insulation lining occupies the space required by material reaction on one hand, and on the other hand, the complexity of equipment manufacturing is increased. The reaction temperature of hydrofining is generally lower than 450 ℃, and an insulating lining is not needed.

Disclosure of Invention

In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a slurry bed hydrogenation reactor system and a catalytic hydrogenation process based on the reactor system, which can greatly reduce the use cost of a solid catalyst and a liquid catalyst, and the treated light oil product has high yield, good quality, energy conservation and emission reduction, simple steps and low cost.

The purpose of the invention is realized by the following technical scheme: a slurry bed hydrogenation reactor system comprises a slurry bed cracking reactor, a slurry bed refining reactor and an injection mixer;

the slurry bed cracking reactor is provided with a first oil gas inlet, a first liquid phase outlet, a first gas phase outlet and a first cold hydrogen inlet, the slurry bed refining reactor is provided with a second oil gas inlet, a second liquid phase outlet, a second gas phase outlet and a second cold hydrogen inlet, and the injection mixer is provided with a gas phase inlet, a liquid phase inlet and a mixing outlet;

the lower part of the slurry bed cracking reactor is a first reaction section, the upper part of the slurry bed cracking reactor is a first separation section, a first oil gas inlet is led in from the bottom of the first reaction section, a first cold hydrogen inlet is led in from the side part of the first reaction section, and a first liquid phase outlet and a first gas phase outlet are respectively led out from the upper part and the lower part of the first separation section;

wherein, the lower part of the slurry bed refining reactor is a second reaction section, the upper part is a second separation section, a second oil gas inlet is led in from the bottom of the second reaction section, a second cold hydrogen inlet is led in from the side part of the second reaction section, and a second liquid phase outlet and a second gas phase outlet are respectively led out from the upper part and the lower part of the second separation section;

the first gas phase outlet of the slurry bed cracking reactor is communicated with the gas phase inlet of the injection mixer, the second liquid phase outlet of the slurry bed refining reactor is communicated with the liquid phase inlet of the injection mixer, and the mixing outlet of the injection mixer is communicated with the second oil gas inlet of the slurry bed refining reactor.

A catalytic hydrogenation process based on the reactor system comprises the steps of finishing a thermal cracking process of heavy oil in a slurry bed cracking reactor under the action of a solid catalyst, leading out unconverted heavy oil and the solid catalyst in a separation section at the upper part of the slurry bed cracking reactor, conveying cracked oil gas and hydrogen generated by cracking to the lower part of a slurry bed refining reactor through a leading-out pipe, mixing the cracked oil gas and the hydrogen with a liquid phase at the top of the refining reactor through an injection mixer by utilizing the self pressure, finishing the self circulation of the liquid phase of the slurry bed refining reactor, finishing a hydrofining process of the cracked oil gas in the slurry bed refining reactor under the action of the liquid catalyst, leading out a hydrogen supply solvent and active components of the liquid catalyst in the separation section at the upper part of the slurry bed refining reactor, and leading out refined oil gas and hydrogen generated by refining from the top of the slurry bed refining reactor.

Preferably, the slurry bed cracking reactor is arranged inside the slurry bed refining reactor, and the diameter of the slurry bed hydrocracking reactor is 0.2-0.8 of the diameter of the slurry bed hydrofining reactor. The height of the slurry bed hydrocracking reactor is smaller than that of the slurry bed hydrofining reactor.

Preferably, the liquid catalyst is an oil-soluble liquid catalyst, and the oil-soluble liquid catalyst is a complex formed by metal molybdenum, iron, cobalt or nickel and an organic matter. More preferably, the oil-soluble liquid catalyst is at least one of an oil-soluble molybdenum amine complex, molybdenum naphthenate, molybdenum alkyl thiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum 2-ethylhexanoate, and molybdenum alkyl thiocarbamate. The oil-soluble liquid catalyst can be mutually soluble with the processed heavy oil or a certain section of distillate oil in the heavy oil, and can be decomposed into nano-scale metal sulfide particles in a slurry bed hydrogenation reactor.

Preferably, the solid catalyst is at least one of activated carbon, semi-coke, clay, natural diatomite and kaolin, and the particle size of the solid catalyst is 1-1000 μm. The solid catalyst can load metal active components such as molybdenum, iron, cobalt or nickel and the like, and can also be called as an adsorbent. The solid catalyst is the solid adsorbent which is expanded or not expanded, has larger specific surface area, low cost and good adsorption effect.

After being added into a slurry bed hydrogenation reactor, the oil-soluble liquid catalyst can be decomposed into MoS₂Or active components such as NiS and the like, and Mo-series and Ni-series catalysts can exert the hydrogenation and anti-coking performances to the maximum extent, and the active components are not easy to inactivate and have slow activity decay speed.

The solid catalyst can adopt active carbon particles with porous structures, plays the role of adsorbing metal sulfides and coke to the maximum extent and has very low price.

Preferably, the addition amount of the oil-soluble liquid catalyst accounts for 0.01-0.10 wt% of the raw oil, and the addition amount of the solid catalyst accounts for 0.5-2.0 wt% of the raw oil. Specifically, the addition amount of the oil-soluble liquid catalyst is determined according to the loss amount of the metal sulfide carried away in the product, so that the concentration of active metal in the slurry bed hydrogenation reactor is ensured to be 0.05-1 wt%.

Preferably, the operating pressure in the slurry hydrocracking reactor is 16-25MPa, the temperature is 440-480 ℃, and the volume ratio of hydrogen to oil is 800-1500: 1, the volume space velocity is 0.3-1.0h^-1。

Preferably, the operating pressure in the slurry bed hydrofining reactor is 14-23MPa, the temperature is 420-460 ℃, and the volume ratio of hydrogen to oil is 800-1500: 1, the volume space velocity is 0.3-1.0h^-1。

Preferably, the slurry bed hydrogenation reactor adopts a structure of bottom inlet and top outlet, and adopts a hollow cylinder structure and a structure with an internal member capable of realizing internal liquid phase circulation or a compulsory external circulation structure adopting an external circulation pump; the outer side wall of the slurry bed hydrogenation reactor is provided with 3-6 layers of cold hydrogen injection ports, each layer is provided with 2-4 cold hydrogen injection ports which are uniformly distributed, and the feed inlets of the slurry bed hydrogenation reactor are conical.

Preferably, the reactor system further comprises a fixed bed reactor, a slurry bed separation system, a fixed bed separation system and a circulating hydrogen compression system;

the fixed bed reactor is provided with a first feeding hole, a third cold hydrogen inlet and a first discharging hole, the slurry bed separation system is provided with a second feeding hole, a third feeding hole, a second discharging hole, a dry gas outlet and an asphalt outlet, the fixed bed separation system is provided with a fourth feeding hole, a dry gas inlet, a dry gas and liquefied gas outlet, a hydrogenated naphtha outlet, a hydrogenated diesel oil outlet and a circulating hydrogen outlet, and the circulating hydrogen compression system is provided with a hydrogen inlet and a cold hydrogen outlet;

the second gas phase outlet of the slurry bed refining reactor is communicated with the first feed inlet of the fixed bed reactor, the first discharge outlet of the fixed bed reactor is communicated with the fourth feed inlet of the fixed bed separation system, the first liquid phase outlet of the slurry bed cracking reactor and the second liquid phase outlet of the slurry bed refining reactor are respectively communicated with the second feed inlet and the third feed inlet of the slurry bed separation system, the slurry bed refining reactor is also provided with a liquid catalyst inlet, and the second discharge outlet of the slurry bed separation system is communicated with the liquid catalyst inlet of the slurry bed refining reactor;

a dry gas outlet of the slurry bed separation system is communicated with a dry gas inlet of the fixed bed separation system, a circulating hydrogen outlet of the fixed bed separation system is communicated with a hydrogen inlet of the circulating hydrogen compression system, and a cold hydrogen outlet of the circulating hydrogen compression system is respectively communicated with a first cold hydrogen inlet of the slurry bed cracking reactor, a second cold hydrogen inlet of the slurry bed refining reactor and a third cold hydrogen inlet of the fixed bed reactor;

and a first oil-gas inlet of the slurry bed cracking reactor is connected with a raw oil injection pipeline, the raw oil injection pipeline is connected with a cold hydrogen injection pipeline, the other end of the cold hydrogen injection pipeline is communicated with a cold hydrogen outlet of the circulating hydrogen compression system, the cold hydrogen injection pipeline is connected with a new hydrogen injection pipeline, a fifth feed port and a solid catalyst inlet are formed in the raw oil injection pipeline, and the fifth feed port is communicated with a second discharge port of the slurry bed separation system.

A liquid catalyst injection pipeline is connected between the second discharge port of the slurry bed separation system and the liquid catalyst inlet of the slurry bed refining reactor.

A catalytic hydrogenation process based on the reactor system comprises the following steps:

adding raw oil, hydrogen and a solid catalyst into a slurry bed cracking reactor for cracking to obtain asphalt, a hydrogen supply solvent, an inactivated solid catalyst, cracked oil gas and hydrogen;

mixing cracked oil gas and hydrogen generated by cracking in the slurry bed cracking reactor with a hydrogen supply solvent and a circulating liquid catalyst active component through an injection mixer to obtain a hydrogen supply solvent, a circulating liquid catalyst active component, cracked heavy oil and hydrogen, then injecting the mixture into a slurry bed refining reactor to finish liquid phase self-circulation of the slurry bed refining reactor, finishing a hydrofining process of the cracked oil gas in the slurry bed refining reactor under the action of a liquid catalyst, and obtaining the hydrogen supply solvent, the circulating liquid catalyst active component and the hydrogen and refined heavy oil;

hydrogen generated by the slurry bed refining reactor and refined heavy oil enter a fixed bed reactor to be hydrogenated under the action of the hydrogen, so that dry gas, liquefied gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated wax oil are obtained;

asphalt, a hydrogen supply solvent, an inactivated solid catalyst and hydrogen supply solvent and circulating liquid catalyst active components which are generated by a slurry bed cracking reactor and a slurry bed refining reactor enter a slurry bed separation system to be separated, so that asphalt, dry gas, the hydrogen supply solvent and the circulating liquid catalyst active components are obtained, the hydrogen supply solvent and the circulating liquid catalyst active components which are generated by the slurry bed separation system are respectively conveyed to the slurry bed cracking reactor and the slurry bed refining reactor, and new liquid catalysts are required to be added when the hydrogen supply solvent and the circulating liquid catalyst active components are conveyed to the slurry bed refining reactor;

dry gas and liquefied gas generated by hydrogenation of a fixed bed reactor, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated wax oil and dry gas generated by separation of a slurry bed separation system enter a fixed bed separation system for separation to obtain the dry gas and the liquefied gas, the hydrogenated naphtha, the hydrogenated diesel oil and circulating hydrogen;

and the circulating hydrogen generated by the separation of the fixed bed separation system is pressurized by the circulating hydrogen compression system and then is respectively conveyed to the slurry bed cracking reactor, the slurry bed refining reactor, the fixed bed reactor and the slurry bed cracking reactor, and the supplemented fresh hydrogen is preferentially conveyed to the inlet of the slurry bed cracking reactor.

The invention has the beneficial effects that:

(1) according to the slurry bed hydrogenation reactor system and the catalytic hydrogenation process based on the reactor, raw oil heavy oil is firstly subjected to a thermal cracking process under the action of a solid catalyst in a slurry bed cracking reactor, unconverted heavy oil and the solid catalyst are led out at a separation section at the upper part of the slurry bed cracking reactor, cracked oil gas and hydrogen generated by cracking are conveyed to the lower part of a slurry bed refining reactor through a lead-out pipe, and are mixed with a liquid phase at the top of the refining reactor through an ejector by utilizing the self pressure, so that the liquid phase self-circulation of the slurry bed refining reactor is completed.

(2) The thermal cracking and demetalization processes of the heavy oil are completed in the hydrocracking reactor, and the characteristics of high reaction temperature and good adsorption performance of the solid catalyst in the hydrocracking reactor can be fully utilized; the refining process of the oil generated by cracking is completed in a hydrofining reactor, and the characteristic of good hydrogenation performance of the liquid catalyst can be fully utilized. The combined use can greatly reduce the use cost of the solid catalyst and the liquid catalyst, and the treated light oil has high yield and good quality, saves energy, reduces emission, has simple steps and low cost.

(3) The slurry bed hydrocracking reactor is arranged inside the slurry bed hydrofining reactor, the characteristic that the temperature of the slurry bed hydrocracking design reactor is higher than the design temperature of the slurry bed hydrofining reactor can be fully utilized, the shell of the slurry bed hydrocracking reactor only bears the pressure difference with the slurry bed hydrofining reactor, the wall thickness required by design is greatly reduced, and further the slurry bed hydrocracking reactor can be made of materials with better temperature resistance, but the total investment of equipment is greatly reduced.

The slurry bed hydrocracking reactor is arranged inside the slurry bed hydrofining reactor, so that the slurry bed hydrocracking reaction which is easier to generate temperature runaway is safer. Even if the hydrocracking reactor generates the temperature runaway, the temperature resistance of the material of the slurry bed hydrocracking reactor is better, the borne pressure difference is smaller, and the buffer cooling effect of the material in the slurry bed hydrofining reactor has smaller influence on the pressure bearing performance of the slurry bed hydrofining reactor, and the possibility of the temperature runaway of the slurry bed hydrofining reaction is lower than that of the slurry bed hydrocracking reaction.

"runaway temperature" refers to the phenomenon that the reaction temperature of a reaction material is increased due to the accumulation of heat released by an exothermic reaction, the reaction rate is increased due to the increase of the reaction temperature, and further more heat is released, so that the reaction temperature continues to rise, and an uncontrollable vicious circle is formed.

(4) A part of circulating oil (S51-hydrogen supply solvent + circulating liquid catalyst active component) of the hydrorefining reaction circulating system of the slurry bed is led into the hydrocracking reactor of the slurry bed, so that on one hand, the problem of recovering the thrown oil outside the hydrorefining reaction circulating system of the slurry bed is solved, and on the other hand, the hydrogenation activity of the catalyst in the hydrocracking reactor of the slurry bed can be improved.

(5) The slurry bed hydrocracking reactor and the slurry bed hydrofining reactor both adopt a structure that the lower part is used as a reaction section and the upper part is used as a gas-liquid separation section, and an additional high-pressure gas-liquid separator is not needed, so that the number of equipment and the investment can be greatly reduced.

Drawings

FIG. 1 is a schematic structural view of embodiment 1 of the present invention;

FIG. 2 is a schematic view of a system according to embodiment 1 of the present invention;

FIG. 3 is a schematic system diagram according to embodiment 2 of the present invention;

the reference signs are: 1-slurry bed cracking reactor; 2-slurry bed refining reactor; 3-ejecting mixer; 4-fixed bed reactor; 5-slurry bed separation system; 6-fixed bed separation system; 7-a recycle hydrogen compression system;

11-a first oil and gas inlet; 12 — an outlet for the first liquid phase; 13 — a first gaseous phase outlet; 14 — a first cold hydrogen inlet;

21-a second oil gas inlet; 22-a second liquid phase outlet; 23-a second gas phase outlet; 24 — a second cold hydrogen inlet;

31-gas phase inlet; 32-liquid phase inlet; 33-a mixing outlet;

s11-raw oil + hydrogen + solid catalyst; s12-asphalt + hydrogen donor solvent + deactivated solid catalyst; s13-cracking oil gas + hydrogen; s14 cooling the hydrogen;

s21 cooling the hydrogen; s22-hydrogen donor solvent + active component of circulating liquid catalyst; s23-hydrogen + refining heavy oil;

s31-hydrogen donor solvent + active component of circulating liquid catalyst; s32-hydrogen donor solvent, active component of circulating liquid catalyst, cracked heavy oil and hydrogen;

s41 cooling the hydrogen; s42-dry gas, liquefied gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated wax oil;

s51-hydrogen donor solvent + active component of circulating liquid catalyst; s52, dry gas;

s61 — recycling hydrogen.

Detailed Description

For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and accompanying fig. 1-3, which are not intended to limit the present invention.

Example 1

Referring to fig. 1-2, a slurry bed hydrogenation reactor system comprises a slurry bed cracking reactor 1, a slurry bed refining reactor 2 and an injection mixer 3;

the slurry bed cracking reactor 1 is provided with a first oil-gas inlet 11, a first liquid-phase outlet 12, a first gas-phase outlet 13 and a first cold hydrogen inlet 14, the slurry bed refining reactor 2 is provided with a second oil-gas inlet 21, a second liquid-phase outlet 22, a second gas-phase outlet 23 and a second cold hydrogen inlet 24, and the injection mixer 3 is provided with a gas-phase inlet 31, a liquid-phase inlet 32 and a mixing outlet 33;

the lower part of the slurry bed cracking reactor 1 is a first reaction section, the upper part is a first separation section, a first oil gas inlet 11 is led in from the bottom of the first reaction section, a first cold hydrogen inlet 14 is led in from the side part of the first reaction section, and a first liquid phase outlet 12 and a first gas phase outlet 13 are respectively led out from the upper part and the lower part of the first separation section;

wherein, the lower part of the slurry bed refining reactor 2 is a second reaction section, the upper part is a second separation section, a second oil gas inlet 21 is introduced from the bottom of the second reaction section, a second cold hydrogen inlet 24 is introduced from the side part of the second reaction section, and a second liquid phase outlet 22 and a second gas phase outlet 23 are respectively led out from the upper part and the lower part of the second separation section;

the first gas phase outlet 13 of the slurry bed cracking reactor 1 is communicated with the gas phase inlet 31 of the injection mixer 3, the second liquid phase outlet 22 of the slurry bed refining reactor 2 is communicated with the liquid phase inlet 32 of the injection mixer 3, and the mixing outlet 33 of the injection mixer 3 is communicated with the second oil gas inlet 21 of the slurry bed refining reactor 2.

A catalytic hydrogenation process based on the reactor system comprises the steps that heavy oil finishes a thermal cracking process in a slurry bed cracking reactor 1 under the action of a solid catalyst, unconverted heavy oil and the solid catalyst are led out from a separation section at the upper part of the slurry bed cracking reactor 1, cracked oil gas and hydrogen generated by cracking are sent to the lower part of a slurry bed refining reactor 2 through a leading-out pipe, the cracked oil gas and the hydrogen are mixed with a liquid phase at the top of the refining reactor through an injection mixer 3 by utilizing the self pressure, the liquid phase self-circulation of the slurry bed refining reactor 2 is finished, the cracked oil gas finishes a hydrofining process in the slurry bed refining reactor 2 under the action of the liquid catalyst, a hydrogen supply solvent and active components of the liquid catalyst are led out from the separation section at the upper part of the slurry bed refining reactor 2, and refined oil gas and hydrogen generated by refining are led out from the top of the slurry bed refining reactor 2.

Example 2

Referring to fig. 3, the present embodiment is different from embodiment 1 described above in that: the reactor system also comprises a fixed bed reactor 4, a slurry bed separation system 5, a fixed bed separation system 6 and a circulating hydrogen compression system 7;

the fixed bed reactor 4 is provided with a first feeding hole, a third cold hydrogen inlet and a first discharging hole, the slurry bed separation system 5 is provided with a second feeding hole, a third feeding hole, a second discharging hole, a dry gas outlet and an asphalt outlet, the fixed bed separation system 6 is provided with a fourth feeding hole, a dry gas inlet, a dry gas and liquefied gas outlet, a hydrogenated naphtha outlet, a hydrogenated diesel oil outlet and a circulating hydrogen outlet, and the circulating hydrogen compression system 7 is provided with a hydrogen inlet and a cold hydrogen outlet;

wherein, the second gas phase outlet 23 of the slurry bed refining reactor 2 is communicated with the first feed inlet of the fixed bed reactor 4, the first discharge outlet of the fixed bed reactor 4 is communicated with the fourth feed inlet of the fixed bed separation system 6, the first liquid phase outlet 12 of the slurry bed cracking reactor 1 and the second liquid phase outlet 22 of the slurry bed refining reactor 2 are respectively communicated with the second feed inlet and the third feed inlet of the slurry bed separation system 5, the slurry bed refining reactor 2 is also provided with a liquid catalyst inlet, and the second discharge outlet of the slurry bed separation system 5 is communicated with the liquid catalyst inlet of the slurry bed refining reactor 2;

a dry gas outlet of the slurry bed separation system 5 is communicated with a dry gas inlet of the fixed bed separation system 6, a circulating hydrogen outlet of the fixed bed separation system 6 is communicated with a hydrogen inlet of the circulating hydrogen compression system 7, and a cold hydrogen outlet of the circulating hydrogen compression system 7 is respectively communicated with a first cold hydrogen inlet 14 of the slurry bed cracking reactor 1, a second cold hydrogen inlet 24 of the slurry bed refining reactor 2 and a third cold hydrogen inlet of the fixed bed reactor 4;

the first oil-gas inlet 11 of the slurry bed cracking reactor 1 is connected with a raw oil injection pipeline, the raw oil injection pipeline is connected with a cold hydrogen injection pipeline, the other end of the cold hydrogen injection pipeline is communicated with a cold hydrogen outlet of the circulating hydrogen compression system 7, the cold hydrogen injection pipeline is connected with a new hydrogen injection pipeline, the raw oil injection pipeline is provided with a fifth feeding hole and a solid catalyst inlet, and the fifth feeding hole is communicated with a second discharging hole of the slurry bed separation system 5.

A liquid catalyst injection pipeline is connected between the second discharge port of the slurry bed separation system 5 and the liquid catalyst inlet of the slurry bed refining reactor 2.

adding (raw oil + hydrogen + solid catalyst) S11 into a slurry bed cracking reactor 1 for cracking to obtain (asphalt + hydrogen donor solvent + deactivated solid catalyst) S12 and (cracked oil gas + hydrogen) S13;

(cracked oil gas + hydrogen gas) S13 generated by cracking in the slurry bed cracking reactor 1 is mixed with (hydrogen supply solvent + circulating liquid catalyst active component) S31 through an injection mixer 3 to obtain (hydrogen supply solvent + circulating liquid catalyst active component + cracked heavy oil + hydrogen gas) S32, then the mixture is injected into the slurry bed refining reactor 2 to complete liquid phase self-circulation of the slurry bed refining reactor 2, the cracked oil gas completes a hydrofining process under the action of a liquid catalyst in the slurry bed refining reactor 2, and (hydrogen supply solvent + circulating liquid catalyst active component) S22 and (hydrogen gas + refined heavy oil) S23 are obtained;

the (hydrogen + refined heavy oil) S23 generated by the slurry bed refining reactor 2 enters the fixed bed reactor 4 to be hydrogenated under the action of hydrogen to obtain (dry gas, liquefied gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated wax oil) S42;

s12 (asphalt + hydrogen supply solvent + inactivated solid catalyst) generated by the slurry bed cracking reactor 1 and S22 (hydrogen supply solvent + circulating liquid catalyst active component) generated by the slurry bed refining reactor 2 enter a slurry bed separation system 5 for separation to obtain asphalt, dry gas S52 and (hydrogen supply solvent + circulating liquid catalyst active component) S51, S51 (hydrogen supply solvent + circulating liquid catalyst active component) generated by the slurry bed separation system 5 are respectively conveyed to the slurry bed cracking reactor 1 and the slurry bed refining reactor 2, and new liquid catalyst is required to be added when the S51 is conveyed to the slurry bed refining reactor 2;

the (dry gas, liquefied gas, hydrogenated naphtha, hydrogenated diesel oil and hydrogenated wax oil) S42 generated by hydrogenation in the fixed bed reactor 4 and the dry gas S52 generated by separation in the slurry bed separation system 5 enter the fixed bed separation system 6 for separation to obtain the dry gas, the liquefied gas, the hydrogenated naphtha, the hydrogenated diesel oil and the circulating hydrogen S61;

the circulating hydrogen S61 generated by the separation of the fixed bed separation system 6 is pressurized by the circulating hydrogen compression system 7, and then is respectively conveyed to the slurry bed cracking reactor 1 (cooling hydrogen S14), the slurry bed refining reactor 2 (cooling hydrogen S21), the fixed bed reactor 4 (cooling hydrogen S41) and the slurry bed cracking reactor 1, and the supplemented fresh hydrogen is preferentially conveyed to the inlet of the slurry bed cracking reactor 1.

Example 3

This embodiment is different from embodiment 2 described above in that:

the oil-soluble liquid catalyst is oil-soluble molybdenum amine complex, molybdenum naphthenate, molybdenum alkyl thiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum 2-ethylhexanoate or molybdenum alkyl thiocarbamate.

The solid catalyst is active carbon, semi-coke, argil, natural diatomite or kaolin, and the particle size of the solid catalyst is 1 μm, 10 μm, 100 μm, 500 μm or 1000 μm.

The addition amount of the oil-soluble liquid catalyst accounts for 0.01 wt%, 0.03 wt%, 0.05 wt%, 0.08 wt% or 0.10 wt% of the raw oil, and the addition amount of the solid catalyst accounts for 0.5 wt%, 1.0 wt%, 1.5 wt% or 2.0 wt% of the raw oil.

The operating pressure in the slurry bed hydrocracking reactor is 16MPa, 18MPa, 20MPa, 22MPa or 25MPa, the temperature is 440 ℃, 450 ℃, 460 ℃, 470 ℃ or 480 ℃, and the volume ratio of hydrogen to oil is 800: 1. 1000: 1. 1200: 1. 1400: 1 or 1500: 1, volume space velocity of 0.3h^-1、0.5h^-1、0.7h^-1、0.9h^-1Or 1.0h^-1(ii) a The operating pressure in the slurry bed hydrofining reactor is 14MPa, 16MPa, 18MPa, 20MPa, 22MPa or 23MPa, the temperature is 420 ℃, 430 ℃, 440 ℃, 450 ℃ or 460 ℃, and the volume ratio of hydrogen to oil is 800: 1. 1000: 1. 1200: 1. 1400: 1 or 1500: 1, volume space velocity of 0.3h^-1、0.5h^-1、0.7h^-1、0.9h^-1Or 1.0h^-1。

The slurry bed hydrogenation reactor adopts a structure of bottom inlet and top outlet, and adopts a hollow cylinder structure and a structure with an internal member capable of realizing internal liquid phase circulation or a compulsory external circulation structure adopting an external circulation pump; the outer side wall of the slurry bed hydrogenation reactor is provided with 3-6 layers of cold hydrogen injection ports, each layer is provided with 2-4 cold hydrogen injection ports which are uniformly distributed, and the feed inlets of the slurry bed hydrogenation reactor are conical.

The slurry bed hydrogenation reactor system and the catalytic hydrogenation process based on the reactor can greatly reduce the use cost of the solid catalyst and the liquid catalyst, and the treated light oil product has high yield, good quality, energy conservation and emission reduction, simple steps and low cost.

The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.

Claims

1. A slurry bed hydrogenation reactor system characterized by: the reactor system comprises a slurry bed cracking reactor, a slurry bed refining reactor and an injection mixer;

the first gas phase outlet of the slurry bed cracking reactor is communicated with the gas phase inlet of the injection mixer, the second liquid phase outlet of the slurry bed refining reactor is communicated with the liquid phase inlet of the injection mixer, and the mixing outlet of the injection mixer is communicated with the second oil gas inlet of the slurry bed refining reactor;

the reactor system also comprises a fixed bed reactor, a slurry bed separation system, a fixed bed separation system and a circulating hydrogen compression system;

a first oil-gas inlet of the slurry bed cracking reactor is connected with a raw oil injection pipeline, the raw oil injection pipeline is connected with a cold hydrogen injection pipeline, the other end of the cold hydrogen injection pipeline is communicated with a cold hydrogen outlet of the circulating hydrogen compression system, the cold hydrogen injection pipeline is connected with a new hydrogen injection pipeline, a fifth feed port and a solid catalyst inlet are formed in the raw oil injection pipeline, and the fifth feed port is communicated with a second discharge port of the slurry bed separation system;

2. A catalytic hydrogenation process based on the reactor system of claim 1, wherein: the method comprises the following steps:

3. The catalytic hydrogenation process of claim 2, wherein: the liquid catalyst is oil-soluble liquid catalyst, and the oil-soluble liquid catalyst is a complex formed by metal molybdenum, iron, cobalt or nickel and organic matters.

4. The catalytic hydrogenation process of claim 3, wherein: the oil-soluble liquid catalyst is at least one of oil-soluble molybdenum amine complex, molybdenum naphthenate, molybdenum alkyl thiophosphate, molybdenum dialkyl dithiocarbamate, molybdenum dialkyl dithiophosphate, molybdenum 2-ethylhexanoate and molybdenum alkyl thiocarbamate.

5. The catalytic hydrogenation process of claim 2, wherein: the solid catalyst is at least one of active carbon, semi-coke, clay, natural diatomite and kaolin, and the particle size of the solid catalyst is 1-1000 μm.

6. The catalytic hydrogenation process of claim 3, wherein: the addition amount of the oil-soluble liquid catalyst accounts for 0.01-0.10 wt% of the raw oil, and the addition amount of the solid catalyst accounts for 0.5-2.0 wt% of the raw oil.

7. The catalytic hydrogenation process of claim 2, wherein: the operating pressure in the slurry bed hydrocracking reactor is 16-25MPa, the temperature is 440-480 ℃, and the volume ratio of hydrogen to oil is 800-1500: 1, the volume space velocity is 0.3-1.0h^-1(ii) a The operating pressure in the slurry bed hydrofining reactor is 14-23MPa, the temperature is 420-460 ℃, and the volume ratio of hydrogen to oil is 800-1500: 1, the volume space velocity is 0.3-1.0h^-1。

8. The catalytic hydrogenation process of claim 2, wherein: the slurry bed hydrogenation reactor adopts a structure of bottom inlet and top outlet, and adopts a hollow cylinder structure and a structure with an internal member capable of realizing internal liquid phase circulation or a compulsory external circulation structure adopting an external circulation pump; the outer side wall of the slurry bed hydrogenation reactor is provided with 3-6 layers of cold hydrogen injection ports, each layer is provided with 2-4 cold hydrogen injection ports which are uniformly distributed, and the feed inlets of the slurry bed hydrogenation reactor are conical.