CN104531212A

CN104531212A - High aromatic hydrocarbon hydrogenation upgrading method by utilizing refined diesel component hydrogenation upgrading reaction process

Info

Publication number: CN104531212A
Application number: CN201410766306.8A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-12-05
Filing date: 2014-12-05
Publication date: 2015-04-22

Abstract

The invention provides a high aromatic hydrocarbon hydrogenation upgrading method by utilizing a refined diesel component hydrogenation upgrading reaction process. The method is suitable for a wide fraction high aromatic hydrocarbon hydrogenation upgrading process. According to the method, a hydrogenation refining reaction effluent R1P is separated into thermal high pressure separation oil THPSL mainly comprising heavy hydrocarbon and thermal high pressure separation vapor THPSV mainly comprising diesel components in a thermal high pressure separation part THPS; at least one part of the THPSV enters a post-posed diesel component upgrading process RD2 for selective ring opening and/or mild hydrocracking to obtain a hydrogenation upgrading reaction effluent RD2P. The method is particularly suitable for the hydrogenation upgrading process of medium-low temperature coal tar, and can be used for realizing low-cost upgrading of hydrogenation refining diesel components.

Description

A kind of high aromatic hydrogenation method for modifying using refined diesel oil component hydrogenation upgrading reaction process

Technical field

The present invention relates to a kind of high aromatic hydrogenation method for modifying using refined diesel oil component hydrogenation upgrading reaction process; Particularly, the present invention relates to a kind of wide fraction height aromatic hydrogenation method for modifying using the high impurity content of refined diesel oil component rearmounted hydrogenation upgrading reaction process; More particularly, the present invention relates to a kind of deep hydrogenation method for modifying of wide fraction coal tar, hydrofining reaction effluent R1P thermal high separate part THPS be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; At least partially hot high score gas THPSV enter refined diesel oil component rearmounted hydrogenation upgrading reaction process carry out selective opening and or mild hydrocracking, obtain hydrogenation upgrading reaction effluent RD2P; The method is particularly suitable for the hydro-upgrading process of middle coalite tar, can realize the low cost upgrading of hydrofining diesel oil component.

Background technology

Below in conjunction with middle coalite tar HDS, the deep hydrofinishing method of existing coal tar is described.

Middle coalite tar HDS of the present invention, the wide fraction oil ratio referring to coalite tar or middle coalite tar in full cut such as normal boiling point is the distillate of coalite tar in 120 ~ 450 DEG C or normal boiling point higher than the coal-tar pitch of coalite tar in 450 DEG C, usually containing multiple organic compounds containing sulfur and organic compounds containing nitrogen, these sulfur-bearings, nitrogenous compound because of the difference of charcoal number and space structure, its hydrogenolysis speed or hydrogenolysis transformation efficiency widely different; Part sulphur, nitrogen belong to heterogeneous ring compound, and these sulphur, nitrogen are positioned on the loop chain of heterogeneous ring compound, such as component listed by table 1.Wide fraction coal tar HDS of the present invention, is commonly referred to as the coal tar that described coal tar contains diesel oil distillate and the high boiling fraction HDSHD higher than diesel oil boiling point, and high boiling fraction HDSHD is usually containing more assorted element such as sulphur, nitrogen.

Part heterogeneous ring compound component in table 1 coal tar

Hydro-upgrading of the present invention generates oil; refer to the part or all of generation oil that raw material hydrocarbon hydro-upgrading process produces; the outer row of the generation oil and the generation of hydro-upgrading process intermediate steps that comprise the generation of hydro-upgrading process final step generates oil; and hydro-upgrading of the present invention generates oil at least containing diesel component and heavy oil component, usually also containing petroleum naphtha component etc.

Hydrofining of the present invention generates oil; refer to the part or all of generation oil that raw material hydrocarbon unifining process produces; the outer row of the generation oil and the generation of unifining process intermediate steps that comprise the generation of unifining process final step generates oil; and hydrofining of the present invention generates oil at least containing diesel component and heavy oil component, usually also containing petroleum naphtha component etc.

The deep hydrogenation upgrading processes of industrialized middle coalite tar comprises deep hydrofinishing process R1 usually, and separation deep hydrofinishing process R1 reaction effluent R1P obtains deep hydrofinishing and generates oily R1PO.Processing normal boiling point be the middle coalite tar of 120 ~ 450 DEG C distillate and or the coal-tar pitch of normal boiling point higher than coalite tar in 450 DEG C time, the deep hydrofinishing liquid hydrocarbon generated in oily R1PO is generally hydrofining petroleum naphtha component (or hydrofining naphtha fraction) R1PN, hydrofining diesel oil component (or hydrofining diesel oil cut) R1PD and hydrofining tail oil component (or hydrofining tail oil fraction) R1PVGO and hydrofining heavy oil component (or hydrofining heavy oil fraction), wherein hydrofining diesel oil component R1PD normally primary target product, therefore, the reaction conditions of deep hydrofinishing process R1 of coalite tar of can being right usually is mainly first and foremost around the quality choice ensureing diesel oil distillate R1PD in other words, when hydrofining tail oil component R1PVGO is as hydrocracking raw material, the nitrogen content of tail oil and density also will become the second target that must take into account, the conversion product that the conversion product that the same charcoal array come from middle coalite tar due to hydrofining diesel oil cut R1PD is divided and more high-carbon array are divided, in most cases, improving or improve hydrofining diesel oil cut R1PD is consistent with the means of the quality of these two products of hydrofining tail oil R1PVGO, such as improves reaction pressure and or improves temperature of reaction and or reduce catalyst space velocities.The hydrofining naphtha fraction R1PN of middle coalite tar, because octane value is low, arene underwater content is high, is typically used as the blend component of raw materials for catalytic reforming device petroleum naphtha.

The problem that the present invention pays close attention to is: at industrialization deep hydrofinishing process R1, how to improve the quality of hydrofining diesel oil cut R1PD economically, and wherein major objective reduces density, raising cetane value; The method of described economy refers to the processing method that investment is low, energy consumption is low, gas yield is low.

Deep hydrofinishing process R1 about middle coalite tar generates the high-quality method of putting forward of diesel oil distillate R1PD in oily R1PO and namely reduces density, improve the method for the low gas yield of cetane value, first method be first be separated and or fractionation in the deep hydrofinishing process R1 of coalite tar generate oily R1PO and obtain diesel oil distillate R1PD, then in the hydrogenation upgrading reactor of independent diesel oil distillate R1PD, highly selective raw material is realized, low impurity environment, suitable low temperature of reaction, the condition of the catalyst efficiency of the saturated or hydrocracking of efficient aromatic hydrogenation, but, this is equivalent to build a set of independently diesel oil hydrogenation device for improving quality, invest too high, it is a kind of uneconomic method for upgrading, it not the goal approach that the present invention pursues.

Deep hydrofinishing process R1 about middle coalite tar generates the high-quality method of putting forward of diesel oil distillate R1PD in oily R1PO and namely reduces density, improve the method for the low gas yield of cetane value, existing second method uses hydrocracking catalyst or diesel oil selective opening catalyzer for deep hydrofinishing process R1 reaction effluent, described hydrocracking catalyst prioritizing selection has and has the hydrocracking catalyst of the function of selectively opened saturated rings to realize low hydrogen consumption to the dicyclo of fractional saturation or polycyclic aromatic hydrocarbons, high liquid is received, efficient upgrading, the advantage of these class methods is that flow process is simple, but exist and cannot select the problem of the diesel modifying catalyzer of channel diameter the best: because the product R1P of the deep hydrofinishing process R1 of wide fraction coal tar is usually containing a large amount of wax oil component, this brings disadvantageous effect to the hydro-upgrading of diesel component: if catalyzer channel diameter is little of being unfavorable for wax oil diffusion of components, be easy to coking, if catalyzer channel diameter is greatly to being beneficial to wax oil diffusion of components, diesel component hydrogenation efficiency is low.

Based on above analysis, the present invention proposes a kind of deep hydrogenation method for modifying of wide fraction coal tar, hydrofining reaction effluent R1P thermal high separate part THPS be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; At least partially hot high score gas THPSV enter rearmounted diesel component grading process RD2 carry out selective opening and or mild hydrocracking, obtain hydrogenation upgrading reaction effluent RD2P; The method is particularly suitable for the hydro-upgrading process of middle coalite tar, can realize the low cost upgrading of hydrofining diesel oil component.

Flow characteristics of the present invention uses thermal high sepn process, complete the relative separation of heavy oil component, diesel component economically, achieve the optimization of refined diesel oil component rearmounted hydrogenation grading process RD2 raw material, high-quality diesel component can be produced with simple flow process under the condition of Low investment, less energy-consumption; Utilize the high feature that thus hydrofining reaction effluent R1P ammonia content is high of coal tar nitrogen content simultaneously, rearmounted diesel component grading process RD2 is had than diesel yield higher under low ammonia condition, higher oil product total recovery.

When the present invention is applicable to the following process of deep hydrofinishing reaction effluent R1P of high aroamtic hydrocarbon raw material, require that hydrofining reaction effluent R1P contains normal boiling point higher than the hydro carbons of 330 DEG C and the normal boiling point hydro carbons between 165 ~ 330 DEG C, certainly, contain heavy constituent particularly containing the situation of a large amount of heavy constituent for hydrofining reaction effluent R1P, effect of the present invention will be more remarkable.Therefore, the present invention is particularly suitable for the following process of the deep hydrofinishing reaction effluent R1P of wide fraction coal tar.

A kind of high aromatic hydrogenation method for modifying of refined diesel oil component hydrogenation upgrading reaction process that uses of the present invention has no report.

The first object of the present invention is to propose a kind of high aromatic hydrogenation method for modifying using refined diesel oil component hydrogenation upgrading reaction process.

The second object of the present invention is to propose a kind of wide fraction height aromatic hydrogenation method for modifying using the high impurity content of refined diesel oil component rearmounted hydrogenation upgrading reaction process.

The third object of the present invention is the deep hydrogenation method for modifying proposing a kind of wide fraction coal tar, the low cost upgrading of hydrofining diesel oil component can be realized, hydrofining reaction effluent R1P thermal high separate part THPS be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; At least partially hot high score gas THPSV enter rearmounted diesel component grading process RD2 carry out selective opening and or mild hydrocracking, obtain hydrogenation upgrading reaction effluent RD2P; The method is particularly suitable for the hydro-upgrading process of middle coalite tar, can realize the low cost upgrading of hydrofining diesel oil component.

The fourth object of the present invention is to propose a kind of high aromatic hydrogenation method for modifying using refined diesel oil component hydrogenation upgrading reaction process, when service temperature is suitable, high pressure hot separator 1THPSE and rearmounted diesel component upgrading reactor RD2E can be combined as a clustered aggregates.

The deep hydrofinishing process R1 containing the high aromatic hydrocarbons material HDS of assorted element containing hydrofining diesel oil component R1PD and hydrofining tail oil component R1PVGO and hydrofining heavy oil component in oily R1PO is generated for its hydrofining, the present invention all can apply, and these logistics can be selected from one or more in following materials:

1. coalite tar or its distillate or its hot procedure gained oil product;

2. coal-tar middle oil or its distillate or its hot procedure gained oil product;

3. coal-tar heavy oil or its distillate or its hot procedure gained oil product;

4. coal liquefaction gained liquefied coal coil or its distillate or its hot procedure gained oil product;

5. shale oil or its distillate or its hot procedure gained oil product;

6. tar sand basic weight oil or its hot procedure gained oil product;

7. ethylene cracking tar;

8. petroleum base wax oil thermal cracking tars;

9. petroleum based heavy fuel oils hot procedure gained oil product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;

The hydrocarbon ils of gluey pitch shape component that what 10. other aromaticity content was high be rich in.

Summary of the invention

A kind of high aromatic hydrogenation method for modifying using refined diesel oil component hydrogenation upgrading reaction process of the present invention, is characterized in that comprising following steps:

1. at hydrofining reaction process R1, under hydrogen and Hydrobon catalyst R1C existence condition, high aromatic hydrocarbons HDS carries out hydrofining reaction R1R and obtains hydrofining reaction effluent R1P, and hydrofining reaction effluent R1P contains normal boiling point higher than the hydro carbons of 330 DEG C and the normal boiling point hydro carbons between 165 ~ 330 DEG C;

2. at thermal high separate part THPS, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition;

3. at hydrogenation upgrading reaction process RD2, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, diesel component R1PD at least partially in hot high score gas THPSV complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain hydrogenation upgrading reaction effluent RD2P;

4. at separate part HPS, hydrogenation upgrading reaction effluent RD2P is separated into and generates oily RD2PO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially.

Height aroamtic hydrocarbon raw material HDS of the present invention, is selected from one or more in following materials usually:

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

4. coal liquefaction gained liquefied coal coil or its distillate;

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

8. tar sand basic weight oil or its hot procedure gained oil product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;

10. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils.

When height aroamtic hydrocarbon raw material HDS of the present invention is coal tar, the operational condition of each step is generally:

1. at hydrofining reaction process R1, temperature be 170 ~ 460 DEG C, pressure is 4.0 ~ 28.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.05 ~ 10.0hr ^-1operational condition under, high aromatic hydrocarbons HDS carries out hydrofining reaction R1 and obtains hydrofining reaction effluent R1P, and in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 20;

2. at thermal high separate part THPS, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 60%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, temperature be 280 ~ 460 DEG C, pressure is 4.0 ~ 28.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.05 ~ 10.0hr ^-1operational condition under, the diesel component R1PD at least partially in hot high score gas THPSV complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain hydrogenation upgrading reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 26;

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily RD2PO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 75%.

1. at hydrofining reaction process R1, temperature be 220 ~ 440 DEG C, pressure is 12.0 ~ 18.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.1 ~ 5.0hr ^-1operational condition under, high aromatic hydrocarbons HDS carries out hydrofining reaction R1 and obtains hydrofining reaction effluent R1P, and in hydrofining reaction effluent R1P, the cetane value of diesel oil distillate is higher than 26;

2. at thermal high separate part THPS, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 75%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, temperature be 300 ~ 440 DEG C, pressure is 12.0 ~ 18.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.15 ~ 5.0hr ^-1operational condition under, the diesel component R1PD at least partially in hot high score gas THPSV complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 32;

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily RD2PO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 80%.

When height aroamtic hydrocarbon raw material HDS of the present invention is coal tar, the operational condition of each step is especially:

1. at hydrofining reaction process R1, temperature be 220 ~ 440 DEG C, pressure is 12.0 ~ 18.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.1 ~ 5.0hr ^-1operational condition under, high aromatic hydrocarbons HDS carries out hydrofining reaction R1 and obtains hydrofining reaction effluent R1P, and in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 32;

2. at thermal high separate part FTHPS, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 75%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 12.0 ~ 18.0MPa at pressure, diesel component R1PD at least partially in hot high score oil 1THPSL complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain hydrogenation upgrading reaction process RD2 reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 40;

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily RD2PO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 85%.

Height aroamtic hydrocarbon raw material HDS of the present invention is middle coalite tar, and the operational condition of each step is generally:

1. hydrofining reaction process R1, be under the operational condition of 13.0 ~ 16.0MPa at pressure, in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 30;

2. at thermal high separate part FTHPS, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 70%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 13.0 ~ 16.0MPa at pressure, diesel component R1PD at least partially in hot high score gas THPSV complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain hydrogenation upgrading reaction process RD2 reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 36:

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily R1PNO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 80%.

1. hydrofining reaction process R1, working pressure is 13.0 ~ 16.0MPa, and in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 34;

3. hydrogenation upgrading reaction process RD2, working pressure is 13.0 ~ 16.0MPa, and in reaction effluent RD2P, the cetane value of diesel component is higher than 44.

When height aroamtic hydrocarbon raw material HDS of the present invention is coal tar, the detailed operational condition of each step is generally:

2. at thermal high separate part FTHPS, temperature be 355 ~ 390 DEG C, under pressure is the operational condition of 13.0 ~ 18.0MPa, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 60%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 4.0 ~ 28.0MPa at pressure, diesel component R1PD at least partially in hot high score oil 1THPSL complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel component is higher than 26;

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily R1PNO primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 75%.

1. at hydrofining reaction process R1, temperature be 170 ~ 460 DEG C, pressure is 13.0 ~ 18.0MPa, the volume space velocity of Hydrobon catalyst R1C is 0.1 ~ 4.0hr ^-1operational condition under, high aromatic hydrocarbons HDS carries out hydrofining reaction R1 and obtains hydrofining reaction effluent R1P, and in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 30;

2. at thermal high separate part FTHPS, temperature be 365 ~ 385 DEG C, under pressure is the operational condition of 13.0 ~ 18.0MPa, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 70%;

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 4.0 ~ 28.0MPa at pressure, diesel component R1PD at least partially in hot high score oil 1THPSL complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 40;

When height aroamtic hydrocarbon raw material HDS of the present invention is coal tar, the detailed operational condition of each step is preferably:

1. at hydrofining reaction process R1, working pressure is 14.0 ~ 17.0MPa, and in hydrofining reaction effluent R1P, the cetane value of diesel component is higher than 34;

2. at thermal high separate part THPS, temperature be 370 ~ 380 DEG C, under pressure is the operational condition of 14.0 ~ 17.0MPa, hydrofining reaction effluent R1P be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition; In hot high score oil THPSL normal boiling point higher than the mass ratio of the hydro carbons of 330 DEG C higher than 70%;

3. the working pressure of hydrogenation upgrading reaction process RD2 is 8.0 ~ 17.0MPa; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 44;

4. at separate part HPS, hydrogen rich gas gas HPV working pressure be 14.0 ~ 17.0MPa.

In order to reduce subsequent separation process energy consumption, the most heavy hydrocarbon component in hydrogenation upgrading reaction effluent RD2P of the present invention is diesel component.

In order to simplify sepn process, hydrogenation upgrading reaction effluent RD2P of the present invention enters separate part HPS combined separation after mixing with hot high score oil THPSL.

The present invention, separate part HPS comprises cold anticyclone separate part LHPS usually, at cold anticyclone separate part LHPS, heat of dissociation high score gas 1THPSV be separated obtain primarily of hydrogen composition cold high score gas gas LHPV and cold high score oil LHPL, cold high score gas gas LHPV be used as hydrogen rich gas gas HPV.

As spy's row, the hot high score device THPSE that the present invention completes thermal high separate part THPS is combined as an integration apparatus with the upgrading reactor RD2E completing hydrogenation upgrading reaction process RD2.

Usually, the hydrogenated oil HDSRPO that the present invention is separated high aromatic hydrocarbons HDS hydro-upgrading process obtains the hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point, part or all of hydro-upgrading heavy oil HDSRPO-DO by hydrocracking reaction process R30 produce diesel oil and more lighting end be converted into hydrocracking reaction effluent R30P; In order to simplify sepn process, hydrocracking reaction effluent R30P is separated after can mixing with reaction effluent RD2P; Combined separation after hydrocracking reaction effluent R30P can mix with hot high score oil THPSL.

In order to further to heavy gas oil upgrading, the hydrogenated oil HDSRPO that the present invention can be separated high aromatic hydrocarbons HDS hydro-upgrading process obtains being the hydro-upgrading cut HDSRPO-DH of 300 ~ 360 DEG C of hydrocarbon compositions primarily of normal boiling point, and part or all of hydro-upgrading cut HDSRPO-DH is circulated to the upgrading that hydrogenation upgrading reaction process RD2 completes this cut.

In order to reduce subsequent separation process energy consumption, when the normal boiling point that the most heavy constituent that hydrogenation upgrading reaction generates oily RD2PO is suitable for generating the most heavy constituent of oily RD2PO as diesel oil distillate such as hydrogenation upgrading reaction is lower than 350 DEG C, hydrogenation upgrading reaction effluent RD2P completes oil product and generates oily RD2PO with the hydrogenation upgrading obtained that is separated of hydrogen, can carry out fractionation separately.

The present invention, in order to reduce subsequent separation process energy consumption and simplify sepn process, hot high score oil THPSL can go hydrocracking reaction process XR30 produce diesel oil and more lighting end be converted into hydrocracking reaction effluent XR30P; Hydrocracking reaction effluent XR30P can be separated with after hydrogenation upgrading reaction effluent RD2P mixes; Hydrocracking reaction effluent XR30P is separated after mixing with hydrogenation upgrading reaction effluent RD2P and obtains mixed hydrogenation and generate oily XMP, separation mixed hydrogenation generates the hydro-upgrading heavy oil XMP-DO that oily XMP obtains forming higher than 330 DEG C of hydrocarbon primarily of normal boiling point, and part or all of hydro-upgrading heavy oil XMP-DO can produce diesel oil and more lighting end by hydrocracking reaction process XR30.

The present invention, the oil product of hydrocracking reaction effluent XR30P and the sepn process of hydrogen can arrange high pressure hot separator XTHPS be separated into hot high score oil XTHPSL and on volume primarily of hydrogen composition hot high score gas XTHPSV, hot high score gas XTHPSV enters separate part HPS combined separation after can mixing with hydrogenation upgrading reaction effluent RD2P, suitable especially when the most heavy hydrocarbon component in hot high score gas XTHPSV is the hydrocarbon component of normal boiling point lower than 355 DEG C.

Embodiment

Below describe the present invention in detail.

Pressure of the present invention, refers to absolute pressure.

Normal boiling point of the present invention refers to the vapour of material under a barometric point, liquid equilibrium temperature.

Conventional boiling range of the present invention refers to the normal boiling point scope of cut.

Proportion of the present invention, unless stated otherwise, refers to the ratio of fluid density and normal pressure under normal pressure, 15.6 DEG C of conditions, 15.6 DEG C of Water Under density.

Conventional gas hydrocarbon of the present invention, is the hydro carbons of gaseous state under referring to normal condition, comprises methane, ethane, propane, butane.

Conventional liq hydrocarbon of the present invention, the hydro carbons be in a liquid state under referring to normal condition, comprises pentane and the higher hydro carbons of boiling point thereof.

Impurity element of the present invention, refers to the non-hydrogen in stock oil, non-carbon, nonmetallic ingredient as oxygen, sulphur, nitrogen, chlorine etc.

Impurity composition of the present invention, refers to the hydrocracking thing of non-hydrocarbon component in stock oil as water, ammonia, hydrogen sulfide, hydrogenchloride etc.

Petroleum naphtha of the present invention refers to normal boiling point lower than the conventional liq hydrocarbon of 165 DEG C.

Diesel component of the present invention refers to the hydro carbons that normal boiling point is 165 ~ 330 DEG C.

Wax oil component of the present invention refers to the hydro carbons that normal boiling point is 330 ~ 530 DEG C.

Heavy oil component of the present invention refers to normal boiling point higher than the hydro carbons of 330 DEG C.

Polycyclic aromatic hydrocarbons mentioned herein, its aromatic ring number is 3 ~ 5.

Condensed-nuclei aromatics mentioned herein, its aromatic ring number is greater than 5.

The composition of component of the present invention or concentration or content or yield value, unless stated otherwise, be weight basis value.

Coal tar of the present invention, refer to the coal tar from the process such as pyrolysis step of pyrolysis of coal or the dry distillation of coal or coal generating gas process or its cut, can be by product coalite tar or its cut of coal generating gas, also can be coal coking pyrolysis of coal process (comprising semi-coking, middle temperature coking, high-temperature coking process) by product coal tar or its cut, can be the mixing oil of above-mentioned coal tar, can be extract oil such as diasphaltene coal tar or its distillate that above-mentioned coal tar obtains through light hydrocarbon solvent extracting.

High-temperature coking belongs to coal high temperature pyrolysis process, and the outlet temperature of pyrolytic process is generally greater than 900 DEG C, usually between 1000 ~ 1400 DEG C.Described coal-tar heavy oil refers to the by product crude tar oil that coal high temperature pyrolysis produces coke and/or the production of town gas process.Coal-tar heavy oil is in primary distillation process, the following product of usual production: the products such as light oil (topping tar), carbolic oil, naphtalene oil, lightweight washing oil, heavy wash oil, lightweight carbolineum, heavy carbolineum, pitch, carbolic oil can be separated into crude phenols and dephenolize oil further, and naphtalene oil can be separated into thick naphthalene and de-naphtalene oil further.Coal-tar heavy oil lighting end of the present invention refers to: carbolineum, washing oil, naphtalene oil, de-naphtalene oil, carbolic oil, dephenolize oil, light oil and mixing oil thereof.

Because raw coal character and coking or gas-making process condition change all within the specific limits, coal tar oil properties also changes within the specific limits.Processing condition and the product requirement of coal tar primary distillation process also change within the specific limits, therefore the character of coal tar lighting end also changes within the specific limits.The character of coal tar lighting end, proportion is generally 0.92 ~ 1.25, normal boiling point is generally 60 ~ 500 DEG C and is generally 120 ~ 460 DEG C, usual metal content is 5 ~ 80PPm, sulphur content is 0.4 ~ 0.8%, nitrogen content is 0.6 ~ 1.4%, oxygen level is 0.4 ~ 9.0%, usual water-content is 0.2 ~ 5.0%, and carbon residue content is generally 0.5 ~ 13%.

Usual normal boiling point lower than the olefin(e) centent of coalite tar distillate is high in 450 DEG C, phenol content high and component containing more easily reaction under mitigation condition as rudimentary organosulfur, polycyclic aromatic hydrocarbons, therefore, the hydrofining reaction process R1 of middle coalite tar lighting end of the present invention comprises either shallow unifining process R11 and deep hydrofinishing process R12 usually; Either shallow unifining process R11, usually uses the single dose of hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination.

Usual normal boiling point is higher than coalite tar last running particularly coal-tar pitch cut in 450 DEG C, its metal content is high, gum level is high, asphalt content is high, therefore, the hydrofining reaction process R1 of middle coalite tar last running of the present invention comprises either shallow unifining process R11 and deep hydrofinishing process R12 usually; Either shallow unifining process R11, usually uses the single dose of hydrogenation protecting agent, hydrodemetallation (HDM) agent, removal of ccr by hydrotreating agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination.

The hydrofining reaction process R1 of dead oil of the present invention or coal tar heavy fractioning or full fraction of coal tar comprises either shallow unifining process R11 and deep hydrofinishing process R12 usually; Either shallow unifining process R11, object is to reduce alkene, phenol, metal, carbon residue content under the operational condition relaxed compared with deep hydrofinishing process R12, be in fact for deep hydrofinishing process R12 prepares the hydrocarbon feed of low carbon residue, low assorted element, usually use the single dose of hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination; Deep hydrofinishing process R12, object is that generating oily R11PO to either shallow hydrofining realizes deep hydrofinishing and produce the good diesel oil distillate of quality, under the operational condition violent compared with either shallow unifining process R11, realize deep hydrodesulfurizationof, deep hydrogenation denitrogenation, deep hydrogenation aromatic saturation, usually use the single dose of hydrogen desulfurization agent, hydrodenitrification agent, hydrogenation aromatic hydrocarbons degree of depth saturator etc. or the series combination of two agent or multi-agent or mixed loading combination.The technique of the hydrofining reaction process R1 of disclosed coal tar lighting end or coal tar heavy fractioning or full fraction of coal tar has multiple, and hydrofining reaction process R1 of the present invention can combinationally use these methods.

Diesel component hydrogenation grading process RD2 of the present invention, according to the difference of raw material composition, upgrading target and catalyst performance, its operating restraint is very wide, and its working pressure is generally 4.0 ~ 28.0MPa, service temperature is generally 320 ~ 450 DEG C, the volume space velocity of catalyzer RD2C is generally 0.1 ~ 5.0hr ^-1, the gas/oil volume ratio of hydrogen is generally 400: 1 ~ 5000: 1, the increase rate of the cetane value of raw material diesel component is generally to 2 ~ 10, is generally 3 ~ 7.

Below describe characteristic of the present invention in detail.

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

4. coal liquefaction gained liquefied coal coil or its distillate;

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

Usually, the hydrogenated oil HDSRPO that the present invention is separated high aromatic hydrocarbons HDS hydro-upgrading process obtains the hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point, part or all of hydro-upgrading heavy oil HDSRPO-DO by hydrocracking reaction process R30 produce diesel oil and more lighting end be converted into hydrocracking reaction effluent R30P.In order to simplify sepn process, hydrocracking reaction effluent R30P is separated after can mixing with reaction effluent RD2P; Combined separation after hydrocracking reaction effluent R30P can mix with hot high score oil THPSL.

High aromatic hydrocarbons HDS hydro-upgrading process flow process scope comprises and enters hydrofining reaction process R1 from high aromatic hydrocarbons HDS and start to terminate to the hydrogen of generation oil of relevant whole hydro-upgrading reaction process and the sepn process of oil product.

The present invention, hydrocracking reaction process R30 can be set, the hydrogenated oil HDSRPO being separated high aromatic hydrocarbons HDS hydro-upgrading process obtains the hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point, hydro-upgrading heavy oil HDSRPO-DO by hydrocracking reaction process R30 produce diesel oil and more light constituent be converted into hydrocracking reaction effluent R30P.Usually, hydrocracking reaction effluent R30P is separated after mixing with the hydro-upgrading reaction effluent of high aromatic hydrocarbons HDS, and such as hydrocracking reaction effluent R30P is separated after mixing with selective hydrogenation upgrading reaction effluent RD2P.

The present invention, when the hot high score oil THPSL obtained at thermal high separate part THPS is made up of higher than the hydrocarbon of 330 DEG C normal boiling point primarily of the component such as higher than 80% during the hydrocarbon composition of normal boiling point higher than 330 DEG C, the hydrocracking reaction process R30 arranged, can directly with the oily THPSL of hot high score for raw material.Now, hydrocracking reaction effluent R30P can be separated with after selective hydrogenation upgrading reaction effluent RD2P mixes, and forms terse flow process.Certainly, the usual hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point being separated that the hydrogenated oil HDSRPO of high aromatic hydrocarbons HDS hydro-upgrading process obtains at fractionating section partly or entirely can also be circulated to the hydrocracking that hydrocracking reaction process R30 completes this cut.Also can by usual be separated that the hydrogenated oil HDSRPO of high aromatic hydrocarbons HDS hydro-upgrading process obtains at fractionating section be 300 ~ 360 DEG C of hydrocarbon compositions primarily of normal boiling point hydro-upgrading cut HDSRPO-DH is partly or entirely circulated to the upgrading that selective hydrogenation upgrading reaction zone RD2 completes this cut.

When the most heavy constituent that selective hydrogenation upgrading reaction generates oily RD2PO is suitable for as diesel oil distillate, when the normal boiling point that such as selective hydrogenation upgrading reaction generates the most heavy constituent of oily RD2PO is lower than 350 DEG C, selective hydrogenation upgrading reaction effluent RD2P can be completed being separated of oil product and hydrogen and carry out fractionation separately afterwards, a large amount of fractionation energy consumption can be saved; For large-scale device, this advantage will be more remarkable.

The present invention, the oil product of hydrocracking reaction effluent R30P and the sepn process of hydrogen can arrange high pressure hot separator 2THPS be separated into hot high score oil 2THPSL and on volume primarily of hydrogen composition hot high score gas 2THPSV.Such as, hydrocracking reaction effluent R30P, at thermal high separate part 1THPS, under pressure is the operational condition that 13.0 ~ 18.0MPa, temperature are suitable, the most heavy hydrocarbon component in hot high score gas 2THPSV is made to be normal boiling point lower than the hydrocarbon component of 355 DEG C, now, separate part HPS combined separation is entered after hot high score gas 2THPSV can being mixed with hydrogenation upgrading reaction effluent RD2P.

The reactor that hydrofining reaction process R1 of the present invention uses, its beds mode of operation can be any suitable form, can be the combination of two or more dissimilar reactors, can be fixed-bed reactor, can be fluidized-bed reactor; Can be downflow reactor, also can be up-flow reactor (usually needing lower hydrogen-oil ratio); Can be bubbling style reactor (usually needing lower hydrogen-oil ratio), can be the liquid phase intensified type reactor (usually needing lower hydrogen-oil ratio) of high liquid phase fraction.Fluidized-bed reactor can be ebullated bed reactor or suspended-bed reactor or upflowing slight expanded-bed.

The reactor that rearmounted diesel component grading process RD2 of the present invention uses, its beds mode of operation can be any suitable form, can be the combination of two or more dissimilar reactors, can be fixed-bed reactor, can be fluidized-bed reactor; Can be suspension bed, can be ebullated bed; Can be downflow reactor, also can be up-flow reactor.The reactor that rearmounted diesel component grading process RD2 of the present invention uses, its beds mode of operation is generally down-flow fixed bed or upflow fixed bed.

As required, any one supplementary sulphur can be added hydrofining reaction process R1 and or rearmounted diesel component grading process RD2, to ensure minimum hydrogen sulfide volumetric concentration such as 500PPm or 1000PPm or prescribed value that reaction process is necessary, to ensure that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum prescribed value.Described supplementary sulphur can be sulfide hydrogen maybe can be converted into hydrogen sulfide to the material of hydroconversion process without undesirable action, such as hydrogen sulfide containing gas or oil product, or generate the dithiocarbonic anhydride of hydrogen sulfide or Methyl disulfide etc. after contacting with high-temperature hydrogen.

Below describe the rule of the recover hydrogen of hydrogenation reaction effluent of the present invention and the high pressure separation process of hydrocarbon ils in detail.

The high pressure separation process of hydrogenation reaction effluent comprises cold high pressure separator usually, when hydrocarbon ils density in hydrogenation reaction effluent large (such as close with water-mass density) viscosity is large or be difficult to be separated with emulsifying water in order to the hydrogenated oil that obtains the condition of high temperature with reduce its sepn process energy consumption or in order to realize specific initial gross separation object time, setting operation temperature is also needed to be generally the high pressure hot separator of 150 ~ 450 DEG C, now hydrogenation reaction effluent enter high pressure hot separator be separated into one on volume primarily of hydrogen composition hot high score gas gas and one primarily of conventional liq hydrocarbon and may exist solid composition hot high score fluid body, hot high score gas enters the cold high pressure separator that service temperature is generally 20 ~ 80 DEG C and is separated into cold high score oil and cold high score gas, because a large amount of high boiling component enters in hot high score fluid body, achieve following target: cold high score oil density diminishes or viscosity diminishes or be easy to be separated with water.The high pressure separation process of hydrogenation reaction effluent arranges high pressure hot separator, also possesses and reduces the advantage of calorific loss, because the process that cools of hot high score fluid body use air cooler that hot high score gas can be avoided to experience or water cooler.Meanwhile, the hydrogenation process being suitable for receiving this hot high score oil that hot for part high score fluid body can be returned to upstream recycles, and to improve the overall raw material character of the hydrogenation process receiving this turning oil, or carries out circulation hydrogenation to this turning oil.

Before hydrogenation reaction effluent or hot high score gas enter cold anticyclone separate part, usually temperature (being generally and reactive moieties charging heat exchange) is first reduced to about 220 ~ 100 DEG C (these temperature should higher than sulphur hydrogenation ammonia Tc in this hydrogenation reaction effluent gas phase), then usually inject washing water wherein and form water filling back end hydrogenation reaction effluent, washing water are used for absorbing ammonia and other impurity issuable as hydrogenchloride etc., and the inevitable absorbing hydrogen sulphide of the aqueous solution after absorbing ammonia.At cold anticyclone separate part, described water filling back end hydrogenation reaction effluent is separated into: one on volume primarily of the cold high score gas of hydrogen composition, cold high score oil primarily of conventional liq hydrocarbon and dissolved hydrogen composition, one primarily of water composition and be dissolved with the cold high score water of ammonia, hydrogen sulfide.Described cold high score water, wherein the content of ammonia is generally 0.5 ~ 15% (w), is preferably 1 ~ 8% (w).An object of note washing water absorbs ammonia in hydrogenation reaction effluent and hydrogen sulfide, prevents from forming sulphur hydrogenation ammonia or many sulphur ammonia Crystallization Plugging heat exchanger channel, increase system pressure drop.The injection rate of described washing water, should determine according to following principle: on the one hand, and washing water are divided into vapour phase water and liquid phase water after injecting hydrogenation reaction effluent, and the liquid phase water yield must be greater than zero, is preferably 30% of washing water total amount or more; Again on the one hand, washing water, for absorbing the ammonia in hydrogenation reaction effluent, prevent the ammonia density of high score gas too high, reduce catalyst activity, the ammonia volumetric concentration of usual high score gas is more low better, is generally not more than 200PPm (v), is preferably not more than 50PPm (v).Described cold high pressure separator working pressure is that hydrogenation reaction partial pressure deducts true pressure and falls, and the difference of cold anticyclone separate part working pressure and hydrogenation reaction pressure is unsuitable too low or too high, is generally 0.35 ~ 3.2MPa, is generally 0.5 ~ 1.5MPa.The hydrogen volume concentration value of described cold high score gas, should not too low (causing device working pressure to rise), generally should be not less than 70% (v), should be not less than 80% (v), preferably be not less than 85% (v).As previously mentioned at least partially, the cold high score gas being generally 85 ~ 100% returns in the use of hydrogenation reaction component loops, with the amounts of hydrogen providing hydrogenation reaction part necessary and hydrogen concentration; In order to improve plant investment efficiency, must ensure that recycle hydrogen concentration is not less than aforesaid low limit value, for this reason, according to concrete feedstock property, reaction conditions, product slates, methane, ethane that the described cold high score gas of a part produces to get rid of reaction can be got rid of.For the cold high score gas of discharge, conventional membrane separation process or pressure swing adsorption technique or oil wash technique can be adopted to realize hydrogen and non-hydrogen gas Component seperation, and the hydrogen reclaimed is used as new hydrogen.

New hydrogen enters the hydrogen adding hydrogen partial and consume with supplementary hydrogenation process, and new hydrogen hydrogen concentration is more high better, generally lower than 95% (v), preferably should not be not less than 99% (v).Whole new hydrogen can be introduced arbitrary hydrogenation reaction part, preferably introduce hydrofining reaction process R1.

The deep hydrofinishing process R1 containing the high aromatic hydrocarbons material HDS of assorted element containing hydrofining diesel oil component R1PD and hydrofining tail oil component R1PVGO and hydrofining heavy oil component in oily R1PO is generated for its hydrofining, the present invention arranges rearmounted diesel component grading process RD2, can obtain following effect:

1. the relative separation of heavy oil component, diesel component is completed economically with simple flow process, achieve the multinomial integrated condition of the highly effective hydrogenation upgrading of hydrofining diesel oil component R1PD: high hydrogen partial pressure, raw material highly selective, selective opening hydrocracking catalyst and suitable low temperature of reaction, thus under Low investment, less energy-consumption condition, High-efficient Production can go out high-quality diesel component;

2. utilize the high feature that thus hydrofining reaction effluent R1P ammonia content is high of coal tar nitrogen content, make rearmounted diesel component grading process RD2 have than diesel yield higher under low ammonia condition, higher oil product total recovery;

When 3. using deep hydrofinishing reaction effluent R1P thermal high separate part 1HPS, be beneficial to the cold anticyclone sepn process oil-water separation of hydrogen and hydrocarbon ils sepn process in energy-conservation and raising deep hydrofinishing reaction effluent R1P simultaneously;

4. when temperature condition is suitable, high pressure hot separator 1THPSE and rearmounted liquid-phase hydrogenatin upgrading reactor R2MH-LRE can be combined as a clustered aggregates, and can at the gas phase hydrogenation upgrading reaction process R2MHL-GR of this combined reactor top additional heat high score gas 1THPV;

5. when the hot high score oil THPSL obtained at thermal high separate part THPS is made up of higher than the hydrocarbon of 330 DEG C normal boiling point primarily of the component such as higher than 80% during the hydrocarbon composition of normal boiling point higher than 330 DEG C, the hydrocracking reaction process R30 arranged, can directly with hot high score oil THPSL for raw material, now, hydrocracking reaction effluent R30P can be separated with after selective hydrogenation upgrading reaction effluent RD2P mixes, and forms terse flow process;

6. the usual hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point being separated that the hydrogenated oil HDSRPO of high aromatic hydrocarbons HDS hydro-upgrading process obtains at fractionating section partly or entirely can also be circulated to the hydrocracking that hydrocracking reaction process R30 completes this cut.Also can by usual be separated that the hydrogenated oil HDSRPO of high aromatic hydrocarbons HDS hydro-upgrading process obtains at fractionating section be 300 ~ 360 DEG C of hydrocarbon compositions primarily of normal boiling point hydro-upgrading cut HDSRPO-DH is partly or entirely circulated to the upgrading that selective hydrogenation upgrading reaction zone RD2 completes this cut;

7. when the most heavy constituent that selective hydrogenation upgrading reaction generates oily RD2PO is suitable for as diesel oil distillate, when the normal boiling point that such as selective hydrogenation upgrading reaction generates the most heavy constituent of oily RD2PO is lower than 350 DEG C, selective hydrogenation upgrading reaction effluent RD2P can be completed being separated of oil product and hydrogen and carry out fractionation separately afterwards, a large amount of fractionation energy consumption can be saved; For large-scale device, this advantage will be more remarkable;

8. the oil product of hydrocracking reaction effluent R30P and the sepn process of hydrogen can arrange high pressure hot separator 2THPS be separated into hot high score oil 2THPSL and on volume primarily of hydrogen composition hot high score gas 2THPSV.Such as, hydrocracking reaction effluent R30P, at thermal high separate part 1THPS, under pressure is the operational condition that 13.0 ~ 18.0MPa, temperature are suitable, the most heavy hydrocarbon component in hot high score gas 2THPSV is made to be normal boiling point lower than the hydrocarbon component of 355 DEG C, now, separate part HPS combined separation is entered after hot high score gas 2THPSV can being mixed with hydrogenation upgrading reaction effluent RD2P.

Embodiment

Embodiment one

The coal tar processing amount 100t/h of coal tar hydrogenating unit, coal tar character is in table 2, adopt the present invention, the high pressure hot separator THPS of deep hydrofinishing process R1 reaction effluent R1P is set, be under the operational condition of 15.5 ~ 17.5MPa at pressure, be separated into primarily of normal boiling point higher than the hot high score oil THPSL of the hydrocarbon composition of 330 DEG C and comprise normal boiling point lower than the hydrocarbon of 330 DEG C on volume primarily of the hot high score gas THPSV of hydrogen composition, then hot high score gas THPSV enters diesel component hydrogenation grading process RD2, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 14.0 ~ 16.0MPa at pressure, selective opening hydrocracking is carried out to diesel component in hot high score gas THPSV, obtain hydrogenation upgrading reaction effluent RD2P, in hydrogenation upgrading reaction effluent RD2P, the cetane value of diesel component improves 3 ~ 7 units,

Be separated hydrogenation upgrading reaction effluent RD2P at cold anticyclone separate part LHPS to obtain being used as hydrogen rich gas gas HPV primarily of the cold high score gas gas LHPV of hydrogen composition and cold high score oil LHPL, cold high score gas gas LHPV.

Adopt the inventive method, operational condition and the results are shown in Table 3 to table 11.

The flowsheeting of the present embodiment calculates and uses flow scheme simulation program PROCESS to complete.

As can be seen from the separating resulting of high pressure hot separator THPS listed by table 9, it is relatively clear that hydrofining heavy oil component R1PVGO is separated with hydrofining diesel oil component R1PD:

1. hot high score oil THPSL, flow is 21.429t/h, normal boiling point exceed higher than the volume fraction of the component of 330 DEG C 70%, normal boiling point higher than the weight fraction of the component of 330 DEG C more than 70%;

2., in hot high score gas THPSV, hydrocarbon ils flow is 75.198t/h, normal boiling point lower than the weight fraction of the component of 355 DEG C more than 93%, normal boiling point lower than the weight fraction of the component of 330 DEG C more than 84%; Hydrofining generates about 87% of diesel component in oily R1PO and that is more than 80% enters in hot high score gas THPSV.

Below describe rearmounted diesel component grading process RD2 in detail.

Rearmounted diesel component grading process RD2, preferentially selects hydrogenation upgrading catalyzer RD2C (diesel oil selective opening cracking catalyst), has following functions:

1. to the petroleum naphtha component in hot high score gas THPSV, there is low cracking function (cracking rate is even lower lower than 5%);

2. to the diesel component in hot high score gas THPSV, there is low cracking rate (cracking rate lower than 15% even lower than 8%), can significantly improve cetane value or fall low-density function, hydrogenation upgrading catalyzer RD2C can be diesel oil high-pressure hydrogenation aromatic hydrocarbon saturation catalyst and or diesel oil selective hydrogenation open loop cracking catalyst.

There is the catalyzer of diesel component selective hydrogenation open loop cracking function, it can be any one suitable diesel oil selective hydrogenation open loop cracking catalyst, it can be typical petroleum base height aromaticity content catalytic diesel oil selective hydrogenation open loop cracking catalyst, these technology have the MCI technology of China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute, the RICH technology etc. of Beijing Research Institute of Petro-Chemical Engineering of Sinopec Group, record the document of this kind of technology in table 12.The lysate diesel yield of the raw material diesel component of rearmounted diesel component grading process RD2: be generally greater than 85%, be usually greater than 90%, more preferably greater than 95%.

Hydrogenation upgrading catalyzer RD2C also can be the single catalyst possessing above-mentioned comprehensive function prepared by specialized designs, also can be two or more catalyst combination schemes possessing above-mentioned comprehensive function formed by multiple catalysts grating.

According to the present invention, rearmounted diesel component grading process RD2 can use down-flow fixed bed hydrogenator or upflow fixed bed hydrogenator.

Embodiment two

Based on embodiment one, the hydrocracking reaction process R30 of setting, directly with hot high score oil THPSL for raw material, now, hydrocracking reaction effluent R30P is separated after mixing with selective hydrogenation upgrading reaction effluent RD2P, forms terse flow process.

Embodiment three

Based on embodiment two, adjustment thermal high separate part THPS service temperature, when the most heavy constituent that selective hydrogenation upgrading reaction generates oily RD2PO is suitable for as diesel oil distillate, when the normal boiling point that such as selective hydrogenation upgrading reaction generates the most heavy constituent of oily RD2PO is lower than 350 DEG C, selective hydrogenation upgrading reaction effluent RD2P is completed being separated of oil product and hydrogen and carry out fractionation separately afterwards, a large amount of fractionation energy consumption can be saved;

The oil product of hydrocracking reaction effluent R30P and the sepn process of hydrogen can arrange high pressure hot separator 2THPS be separated into hot high score oil 2THPSL and on volume primarily of hydrogen composition hot high score gas 2THPSV.Such as, hydrocracking reaction effluent R30P, at thermal high separate part 1THPS, under pressure is the operational condition that 13.0 ~ 18.0MPa, temperature are suitable, the most heavy hydrocarbon component in hot high score gas 2THPSV is made to be normal boiling point lower than the hydrocarbon component of 355 DEG C, now, separate part HPS combined separation is entered after hot high score gas 2THPSV can being mixed with hydrogenation upgrading reaction effluent RD2P.

The character of table 2 dehydrated coal tar

The physico-chemical property of table 3 catalyzer

Table 4 unifining process R1 reaction conditions

Table 5 unifining process R1 material balance and product slates

Project	Data
		H ₂S/NH ₃/H ₂O	0.16/1.03/7.62
C ₁/C ₂	0.66/0.38
		C ₃/iC ₄/nC ₄	0.65/0.04/0.16
C ₅～150℃	12.37
		150～180℃	16.32
180～260℃	20.27
		260～310℃	16.11
310～350℃	14.32
		350～370℃	7.35
＞370℃	20.19
		C ₅ ⁺Liquid is received	94.46
Chemical hydrogen consumption	5.20

Table 6 hydrofining naphtha fraction character

Table 7 hydrofining diesel oil cut R1PD character

The heavy R1PVGO oil nature of table 8 hydrofining

Table 9 operational condition summary sheet

Table 10 hot high score oil THPSL distills data

Table 11 hot high score gas THPSV oil product data

The publication of selective hydrogenation open loop dearomatization catalyst recorded by table 12

Claims

1. use a high aromatic hydrogenation method for modifying for refined diesel oil component hydrogenation upgrading reaction process, it is characterized in that comprising following steps:

2. method according to claim 1, is characterized in that:

High aroamtic hydrocarbon raw material HDS, is selected from one or more in following materials:

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

4. coal liquefaction gained liquefied coal coil or its distillate;

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

3. method according to claim 1, it is characterized in that: high aroamtic hydrocarbon raw material HDS is coal tar, the operational condition of each step is:

4. method according to claim 1, is characterized in that: nitrogenous high aroamtic hydrocarbon raw material HDS is coal tar, and the operational condition of each step is:

5. method according to claim 1, is characterized in that: nitrogenous high aroamtic hydrocarbon raw material HDS is coal tar, and the operational condition of each step is:

6. method according to claim 1, it is characterized in that: high aromatic hydrocarbons HDS is middle coalite tar, the operational condition of each step is:

3. hot high score gas THPSV enters hydrogenation upgrading reaction process RD2 at least partially, under hydrogen and hydrogenation upgrading catalyzer RD2C existence condition, be under the operational condition of 13.0 ~ 16.0MPa at pressure, diesel component R1PD at least partially in hot high score gas THPSV complete diesel component upgrading reaction RD2R carry out deep hydrogenation aromatic saturation and or selective opening and or hydrocracking, obtain hydrogenation upgrading reaction process RD2 reaction effluent RD2P; In reaction effluent RD2P, the cetane value of diesel oil distillate is higher than 36;

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily R1PN0 primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 80%.

7. method according to claim 6, it is characterized in that: high aromatic hydrocarbons HDS is middle coalite tar, the operational condition of each step is:

8. method according to claim 1 or 3 or 4 or 5 or 6 or 7, it is characterized in that: high aroamtic hydrocarbon raw material HDS is coal tar, the operational condition of each step is:

4. at separate part HPS, reaction effluent RD2P is separated into and generates oily R1PN0 primarily of the hydrogen rich gas gas HPV of hydrogen composition and hydrogenation upgrading at least partially, and hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially; The hydrogen volume concentration of hydrogen rich gas gas HPV is higher than 75%.

9. method according to claim 1 or 3 or 4 or 5 or 6 or 7, it is characterized in that: high aroamtic hydrocarbon raw material HDS is coal tar, the operational condition of each step is:

10. method according to claim 9, it is characterized in that: high aroamtic hydrocarbon raw material HDS is coal tar, the operational condition of each step is:

11. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

Most heavy hydrocarbon component in hydrogenation upgrading reaction effluent RD2P is diesel component.

12. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

Hydrogenation upgrading reaction effluent RD2P enters separate part HPS combined separation after mixing with hot high score oil THPSL.

13. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

4. separate part HPS comprises cold anticyclone separate part LHPS, at cold anticyclone separate part LHPS, heat of dissociation high score gas 1THPSV be separated obtain primarily of hydrogen composition cold high score gas gas LHPV and cold high score oil LHPL, cold high score gas gas LHPV be used as hydrogen rich gas gas HPV.

14. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

2. the hot high score device THPSE completing thermal high separate part THPS and the upgrading reactor RD2E completing hydrogenation upgrading reaction process RD2 is combined as an integration apparatus.

15. methods according to claim 1, is characterized in that:

5. the hydrogenated oil HDSRPO being separated high aromatic hydrocarbons HDS hydro-upgrading process obtains the hydro-upgrading heavy oil HDSRPO-DO formed higher than 330 DEG C of hydrocarbon primarily of normal boiling point, part or all of hydro-upgrading heavy oil HDSRPO-DO by hydrocracking reaction process R30 produce diesel oil and more lighting end be converted into hydrocracking reaction effluent R30P.

16., according to method described in claim 15, is characterized in that:

5. hydrocracking reaction effluent R30P is separated after mixing with reaction effluent RD2P.

17., according to method described in claim 15, is characterized in that:

5. hydrocracking reaction effluent R30P mixes rear combined separation with hot high score oil THPSL.

18. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

The hydrogenated oil HDSRPO being separated high aromatic hydrocarbons HDS hydro-upgrading process obtains being the hydro-upgrading cut HDSRPO-DH of 300 ~ 360 DEG C of hydrocarbon compositions primarily of normal boiling point, and part or all of hydro-upgrading cut HDSRPO-DH is circulated to the upgrading that hydrogenation upgrading reaction process RD2 completes this cut.

19. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

When the most heavy constituent that hydrogenation upgrading reaction generates oily RD2PO is suitable for as diesel oil distillate, the hydrogenation upgrading obtained that is separated that hydrogenation upgrading reaction effluent RD2P completes oil product and hydrogen generates oily RD2PO and carries out fractionation separately.

20., according to method described in claim 19, is characterized in that:

Hydrogenation upgrading reaction generates the normal boiling point of the most heavy constituent of oily RD2PO lower than 350 DEG C.

21. according to claim 1 or 3 or 4 or 5 or 6 or 7 method, it is characterized in that:

Hot high score oil THPSL go hydrocracking reaction process XR30 produce diesel oil and more lighting end be converted into hydrocracking reaction effluent XR30P.

22., according to method described in claim 21, is characterized in that:

Hydrocracking reaction effluent XR30P is separated after mixing with hydrogenation upgrading reaction effluent RD2P.

23., according to method described in claim 21, is characterized in that:

Hydrocracking reaction effluent XR30P is separated after mixing with hydrogenation upgrading reaction effluent RD2P and obtains mixed hydrogenation and generate oily XMP, separation mixed hydrogenation generates the hydro-upgrading heavy oil XMP-DO that oily XMP obtains forming higher than 330 DEG C of hydrocarbon primarily of normal boiling point, and part or all of hydro-upgrading heavy oil XMP-DO produces diesel oil and more lighting end by hydrocracking reaction process XR30.

24., according to method described in claim 21, is characterized in that:

The oil product of hydrocracking reaction effluent XR30P and the sepn process of hydrogen arrange high pressure hot separator XTHPS be separated into hot high score oil XTHPSL and on volume primarily of hydrogen composition hot high score gas XTHPSV, hot high score gas XTHPSV enters separate part HPS combined separation after mixing with hydrogenation upgrading reaction effluent RD2P.

25., according to method described in claim 24, is characterized in that:

At high pressure hot separator XTHPS, the most heavy hydrocarbon component in hot high score gas XTHPSV is normal boiling point lower than the hydrocarbon component of 355 DEG C.