CN104250566A

CN104250566A - Hydrogenation method of inferior hydrocarbons containing easy-to-hydrogenolyze metallic compounds

Info

Publication number: CN104250566A
Application number: CN201410378452.3A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-07-29
Filing date: 2014-07-29
Publication date: 2014-12-31

Abstract

A hydrogenation method of inferior hydrocarbons containing easy-to-hydrogenolyze metallic compounds is especially suitable for hydrogenation demetalization reaction process namely shallow prehydrogenation reaction process R11 of the easy-to-hydrogenolyze metallic compounds MX such as iron naphthenate and calcium naphthenate of medium and low temperature coal tar HMS; on the contrary to a conventional technology concept, according to the hydrogenation method, the low deposition rate conditions are set, in the presence of hydrogen and hydrogen sulfide, hydrogenolyzed metal M and/or metal sulfide MS in fine granularity are/is mainly dispersed in a liquid phase of a reaction space material flow to form slurry and leave a shallow prehydrogenation reaction space along with fluid, the metal sulfide MS usually has no reactivity on a subsequent hydrogenation catalyst, can easily pass through a subsequent bed along with the liquid phase fluid, can effectively reduce the bed porosity decreasing rate, and prolongs the continuous running cycle, wherein the conventional technology concept is as follows: after conventional metal deposition interception by use of a hydrogenation protective agent and/or a hydrogenation demetalization agent, the hydrogenation protective agent and/or the hydrogenation demetalization agent may not enter the subsequent hydrogenation catalyst bed.

Description

A kind of hydrocarbon method of hydrotreating inferior containing easy hydrogenolysis metallic compound

Technical field

The present invention relates to a kind of hydrocarbon method of hydrotreating inferior containing easy hydrogenolysis metallic compound, be particularly suitable for the easy hydrogenolysis metallic compound MX of middle coalite tar HMS as iron naphthenate, the hydrodemetallation (HDM) reaction process of calcium naphthenate and either shallow pre-hydrotreating reaction process R11, with use hydrogenation protecting agent with or hydrodemetallation (HDM) agent make metal M be deposited on catalyst surface realize particulate matter to be separated with oil product or to make metal M to be deposited on catalyst surface to realize not entering after particulate matter is tackled the routine techniques theory of follow-up hydrogenation beds contrary, the present invention arranges low deposition rate condition, at hydrogen, under hydrogen sulfide existence condition, the metal M that hydrogenolysis is gone out and or metal sulfide M S be mainly dispersed in the liquid phase of reaction compartment logistics with trickle granularity and form slurry and leave either shallow pre-hydrotreating reaction space with fluid, metal sulfide M S does not have reactive behavior to follow-up hydrogenation catalyzer usually, be easy to penetrate follow-up bed with liquid phase fluid, effectively can reduce follow-up bed porosity rate of descent, extend the continuous cycle of operation, there is the advantage reducing deposit filler consumption.

Background technology

Below in conjunction with the deep hydrogenation upgrading processes of middle coalite tar, the existing hydrocarbon method of hydrotreating being rich in gluey pitch shape component is described.

Middle coalite tar HMS of the present invention, it can be the coal-tar pitch of the distillate such as middle coalite tar of coalite tar or middle coalite tar in full cut, usually grade containing the easy reactive component of pre-hydrogenation such as metal, alkene, phenol, polycyclic aromatic hydrocarbons, gluey pitch shape component, ash, the described easy reactive component of pre-hydrogenation causes catalyst surface coking or deposition of solids usually at reaction conditions.Middle coalite tar HMS, usually containing polycyclic aromatic hydrocarbons, condensed-nuclei aromatics, gluey pitch shape component.The aromatic ring number of condensed-nuclei aromatics mentioned herein is greater than 5, and the aromatic ring number of polycyclic aromatic hydrocarbons is 3 ~ 5.

For pre-hydrogenation easy reactive component content high be rich in coalite tar HMS in the poor quality of gluey pitch shape component, its target product is that the deep hydrogenation upgrading processes of diesel oil distillate generally includes the pre-hydrotreating reaction process R1 of coal tar HMS and the deep hydrogenation upgrading reaction process R2 of pre-hydrotreating reaction effluent R1P, in order to obtain light-end products to greatest extent as gasoline, diesel oil distillate, usually the normal boiling point in oil to comprise heat cracking reaction second heat processing (such as hydrocracking or hydrocracking or coking or catalytic cracking or catalytic pyrolysis etc.) higher than the hydrocarbon component of 350 DEG C is generated to the deep hydrogenation upgrading of gluey pitch shape component.

At the pre-hydrotreating reaction process R1 of middle coalite tar HMS, usual use catalyst for pre-hydrogenation R1C, catalyst for pre-hydrogenation R1C can be hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent, the single dose of aromatic hydrogenation fractional saturation catalyzer etc. or the series combination of two agent or multi-agent or mixed loading combination, under catalyst for pre-hydrogenation R1C existence condition, described middle coalite tar HMS and hydrogen carry out hydrogenation reaction, generate one by hydrogen, impurity component, conventional gas hydrocarbon, the pre-hydrotreating reaction effluent R1P of conventional liq hydrocarbon composition, object based on pre-hydrotreating reaction process R1 is filtering and removing mechanical impurity, olefin saturated, remove metal, remove the organic oxygen of part (such as organic phenol), remove part organosulfur and to the easy reactive component hydrogenation of other parts (hydrotreated lube base oil of first aromatic ring in such as polycyclic aromatic hydrocarbons), therefore the reaction conditions of pre-hydrotreating reaction process R1 comparatively relaxes than the reaction conditions of deep hydrogenation upgrading reaction process R2, usually, the good operational condition of pre-hydrotreating reaction process R1 is: temperature is 170 ~ 390 DEG C, pressure is 4.0 ~ 30.0MPa, catalyst for pre-hydrogenation R1C volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1, usual chemical pure hydrogen consumption is 0.5 ~ 2.5% (weight of centering coalite tar HMS).

At deep hydrogenation upgrading reaction process R2, under deep hydrogenation modifying catalyst R2C (usually at least using the deep hydrogenation possessing hydrofining function exquisite catalyzer R21C, sometimes conbined usage to possess the catalyzer R22C of hydrocracking function) existence condition, described pre-hydrotreating reaction effluent R1P carries out the reaction of deep hydrogenation upgrading, generates a deep hydrogenation upgrading reaction effluent R2P be made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon; Based on the index request of the upgraded product that deep hydrogenation upgrading reaction process R2 expects; deep hydrogenation upgrading reaction process R2 usually must remove most of sulphur, removes most of the nitrogen, significantly reduces density of aromatic hydrocarbon, improves cetane value, reduce density; usual chemical pure hydrogen consumption is 2.5 ~ 7.5% (weight to coal tar HMS), and the temperature of reaction of deep hydrogenation upgrading reaction process R2 is generally high more than 20 DEG C, usually high more than 50 DEG C, higher more than 90 DEG C especially than the temperature of reaction of pre-hydrotreating reaction process R1.The operational condition of the exquisite catalyzer R21C of deep hydrogenation of deep hydrogenation upgrading reaction process R2 is generally: temperature is 260 ~ 440 DEG C, pressure is 4.0 ~ 30.0MPa, catalyst for refining R21C volume space velocity is 0.1 ~ 4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1.Deep hydrogenation upgrading reaction process R2 sometimes conbined usage possesses the catalyzer R22C of hydrocracking function, and the operational condition of catalyzer R22C is generally: temperature is 300 ~ 440 DEG C, pressure is 4.0 ~ 30.0MPa, catalyzer R22 volume space velocity is 0.5 ~ 4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1.

At the pre-hydrotreating reaction process R1 of middle coalite tar HMS, the hydrodemetallation (HDM) reaction of usual generation metallorganics, according to the complexity of deviating from metal self-metallization compound, it is divided into two classes by the present invention substantially: category-A be the metallic compound of difficult hydrogenolysis as complex compound Porphyrin Nickel, porphyrin vanadium, ferrous porphyrin etc., category-B is that the metallic compound of easy hydrogenolysis is as naphthenate etc.The catalytic hydrodemetallation process that category-A metallic compound normally just can must complete on the hydrodemetallation (HDM) agent surface with suitable intensity hydrogenating function as the subtractive process of complex compound.And the easy hydrogenolysis metallic compound of category-B is as naphthenate, comprise iron naphthenate, calcium naphthenate etc., its hydrogenolysis belongs to on-catalytic thermal response usually, namely metal can be solved by Fast Hydrogen under certain temperature condition, in the hydrogen gas atmosphere, under hydrogen sulfide existence condition, usually sulfide is rapidly converted into as iron sulphide, sulfurated lime, the hydrogenating function that calcium hydrogenation hydrogenolysis process does not need the active metal of hydrogenation catalyst to provide substantially.There is significant difference in the two hydrogenation decomposition condition such as temperature, catalyst activity.The present invention is mainly for the on-catalytic thermal response of the easy hydrogenolysis metallic compound of category-B or catalytic hydrogenolysis process.

Category-B is the hydrogenating function that the hydrogenation hydrogenolysis process of the metallic compound of easy hydrogenolysis does not need the active metal of hydrogenation catalyst to provide substantially, but because conventional protective material such as porcelain Raschig ring or interpolation possess the active Raschig ring ball of hydrogenating function metal component on a small quantity for certain absorption hydrocarbon ils ability, make these fillers become hydrocarbon ils and expand gas, the carrier of liquid contact area, local reaction can be accelerated, by between sulfide and filler, the magnetism existed between the sulfide of deposition, sulfide is just attached in protectant part, outside surface, and form the deposition of to a certain degree (thickness), grow up, certainly, in up-flow reactor bed, under the condition that there is granules of catalyst and other granuloplastic collision, also can there is settling to come off, particularly for slight expanded-bed that is upflow fixed bed or pole low thermal expansion, beds expands smaller, therefore there is certain deposition between particles in settling, grow up, shedding machine meeting, therefore, when the first pre-hydrodemetallation (HDM) reaction effluent enters follow-up fixed bed hydrogenation reactor, should prevent these particulate matter come off from entering subsequent catalyst bed, when the first pre-hydrodemetallation (HDM) reaction effluent enters follow-up upflowing hydrogenator, should prevent the granularity the greater in these particulate matter come off from entering subsequent catalyst bed, or be deposited on the normal production of impact in valve, equipment, pipeline.

Along with the in poor quality of coal tar raw material, its metal content, gum asphaltic content are more and more higher, according to the analytical data of the ground coal tar such as Xinjiang of China Hami Prefecture, its Causes in Yulin District, substantially there is high, medium and low third gear in the content distribution of the metal in middle coalite tar particularly iron, calcium, magnesium, sodium, the long-term operation solution of the different easily coal tar hydrogenating process catalyst bed of hydrogenolysis metal content is necessarily different.

Easy hydrogenolysis metallic compound person as low in naphthenate content in coal tar, such as iron, calcium, magnesium, the content of sodium can be respectively≤10PPm, 10PPm, 10PPm, 5PPm, so low metal content, even if the hydrogenation protecting agent adopting its conversion product major part of conventional scheme or be almost all deposited in pre-hydrogenator, in hydrodemetallation (HDM) agent bed, owing to substantially not containing particulate matter or a small amount of particulate matter only containing minimum granularity in end reaction effluent, the separation system of end reaction effluent and generate separating of oil system and need not consider solid-liquor separation or gas solid separation, flow process is simple and direct, invest low, energy consumption is low.This scheme is option A, is a kind of economical process for demetalizating, because synchronously complete convert metals thing and generate oil separating.Wherein, the easy hydrogenolysis metallic compound hydrodemetallation (HDM) process of bed technology all uses the hydrogenation catalyst with weak hydrogenation activity or the porcelain filler without hydrogenation activity, and its profile is generally seven apertures in the human head porcelain ball, porcelain Raschig ring shape, porcelain four impeller, porcelain Herba Galii Bungei etc.

The medium person of easy hydrogenolysis metallic compound content in coal tar, the content of such as iron, calcium, magnesium, sodium can reach 10 ~ 30PPm, 10 ~ 30PPm, 10 ~ 30PPm, 5 ~ 10PPm respectively, as adopt scheme C, then invest high, energy consumption is high, uneconomical; As adopted option A, then cycle of operation is short, and device working rate is low, also uneconomical.The medium person of easy hydrogenolysis metal content in coal tar, the present inventor has proposed a kind of method extending the hydrogenation process continuous cycle of operation, namely a kind of raw material that comprises is connected along separate routes the hydrocarbon hydrogenation modification method inferior of pre-hydrogenation process, see Chinese patent application publication No. CN103897730A, the method can be applicable to upflowing pre-hydrogenator, but is more suitable for down-flow fixed bed pre-hydrogenator.For the medium person of easy hydrogenolysis metal content in coal tar, the present inventor has proposed a kind of pre-method of hydrotreating and the deep hydrogenation method for modifying that are applicable to upflowing pre-hydrogenator, its object is to the particulate matter of tackling greater particle size, be particularly suitable for using in upflowing slight expanded-bed reaction zone.This scheme is category-B scheme.

Easy hydrogenolysis metallic compound content height person in coal tar, such as iron, calcium, magnesium, the content of sodium can respectively up to 130PPm, 2100PPm, 50PPm, 25PPm, so high metal content, if its conversion product is all deposited in hydrogenation protecting reactor, the hydrogenation protecting capital cost of reactor of pre-hydrotreating reaction process R1 is inevitable excessive, pressure drop is inevitable excessive, catalyst consumption is inevitable excessive, say it is impracticable from engineering route, therefore a kind of economical reactor assembly newly must be proposed, the conversion product realizing this metalloid discharges reactive system continuously, to this, existing technical scheme is suspension bed, the technology such as ebullated bed.Wherein, the easy hydrogenolysis metallic compound hydrodemetallation (HDM) process of ebullated bed technology uses has the hydrogenation catalyst of weak hydrogenation activity or the porcelain filler without hydrogenation activity, its profile is generally ball-type or cylinder shape etc., use hydrogenation protecting agent and or hydrodemetallation (HDM) agent make metal deposit interception after do not enter follow-up hydrogenation beds; The easy hydrogenolysis metallic compound hydrodemetallation (HDM) process of suspension bed technology uses the hydrogenation catalyst with weak hydrogenation activity or without the dispersed catalyzer of hydrogenation activity or external additive; such as common Containing Sulfur iron substance or moly-sulfide crystallite or nanometer or particulate semicoke etc., use hydrogenation protecting agent with or hydrodemetallation (HDM) agent make metal M be deposited on catalyst surface to realize particulate matter and be separated with oil product.The general character of these technology is: the conversion product such as deposition of sulfides that easy hydrogenolysis metallic compound MX is formed hydrogenation protecting agent and or hydrodemetallation (HDM) agent on; therefore; hydrogenation protecting agent and or the consumption of hydrodemetallation (HDM) agent must increase; the solid matter produced must increase, and the separation costs of solid and liquid phase oil product must increase.Such as, for 200,000 tons/year of coal-tar middle oil hydrogenation units, assuming that coal-tar middle oil easy hydrogenolysis metal content 600PPm, coal-tar middle oil is 120 tons/year containing easy hydrogenolysis metal content conversion, by being all iron calculating, iron sulphide product amount 188.6 tons/year, be the accommodation settling ratio of the bed filler of 0.5 ton/cubic metre according to bulk density be 0.25 ton of/cubic metre of calculating, bed filler 754 cubic metres/year is needed to amount to 377 tons/year, clearly, if ensure the continuous seepage cycle of 1 year, if employing ebullated bed, need substantially to consume bed filler 754 cubic metres/year and amount to 377 tons/year, calculated by 8000 hours/year, 0.094 cubic metre/time 94 ls/h.Only 377 tons/year of bed fillers, according to 40,000 yuan/ton of calculating, cost is 1,508 ten thousand yuan/year.Consequently, the bed filler of consumption is all converted into solid waste, and not yet counts in order to the cost processed required for these solid waste meet the requirement of environmental protections.

For the easy hydrogenolysis metallic compound MX of middle coalite tar HMS as iron naphthenate, the hydrodemetallation (HDM) reaction process R11 of calcium naphthenate, in order to reduce the hydrodemetallation (HDM) process of easy hydrogenolysis metallic compound hydrogenation protecting agent and or the consumption of hydrodemetallation (HDM) agent, reduce solid matter output, reduce the separation costs of solid and liquid phase oil product, based on easy hydrogenolysis metallic compound as hydrogenolysis and the reaction that is deposited as sulfide mainly belong to the feature of on-catalytic thermal response, contrary with existing routine techniques theory, the present invention proposes a kind of method of hydrogenation demetalization of easy hydrogenolysis metallic compound of overcast rate, at hydrogen, under hydrogen sulfide existence condition, the metal M that hydrogenolysis is gone out and or metal sulfide M S be mainly dispersed in the liquid phase of reaction compartment logistics with trickle granularity and form slurry and leave reaction compartment with fluid, metal sulfide M S does not have reactive behavior to follow-up hydrogenation catalyzer usually, be easy to penetrate follow-up bed with liquid phase fluid, effectively can reduce bed porosity rate of descent, extend the continuous cycle of operation, at the inapplicable filler of reaction compartment or use low deposition rate filler as having the Stainless Steel Helices of mixing functions.

For deep hydrogenation upgrading processes particularly its pre-hydrotreating reaction process R1 containing the easy hydrogenolysis metallic compound particularly easy hydrocarbon material HMS that hydrogenolysis metallic compound content is high, 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;

10. the hydrocarbon ils that other easy hydrogenolysis metal content is high.

Processing method of the present invention has no report.

The first object of the present invention is to propose a kind of hydrocarbon method of hydrotreating inferior containing easy hydrogenolysis metallic compound.

The second object of the present invention is to propose a kind of hydrocarbon method of hydrotreating inferior containing easy hydrogenolysis metallic compound, is applicable to the hydrogenation process of the middle coalite tar being rich in easy hydrogenolysis metal.

Summary of the invention

A kind of hydrocarbon method of hydrotreating inferior containing easy hydrogenolysis metallic compound of the present invention, is characterized in that comprising following steps:

(1) at pre-hydrotreating reaction process R1, under hydrogen existence condition, the pre-hydrotreating reaction R1R that the hydrocarbon feed HMS containing easy hydrogenolysis metallic compound carries out the overcast rate hydrodemetallation (HDM) reaction comprising easy hydrogenolysis metallic compound obtains pre-hydrotreating reaction effluent R1P;

At either shallow pre-hydrotreating reaction process R11, under hydrogen existence condition, the hydrodemetallation (HDM) reaction R11R that hydrocarbon feed HMS carries out the overcast rate of easy hydrogenolysis metallic compound obtains either shallow pre-hydrotreating reaction effluent R11P; The metal M that hydrogenolysis goes out and or metal sulfide M S be mainly dispersed in the liquid phase of reaction compartment logistics with trickle granularity and form slurry and leave reaction compartment with either shallow pre-hydrotreating reaction effluent R11P;

Described easy hydrogenolysis metallic compound MX, refers to the metallic compound that its hydrogenolysis is mainly thermal response, comprises naphthenate, naphthenate at least comprise iron naphthenate and or calcium naphthenate;

(2) at deep hydrogenation upgrading reaction process R2, under deep hydrogenation modifying catalyst R2C existence condition, described pre-hydrotreating reaction effluent R1P carries out the reaction of deep hydrogenation upgrading, generates a deep hydrogenation upgrading reaction effluent R2P be made up of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;

(3) at separate part HPS, be separated deep hydrogenation upgrading reaction effluent R2P and obtain generating oily R2P0 primarily of the hydrogen rich gas gas HPV of hydrogen composition and deep hydrogenation upgrading, hydrogen rich gas gas HPV returns hydrogenation process and recycles at least partially.

The present invention arranges degree of depth pre-hydrotreating reaction process R12 usually, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, at degree of depth pre-hydrotreating reaction process R12, under hydrogen, hydrogen sulfide and degree of depth catalyst for pre-hydrogenation R12C existence condition, pre-hydrotreating reaction effluent R11P or its isolated liquid phase stream, carry out comprising catalytic hydrodemetallation reaction and or the shortening degree of depth pre-hydrotreating reaction R12R that takes off carbon residue reaction obtain degree of depth pre-hydrotreating reaction effluent R12P; Degree of depth pre-hydrotreating reaction effluent R12P is used as pre-hydrotreating reaction effluent R1P; Catalyst for pre-hydrogenation R1C comprises degree of depth catalyst for pre-hydrogenation R12C.

The present invention, at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, can use the bed filler R11C without hydrogenation activity, such as have the Stainless Steel Helices of mixing functions.

The present invention, can arrange the high pressure hot separator 1THPS being separated pre-hydrotreating reaction effluent R1P, removes deep hydrogenation upgrading reaction process R2, it is characterized in that after hot high score oil 1THPL removes solid:

(1) at pre-hydrotreating reaction process R1, pre-hydrotreating reaction effluent R1P enters high pressure hot separator 1THPS and is separated into heat of dissociation high score gas gas 1THPV and hot high score oil 1THPL; Hot high score gas 1THPV penetration depth hydro-upgrading reaction process R2 contacts with deep hydrogenation modifying catalyst R2C at least partially; Obtain de-solid hydrocarbon ils 1THPL-L after hot high score oil 1THPL removes solid particulate, de-solid hydrocarbon ils 1THPL-L penetration depth hydro-upgrading reaction process R2 contacts with deep hydrogenation modifying catalyst R2C at least partially.

The present invention, can arrange the high pressure hot separator 1THPS being separated pre-hydrotreating reaction effluent R1P, and hot high score oil 1THPL removes solid particulate, remove normal boiling point removes deep hydrogenation upgrading reaction process R2 higher than after 530 DEG C of hydrocarbon components, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, pre-hydrotreating reaction effluent R1P enters high pressure hot separator 1THPS and is separated into heat of dissociation high score gas gas 1THPV and hot high score oil 1THPL; Hot high score gas 1THPV penetration depth hydro-upgrading reaction process R2 contacts with deep hydrogenation modifying catalyst R2C at least partially; Hot high score oil 1THPL removes solid particulate, remove normal boiling point obtains hydrocarbon ils 1THPL-L higher than after 530 DEG C of hydrocarbon components, and hydrocarbon ils 1THPL-L penetration depth hydro-upgrading reaction process R2 contacts with deep hydrogenation modifying catalyst R2C at least partially.

The present invention, at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, can use the bed filler R11C without hydrogenation activity; The mode of operation of filler R11C bed R11CB, can be selected from one or more in following pattern:

1. upflowing suspension bed;

2. upflowing ebullated bed;

3. upflowing slight expanded-bed, described upflowing slight expanded-bed, the beds of its reactor respond raw material by time the maximum height CWH of working order and the ratio K BED of height CUH of empty bed static condition of the beds of reactor be defined as bed expansion ratio, KBED is lower than 1.10;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

The present invention, before the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, the preposition catalyst for pre-hydrogenation bed of one or more can connected in the following pattern bed of use, such as carry out olefin saturation etc., preposition catalyst for pre-hydrogenation particle does not enter either shallow pre-hydrotreating reaction process R11:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

3. upflowing is expanded bed, described upflowing slight expanded-bed, the beds of its reactor respond raw material by time the maximum height CWH of working order and the ratio K BED of height CUH of empty bed static condition of the beds of reactor be defined as bed expansion ratio, KBED is lower than 1.10;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

The present invention, at the degree of depth pre-hydrotreating reaction process R12 of pre-hydrotreating reaction process R1, uses the bed filler R12C having hydrogenation activity; The mode of operation of filler R12C bed R12CB, can be selected from one or more in following pattern:

1. upflowing suspension bed;

2. upflowing ebullated bed;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

The present invention, the beds mode of operation of deep hydrogenation upgrading reaction process R2, can be selected from upflowing bed and or downflow system bed, be such as selected from one or more in following pattern:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

The present invention, hydrocarbon feed HMS can be 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;

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.

The present invention, hydrocarbon feed HMS, when the easy hydrogenolysis metal concentration being benchmark with hydrogenolysis metallic compound easy contained by it is lower than 50PPm, pre-hydrotreating reaction effluent R1P can direct penetration depth hydro-upgrading reaction process R2.

The present invention, hydrocarbon feed HMS, the easy hydrogenolysis metal concentration being benchmark with hydrogenolysis metallic compound easy contained by it higher than 100PPm particularly higher than 200PPm time, usually arrange the high pressure hot separator 1THPS being separated pre-hydrotreating reaction effluent R1P, hot high score oil 1THPL removes solid particulate and or removes normal boiling point and remove deep hydrogenation upgrading reaction process R2 higher than after 530 DEG C of hydrocarbon components.

The present invention, can introduce pre-hydrotreating reaction process R1 by hydrogen supply hydrocarbon stream, contact and combine processing with hydrocarbon feed HMS.

The present invention, Action Target is generally:

(1) at pre-hydrotreating reaction process R1, hydrocarbon feed HMS is middle coalite tar; The metal content of the conventional liq hydrocarbon in pre-hydrotreating reaction effluent R1P is lower than 10PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrotreating reaction effluent R1P is lower than 1.5%;

(2) the full cut diesel-fuel cetane number in deep hydrogenation upgrading reaction effluent R2P is higher than 26.

The present invention, Action Target is generally:

(1) at pre-hydrotreating reaction process R1, hydrocarbon feed HMS is middle coalite tar; The metal content of the conventional liq hydrocarbon in pre-hydrotreating reaction effluent R1P is lower than 5PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrotreating reaction effluent R1P is lower than 0.5%;

(2) the full cut diesel-fuel cetane number in deep hydrogenation upgrading reaction effluent R2P is higher than 35.

The present invention, hydrocracking reaction process R3 can be set, the hydro-upgrading heavy oil R2P0-D0 formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2P0 gained being separated deep hydrogenation upgrading reaction effluent R2P, for raw material, is converted into hydrocracking reaction effluent R3P at hydrocracking reaction process R3; Hydrocracking reaction effluent R3P is separated after can mixing with hydrogenation reaction effluent R2P.

The present invention, separate part HPS, usually cold anticyclone separate part LHPS is comprised, at cold anticyclone separate part LHPS, be separated deep hydrogenation upgrading reaction effluent R2P and obtain cold high score gas gas HPV primarily of hydrogen composition and cold high score oil LHPL, cold high score oil LHPL generates oily R2P0 as deep hydrogenation upgrading.

The present invention, when separate part HPS comprises thermal high separate part THPS and cold anticyclone separate part LHPS, at thermal high separate part THPS, is separated deep hydrogenation upgrading reaction effluent R2P and obtains hot high score gas gas THPV and hot high score oil THPL; At cold anticyclone separate part LHPS, heat of dissociation high score gas gas THPV obtain primarily of hydrogen composition cold high score gas gas HPV and cold high score oil LHPL, deep hydrogenation upgrading generate oily R2P0 comprise hot high score oil THPL and cold high score oil LHPL.

The present invention, detailed operational condition is generally:

The operational condition of pre-hydrotreating reaction process R1 is: temperature is 170 ~ 390 DEG C, pressure is 4.0 ~ 30.0MPa, catalyst for pre-hydrogenation R1C volume space velocity is 0.05 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 100: 1 ~ 4000: 1, chemical pure hydrogen consumption is 0.15 ~ 2.5% (weight of centering coalite tar HMS);

The operational condition of bed filler R11C is: temperature is 170 ~ 330 DEG C, pressure is 4.0 ~ 30.0MPa, the liquid phase residence time is greater than 10 seconds, hydrogen/stock oil volume ratio is 100: 1 ~ 4000: 1;

The operational condition of bed filler R12C is: temperature is 170 ~ 330 DEG C, pressure is 4.0 ~ 30.0MPa, volume space velocity is 0.15 ~ 15.0hr ^-1, hydrogen/stock oil volume ratio is 100: 1 ~ 4000: 1;

(2) the full cut diesel-fuel cetane number in deep hydrogenation upgrading reaction effluent R2P is higher than 26;

The operational condition of deep hydrogenation upgrading reaction process R2 is often: temperature is 260 ~ 440 DEG C, pressure is 4.0 ~ 30.0MPa, catalyst for refining R21C volume space velocity is 0.1 ~ 4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1 ~ 4000: 1.

The present invention, detailed operational condition is generally:

The operational condition of pre-hydrotreating reaction process R1 is: temperature is 210 ~ 350 DEG C, pressure is 12.0 ~ 18.0MPa, catalyst for pre-hydrogenation R1C volume space velocity is 0.2 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 200: 1 ~ 2000: 1, chemical pure hydrogen consumption is 0.35 ~ 1.5% (weight of centering coalite tar HMS);

The operational condition of either shallow pre-hydrotreating reaction process R11 is: temperature is 210 ~ 280 DEG C, pressure is 12.0 ~ 18.0MPa, the liquid phase residence time is greater than 20 seconds, hydrogen/stock oil volume ratio is 200: 1 ~ 2000: 1;

The operational condition of bed filler R12C is: temperature is 210 ~ 280 DEG C, pressure is 12.0 ~ 18.0MPa, volume space velocity is 0.3 ~ 5.0hr ^-1, hydrogen/stock oil volume ratio is 200: 1 ~ 2000: 1;

(2) the full cut diesel-fuel cetane number in deep hydrogenation upgrading reaction effluent R2P is higher than 35;

The operational condition of deep hydrogenation upgrading reaction process R2 is often: temperature is 300 ~ 420 DEG C, pressure is 12.0 ~ 18.0MPa, catalyst for refining R21C volume space velocity is 0.2 ~ 2.0hr ^-1, hydrogen/stock oil volume ratio is 800: 1 ~ 2000: 1.

The present invention, at pre-hydrotreating reaction process R1, new hydrogen is preferentially selected in the hydrogen rich gas logistics injecting pre-hydrogenator.

The present invention, at pre-hydrotreating reaction process R1, inject bed filler R11C hydrogen rich gas logistics preferentially select new hydrogen.

The present invention, at pre-hydrotreating reaction process R1, in pre-hydrogenator, hydrogen sulfide in gas phase volumetric concentration is generally 0.1 ~ 5%, is generally 0.3 ~ 1.0%.

The present invention, at pre-hydrotreating reaction process R1, can be combined to form integrated reactor by filler R11C bed and filler R12C bed; Integrated up-flow reactor can contain 1 or 2 or multiple filler R11C beds, and integrated reactor can contain 1 or 2 or multiple filler R12C beds.

The present invention, at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, use the bed filler R11C without hydrogenation activity, filler R11C can be divided into the filling batch of 2 layers or 3 layers load in series.

The present invention, the mode of operation of each reaction zone filler of recommendation, first scheme is:

(1) either shallow pre-hydrotreating reaction process R11, uses tubular reactor, with easy hydrogenolysis convert metals thing for suspended particle; In pipe, velocity of medium is usually greater than 0.3 meter per second, is generally greater than 0.8 meter per second, is greater than 1.5 meter per seconds especially;

Degree of depth pre-hydrotreating reaction process R12, hydrogenation catalyst bed mode of operation is upflowing slight expanded-bed;

(2) at deep hydrogenation upgrading reaction process R2, hydrogenation catalyst bed mode of operation is down-flow fixed bed.

The present invention, the mode of operation of each reaction zone filler of recommendation, alternative plan is:

(1) either shallow pre-hydrotreating reaction process R11, uses tubular reactor, with easy hydrogenolysis convert metals thing for suspended particle;

Degree of depth pre-hydrotreating reaction process R12, hydrogenation catalyst bed mode of operation is upflowing ebullated bed;

The present invention, the mode of operation of each reaction zone filler of recommendation, third program is:

Degree of depth pre-hydrotreating reaction process R12, hydrogenation catalyst bed mode of operation is upflowing suspension bed;

The present invention, the mode of operation of each reaction zone filler of recommendation, fourth program is:

Degree of depth pre-hydrotreating reaction process R12, hydrogenation catalyst bed mode of operation is upflow fixed bed, should use open grain bed filler, can be selected from one or more in following pattern:

1. porous ball;

2. Raschig ring;

3. four impellers;

4. Herba Galii Bungei;

5. other open grain bed filler;

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.

Petroleum naphtha of the present invention refers to normal boiling point lower than the conventional liq hydrocarbon of 180 DEG C.

Diesel component of the present invention refers to the hydro carbons that normal boiling point is 180 ~ 355 DEG C.

Wax oil component of the present invention refers to the hydro carbons that normal boiling point is 355 ~ 490 DEG C.

Heavy oil component of the present invention refers to normal boiling point higher than the hydro carbons of 350 DEG C.

The aromatic ring number of condensed-nuclei aromatics mentioned herein is greater than 5, and the aromatic ring number of polycyclic aromatic hydrocarbons is 3 ~ 5.

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

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

Easy hydrogenolysis metal component of the present invention, refer to the metallic compound that hydrogenolysis can occur fast at necessarily high temperature and hydrogen existence condition, be commonly referred to as oil soluble metal compound as iron naphthenate, calcium naphthenate etc., these components can be rapidly converted into sulfide as iron sulphide, sulfurated lime under hydrogen sulfide existence condition, and granular precipitates or coprecipitate can be formed, under certain condition, particle size can be grown up.

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 that coal coking pyrolysis of coal process (comprises semi-coking, middle temperature coking, high-temperature coking process) by product coal tar or its cut, coal tar of the present invention can also be the mixing oil of above-mentioned coal tar, coal tar of the present invention can also be extract oil such as the 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%.

The olefin(e) centent of usual coal tar lighting end is high, the high component also containing more easily reaction under mitigation condition of phenol content; therefore; the pre-hydrogenation process of coal tar lighting end of the present invention, usually uses the single dose of hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination.

Coal tar heavy fractioning is coal-tar pitch cut particularly; its metal content is high, gum level is high, asphalt content is high; therefore; the pre-hydrogenation process of coal tar heavy fractioning of the present invention, usually uses the single dose of hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent etc. or the series combination of two agent or multi-agent or mixed loading combination

The overwhelming majority due to metal concentrates on normal boiling point higher than 350 DEG C particularly higher than in the cut of 450 DEG C, the therefore pre-hydrogenation process of Main Analysis coal tar heavy fractioning of the present invention.

Experimental study and full scale plant running all show, the pre-hydrotreating reaction process R1 of middle coalite tar, and raw material different components temperature of reaction is realistic according to being divided into following steps from low to high substantially:

Easy hydrogenolysis metal fever decomposes < high reactivity condensed-nuclei aromatics thermal condensation and the hydrogenating desulfurization of hydrotreated lube base oil < rudimentary sulphur compound, organometallic complex catalytic hydrogenolysis, rudimentary organic phenol catalytic deoxidation, polycyclic aromatic hydrocarbons take off carbon residue

Said temperature scope is generally 220 ~ 330 DEG C, clearly, this is the temperature of reaction interval of a wide region, should control as first, second, third step of differing temps section is according to carrying out stage by stage from low to high, be beneficial to reduction metallic sulfide formation speed, reduce pyrocondensation compound formation speed, prevent from forming superposition peak value, realize the depth profiles of easy hydrogenolysis metal deposit at beds, improve the controllability of deposition reaction.

Below describe characteristic of the present invention in detail.

1. upflowing suspension bed;

2. upflowing ebullated bed;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

The present invention, before the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, the preposition catalyst for pre-hydrogenation bed of one or more can connected in the following pattern bed of use, preposition catalyst for pre-hydrogenation particle does not enter either shallow pre-hydrotreating reaction process R11:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

1. upflowing suspension bed;

2. upflowing ebullated bed;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

1. upflowing ebullated bed;

2. upflowing bubbling bed;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

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;

The present invention, Action Target is generally:

The present invention, detailed operational condition is generally:

1. porous ball;

2. Raschig ring;

3. four impellers;

4. Herba Galii Bungei;

5. other open grain bed filler;

As required, any one supplementary sulphur can be added pre-hydrotreating reaction process R1 and or deep hydrogenation upgrading reaction process R2, to ensure minimum concentration of hydrogen sulfide such as 500PPm (v) or 1000PPm (v) that reaction process is necessary or prescribed value, 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.When the dilution hydrocarbon of pre-hydrotreating reaction process R1 provides with hydrogen sulfide containing hydrogenation reaction effluent form, if hydrogen sulfide quantity wherein meets the needs of pre-hydrotreating reaction process R1, sulfur supplementary agent can not be re-used.

Below describe the rule of the high pressure separation process of hydrogenation reaction effluent of the present invention 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) or viscosity is large or when being difficult to be separated with emulsifying water, 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., the hydrogenation process that hot for part high score fluid body returns to upstream can be recycled meanwhile, to improve the overall raw material character of the hydrogenation process receiving this turning oil, or circulation hydrogenation is carried out 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 pre-hydrotreating reaction process R1.

Either shallow pre-hydrotreating reaction process R11, use tubular reactor, use the hybrid element of the high low deposition effect of mixture strength can strengthen reflection effect, be beneficial to and strengthen easy hydrogenolysis metallic compound MX as the dispersity meeting of the hydrodemetallation (HDM) reaction process R11 product of iron naphthenate, calcium naphthenate, reduce the particle diameter of particle.

The invention has the advantages that; contrary with routine techniques theory; adopt a kind of method of hydrogenation demetalization of easy hydrogenolysis metallic compound of overcast rate; can effectively reduce the hydrodemetallation (HDM) process of easy hydrogenolysis metallic compound hydrogenation protecting agent and or the consumption of hydrodemetallation (HDM) agent; reduce solid matter output; reduce the separation costs of solid and liquid phase oil product, be particularly suitable for the easy hydrogenolysis metallic compound MX of middle coalite tar HMS as the hydrodemetallation (HDM) reaction process R11 of iron naphthenate, calcium naphthenate.

The present invention, can be applied to the hydrogenation process of any hydrocarbon stream containing easy hydrogenolysis metallic compound.

Claims

1., containing a hydrocarbon method of hydrotreating inferior for easy hydrogenolysis metallic compound, it is characterized in that comprising following steps:

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

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

(1) at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, the bed filler R11C without hydrogenation activity is used.

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

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

6. method according to claim 3, is characterized in that:

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

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

9. method according to claim 3, is characterized in that:

10. method according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9, is characterized in that:

(1) at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, the bed filler R11C without hydrogenation activity is used; The mode of operation of filler R11C bed R11CB, is selected from one or more in following pattern:

1. upflowing suspension bed;

2. upflowing ebullated bed;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

11. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

At pre-hydrotreating reaction process R1, before either shallow pre-hydrotreating reaction process R11, series connection uses the preposition catalyst for pre-hydrogenation bed of one or more in following pattern bed, and preposition catalyst for pre-hydrogenation particle does not enter either shallow pre-hydrotreating reaction process R11:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

12. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at the degree of depth pre-hydrotreating reaction process R12 of pre-hydrotreating reaction process R1, the bed filler R12C having hydrogenation activity is used; The mode of operation of filler R12C bed R12CB, is selected from one or more in following pattern:

1. upflowing suspension bed;

2. upflowing ebullated bed;

4. upflowing bubbling bed;

5. upflowing moving-bed;

6. upflow fixed bed;

7. down-flow fixed bed;

8. downflow system moving-bed;

9. horizontal bed;

10. tilting bed.

13. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

The beds mode of operation of deep hydrogenation upgrading reaction process R2, is selected from upflowing bed and or downflow system bed.

14. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

The beds mode of operation of deep hydrogenation upgrading reaction process R2, is selected from one or more in following pattern:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

4. upflow fixed bed;

5. upflowing moving-bed;

6. down-flow fixed bed;

7. downflow system moving-bed;

8. horizontal bed;

9. tilting bed.

15. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

Hydrocarbon feed HMS 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;

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

Hydrocarbon feed HMS, the easy hydrogenolysis metal concentration being benchmark with hydrogenolysis metallic compound easy contained by it is lower than 50PPm.

17. want method described in 4 or 5 or 6 or 7 or 8 or 9 according to right, it is characterized in that:

Hydrocarbon feed HMS, the easy hydrogenolysis metal concentration being benchmark with hydrogenolysis metallic compound easy contained by it is higher than 100PPm.

18. according to claim 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

Hydrocarbon feed HMS, the easy hydrogenolysis metal concentration being benchmark with hydrogenolysis metallic compound easy contained by it is higher than 200PPm.

19. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

Hydrogen supply hydrocarbon stream enters pre-hydrotreating reaction process R1, contacts and combine processing with hydrocarbon feed HMS.

20. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

21. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

22. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(4) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2P0-D0 formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2P0 gained being separated deep hydrogenation upgrading reaction effluent R2P, for raw material, is converted into hydrocracking reaction effluent R3P at hydrocracking reaction process R3.

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

24. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(4) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2P0-D0 formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2P0 gained being separated deep hydrogenation upgrading reaction effluent R2P is for raw material, be converted into hydrocracking reaction effluent R3P at hydrocracking reaction process R3, be separated after hydrocracking reaction effluent R3P mixes with hydrogenation reaction effluent R2P.

25. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(3) separate part HPS comprises cold anticyclone separate part LHPS, at cold anticyclone separate part LHPS, be separated deep hydrogenation upgrading reaction effluent R2P and obtain cold high score gas gas HPV primarily of hydrogen composition and cold high score oil LHPL, cold high score oil LHPL generates oily R2P0 as deep hydrogenation upgrading.

26. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(3) separate part HPS comprises thermal high separate part THPS and cold anticyclone separate part LHPS;

At thermal high separate part THPS, be separated deep hydrogenation upgrading reaction effluent R2P and obtain hot high score gas gas THPV and hot high score oil THPL;

At cold anticyclone separate part LHPS, heat of dissociation high score gas gas THPV obtain primarily of hydrogen composition cold high score gas gas HPV and cold high score oil LHPL, deep hydrogenation upgrading generate oily R2P0 comprise hot high score oil THPL and cold high score oil LHPL.

27. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

28. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

29. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, the hydrogen rich gas logistics injecting pre-hydrogenator is new hydrogen.

30. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, inject bed filler R11C hydrogen rich gas logistics be new hydrogen.

31. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, in pre-hydrogenator, hydrogen sulfide in gas phase volumetric concentration is 0.1 ~ 5%.

32. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, in pre-hydrogenator, hydrogen sulfide in gas phase volumetric concentration is 0.3 ~ 1.0%.

33. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1, filler R11C bed and filler R12C bed are combined to form integrated reactor.

34., according to method described in claim 33, is characterized in that:

(1) at pre-hydrotreating reaction process R1, filler R11C bed and filler R12C bed are combined to form integrated reactor; Integrated up-flow reactor contains 1 or 2 or multiple filler R11C beds, and integrated reactor contains 1 or 2 or multiple filler R12C beds.

35. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at the either shallow pre-hydrotreating reaction process R11 of pre-hydrotreating reaction process R1, use the bed filler R11C without hydrogenation activity, filler R11C is divided into the filling batch of 2 layers of load in series.

36. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

(1) at pre-hydrotreating reaction process R1 at either shallow pre-hydrotreating reaction process R11, use without the bed filler R11C of hydrogenation activity, filler R11C is divided into the filling batch of 3 layers of load in series.

37. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

38., according to method described in claim 37, is characterized in that:

(1) at pre-hydrotreating reaction process R1, either shallow pre-hydrotreating reaction process R11, uses tubular reactor, and in pipe, velocity of medium is greater than 0.3 meter per second.

39., according to method described in claim 37, is characterized in that:

(1) at pre-hydrotreating reaction process R1, either shallow pre-hydrotreating reaction process R11, uses tubular reactor, and in pipe, velocity of medium is greater than 0.8 meter per second.

40., according to method described in claim 37, is characterized in that:

(1) at pre-hydrotreating reaction process R1, either shallow pre-hydrotreating reaction process R11, uses tubular reactor, and in pipe, velocity of medium is greater than 1.5 meter per seconds.

41. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

42. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

43. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 method, it is characterized in that:

Degree of depth pre-hydrotreating reaction process R12, hydrogenation catalyst bed mode of operation is upflow fixed bed;

44., according to method described in claim 43, is characterized in that:

(1) at the degree of depth pre-hydrotreating reaction process R12 of pre-hydrotreating reaction process R1, hydrogenation catalyst bed mode of operation is upflow fixed bed, uses open grain bed filler.

45., according to method described in claim 43, is characterized in that:

(1) at the degree of depth pre-hydrotreating reaction process R12 of pre-hydrotreating reaction process R1, hydrogenation catalyst bed mode of operation is upflow fixed bed, and the open grain bed filler of use, is selected from one or more in following pattern:

1. porous ball;

2. Raschig ring;

3. four impellers;

4. Herba Galii Bungei;

5. other open grain bed filler.