CN104178209A

CN104178209A - Joint hydrogenation method for different fractions of high aromatic hydrocarbons

Info

Publication number: CN104178209A
Application number: CN201410381304.7A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-07-31
Filing date: 2014-07-31
Publication date: 2014-12-03

Abstract

The invention discloses a joint hydrogenation method for different fractions of high aromatic hydrocarbons, which is suitable for a joint hydrogenation process of heavy fraction HS and light fraction LS of medium and low-temperature coal tar. The heavy fraction HS is subjected to a pre-hydrogenation process comprising hydrodemetallization and hydrodepolymerization of colloidal pitch components in the pre-hydrogenation refining reaction process R1 under the appropriate low-temperature condition; the light fraction LS and a pre-hydrogenation refining reaction product R1PS enter a middle hydrogenation refining reaction process RM; R1PS is gradually heated by using the reaction heat of pre-hydrogenation reaction RMLSR of the light fraction LS to form an overall raising reaction temperature curve; step-by-step warming middle hydrogenation refining reaction RMHSR is formed on the R1PS containing polycyclic aromatic hydrocarbon; recovery of the reaction heat of pre-hydrogenation reaction process RMLSR of the light fraction LS is facilitated; the reduction of the yield of a thermal condensation compound of the polycyclic aromatic hydrocarbon is facilitated; and the middle hydrogenation refining reaction product RMPS enters a deep hydrogenation refining reaction process R1 for deep hydrogenation refining reaction R2R.

Description

The combined hydrogenation method of the high aromatic hydrocarbons of a kind of different fractions

Technical field

The present invention relates to the combined hydrogenation method of the high aromatic hydrocarbons of a kind of different fractions, the Unionfining process that is suitable for last running HS and the lighting end LS of middle coalite tar, last running HS comprises the pre-hydrogenation process of hydrodemetallation (HDM) and gluey pitch shape component hydrodepolymerization under suitable low temperature condition at pre-hydrofining reaction process R1; Hydrofining reaction process RM in the middle of lighting end LS and pre-hydrofining reaction product R1PS enter, utilize the reaction heat of lighting end LS pre-hydrotreating reaction RMLSR progressively to heat the temperature of reaction curve that R1PS forms overall rising, the R1PS that comprises condensed-nuclei aromatics is formed to the middle hydrofining reaction RMHSR of cascade raising temperature, be beneficial to the reaction heat that reclaims lighting end LS pre-hydrotreating reaction process RMLSR, be beneficial to the thermal condensation produce amount that reduces condensed-nuclei aromatics; Middle hydrofining reaction product RMPS penetration depth hydrofining reaction process R2 carries out deep hydrofinishing reaction R2R.

Background technology

Below describe and be existingly rich in gluey pitch shape component and or be rich in the deep hydrogenation upgrading process of the middle coalite tar HMS of easy hydrogenolysis metallic compound.

Middle coalite tar HMS of the present invention, can be that the distillate of coalite tar or middle coalite tar in full cut is such as the coal-tar pitch of middle coalite tar, conventionally contain the easy reactive component of pre-hydrogenation and grade 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 conventionally under reaction conditions.Middle coalite tar HMS, contains polycyclic aromatic hydrocarbons, condensed-nuclei aromatics, gluey pitch shape component conventionally.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 coalite tar HMS in the high poor quality that is rich in gluey pitch shape component of the easy reactive component content of pre-hydrogenation, its target product is that the deep hydrogenation upgrading process 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 to greatest extent light-end products as gasoline, diesel oil distillate, conventionally the deep hydrogenation upgrading of gluey pitch shape component is generated to the second heat processing (such as hydrocracking or hydrocracking or coking or catalytic cracking or catalytic pyrolysis etc.) that conventional boiling point in oil comprises heat cracking reaction higher than the hydrocarbon component of 350 ℃.

Pre-hydrotreating reaction process R1 at middle coalite tar HMS, conventionally 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 series combination or the mixed loading combination of two agent or multi-agent, 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 that conventional liq hydrocarbon forms, 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 (such as the hydrogenation of first aromatic ring in polycyclic aromatic hydrocarbons is saturated), therefore the reaction conditions of pre-hydrotreating reaction process R1 comparatively relaxes than the reaction conditions of deep hydrogenation upgrading reaction process R2, conventionally, the good operational condition of pre-hydrotreating reaction process R1 is: temperature is 170～350 ℃, pressure is 4.0～30.0MPa, catalyst for pre-hydrogenation R1C volume space velocity is 0.05～10.0hr ^-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) conventionally.

At deep hydrogenation upgrading reaction process R2, at deep hydrogenation modifying catalyst R2C, (conventionally at least use the exquisite catalyzer R21C of deep hydrogenation that possesses hydrofining function, sometimes combine and use the catalyzer R22C possess hydrocracking function) under existence condition, described pre-hydrotreating reaction effluent R1P carries out the reaction of deep hydrogenation upgrading, generate one by hydrogen, impurity component, conventional gas hydrocarbon, the deep hydrogenation upgrading reaction effluent R2P that conventional liq hydrocarbon forms: the index request of the upgraded product based on deep hydrogenation upgrading reaction process R2 expection, deep hydrogenation upgrading reaction process R2 must remove most of sulphur conventionally, remove most of the nitrogen, significantly reduce density of aromatic hydrocarbon, improve cetane value, reduce density, conventionally chemical pure hydrogen consumption is 2.5～7.5% (weight to coal tar HMS), the temperature of reaction of deep hydrogenation upgrading reaction process R2 is general higher more than 20 ℃ than the temperature of reaction of pre-hydrotreating reaction process R1, conventionally high more than 50 ℃, high more than 90 ℃ especially.The operational condition of the exquisite catalyzer R21C of the deep hydrogenation of deep hydrogenation upgrading reaction process R2 is generally: temperature is that 300～450 ℃, pressure are that 4.0～30.0MPa, catalyst for refining R21C volume space velocity are 0.1～4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.Deep hydrogenation upgrading reaction process R2 sometimes combines and uses the catalyzer R22C possess hydrocracking function, and the operational condition of catalyzer R22C is generally: temperature is that 330～440 ℃, pressure are that 4.0～30.0MPa, catalyzer R22 volume space velocity are 0.5～4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.

The full cut of middle coalite tar is wide fraction mixture, comprises last running HS and lighting end LS.

Described middle coalite tar last running HS, refer to common conventional boiling point higher than 350 ℃ especially conventional boiling point higher than the middle coalite tar cut of 450 ℃, conventionally contain more thermal condensation and be inclined to serious gum asphalt component, contain more metal simultaneously.Centering coalite tar HMS, most of or the overwhelming majority of its metal-containing compound concentrate on conventional boiling point higher than 350 ℃ particularly higher than in the last running HS of 450 ℃, the overwhelming majority of the carbon residue precursor such as its contained condensed-nuclei aromatics concentrate on conventional boiling point higher than 350 ℃ particularly higher than in the last running HS of 450 ℃.

Described middle coalite tar lighting end LS, refer to common conventional boiling point lower than 350 ℃ especially conventional boiling point lower than the middle coalite tar cut of 450 ℃, conventionally contain more alkene, phenols, contain less metal simultaneously.

Temperature of reaction matching problem between the pre-hydrotreating reaction process R1 of following detailed analysis coal tar heavy fractioning and deep hydrogenation upgrading reaction process R2.

Pre-hydrotreating reaction process R1 at middle coalite tar HMS, conventionally there is the hydrodemetallation (HDM) reaction of metallorganics, according to the complexity of deviating from metal self-metallization compound, the present invention is divided into two classes substantially by it: easily the metallic compound of hydrogenolysis is as naphthenate etc., and the metallic compound of difficult hydrogenolysis is as complex compound Porphyrin Nickel, porphyrin vanadium, ferrous porphyrin etc.Conventionally, the metallic compound containing in middle coalite tar be take the metallic compound of easy hydrogenolysis as main, and this point forms and take complex compound Porphyrin Nickel, porphyrin vanadium as main just contrary with the metal of petroleum base residual oil.

Easily hydrogenolysis metallic compound is as naphthenate, comprise iron naphthenate, calcium naphthenate etc., its hydrogenolysis belongs to on-catalytic thermal response conventionally, under certain temperature condition, can solve metal by Fast Hydrogen in hydrogen environment, under hydrogen sulfide existence condition, conventionally rapid conversion be sulfide 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.The shortening demetalization process that the metallic compound of difficult hydrogenolysis normally must just can complete on the hydrodemetallation (HDM) agent surface with suitable intensity hydrogenating function as the subtractive process of complex compound, and need higher temperature of reaction, the hydrogenation and removing reaction start-up temperature of the easier hydrogenolysis metallic compound of start-up temperature of its reaction is higher, such as exceeding 30～70 ℃.There is significant difference as temperature, catalyst activity in the hydrogenation decomposition condition of the two.

Experimental study and full scale plant running all show, the pre-hydrotreating reaction process R1 of middle coalite tar, raw material different components temperature of reaction is realistic according to being divided into following steps from low to high substantially: 1. easily hydrogenolysis metal fever decomposes the 2. thermal condensation of high reactivity condensed-nuclei aromatics and 3. rudimentary sulphur compound hydrogenating desulfurization of the saturated < of hydrogenation of <, organometallic complex catalytic hydrogenolysis, rudimentary organic phenol catalytic deoxidation, the de-carbon residue of polycyclic aromatic hydrocarbons; Said temperature scope is generally 220～330 ℃, clearly, this is the temperature of reaction interval of a wide region, should control first, second, third step for differing temps section 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 stack peak value, realize easy hydrogenolysis metal deposit in the depth profiles of beds, improve the controllability of deposition reaction.

On the other hand, experimental study and full scale plant running all show, the temperature of reaction of the deep hydrogenation upgrading reaction process R2 of middle coalite tar is such as 330～420 ℃ of temperature of reaction far above pre-hydrotreating reaction process R1 are as 210～330 ℃, between R1 and R2, exist the obvious heating step that increasing extent of temperature reaches 30～70 ℃, conventional temperature raising method is to use process furnace heating pre-hydrotreating reaction product R1P, or inject high warm logistics as hot hydrogen, deep fat, the shortcoming of these class methods is:

1. to the large deep hydrogenation upgrading reaction process R2 of thermal discharge, add heat energy, increased the recovery load of the reaction heat of deep hydrogenation upgrading reaction process, will increase the rate of recovery of investment, reduction reaction heat;

2. to the large deep hydrogenation upgrading reaction process R2 of thermal discharge, added heat energy, increased quenching hydrogen that the control catalyst average temperature process of deep hydrogenation upgrading reaction process used and or the quantity of quenching oil, will increase investment, reduce the rate of recovery of reaction heat;

3. owing to cannot the macromole such as condensed-nuclei aromatics being formed the middle hydrofining reaction process of cascade raising temperature, its deep hydrofinishing reaction has formed the initial action section of actual excess Temperature, increase the output of this class component at deep hydrofinishing reaction process R2 pyrocondensation compound, shortened the life-span of associated catalysts;

4. deep hydrofinishing reaction process R2 exists temperature runaway dangerous: once pre-hydrotreating reaction product R1P stock oil interrupts, the inevitable low fast rise that will form deep hydrogenation upgrading reaction process R2 temperature in, its amplitude can reach 40～60 ℃ even higher, very easily bring out deep hydrogenation upgrading reaction process R2 and form temperature runaway, the mechanical property of R2 reactor and catalyst performance are formed to the strong harm of Strong;

5. in ordinary method, light constituent LS enters pre-hydrotreating reaction process R1, and alkene in lighting end LS, phenols and gum asphalt component in last running HS coexist and easily increase thermal condensation and react, and must increase the thermal condensation produce amount of pre-hydrotreating reaction process R1;

6. in ordinary method, light constituent LS enters pre-hydrotreating reaction process R1, and the water component that the contained more phenol hydrogenation of lighting end generates increases steam partial pressure, is unfavorable for that pre-hydrotreating reaction process R1 implements low hydrogen/gasoline ratio operation.

Due to middle coalite tar last running, its boiling point is higher, metal content is higher, gluey pitch shape component aromatic ring number is more, the initial reaction temperature of its pre-hydrotreating reaction process R1 decreases, but the medial temperature of its deep hydrofinishing process can increase, the temperature of reaction difference existing between pre-hydrofining reaction process R1 and deep hydrofinishing reaction process R2, to increase, above-mentioned technique shortcoming will be more obvious thereupon.

Above-mentioned in order to reduce " the temperature of reaction difference existing between pre-hydrofining reaction process R1 and deep hydrofinishing reaction process R2 ", " continuous transition and the linking " of realization response temperature as far as possible, the present invention proposes the concept of a kind of " hydrofining reaction process RM in the middle of arranging ", the combined hydrogenation method that belongs to the coal tar fraction that boiling range is different, it is imagined substantially: last running HS comprises the pre-hydrogenation process of hydrodemetallation (HDM) and gluey pitch shape component hydrodepolymerization under suitable low temperature condition at pre-hydrofining reaction process R1; Hydrofining reaction process RM in the middle of lighting end LS and pre-hydrofining reaction product R1PS enter, utilize the reaction heat of lighting end LS pre-hydrotreating reaction RMLSR progressively to heat the temperature of reaction curve that R1PS forms overall rising, the R1PS that comprises condensed-nuclei aromatics is formed to the middle hydrofining reaction RMHSR of cascade raising temperature, be beneficial to the reaction heat that reclaims lighting end LS pre-hydrotreating reaction process RMLSR, be beneficial to the thermal condensation produce amount that reduces condensed-nuclei aromatics; Middle hydrofining reaction product RMPS penetration depth hydrofining reaction process R2 carries out deep hydrofinishing reaction R2R.

The present invention is particularly suitable for metal, alkene, phenol, colloid, the deep hydrogenation upgrading process of the middle coalite tar that the pre-easy reactive component content of hydrogenation such as bituminous matter is high, advantage is: can reduce hydrocarbon feed preheating temperature inferior, be beneficial to the stepwise reaction of realizing metallic compound and gluey pitch shape component in stock oil, be beneficial to and make metal deposition, pyrocondensation compound is deposited on beds and forms depth profiles, be beneficial to and improve the reaction heat rate of recovery, be beneficial to and reduce catalyzer average reaction temperature, be beneficial to optimization of catalysts function, be beneficial to the extending catalyst life-span, be beneficial to minimizing fuel consumption, be beneficial to reduction construction investment.

A kind of application form of the present invention is, for the pre-high middle coalite tar of the easy reactive component content of hydrogenation such as metal, alkene, phenol, colloid, bituminous matter, first the full cut of middle coalite tar is separated into lighting end and last running, then apply the present invention, formed novel middle coalite tar hydrogenation of total effluent technique.

The method of the invention has no report.

The first object of the present invention is to propose the combined hydrogenation method of the high aromatic hydrocarbons of a kind of different fractions.

The second object of the present invention is to propose a kind of combined hydrogenation method of different fractions coal tar.

The 3rd object of the present invention is to propose the combined hydrogenation method of coalite tar in a kind of different fractions.

Deep hydrogenation upgrading process for the high hydrocarbon material HMS of the pre-easy reactive component content of hydrogenation such as metal, alkene, phenol, colloid, bituminous matter is special, and the present invention all can apply, and these logistics can be selected from one or more in following material:

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. gelatin liquefaction process 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 thermally splitting tar;

9. petroleum base heavy oil thermal course of processing gained oil product, hot procedure is coking heavy oil process or heavy oil catalytic cracking process or heavy oil catalytic pyrolysis process;

10. the high hydrocarbon ils of other easy hydrogenolysis metal content.

Summary of the invention

The combined hydrogenation method of the high aromatic hydrocarbons of a kind of different fractions of the present invention, is characterized in that comprising following steps:

(1), at pre-hydrofining reaction process R1, under hydrogen and pre-Hydrobon catalyst R1C existence condition, the pre-hydrofining reaction R1R that high aromatic hydrocarbons last running HS comprises hydrodemetallation (HDM) reaction obtains pre-hydrofining reaction effluent R1P; Based on pre-hydrofining reaction effluent R1P comprise the pre-hydrofining of at least a portion generate oily logistics R1PS enter in the middle of hydrofining reaction process RM;

(2), at middle hydrofining reaction process RM, under hydrogen and middle Hydrobon catalyst RMC existence condition, high aromatic hydrocarbons lighting end LS and logistics R1PS carry out centre hydrofining reaction RMR and obtain middle hydrofining reaction effluent RMP; The service temperature of middle hydrofining reaction effluent RMP is higher than the service temperature of pre-hydrofining reaction effluent R1P; The average conventional boiling point of lighting end LS is lower than the average conventional boiling point of last running HS;

(3) at deep hydrofinishing reaction process R2, under deep hydrofinishing catalyzer R2C existence condition, in the middle of described, hydrofining reaction effluent RMP carries out deep hydrofinishing reaction, generates a deep hydrofinishing reaction effluent R2P who is comprised of hydrogen, impurity component, conventional gas hydrocarbon, conventional liq hydrocarbon;

(4) at separate part HPS, hydrogen rich gas gas HPV and deep hydrofinishing that separated deep hydrofinishing reaction effluent R2P obtains mainly hydrogen, consisting of generate oily R2P0, and at least a portion hydrogen rich gas gas HPV returns to hydrogenation process and recycles.

Conventionally, the pre-hydrofining reaction process of the present invention R1 also comprises gluey pitch shape component hydrodepolymerization reaction, it is characterized in that:

(1) at pre-hydrofining reaction process R1, under hydrogen and pre-Hydrobon catalyst R1C existence condition, the pre-hydrofining reaction R1R that last running HS comprises hydrodemetallation (HDM) reaction and the reaction of gluey pitch shape component hydrodepolymerization obtains pre-hydrofining reaction effluent R1P;

(2) at middle hydrofining reaction process RM, under hydrogen and middle Hydrobon catalyst RMC existence condition, lighting end LS and and logistics R1PS carry out centre hydrofining reaction RMR and obtain centre hydrofining reaction effluent RMP; Utilize the reaction heat of lighting end LS progressively to heat the temperature of reaction curve that R1P forms overall rising, the R1PS that comprises condensed-nuclei aromatics carries out centre hydrofining reaction RMHSR; The service temperature of middle hydrofining reaction effluent RMP is higher than the service temperature of pre-hydrofining reaction effluent R1P; The average conventional boiling point of lighting end LS is lower than at least 50 ℃ of the average conventional boiling points of last running HS.

Conventionally, preferably reaction temperature profile of the present invention is:

(2) at middle hydrofining reaction process RM, the origin temp of middle hydrofining reaction process RM is lower than the terminal temperature of pre-hydrofining reaction process R1, and the terminal temperature of middle hydrofining reaction process RM is higher than the origin temp of deep hydrofinishing reaction process R2; The average conventional boiling point of lighting end LS is lower than at least 100 ℃ of the average conventional boiling points of last running HS.

The present invention, can arrange thermal high separating step 1THPS at pre-hydrofining reaction process R1, it is characterized in that:

(1), at pre-hydrofining reaction process R1, at thermal high separating step 1THPS, pre-hydrofining reaction effluent R1P is separated into hot high score gas gas 1THPV and hot high score oil 1THPL; In the middle of the hot high score gas of at least a portion 1THPV enters, hydrofining reaction process RM contacts with middle Hydrobon catalyst RMC; After hot high score oil 1THPL removes solid particulate, obtain de-solid hydrocarbon ils 1THPL-L, in the middle of the de-solid hydrocarbon ils 1THPL-L of at least a portion enters, hydrofining reaction process RM contacts with middle Hydrobon catalyst RMC.

The present invention, can arrange thermal high separating step MTHPS at middle hydrofining reaction process RM, it is characterized in that:

(2), at middle hydrofining reaction process RM, at thermal high separating step MTHPS, middle hydrofining reaction effluent RMP is separated into hot high score gas gas MTHPV and hot high score oil MTHPL; The hot high score gas of at least a portion MTHPV penetration depth hydrofining reaction process R2 contacts with deep hydrofinishing catalyzer R2C; After hot high score oil MTHPL removes solid particulate, obtain de-solid hydrocarbon ils MTHPL-L, the de-solid hydrocarbon ils MTHPL-L penetration depth hydrofining reaction process R2 of at least a portion contacts with deep hydrofinishing catalyzer R2C.

The present invention, at the pre-hydrofining reaction process of the shallow degree R11 of pre-hydrofining reaction process R1, the hydrodemetallation (HDM) reaction of carrying out easy hydrogenolysis metal is the pre-hydrofining reaction R11R of shallow degree, 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 microdilatancy bed, described upflowing microdilatancy bed, the beds of its reactor respond raw material by time the maximum height CWH of working order and the ratio K BED of the height CUH of the 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, at pre-hydrofining reaction process R1, before the pre-hydrofining reaction process of shallow degree R11, the preposition catalyst for pre-hydrogenation bed of one or more that can connect in the following pattern bed of use, be mainly used in carrying out olefins hydrogenation reaction etc., preposition catalyst for pre-hydrogenation particle does not enter the pre-hydrofining reaction process of shallow degree R11:

1. upflowing ebullated bed;

2. upflowing bubbling bed;

3. upflowing is expanded bed, described upflowing microdilatancy bed, the beds of its reactor respond raw material by time the maximum height CWH of working order and the ratio K BED of the height CUH of the 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 pre-hydrofining reaction process of the degree of depth R12 of pre-hydrofining reaction process R1, uses the bed filler R12C that has hydrogenation activity, carry out shortening demetalization reaction and or removal of ccr by hydrotreating reaction be the pre-hydrofining reaction R12R of the degree of depth; 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, at middle hydrofining reaction process RM, the mode of operation of the bed RMCB of the middle Hydrobon catalyst RMC of use, 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 hydrofinishing reaction process R2, can be 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, last running HS, lighting end LS are selected from one or more in following material:

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

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

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermally splitting tar;

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.

Last running HS of the present invention, take the easy hydrogenolysis metal concentration that its contained easy hydrogenolysis metallic compound is benchmark, can be lower than 50PPm or higher than 100PPm or higher than 200PPm.

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

Last running HS mainly by conventional boiling point higher than in 350 ℃ during coalite tar fractions consisting, Action Target of the present invention is generally:

(1) at pre-hydrofining reaction process R1, last running HS mainly by conventional boiling point higher than coalite tar fractions consisting in 350 ℃; The metal content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 10PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 1.5%;

(2) at middle hydrofining reaction process RM, lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 350 ℃; The full cut diesel-fuel cetane number of middle hydrofining reaction effluent RMP is higher than 5;

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

(1) at pre-hydrofining reaction process R1, last running HS mainly by conventional boiling point higher than coalite tar fractions consisting in 350 ℃; The metal content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 5PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 0.5%;

(2) at middle hydrofining reaction process RM, lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 350 ℃; The full cut diesel-fuel cetane number of middle hydrofining reaction effluent RMP is higher than 10;

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

Last running HS mainly by conventional boiling point higher than in 450 ℃ during coalite tar fractions consisting, Action Target of the present invention is generally:

(1), at pre-hydrofining reaction process R1, last running HS is mainly heated up in a steamer and forms minute higher than coalite tar in 450 ℃ by conventional boiling point; The metal content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 10PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 1.5%;

(2) at middle hydrofining reaction process RM, lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 450 ℃; The full cut diesel-fuel cetane number of middle hydrofining reaction effluent RMP is higher than 5;

(1) at pre-hydrofining reaction process R1, last running HS mainly by conventional boiling point higher than coalite tar fractions consisting in 450 ℃; The metal content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 5PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 0.5%;

(2) at middle hydrofining reaction process RM, lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 450 ℃; The full cut diesel-fuel cetane number of middle hydrofining reaction effluent RMP is higher than 10;

The present invention, hydrocracking reaction process R3 can be set, the hydro-upgrading heavy oil R2P0-D0 that the hydrogenated oil R2P0 gained of separated deep hydrofinishing reaction effluent R2P of take is mainly comprised of higher than 350 ℃ of hydrocarbon conventional boiling point is raw material, at hydrocracking reaction process R3, is converted into hydrocracking reaction effluent R3P; Hydrocracking reaction effluent R3P is separated after can mixing with hydrogenation reaction effluent R2P.

The present invention, separate part HPS comprises cold anticyclone separate part LHPS conventionally, at cold anticyclone separate part LHPS, separated deep hydrofinishing reaction effluent R2P obtains the cold high score gas gas HPV and the cold high score oil LHPL that mainly hydrogen, consist of, and cold high score oil LHPL generates oily R2P0 as deep hydrofinishing.

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, separated deep hydrofinishing reaction effluent R2P 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 obtains the cold high score gas gas HPV and the cold high score oil LHPL that mainly hydrogen, consist of, and deep hydrofinishing generates oily R2P0 and comprises hot high score oil THPL and cold high score oil LHPL.

Last running HS mainly by conventional boiling point higher than in 450 ℃ during coalite tar fractions consisting, detailed behaviour's condition of the present invention is generally:

(1) at pre-hydrofining reaction process R1, last running HS mainly by conventional boiling point higher than coalite tar fractions consisting in 450 ℃; The metal content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 10PPm; The carbon residue content of the conventional liq hydrocarbon in pre-hydrofining reaction effluent R1P is lower than 1.5%;

The operational condition of pre-hydrofining reaction process R1 is: temperature is that 170～350 ℃, pressure are that 4.0～30.0MPa, catalyst for pre-hydrogenation R1C volume space velocity are 0.05～10.0hr ^-1, hydrogen/stock oil volume ratio is 100: 1～4000: 1, chemical pure hydrogen consumption is 0.15～2.5% (weight to last running HS);

(2) lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 450 ℃; Full cut diesel-fuel cetane number in middle hydrofining reaction effluent RMP is higher than 5;

The operational condition of middle hydrofining reaction process RM is: temperature is that 260～380 ℃, pressure are that 4.0～30.0MPa, middle Hydrobon catalyst RMC volume space velocity are 0.05～5.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1;

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

The operational condition of deep hydrofinishing reaction process R2 is: temperature is that 300～450 ℃, pressure are that 4.0～30.0MPa, catalyst for refining R21C volume space velocity are 0.1～4.0hr ^-1, hydrogen/stock oil volume ratio is 500: 1～4000: 1.

The operational condition of pre-hydrofining reaction process R1 is: temperature be 210～330 ℃, pressure for, catalyst for pre-hydrogenation R1C volume space velocity be 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 to last running HS);

(2) lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 450 ℃; Full cut diesel-fuel cetane number in middle hydrofining reaction effluent RMP is higher than 10;

The operational condition of middle hydrofining reaction process RM is: temperature is that 280～350 ℃, 12.0～18.0MPa, middle Hydrobon catalyst RMC volume space velocity are 0.2～5.0hr ^-1, hydrogen/stock oil volume ratio is 800: 1～3000: 1;

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

The operational condition of deep hydrofinishing reaction process R2 is: temperature is that 330～420 ℃, pressure are that 12.0～18.0MPa, catalyst for refining R21C volume space velocity are 0.1～2.0hr ^-1, hydrogen/stock oil volume ratio is 800: 1～3000: 1.

Last running HS mainly by conventional boiling point higher than in 350 ℃ during coalite tar fractions consisting, detailed behaviour's condition of the present invention is generally:

(2) lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 350 ℃; Full cut diesel-fuel cetane number in middle hydrofining reaction effluent RMP is higher than 5;

(2) lighting end LS mainly by conventional boiling point lower than coalite tar fractions consisting in 350 ℃; Full cut diesel-fuel cetane number in middle hydrofining reaction effluent RMP is higher than 10;

The present invention, the hot high score oil 1THPL of the thermal high separating step 1THPS of pre-hydrofining reaction process R1, conventionally mainly by conventional boiling point higher than the hydrocarbon of 330 ℃ form, it is general main that by conventional boiling point, the hydrocarbon higher than 380 ℃ forms.

The present invention, at thermal high separating step 1THPS, can arrange the air lift step of hot high score oil 1THPL:

(1), at pre-hydrofining reaction process R1, at thermal high separating step 1THPS, pre-hydrofining reaction effluent R1P is separated into hot high score gas gas 1THPV and hot high score oil 1THPL; In the middle of the hot high score gas of at least a portion 1THPV enters, hydrofining reaction process RM contacts with middle Hydrobon catalyst RMC; After hot high score oil 1THPL contacts with hydrogen rich gas gas stripping gas VH1, be separated into the hot high score oil 1THPLV-L of de-light constituent and air lift and deviate from gas 1THPLV-V; At least a portion air lift deviate from gas 1THPLV-V enter in the middle of hydrofining reaction process RM contact with middle Hydrobon catalyst RMC; After the hot high score oil of de-light constituent 1THPLV-L removes solid particulate, obtain de-solid hydrocarbon ils 1THPLV-L, in the middle of the de-solid hydrocarbon ils 1THPLV-L of at least a portion enters, hydrofining reaction process RM contacts with middle Hydrobon catalyst RMC.

The present invention, the hot high score oil MTHPL of the thermal high separating step MTHPS of middle hydrofining reaction process RM, conventionally mainly by conventional boiling point higher than the hydrocarbon of 330 ℃ form, it is general main that by conventional boiling point, the hydrocarbon higher than 380 ℃ forms.

The present invention, at thermal high separating step MTHPS, can arrange the air lift step of hot high score oil MTHPL:

(1), at middle hydrofining reaction process RM, at thermal high separating step MTHPS, middle hydrofining reaction effluent RMP is separated into hot high score gas gas MTHPV and hot high score oil MTHPL; The hot high score gas of at least a portion MTHPV penetration depth hydrofining reaction process R2 contacts with deep hydrofinishing catalyzer R2C; After hot high score oil MTHPL contacts with hydrogen rich gas gas stripping gas VH2, be separated into the hot high score oil MTHPLV-L of de-light constituent and air lift and deviate from gas MTHPLV-V; At least a portion air lift is deviate from gas MTHPLV-V penetration depth hydrofining reaction process R2 and is contacted with deep hydrofinishing catalyzer R2C; After removing solid particulate, the hot high score oil of de-light constituent MTHPLV-L obtains de-solid hydrocarbon ils MTHPLV-L, the de-solid hydrocarbon ils MTHPLV-L penetration depth Hydrobon catalyst R2C contact of at least a portion.

The present invention, at pre-hydrofining reaction process R1, injects the new hydrogen of the preferential use of hydrogen rich gas logistics of pre-hydrofining reactor.

The present invention, at pre-hydrofining reaction process R1, injects the new hydrogen of the preferential use of hydrogen rich gas logistics of bed filler R11C.

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

The present invention, at pre-hydrofining reaction process R1, can be combined to form integrated reactor by filler R11C bed and filler R12C bed; Integrated up-flow reactor contains 1 or 2 or a plurality of filler R11C bed, and integrated reactor contains 1 or 2 or a plurality of filler R12C bed.

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

The present invention, the first assembled scheme of each reaction process filling batch pattern is:

(1) the pre-hydrofining reaction process of shallow degree R11, is used tubular reactor, and the easy hydrogenolysis metal conversion product of take is suspended particle; Velocity of medium in the pipe of tubular reactor, is conventionally 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;

The pre-hydrofining reaction process of degree of depth R12, hydrogenation catalyst bed mode of operation is upflowing microdilatancy bed;

(2), at middle hydrofining reaction process RM, hydrogenation catalyst bed mode of operation is upflowing microdilatancy bed;

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

The present invention, the second assembled scheme of each reaction process filling batch pattern is:

(1) the pre-hydrofining reaction process of shallow degree R11, is used tubular reactor, and the easy hydrogenolysis metal conversion product of take is suspended particle;

The pre-hydrofining reaction process of degree of depth R12, hydrogenation catalyst bed mode of operation is upflowing ebullated bed;

(2) at middle hydrofining reaction process RM, hydrogenation catalyst bed mode of operation is upflowing ebullated bed;

The present invention, the third assembled scheme of each reaction process filling batch pattern is:

The pre-hydrofining reaction process of degree of depth R12, hydrogenation catalyst bed mode of operation is upflowing suspension bed;

(2) at middle hydrofining reaction process RM, hydrogenation catalyst bed mode of operation is upflowing suspension bed;

The present invention, the 4th kind of assembled scheme of each reaction process filling batch pattern is:

The pre-hydrofining reaction process of degree of depth R12, hydrogenation catalyst bed mode of operation is upflow fixed bed, uses 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;

(2) at middle hydrofining reaction process RM, hydrogenation catalyst bed mode of operation is upflow fixed bed;

The present invention, the pre-hydrofining reaction process of the shallow degree R11 at pre-hydrofining reaction process R1, can be used a kind or 2 kinds or the multiple bed filler R11C without hydrogenation activity, also can use the bed filler R11CH of hydrogenation activity.

The present invention, at middle hydrofining reaction process RM, the pre-hydrofining reaction process of lighting end LSR1 can be set, under hydrogen and the pre-Hydrobon catalyst LSRMC of lighting end existence condition, lighting end LS carries out the pre-hydrofining reaction LSR1R of lighting end and obtains the pre-hydrofining reaction effluent of lighting end LSR1P; Based on the pre-hydrofining reaction effluent of lighting end LSR1P comprise the pre-hydrofining of at least a portion lighting end generate oily logistics LSR1PS enter in the middle of hydrofining reaction process RM.

Embodiment

Below describe the present invention in detail.

Pressure of the present invention, refers to absolute pressure.

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

Conventional boiling range of the present invention refers to the conventional boiling spread of cut.

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

It is the hydro carbons of 180～355 ℃ that diesel component of the present invention refers to conventional boiling point.

It is the hydro carbons of 355～490 ℃ that wax oil component of the present invention refers to conventional boiling point.

Heavy oil component of the present invention refers to conventional boiling point higher than the hydro carbons of 350 ℃.

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 ℃ of conditions, 15.6 ℃ of Water Under density.

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

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

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 under certain high temperature and hydrogen existence condition, be commonly referred to as oil soluble metal compound as iron naphthenate, calcium naphthenate etc., these components can rapid conversion be that sulfide is as iron sulphide, sulfurated lime under hydrogen sulfide existence condition, and can form particulate state throw out or coprecipitate, under certain condition, particulate matter particle diameter can be grown up.

Coal tar of the present invention, refer to coal tar or its cut from the processes such as pyrolysis step of pyrolysis of coal or the dry distillation of coal or coal generating gas process, 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, coal tar of the present invention can also be the mixing oil of above-mentioned coal tar, and coal tar of the present invention can also be that the extract oil that obtains through light hydrocarbon solvent extraction of above-mentioned coal tar is such as diasphaltene coal tar or its distillate.

High-temperature coking belongs to coal high temperature pyrolysis process, and the outlet temperature of pyrolytic process is generally greater than 900 ℃, conventionally between 1000～1400 ℃.Described coal-tar heavy oil refers to the by product crude tar oil that coal high temperature pyrolysis is produced coke and/or the production of town gas process.Coal-tar heavy oil is in primary distillation process, conventionally produce following product: 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 further be separated into crude phenols and dephenolize oil, and naphtalene oil can further be separated into thick naphthalene and de-naphtalene oil.Coal-tar heavy oil lighting end of the present invention refers to: carbolineum, Shen oil, naphtalene oil, de-naphtalene oil, carbolic oil, dephenolize oil, light oil and mixing oil thereof.

Due to raw coal character and coking or all variations within the specific limits of gas-making process condition, coal tar oil properties also changes within the specific limits.The processing condition of coal tar primary distillation process and product requirement 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, conventional boiling point is generally 60～500 ℃ and is generally 120～460 ℃, conventionally metal content is that 5～80PPm, sulphur content are 0.4～0.8%, nitrogen content is 0.6～1.4%, oxygen level is 0.4～9.0%, conventionally water-content is 0.2～5.0%, and carbon residue content is generally 0.5～13%.

Conventionally the olefin(e) centent of coal tar lighting end is high, phenol content is high and contain more component of easily reacting under mitigation condition; therefore; the pre-hydrogenation process of coal tar lighting end of the present invention, is used the single dose of hydrogenation protecting agent, olefins hydrogenation agent, hydrogenation deoxidation agent, hydrogen desulfurization agent etc. or series combination or the mixed loading combination of two agent or multi-agent conventionally.

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, is used the single dose of hydrogenation protecting agent, hydrodemetallation (HDM) agent, hydrogen desulfurization agent etc. or series combination or the mixed loading combination of two agent or multi-agent conventionally

Due to the overwhelming majority of metal concentrate on conventional boiling point higher than 350 ℃ particularly higher than in the cut of 450 ℃, so 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:

The easily decomposition < high reactivity condensed-nuclei aromatics thermal condensation of hydrogenolysis metal fever and the rudimentary sulphur compound hydrogenating desulfurization of the saturated < of hydrogenation, organometallic complex catalytic hydrogenolysis, rudimentary organic phenol catalytic deoxidation, the de-carbon residue of polycyclic aromatic hydrocarbons

Said temperature scope is generally 170～350 ℃, is generally 210～330 ℃, clearly, this is the temperature of reaction interval of a wide region, should control first, second, third step for differing temps section 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 stack peak value, realize easy hydrogenolysis metal deposit in the depth profiles of 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.

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 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. gelatin liquefaction process gained liquefied coal coil or its distillate;

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermally splitting tar;

The operational condition of pre-hydrofining reaction process R1 is: temperature is that 170～3500 ℃, pressure are that 4.0～30.0MPa, catalyst for pre-hydrogenation R1C volume space velocity are 0.05～10.0hr ^-1, hydrogen/stock oil volume ratio is 100: 1～4000: 1, chemical pure hydrogen consumption is 0.15～2.5% (weight to last running HS);

1. porous ball;

2. Raschig ring;

3. four impellers;

4. Herba Galii Bungei;

5. other open grain bed filler;

As required, any supplementary sulphur can be added to arbitrary hydrogenation process, but normally join the hydrogenation process entrance of upstream, to guarantee that the necessary minimum concentration of hydrogen sulfide of reaction process is such as 500PPm (v) or 1000PPm (v) or prescribed value, to guarantee that the necessary hydrogen sulfide sectional pressure of catalyzer is not less than minimum prescribed value.Described supplementary sulphur can be the material without undesirable action to hydroconversion process that sulfide hydrogen maybe can be converted into hydrogen sulfide, such as hydrogen sulfide containing gas or oil product, or after contacting with high-temperature hydrogen, generates the dithiocarbonic anhydride of hydrogen sulfide or Methyl disulfide etc.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, can not re-use sulfur supplementary agent.

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 conventionally, hydrocarbon ils density large (such as approaching with water-mass density) or viscosity is large or be difficult to when separated with emulsifying water in hydrogenation reaction effluent, also need setting operation temperature to be generally the high pressure hot separator of 150～450 ℃, now hydrogenation reaction effluent enters high pressure hot separator and be separated into the hot high score fluid body that the hot high score gas gas being mainly comprised of hydrogen and are mainly comprised of conventional liq hydrocarbon and the solid that may exist on volume, hot high score gas enters the cold high pressure separator that service temperature is generally 20～80 ℃ and is separated into cold high score oil and cold high score gas, because a large amount of high boiling components enter in hot high score fluid body, realized following target: cold high score oil density diminishes or viscosity diminishes or be easy to separated with water.The high pressure separation process of hydrogenation reaction effluent arranges high pressure hot separator, also possesses the advantage that reduces calorific loss, because hot high score fluid body can be avoided the use air cooler of hot high score gas experience or the process that cools of water cooler.Meanwhile, the hydrogenation process that the hot high score fluid of part body can be returned to upstream recycles, to improve the overall feedstock property of the hydrogenation process that receives this turning oil, or to this turning oil hydrogenation that circulates.

Before hydrogenation reaction effluent or hot high score gas enter cold anticyclone separate part, conventionally first reduce temperature (being generally and reactive moieties charging heat exchange) to approximately 220～100 ℃ (these temperature should higher than sulphur hydrogenation ammonia Tc in this hydrogenation reaction effluent gas phase), then conventionally inject wherein washing water and form water filling back end hydrogenation reaction effluent, washing water for absorbing ammonia and issuable other impurity 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: the cold high score gas being mainly comprised of hydrogen on volume, cold high score oil, the main cold high score water that be comprised of water and that be dissolved with ammonia, hydrogen sulfide being mainly comprised of conventional liq hydrocarbon and dissolved hydrogen.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 is ammonia and the hydrogen sulfide absorbing in hydrogenation reaction effluent, prevents from forming sulphur hydrogenation ammonia or many sulphur ammonia Crystallization Plugging heat exchanger channel, increases system pressure drop.The injection rate of described washing water, should determine according to following principle: on the one hand, 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% or more of washing water total amount; Again on the one hand, washing water, for absorbing the ammonia of hydrogenation reaction effluent, prevent that the ammonia concentration of high score gas is too high, reduce catalyst activity, conventionally the ammonia volumetric concentration of 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 be 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 a portion, be generally 85～100% cold high score gas and return in hydrogenation reaction and partly recycle, so that the necessary amounts of hydrogen of hydrogenation reaction part and hydrogen concentration to be provided; In order to improve plant investment efficiency, must guarantee that recycle hydrogen concentration is not less than aforesaid low limit value,, according to concrete feedstock property, reaction conditions, product, distribute for this reason, can get rid of methane, ethane that the described cold high score gas of a part produces to get rid of reaction.Cold high score gas for discharge, can adopt conventional membrane separation process or pressure swing adsorption technique or oil wash technique to realize hydrogen separated with non-hydrogen component, and the hydrogen reclaiming is used as to new hydrogen.

New hydrogen enters and adds the hydrogen that hydrogen partial consumes to supplement hydrogenation process, and new hydrogen hydrogen concentration is more high better, generally should not, lower than 95% (v), preferably be not less than 99% (v).All new hydrogen can be introduced to arbitrary hydrogenation reaction part, preferably introduce pre-hydrotreating reaction process R1.

The present invention, for metal, alkene, phenol, colloid, the deep hydrogenation upgrading process of the middle coalite tar that the pre-easy reactive component content of hydrogenation such as bituminous matter is high, hydrofining reaction process RM in the middle of arranging, to pre-hydrofining reaction process R1 and deep hydrofinishing reaction process R2, be beneficial to " continuous transition and the linking " of realization response temperature, its advantage is: can reduce hydrocarbon feed preheating temperature inferior, be beneficial to the stepwise reaction of realizing metallic compound and gluey pitch shape component in stock oil, be beneficial to and make metal deposition, pyrocondensation compound is deposited on beds and forms depth profiles, be beneficial to and improve the reaction heat rate of recovery, be beneficial to and reduce catalyzer average reaction temperature, be beneficial to optimization of catalysts function, be beneficial to the extending catalyst life-span, be beneficial to minimizing fuel consumption, be beneficial to reduction construction investment.

The present invention, can be applied to the Unionfining process of any suitable high aromatic hydrocarbons of different fractions.

Claims

1. a combined hydrogenation method for the high aromatic hydrocarbons of different fractions, is characterized in that comprising following steps:

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

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

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

(1), at the pre-hydrofining reaction process of the shallow degree R11 of pre-hydrofining reaction process R1, the hydrodemetallation (HDM) reaction of carrying out easy hydrogenolysis metal is the pre-hydrofining reaction R11R of shallow degree, uses the bed filler R11C without hydrogenation activity; 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 method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9, it is characterized in that:

At pre-hydrofining reaction process R1, before the pre-hydrofining reaction process of shallow degree R11, the preposition catalyst for pre-hydrogenation bed of one or more in the following pattern bed of series connection use, preposition catalyst for pre-hydrogenation particle does not enter the pre-hydrofining reaction process of shallow degree 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 method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9, it is characterized in that:

(1) at the pre-hydrofining reaction process of the degree of depth R12 of pre-hydrofining reaction process R1, use the bed filler R12C that has hydrogenation activity, carry out shortening demetalization reaction and or removal of ccr by hydrotreating reaction be the pre-hydrofining reaction R12R of the degree of depth; 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 method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9, it is characterized in that:

(2) at middle hydrofining reaction process RM, the mode of operation of the bed RMCB of the middle Hydrobon catalyst RMC of use, 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.

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

The beds mode of operation of deep hydrofinishing 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 method described in claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9, it is characterized in that:

Last running HS, lighting end LS are selected from one or more in following material:

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

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

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermally splitting tar;

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

Last running HS, take easy hydrogenolysis metal concentration that its contained easy hydrogenolysis metallic compound is benchmark lower than 50PPm.

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

Last running HS, take easy hydrogenolysis metal concentration that its contained easy hydrogenolysis metallic compound is benchmark higher than 100PPm.

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

Last running HS, take easy hydrogenolysis metal concentration that its contained easy hydrogenolysis metallic compound is benchmark higher than 200PPm.

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

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

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

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

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

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

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

(5) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2P0-D0 that the hydrogenated oil R2P0 gained of separated deep hydrofinishing reaction effluent R2P of take is mainly comprised of higher than 350 ℃ of hydrocarbon conventional boiling point is raw material, at hydrocracking reaction process R3, is converted into hydrocracking reaction effluent R3P.

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

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

(5) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2P0-D0 that the hydrogenated oil R2P0 gained of separated deep hydrofinishing reaction effluent R2P of take is mainly comprised of higher than 350 ℃ of hydrocarbon conventional boiling point is raw material, at hydrocracking reaction process R3, be converted into hydrocracking reaction effluent R3P, hydrocracking reaction effluent R3P is separated after mixing with hydrogenation reaction effluent R2P.

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

(4) separate part HPS comprises cold anticyclone separate part LHPS, at cold anticyclone separate part LHPS, separated deep hydrofinishing reaction effluent R2P obtains the cold high score gas gas HPV and the cold high score oil LHPL that mainly hydrogen, consist of, and cold high score oil LHPL generates oily R2P0 as deep hydrofinishing.

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

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

At thermal high separate part THPS, separated deep hydrofinishing reaction effluent R2P 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 obtains the cold high score gas gas HPV and the cold high score oil LHPL that mainly hydrogen, consist of, and deep hydrofinishing generates oily R2P0 and comprises hot high score oil THPL and cold high score oil LHPL.

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

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

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

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

33. according to method described in claim 4 or 5 or 6, it is characterized in that:

(1), at the thermal high separating step 1THPS of pre-hydrofining reaction process R1, mainly by conventional boiling point, the hydrocarbon higher than 330 ℃ forms hot high score oil 1THPL.

34. according to method described in claim 4 or 5 or 6, it is characterized in that:

(1), at the thermal high separating step 1THPS of pre-hydrofining reaction process R1, mainly by conventional boiling point, the hydrocarbon higher than 380 ℃ forms hot high score oil 1THPL.

35. according to method described in claim 4 or 5 or 6, it is characterized in that:

36. according to method described in claim 7 or 8 or 9, it is characterized in that:

(2), at the thermal high separating step MTHPS of middle hydrofining reaction process RM, mainly by conventional boiling point, the hydrocarbon higher than 330 ℃ forms hot high score oil MTHPL.

37. according to method described in claim 7 or 8 or 9, it is characterized in that:

(2), at the thermal high separating step MTHPS of middle hydrofining reaction process RM, mainly by conventional boiling point, the hydrocarbon higher than 380 ℃ forms hot high score oil MTHPL.

38. according to method described in claim 7 or 8 or 9, it is characterized in that:

(1), at middle hydrofining reaction process RM, at thermal high separating step MTHPS, middle hydrofining reaction effluent RMP is separated into hot high score gas gas MTHPV and hot high score oil MTHPL; The hot high score gas of at least a portion MTHPV penetration depth hydrofining reaction process R2 contacts with deep hydrofinishing catalyzer R2C; After hot high score oil MTHPL contacts with hydrogen rich gas gas stripping gas VH2, be separated into the hot high score oil MTHPLV-L of de-light constituent and air lift and deviate from gas MTHPLV-V;

At least a portion air lift is deviate from gas MTHPLV-V penetration depth hydrofining reaction process R2 and is contacted with deep hydrofinishing catalyzer R2C; After removing solid particulate, the hot high score oil of de-light constituent MTHPLV-L obtains de-solid hydrocarbon ils MTHPLV-L, the de-solid hydrocarbon ils MTHPLV-L penetration depth Hydrobon catalyst R2C contact of at least a portion.

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

(1) at pre-hydrofining reaction process R1, the hydrogen rich gas logistics of injecting pre-hydrofining reactor is new hydrogen.

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

(1), at pre-hydrofining reaction process R1, the hydrogen rich gas logistics of injecting bed filler R11C is new hydrogen.

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

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

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

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

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

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

44. according to method described in claim 36, it is characterized in that:

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

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

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

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

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

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

48. according to method described in claim 47, it is characterized in that:

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

49. according to method described in claim 47, it is characterized in that:

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

50. according to method described in claim 47, it is characterized in that:

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

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

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

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

The pre-hydrofining reaction process of degree of depth R12, hydrogenation catalyst bed mode of operation is upflow fixed bed;

54. according to method described in claim 53, it is characterized in that:

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

55. according to method described in claim 53, it is characterized in that:

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

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

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

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

(1), at pre-hydrofining reaction process R1, the pre-hydrofining reaction process of shallow degree R11, is used the bed filler R11CH that has hydrogenation activity.

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

(2) at middle hydrofining reaction process RM, the pre-hydrofining reaction process of lighting end LSR1 is set, under hydrogen and the pre-Hydrobon catalyst LSRMC of lighting end existence condition, lighting end LS carries out the pre-hydrofining reaction LSR1R of lighting end and obtains the pre-hydrofining reaction effluent of lighting end LSR1P; Based on the pre-hydrofining reaction effluent of lighting end LSR1P comprise the pre-hydrofining of at least a portion lighting end generate oily logistics LSR1PS enter in the middle of hydrofining reaction process RM.