CN104263407A - Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series - Google Patents

Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series Download PDF

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CN104263407A
CN104263407A CN201410373486.3A CN201410373486A CN104263407A CN 104263407 A CN104263407 A CN 104263407A CN 201410373486 A CN201410373486 A CN 201410373486A CN 104263407 A CN104263407 A CN 104263407A
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bed
reaction
oil
hydrogen
hydrotreating reaction
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何巨堂
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何巨堂
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G67/00Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only

Abstract

The invention discloses a hydrocarbon hydrogenation method with an up-flow bed layer and a fixed bed operated in series. The method is particularly suitable for the deep hydro-conversion process of medium and low-temperature coal tar containing a moderate quantity of hydrogenolytic metal compounds. A reaction product in an up-flow pre-hydrogenation reaction area R11 contains particles, and particles of predetermined granularity are intercepted in series by a particle intercepting bed arranged in a pre-hydrogenation reaction area R12 of a fixed bed, so that the quantity of particles filling a catalyst bed layer of the fixed bed in a deep hydro-upgrading process R2 for processing an R12 reaction product is reduced. The up-flow pre-hydrogenation reaction area R11 can be an up-flow micro-expansion bed, an up-flow suspension bed, an up-flow boiling bed, an up-flow fixed bed, an up-flow bubbling bed and the like. The porosity or gap equivalent diameter of the catalyst bed layer of the fixed bed in the pre-hydrogenation reaction area R12 is smaller than the porosity or gap equivalent diameter of the catalyst bed layer of the fixed bed in the deep hydro-upgrading process R2.

Description

The hydrocarbon method of hydrotreating of a kind of upflowing bed and fixed bed serial operation
Technical field
The present invention relates to the hydrocarbon method of hydrotreating of a kind of upflowing bed and fixed bed serial operation, be particularly suitable for the deep hydrogenation conversion process of the middle coalite tar containing moderate quatity easy hydrogenolysis metallic compound, containing particulate matter in upflowing pre-hydrotreating reaction district R11 reaction product, the particulate matter interception bed being connected in series through fixed bed pre-hydrotreating reaction district R12 setting retains the particulate matter of predetermined particle size, thus reduces the quantity of the fixed bed catalyst bed filler particles thing of the deep hydrogenation upgrading reaction process R2 of processing R12 reaction product.Upflowing pre-hydrotreating reaction district R11 can be the upflowing patterns such as slight expanded-bed, suspension bed, ebullated bed, fixed bed, bubbling bed, the porosity of pre-hydrotreating reaction district R12 fixed bed catalyst bed or space equivalent diameter, be less than porosity or the space equivalent diameter of the fixed bed catalyst bed of deep hydrogenation upgrading reaction process R2.
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 raw material 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 raw material 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 raw material 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 metal 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.
Easy hydrogenolysis metal 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, the present inventor separately has technological method to propose, namely must adopt upflowing reactive system and arrange pre-hydrotreating reaction effluent high pressure hot separator makes solid particulate discharge reactive system continuously, and need after the separating of oil solid of hot high score to be delivered to deep hydrogenation process through high-pressure pump, scheme is reliable, invest high, energy consumption is high.This scheme is option b.
The medium person of easy hydrogenolysis metal 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 option b, 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.Therefore need to propose a kind of suitable economical plan, reduce particulate matter quantity and the sinkability of penetration depth hydro-upgrading reaction process R2 beds, effectively suppress the reduction of its porosity, extend the continuous cycle of operation.
For 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 object of the invention is to the hydrocarbon method of hydrotreating proposing a kind of upflowing bed and fixed bed serial operation, it is imagined substantially, containing particulate matter in upflowing pre-hydrotreating reaction district R11 reaction product, the particulate matter interception bed being connected in series through fixed bed pre-hydrotreating reaction district R12 setting retains the particulate matter of predetermined particle size, thus reduces the quantity of the fixed bed catalyst bed filler particles thing of the deep hydrogenation upgrading reaction process R2 of processing R12 reaction product.Upflowing pre-hydrotreating reaction district R11 can be the upflowing patterns such as slight expanded-bed, suspension bed, ebullated bed, fixed bed, bubbling bed, the porosity of pre-hydrotreating reaction district R12 fixed bed catalyst bed or space equivalent diameter, be less than porosity or the space equivalent diameter of the fixed bed catalyst bed of deep hydrogenation upgrading reaction process R2.
For deep hydrogenation upgrading processes particularly its pre-hydrotreating reaction process R1 of the medium hydrocarbon material HMS of easy hydrogenolysis metal content, 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 the hydrocarbon method of hydrotreating proposing a kind of upflowing bed and fixed bed serial operation.
The second object of the present invention is the hydrocarbon method of hydrotreating proposing a kind of upflowing bed and fixed bed serial operation, is applicable to the hydrogenation process of the medium middle coalite tar of easy hydrogenolysis metal content.
Summary of the invention
The hydrocarbon method of hydrotreating of a kind of upflowing bed of the present invention and fixed bed serial operation, is characterized in that comprising following steps:
(1) at pre-hydrotreating reaction process R1, under hydrogen, hydrogen sulfide and catalyst for pre-hydrogenation R1C existence condition, the pre-hydrotreating reaction R1R that hydrocarbon feed HMS containing easy hydrogenolysis metallic compound carries out the hydrodemetallation (HDM) reaction comprising easy hydrogenolysis metallic compound obtains pre-hydrotreating reaction effluent R1P, hydrocarbon feed HMS changes the process of pre-hydrotreating reaction effluent R1P at least through a fixed bed pre-hydrotreating reaction district R12, and the particulate matter R11S at least partially from upstream logistics falls in the filler R12C bed in fixed bed pre-hydrotreating reaction district R12;
Described easy hydrogenolysis metallic compound, refers to the metallic compound that its hydrogenolysis is mainly thermal response, comprises naphthenate, naphthenate at least comprise iron naphthenate and or calcium naphthenate;
The deposition reaction of described naphthenate, to refer under certain temperature condition, in the hydrogen gas atmosphere hydrogenolysis go out metal M, under hydrogen sulfide existence condition, metal M is converted into sulfide M S, on the bed filler R11C that at least part of sulfide M S is deposited on the hydrogenolysis district of easy hydrogenolysis metal M and or filler R11C particle between;
Bed filler R11C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
Bed filler R12C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
At the hydrodemetallation (HDM) reactive moieties R11 of easy hydrogenolysis metallic compound, use upflowing filling batch R11CB, under hydrogen, hydrogen sulfide existence condition, hydrocarbon feed HMS enters fixed bed pre-hydrotreating reaction district R12, by producing after upflowing filling batch R11CB by least part of solid particles sediment in the logistics of fixed bed pre-hydrotreating reaction district R12 in the filler R12C bed of fixed bed pre-hydrotreating reaction district R12 containing the pre-hydrogenation intermediate reaction effluent R11MP of particulate matter or end reaction effluent R11NP;
(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 R2PO 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.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12 last step filling batch R12YB porosity or space equivalent diameter, be less than deep hydrogenation upgrading processes R2 catalyst bed layer porosity or space equivalent diameter usually.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, can comprise the filling batch of 1 layer or 2 layers of load in series or multilayer load in series.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, comprise the filling batch of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage filling batch or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage bed usually.
According to the present invention, at deep hydrogenation upgrading reaction process R2, comprise the beds of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage beds or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage beds usually.
The mode of operation of upflowing filling batch R11CB, can be selected from one or more in following pattern:
1. upflowing ebullated bed;
2. upflowing bubbling 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 moving-bed;
5. upflow fixed bed.
At pre-hydrotreating reaction process R1, before upflowing filling batch R11CB, the hydrogenation catalyst bed of one or more used in following pattern bed of can connecting:
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 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;
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.
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;
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;
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. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils.
Hydrocarbon feed HMS, when its easy hydrogenolysis metal compound concentrations is lower than 50PPm, pre-hydrotreating reaction effluent R1P penetration depth hydro-upgrading reaction process R2, enters deep hydrogenation upgrading reaction process R2 and uses down-type fixed-bed reactor.
Hydrocarbon feed HMS, its easy hydrogenolysis metal compound concentrations higher than 100PPm particularly higher than 200PPm time, pre-hydrotreating reaction effluent R1P enter thermal high sepn process 1THPS be separated into hot high score gas gas 1THPV and hot high score oil 1THPL; Hot high score gas gas 1THPV penetration depth hydro-upgrading reaction process R2, hot high score oil 1THPL removes particulate matter gained oil product 1THPL-L penetration depth hydro-upgrading reaction process R2.
Hydrogen supply hydrocarbon stream can be introduced pre-hydrotreating reaction process R1, contact with hydrocarbon feed HMS and combine processing.
Action Target of the present invention 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.
Action Target of the present invention 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.
According to the present invention, hydrocracking reaction process R3 can be set, the hydro-upgrading heavy oil R2PO-DO formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2PO 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.
According to the present invention, separate part HPS comprises cold anticyclone separate part LHPS usually, 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 R2PO as deep hydrogenation upgrading.
According to 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, 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 R2PO comprise hot high score oil THPL and cold high score oil LHPL.
Detailed operational condition of the present invention 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%;
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, volume space velocity is 0.15 ~ 15.0hr -1, 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 operation bar 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.
Detailed operational condition of the present invention 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%;
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 bed filler R11C 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;
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 operation bar 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.
A kind of generalized flowsheet of the present invention is: pre-hydrotreating reaction process R1, and 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 effluent R2P 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 effluent R2P contacts with deep hydrogenation modifying catalyst R2C at least partially.
At pre-hydrotreating reaction process R1, inject the hydrogen rich gas logistics of pre-hydrogenator, preferentially should use new hydrogen.
At pre-hydrotreating reaction process R1, inject the hydrogen rich gas logistics of bed filler R11C, preferentially should use new hydrogen.
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%.
At pre-hydrotreating reaction process R1, filler R11C bed and filler R12C bed can be 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.
At pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, when comprising the filling batch of 2 layers of load in series, the 1st layer can be 4 impeller shapes, and the 2nd layer can be 4 leaf grass shapes.
At the fixed bed pre-hydrotreating reaction district R12 of pre-hydrotreating reaction process R1, when comprising the filling batch of 3 layers of load in series, the 1st layer can be Raschig ring shape, and the 2nd layer can be 4 impeller shapes, and the 3rd layer can be 4 leaf grass shapes.
At deep hydrogenation upgrading reaction process R2, when comprising the filling batch of 2 layers of load in series, the 1st layer can be 4 leaf grass shapes, and the 2nd layer can be 3 leaf grass shapes.
At deep hydrogenation upgrading reaction process R2, when comprising the filling batch of 3 layers of load in series, the 1st layer can be 4 impeller shapes, and the 2nd layer can be 4 leaf grass shapes, and the 3rd layer can be 3 leaf grass shapes.
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.
The hydrocarbon method of hydrotreating of a kind of upflowing bed of the present invention and fixed bed serial operation, is characterized in that comprising following steps:
(1) at pre-hydrotreating reaction process R1, under hydrogen, hydrogen sulfide and catalyst for pre-hydrogenation R1C existence condition, the pre-hydrotreating reaction R1R that hydrocarbon feed HMS containing easy hydrogenolysis metallic compound carries out the hydrodemetallation (HDM) reaction comprising easy hydrogenolysis metallic compound obtains pre-hydrotreating reaction effluent R1P, hydrocarbon feed HMS changes the process of pre-hydrotreating reaction effluent R1P at least through a fixed bed pre-hydrotreating reaction district R12, and the particulate matter R11S at least partially from upstream logistics falls in the filler R12C bed in fixed bed pre-hydrotreating reaction district R12;
Described easy hydrogenolysis metallic compound, refers to the metallic compound that its hydrogenolysis is mainly thermal response, comprises naphthenate, naphthenate at least comprise iron naphthenate and or calcium naphthenate;
The deposition reaction of described naphthenate, to refer under certain temperature condition, in the hydrogen gas atmosphere hydrogenolysis go out metal M, under hydrogen sulfide existence condition, metal M is converted into sulfide M S, on the bed filler R11C that at least part of sulfide M S is deposited on the hydrogenolysis district of easy hydrogenolysis metal M and or filler R11C particle between;
Bed filler R11C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
Bed filler R12C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
At the hydrodemetallation (HDM) reactive moieties R11 of easy hydrogenolysis metallic compound, use upflowing filling batch R11CB, under hydrogen, hydrogen sulfide existence condition, hydrocarbon feed HMS enters fixed bed pre-hydrotreating reaction district R12, by producing after upflowing filling batch R11CB by least part of solid particles sediment in the logistics of fixed bed pre-hydrotreating reaction district R12 in the filler R12C bed of fixed bed pre-hydrotreating reaction district R12 containing the pre-hydrogenation intermediate reaction effluent R11MP of particulate matter or end reaction effluent R11NP;
(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 R2PO 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.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12 last step filling batch R12YB porosity or space equivalent diameter, be less than deep hydrogenation upgrading processes R2 catalyst bed layer porosity or space equivalent diameter usually.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, can comprise the filling batch of 1 layer or 2 layers of load in series or multilayer load in series.
According to the present invention, at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, comprise the filling batch of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage filling batch or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage bed usually.
According to the present invention, at deep hydrogenation upgrading reaction process R2, comprise the beds of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage beds or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage beds usually.
The mode of operation of upflowing filling batch R11CB, can be selected from one or more in following pattern:
1. upflowing ebullated bed;
2. upflowing bubbling 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 moving-bed;
5. upflow fixed bed.
At pre-hydrotreating reaction process R1, before upflowing filling batch R11CB, the hydrogenation catalyst bed of one or more used in following pattern bed of can connecting:
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 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;
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.
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;
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;
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. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils.
Hydrocarbon feed HMS, when its easy hydrogenolysis metal compound concentrations is lower than 50PPm, pre-hydrotreating reaction effluent R1P penetration depth hydro-upgrading reaction process R2, enters deep hydrogenation upgrading reaction process R2 and uses down-type fixed-bed reactor.
Hydrocarbon feed HMS, its easy hydrogenolysis metal compound concentrations higher than 100PPm particularly higher than 200PPm time, pre-hydrotreating reaction effluent R1P enter thermal high sepn process 1THPS be separated into hot high score gas gas 1THPV and hot high score oil 1THPL; Hot high score gas gas 1THPV penetration depth hydro-upgrading reaction process R2, hot high score oil 1THPL removes particulate matter gained oil product 1THPL-L penetration depth hydro-upgrading reaction process R2.
Hydrogen supply hydrocarbon stream can be introduced pre-hydrotreating reaction process R1, contact with hydrocarbon feed HMS and combine processing.
Action Target of the present invention 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.
Action Target of the present invention 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.
According to the present invention, hydrocracking reaction process R3 can be set, the hydro-upgrading heavy oil R2PO-DO formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2PO 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.
According to the present invention, separate part HPS comprises cold anticyclone separate part LHPS usually, 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 R2PO as deep hydrogenation upgrading.
According to 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, 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 R2PO comprise hot high score oil THPL and cold high score oil LHPL.
Detailed operational condition of the present invention 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%;
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, volume space velocity is 0.15 ~ 15.0hr -1, 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 operation bar 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.
Detailed operational condition of the present invention 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%;
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 bed filler R11C 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;
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 operation bar 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.
A kind of generalized flowsheet of the present invention is: pre-hydrotreating reaction process R1, and 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 effluent R2P 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 effluent R2P contacts with deep hydrogenation modifying catalyst R2C at least partially.
At pre-hydrotreating reaction process R1, inject the hydrogen rich gas logistics of pre-hydrogenator, preferentially should use new hydrogen.
At pre-hydrotreating reaction process R1, inject the hydrogen rich gas logistics of bed filler R11C, preferentially should use new hydrogen.
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%.
At pre-hydrotreating reaction process R1, filler R11C bed and filler R12C bed can be 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.
At pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, when comprising the filling batch of 2 layers of load in series, the 1st layer can be 4 impeller shapes, and the 2nd layer can be 4 leaf grass shapes.
At the fixed bed pre-hydrotreating reaction district R12 of pre-hydrotreating reaction process R1, when comprising the filling batch of 3 layers of load in series, the 1st layer can be Raschig ring shape, and the 2nd layer can be 4 impeller shapes, and the 3rd layer can be 4 leaf grass shapes.
At deep hydrogenation upgrading reaction process R2, when comprising the filling batch of 2 layers of load in series, the 1st layer can be 4 leaf grass shapes, and the 2nd layer can be 3 leaf grass shapes.
At deep hydrogenation upgrading reaction process R2, when comprising the filling batch of 3 layers of load in series, the 1st layer can be 4 impeller shapes, and the 2nd layer can be 4 leaf grass shapes, and the 3rd layer can be 3 leaf grass shapes.
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.
The invention has the advantages that, the particulate matter quantity of penetration depth hydro-upgrading reaction process R2 beds can be reduced, effectively suppress the reduction of its porosity, extend the continuous cycle of operation.

Claims (34)

1. a hydrocarbon method of hydrotreating for upflowing bed and fixed bed serial operation, is characterized in that comprising following steps:
(1) at pre-hydrotreating reaction process R1, under hydrogen, hydrogen sulfide and catalyst for pre-hydrogenation R1C existence condition, the pre-hydrotreating reaction R1R that hydrocarbon feed HMS containing easy hydrogenolysis metallic compound carries out the hydrodemetallation (HDM) reaction comprising easy hydrogenolysis metallic compound obtains pre-hydrotreating reaction effluent R1P, hydrocarbon feed HMS changes the process of pre-hydrotreating reaction effluent R1P at least through a fixed bed pre-hydrotreating reaction district R12, and the particulate matter R11S at least partially from upstream logistics falls in the filler R12C bed in fixed bed pre-hydrotreating reaction district R12;
Described easy hydrogenolysis metallic compound, refers to the metallic compound that its hydrogenolysis is mainly thermal response, comprises naphthenate, naphthenate at least comprise iron naphthenate and or calcium naphthenate;
The deposition reaction of described naphthenate, to refer under certain temperature condition, in the hydrogen gas atmosphere hydrogenolysis go out metal M, under hydrogen sulfide existence condition, metal M is converted into sulfide M S, on the bed filler R11C that at least part of sulfide M S is deposited on the hydrogenolysis district of easy hydrogenolysis metal M and or filler R11C particle between;
Bed filler R11C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
Bed filler R12C, for have hydrogenation activity bed filler and or without the bed filler of hydrogenation activity;
At the hydrodemetallation (HDM) reactive moieties R11 of easy hydrogenolysis metallic compound, use upflowing filling batch R11CB, under hydrogen, hydrogen sulfide existence condition, hydrocarbon feed HMS enters fixed bed pre-hydrotreating reaction district R12, by producing after upflowing filling batch R11CB by least part of solid particles sediment in the logistics of fixed bed pre-hydrotreating reaction district R12 in the filler R12C bed of fixed bed pre-hydrotreating reaction district R12 containing the pre-hydrogenation intermediate reaction effluent R11MP of particulate matter or end reaction effluent R11NP;
(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 R2PO 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.
2. method according to claim 1, is characterized in that:
(1) at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12 last step filling batch R12YB porosity or space equivalent diameter, be less than deep hydrogenation upgrading processes R2 catalyst bed layer porosity or space equivalent diameter.
3. method according to claim 2, is characterized in that:
(1) at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, comprises the filling batch of 1 layer or 2 layers of load in series or multilayer load in series.
4. method according to claim 2, is characterized in that:
(1) at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, comprise the filling batch of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage filling batch or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage bed.
5. method according to claim 1, is characterized in that:
(2) at deep hydrogenation upgrading reaction process R2, comprise the beds of 1 layer or 2 layers of load in series or multilayer load in series, according to working-fluid flow direction, after arriving before having, the porosity of rear stage beds or space equivalent diameter, be less than porosity or the space equivalent diameter of previous stage beds.
6. method according to claim 1, is characterized in that:
The mode of operation of upflowing filling batch R11CB, is selected from one or more in following pattern:
1. upflowing ebullated bed;
2. upflowing bubbling 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 moving-bed;
5. upflow fixed bed.
7. method according to claim 1, is characterized in that:
At pre-hydrotreating reaction process R1, before upflowing filling batch R11CB, series connection uses the hydrogenation catalyst bed of one or more in following pattern bed:
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.
8. method according to claim 1, 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.
9. method according to claim 1, 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;
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.
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:
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;
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;
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. other aromatic hydrocarbons weight content higher than 50% gluey pitch shape composition weight content higher than 15% hydrocarbon ils.
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:
Hydrocarbon feed HMS, its easy hydrogenolysis metal compound concentrations is lower than 50PPm, and pre-hydrotreating reaction effluent R1P penetration depth hydro-upgrading reaction process R2, enters deep hydrogenation upgrading reaction process R2 and use down-type fixed-bed reactor.
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:
Hydrocarbon feed HMS, its easy hydrogenolysis metal compound concentrations is higher than 100PPm, and pre-hydrotreating reaction effluent R1P enters thermal high sepn process 1THPS and is separated into hot high score gas gas 1THPV and hot high score oil 1THPL;
Hot high score gas gas 1THPV penetration depth hydro-upgrading reaction process R2, hot high score oil 1THPL removes particulate matter gained oil product 1THPL-L penetration depth hydro-upgrading reaction process R2.
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:
Hydrocarbon feed HMS, its easy hydrogenolysis metal compound concentrations is higher than 200PPm, and pre-hydrotreating reaction effluent R1P enters thermal high sepn process 1THPS and is separated into hot high score gas gas 1THPV and hot high score oil 1THPL;
Hot high score gas gas 1THPV penetration depth hydro-upgrading reaction process R2, hot high score oil 1THPL removes particulate matter gained oil product 1THPL-L penetration depth hydro-upgrading reaction process R2.
14. methods according to claim 1, is characterized in that:
Hydrogen supply hydrocarbon stream enters pre-hydrotreating reaction process R1, contacts and combine processing with hydrocarbon feed HMS.
15. methods according to claim 1, is characterized in that:
(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.
16. methods according to claim 1, is characterized in that:
(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.
17. 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 R2PO-DO formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2PO gained being separated deep hydrogenation upgrading reaction effluent R2P, for raw material, is converted into hydrocracking reaction effluent R3P at hydrocracking reaction process R3.
18., according to method described in claim 11, is characterized in that:
(4) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2PO-DO formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2PO gained being separated deep hydrogenation upgrading reaction effluent R2P, for raw material, is converted into hydrocracking reaction effluent R3P at hydrocracking reaction process R3.
19., according to method described in claim 18, is characterized in that:
(4) hydrocracking reaction process R3 is set, the hydro-upgrading heavy oil R2PO-DO formed higher than 350 DEG C of hydrocarbon primarily of normal boiling point with the hydrogenated oil R2PO 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.
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:
(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 R2PO as deep hydrogenation upgrading.
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:
(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 R2PO comprise hot high score oil THPL and cold high score oil LHPL.
22. methods according to claim 1, is characterized in that:
(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%;
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, volume space velocity is 0.15 ~ 15.0hr -1, 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 operation bar 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.
23. methods according to claim 1, is characterized in that:
(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%;
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 bed filler R11C 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;
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 operation bar 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.
24. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 22 or 23 method, 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 effluent R2P 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 effluent R2P contacts with deep hydrogenation modifying catalyst R2C at least partially.
25. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 22 or 23 method, it is characterized in that:
(1) at pre-hydrotreating reaction process R1, the hydrogen rich gas logistics injecting pre-hydrogenator is new hydrogen.
26. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 23 method, it is characterized in that:
(1) at pre-hydrotreating reaction process R1, the hydrogen rich gas logistics injecting bed filler R11C is new hydrogen.
27. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 22 or 23 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%.
28. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 22 or 23 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%.
29. according to claim 1 or 2 or 3 or 4 or 5 or 6 or 7 or 8 or 9 or 22 or 23 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.
30., according to method described in claim 29, 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.
31. methods according to claim 4, is characterized in that:
(1) at pre-hydrotreating reaction process R1, fixed bed pre-hydrotreating reaction district R12, comprises the filling batch of 2 layers of load in series, and the 1st layer is 4 impeller shapes, and the 2nd layer is 4 leaf grass shapes.
32. methods according to claim 4, is characterized in that:
(1) at the fixed bed pre-hydrotreating reaction district R12 of pre-hydrotreating reaction process R1, comprise the filling batch of 3 layers of load in series, the 1st layer is Raschig ring shape, and the 2nd layer is 4 impeller shapes, and the 3rd layer is 4 leaf grass shapes.
33. methods according to claim 5, is characterized in that:
(2) at deep hydrogenation upgrading reaction process R2, comprise the filling batch of 2 layers of load in series, the 1st layer is 4 leaf grass shapes, and the 2nd layer is 3 leaf grass shapes.
34. methods according to claim 5, is characterized in that:
(2) at deep hydrogenation upgrading reaction process R2, comprise the filling batch of 3 layers of load in series, the 1st layer is 4 impeller shapes, and the 2nd layer is 4 leaf grass shapes, and the 3rd layer is 3 leaf grass shapes.
CN201410373486.3A 2014-07-26 2014-07-26 Hydrocarbon hydrogenation method with up-flow bed layer and fixed bed operated in series Pending CN104263407A (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1903994A (en) * 2006-08-03 2007-01-31 湖南长岭石化科技开发有限公司 Method of producing fuel oil by coal tar hydrogenation modifying
CN101240193A (en) * 2007-02-09 2008-08-13 中国石油化工股份有限公司 Coal tar multistage hydrogenation treatment technique
CN101314733A (en) * 2007-05-31 2008-12-03 中国石油化工股份有限公司 Hydrogenation depickling method for high-metal acid containing primary oil
CN101890382A (en) * 2009-05-19 2010-11-24 中国石油化工股份有限公司 Hydrodemetallization catalyst and application thereof
CN102443428A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Heavy-hydrocarbon hydrogenation treatment method
CN103897730A (en) * 2014-03-19 2014-07-02 何巨堂 Inferior hydrocarbon hydro-upgrading method comprising raw material shunt series prehydrogenation process

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1903994A (en) * 2006-08-03 2007-01-31 湖南长岭石化科技开发有限公司 Method of producing fuel oil by coal tar hydrogenation modifying
CN101240193A (en) * 2007-02-09 2008-08-13 中国石油化工股份有限公司 Coal tar multistage hydrogenation treatment technique
CN101314733A (en) * 2007-05-31 2008-12-03 中国石油化工股份有限公司 Hydrogenation depickling method for high-metal acid containing primary oil
CN101890382A (en) * 2009-05-19 2010-11-24 中国石油化工股份有限公司 Hydrodemetallization catalyst and application thereof
CN102443428A (en) * 2010-10-13 2012-05-09 中国石油化工股份有限公司 Heavy-hydrocarbon hydrogenation treatment method
CN103897730A (en) * 2014-03-19 2014-07-02 何巨堂 Inferior hydrocarbon hydro-upgrading method comprising raw material shunt series prehydrogenation process

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