CN104927914A

CN104927914A - Higher aromatic hydrogenation method with low-hydrogen-oil-ratio pre-hydrogenation process with hydrogen-donor hydrocarbon

Info

Publication number: CN104927914A
Application number: CN201410119049.9A
Authority: CN
Inventors: 何巨堂
Original assignee: Individual
Current assignee: Individual
Priority date: 2014-03-23
Filing date: 2014-03-23
Publication date: 2015-09-23

Abstract

The invention relates to a higher aromatic hydrogenation method with a low-hydrogen-oil-ratio pre-hydrogenation process with hydrogen-donor hydrocarbon. According to the invention, the hydrogen-oil ratio is at an appropriate low value, such that the hydrocarbon oil liquid-phase separation rate in a catalyst bed layer is at a high value. A catalyst surface hydrocarbon oil liquid phase is prevented from forming severe lower aromatic phase-higher aromatic phase double liquid phase with combined reaction diluent oil rich in hydrogen-donor hydrocarbon, such that the concentration of high-viscosity heavy hydrocarbon in the catalyst surface high aromatic liquid phase is at a low value, and good dispersion, fluidity and active-hydrogen-acquisition capacity are maintained. The method provided by the invention is especially suitable for medium-low-temperature coal tar deep hydro-conversion processes. With the method, catalyst coking can be effectively inhibited, continuous operation period can be prolonged, and catalyst efficiency can be improved.

Description

Comprise the high aromatics hydrogenation process of the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon

Technical field

The present invention relates to a kind of high aromatics hydrogenation process comprising the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon, particularly, the present invention relates to a kind of method of hydrotreating being rich in the hydrocarbon ils of gluey pitch shape component and the reactor thereof that use the low hydrogen/gasoline ratio of hydrogen supply hydrocarbon, more particularly, the present invention relates to coalite tar hydrogenating conversion process and reactor thereof in one, for the pre-hydrogenation process of the deep hydrogenation upgrading processes of the coal-tar pitch of middle coalite tar, use mutual solubility is excellent, reaction competition is poor, preferably be rich in the association response dilution hydrocarbon of hydrogen supply hydrocarbon, control hydrogen-oil ratio is in suitable low value makes the hydrocarbon ils liquid phase fraction in beds be in high level, to keep liquid phase medium-high viscosity heavy hydrocarbon components R1LHDC (the middle conversion product of the gluey pitch shape component such as in coalite tar and pre-hydroconversion process thereof), there is good dispersiveness (liquid phase homogeneity is high), good mobility (viscosity is little), relatively strong hydrogenation reaction selectivity, high catches active hydrogen speed, thus make the mutual solubility of the liquid phase formation high viscosity heavy hydrocarbon components R1LHDC of catalyst surface dissolving high viscosity heavy hydrocarbon components R1LHDC good, good security, the dilute solution that dispersity is high, the high density liquid phase preventing catalyst surface from forming high viscosity heavy hydrocarbon even reaches phase separation makes bituminous matter aggregate and precipitate depart from main body hydrocarbon ils liquid phase and form in fact the bituminous matter coagulation phase of easy rapid condensation coking.

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 F1 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 F1, 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 F1 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 F1 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 F1, 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 F1 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 F1).

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 F1), 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 middle coalite tar F1 is in the deep hydrogenation upgrading processes of diesel oil distillate with target product, gluey pitch shape component contained by middle coalite tar F1, experienced by hydrogenolysis lightweight and turn to comparatively small molecules, hydrotreated lube base oil, the hydro-upgrading processes such as removing impurities matter, substantially experiencing the reaction mechanism of " the bituminous matter more much higher Polycyclic aromatic hydrocarbons → naphthenic hydrocarbon of polycyclic aromatic hydrocarbons → saturation ratio that component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons → saturation ratio is lower ", certain different molecular weight, different boiling, the course of the reactant composition of different characterization of adsorption can not be identical, and due to the hydrogenation and removing of assorted element, the lytic effect that acidity of catalyst center is caused, the thermo-crackings that pyroreaction causes etc. also can generating portion " apparent cracking reaction " or " refining property cracking reaction ", but foregoing description bitum hydro-upgrading course is realistic substantially.Certainly, when the most downstream series connection of the beds of coal tar hydrogenation modification process uses hydrocracking catalyst, foregoing description bitum hydro-upgrading course also will continue continuity and carry out the process of " outer ring open loop → aromatic ring saturated → outer ring open loop ", but, because the usual nitrogen content of coal tar is too high, hydro-upgrading process reaction effluent contains a large amount of amino molecule, there is extremely strong adsorptive power in the acid cracking active centre of these amino molecules to hydrocracking catalyst, thus occupy a large amount of active centre and seriously reduce the activity of hydrocracking catalyst thus reduce cracking activity or cause the raising of cracking reaction temperature and aggravate non-selective cracking reaction and increase coke (i.e. catalyst surface coking) and the productive rate of conventional gas component, add the massive diesel-fuel contained in cracking reaction raw material, the light hydrocarbons such as gasoline can generate conventional gas hydrocarbon thus reduce liquid oil total recovery by overcracking, so, the deep hydrogenation upgrading of usual coal-tar pitch is based on hydrofining, wax oil in deep hydrogenation upgrading conversion product or heavier cut carry out efficient (high liquid yield usually under the condition removing ammonia, high oil quality index, long period) hydrocracking produces the product such as diesel oil distillate.

At middle coalite tar F1 is in the deep hydrogenation upgrading processes of diesel oil distillate with target product, gluey pitch shape component is longer compared with the hydro-upgrading course of other lower molecular weight components, this be middle coalite tar F1 be that the deep hydrogenation upgrading processes of diesel oil distillate requires that deep hydrogenation upgrading generates normal boiling point in oil and is usually reduced to below 50PPm higher than the nitrogen content of the hydrocarbon component of 350 DEG C usually with target product, generally be reduced to below 20PPm, preferably be reduced to the hydrogenation depth (hydrodenitrification of below 10PPm defined, hydrogenation aromatic saturation) determine, that is, gluey pitch shape component is compared with other lower molecular weight components, realize deep hydrogenation aromatics saturation process, the reactions steps that deep hydrogenation denitrification process experiences is more, the effective reaction time needed is longer, need to contact more frequently with catalyst active center, compared with the hydro-upgrading process of condensed-nuclei aromatics, gluey pitch shape component first must complete the conversion of " bituminous matter component → colloid → condensed-nuclei aromatics " substantially, in other words, the pre-hydrogenation process of gluey pitch shape component should be divided into the pre-hydrogenation process AR1 of either shallow and the pre-hydrogenation process BR1 of the degree of depth, requires the pre-hydrogenation process of either shallow of reasonable arrangement selectivity preferably gluey pitch shape component.Because gluey pitch shape component and conversion product thereof are mostly the high boiling substance of macromolecule, its pre-hydrotreating reaction process particularly either shallow pre-hydrotreating reaction process mainly must belong to liquid phase reaction, and therefore the characteristic of this liquid phase is most important.For middle coalite tar deep hydrogenation upgrading processes, it is a significant initial conversion step that the hydrogenolysis lightweight of gluey pitch shape component turns to the pre-hydrogenation process of more micromolecular either shallow, its success or failure determine the success or failure of middle coalite tar deep hydrofinishing overall process, because gluey pitch shape component molecular amount is maximum, component size is maximum, movement velocity is the slowest, polarity is the strongest, viscosity is maximum, boiling point is minimum, Hydrocarbon saturation is minimum, in hydro-upgrading process, overall hydrogenation reaction speed is the slowest, also the longest to the requirement of the liquid phase residence time, the easiest polycondensation and dispersity the poorest, maximum to catalyst surface coking contribution, property of liquid phase in the reaction conditions of the therefore pre-hydrogenation process of either shallow of gluey pitch shape component becomes the key object improving Technology.

It is a principal object of the present invention to the method for the pre-hydrotreating reaction condition proposing gluey pitch shape component in coalite tar deep hydrogenation upgrading processes in a kind of improvement, form the pre-hydrogenation upgraded condition of high performance liquid phase of gluey pitch shape component, and the coupling of the hydrogenation speed of coalite tar coal-tar pitch and middle coalite tar lighting end in controlling, pre-hydrotreating reaction process liquid solution is kept to have good homogeneity, the final middle coalite tar highly effective hydrogenation method for transformation forming a kind of continuous cycle of operation length.Therefore, emphasis of the present invention turns to the reaction conditions of the pre-hydrogenation process of either shallow required by the former steps " bituminous matter component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons " in the deep hydrofinishing reaction mechanism of more micromolecular " the bituminous matter more much higher Polycyclic aromatic hydrocarbons → naphthenic hydrocarbon of polycyclic aromatic hydrocarbons → saturation ratio that component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons → saturation ratio is lower " in conjunction with gluey pitch shape component hydrogenolysis lightweight, discusses process thought of the present invention and technological method.

Below based on coal tar distillation experimental result, analytic routines boiling temperature is molecular structure or the supramolecular aggregation structure of gluey pitch shape component in the middle coalite tar cut of 130 ~ 480 DEG C.Normal boiling point temperature is containing a large amount of gluey bituminous substances in the middle coalite tar cut of 130 ~ 480 DEG C, because the activity of these gluey pitch shape components is strong, change sample solution temperature process as distillation, Rapid Thermal polycondensation and coking reaction must be there is in the heating steps of carbon residue analytic process, change sample solution composition process as distillation later stage, using the lower hydro carbons of aromatic hydrocarbons degree to carry out extraction process etc. causes gluey pitch shape concentration of component to become the condensation reaction that gluey pitch shape must occur large step, the character that the gluey pitch shape component that in almost can changing in these processes, in coalite tar sample, dispersion state exists possesses, in thermal treatment, concentrated process increases condenses quantity usually, cause carbon residue, coking value, benzene insoluble, toluene insolubles, increasing considerably of quinoline insolubles desired value, analytical results serious distortion.The a large amount of gluey bituminous substances contained in middle coalite tar cut, be difficult to use its character of petroleum analysis analytical procedure truly expressed, the unit molecule structural information of these components is more difficult to obtain, it is caused to become " mysterious component ", and consciously or unconsciously misapplied in analysis by portion of techniques personnel, and the inference led to errors and propagation; But absolute mystery is non-existent, the course condition produced in coal by these components and its distillation expression behaviour, can obtain qualitative analysis accurately to its internal structure substantially; middle coalite tar originates from coal generating gas or middle low-temperature coal carbonization process and have passed through storage process, belong to the secondary reaction thing (the new gathering component of the supramolecular structure that second heat reaction volatile matter and the collision of condensation process liquid phase molecule thereof generate) of a hydro carbons volatile matter that coal charge molecular heat solution preocess cracking under cold condition goes out and a hydro carbons volatile matter, under middle low temperature pyrogenation condition, macromole hydrocarbon in a hydro carbons volatile matter is based on polycyclic aromatic hydrocarbons, be secondary with condensed-nuclei aromatics, namely the aromatic ring number of macromole hydrocarbon generally can not too much (usual great majority are not more than 5 aromatic rings), the probability that coal molecule By Direct Pyrolysis goes out the gluey pitch shape component of especially big molecular weight is lower, and the charcoal number of the side chain of condensed-nuclei aromatics in coal tar is less, even all carbon atom all belongs to aromatic carbon, its two-dimension plane structure is beneficial to large π key and attracts and form associated complex, the associated complex that gluey pitch shape component in middle coalite tar has the second heat condensation reaction of part from the condensed-nuclei aromatics in a hydro carbons volatile matter and the attraction by large π key to be formed, the hydrogen bond that certain phenolic hydroxyl group provides also serves certain effect.Because middle Low Temperature Pyrolysis Process is particularly according to Low Temperature Pyrolysis Process in the work of internal-heating gas thermal barrier mode, hydro carbons volatile matter is very fast reduces temperature with thermal barrier and coal charge counter current contact, so the second heat condensation reaction of a hydro carbons volatile matter is terminated very soon, the comparatively small amt of a condensation hydro carbons volatile matter elementary cell together.Above-mentioned analysis is correct substantially, because following cut distillation test result could be explained only so: normal boiling point temperature is the gelatinoid that the middle coalite tar cut of 220 ~ 350 DEG C contains 15 ~ 25 % by weight, normal boiling point temperature is middle coalite tar cut (simulation distil 98% distillates a temperatures as high 730 ~ 780 DEG C) the gluey bituminous substances containing 30 ~ 40 % by weight of 130 ~ 480 DEG C, and these " gelatinoids " are from the condensation of normal boiling point temperature lower than the monomolecular gases hydrocarbon component of 480 DEG C, the conversion of storage process, and can substantially whole carburation by evaporations under described temperature condition, separately only there is the carbon residue being usually less than 3% weight, this illustrates, main not being dependence covalent linkage but relying on the more weak mode of action to attract to associate between the elementary cell of these jellies, in fact, this known phenomenon of the anthracene component crystallizes in carbolineum have leaked this secret to us already.Because normal boiling point temperature is that gluey bituminous substances content in 130 ~ 480 DEG C in coalite tar cut is up to 30 ~ 40 % by weight, can say definitely, normal boiling point temperature is that the major part of gluey pitch shape component in the middle coalite tar cut of 130 ~ 480 DEG C is even most, belongs to and accounts for leading macromole associated complex by association; Same reason, the part that the normal boiling point in middle coalite tar is greater than the glial component of the coal-tar pitch HMC of 480 DEG C is even most of, also belongs to and accounts for leading macromole associated complex by association.

Below based on coal tar distillation experimental result and deep hydrogenation upgrading experimental result, the normal boiling point in analysis in coalite tar is greater than molecular structure or the supramolecular aggregation structure of the gluey pitch shape component of the coal-tar pitch HMC of 480 DEG C.Analytical data shows, usually, the total content about 10% of the stable hydrocarbon in the coal-tar pitch HMC of middle coalite tar and aromatic hydrocarbon, all the other 85 ~ 93% are all gluey pitch shape component, ash content simultaneously containing minute quantity and particle insolubles, particle insolubles is based on semi-coke powder, coal dust.Gluey pitch shape component concentration up to 35 ~ 50 % by weight, nitrogen content up to 0.6 ~ 1.2 % by weight, the simulation distil 90% typical deep hydrogenation upgraded condition that distillates coalite tar (comprising coal-tar pitch cut) in the full cut of a temperatures as high 750 ~ 830 DEG C is: the hydrogen partial pressure of 14.0 ~ 16.0MPa, the pre-hydrogenation temperature of 250 ~ 370 DEG C, the deep hydrogenation upgrading temperature of 300 ~ 420 DEG C, suitable catalyst for pre-hydrogenation and deep hydrogenation modifying catalyst, catalyst for pre-hydrogenation volume space velocity is 0.4 ~ 1.0hr ^-1, deep hydrogenation modifying catalyst volume space velocity is 0.25 ~ 0.5hr ^-1, hydrogen/stock oil volume ratio is 800: 1 ~ 2000: 1.Under above-mentioned Hydrofinishing conditions, instead of under the hydrocracking condition that thermally splitting function is strong, deep hydrogenation upgrading processes acquisition distillation can be completed and do hydrofining generation oil (normal boiling point is greater than the nitrogen content of 350 DEG C of cuts lower than≤10 ~ 40PPm) that normal boiling point temperature is 520 ~ 560 DEG C, total nitrogen content is 3 ~ 10PPm; This deep hydrogenation upgrading experimental result explanation, the inside of the structures alone molecule in the supramolecular structure of the gluey pitch shape component of coal-tar pitch HMC, the part bridged bond formed between the basic structural unit of monomer molecule and condensation aromatic ring structure unit belongs to the lower bridge chain belonging to the fracture of easy hydrogenation in other words of bond energy, and these bridged bonds can be two mesomethylene carbon bridges in fat carbon bridge such as methylene bridge, heteroatom bridges such as oxo bridge or sulphur bridge, hydrogenation of aromatics ring; This deep hydrogenation upgrading experimental result also illustrates, the association of the structures alone molecule in the supramolecular structure of the gluey pitch shape component of coal-tar pitch HMC, can be formed by highly effective hydrogenation solution, it clearly shows the deep hydrogenation upgrading processes of coalite tar in full cut (comprising coal-tar pitch cut), says it is possible, feasible from the angle of shortening chemical conversion.

Below analyze in full cut, in coalite tar hydro-upgrading process, large component is contributed to coking value.Based on coal tar distillation experimental result and deep hydrogenation upgrading experimental result, clearly, be in 130 ~ 480 DEG C compared with coalite tar cut with normal boiling point temperature, gluey pitch shape component concentration in coal-tar pitch HMC is higher, relative molecular weight is larger, structure is more huge, the higher structures alone in other words of asphalt content wherein molecule is more, relative molecular weight is larger, three-dimensional scantlings of the structure is larger, the average carbon atom number of structures alone molecule is more, the average aromatic carbon ratio of structures alone molecule is higher, coking value is higher, the significant contributor of the carbon residue of coalite tar in full cut, also be the main object of coalite tar hydro-upgrading process slagging prevention in full cut.Mandatory declaration be a bit, in full cut in coalite tar hydro-upgrading process, the activity of glial component is comparatively strong, also exist two kinds transform may: may hydrocracking be all namely light ends, also considerably pyrocondensation may be combined into bituminous matter and then dehydrogenative condensation is coke; On the other hand, the enormous amount of glial component, strong impact even determines the property of liquid phase of coal tar, must special concern in mandatory declaration.

Below based on mutual solubility experiment, analyze the mutual solubility relation that coal tar deep hydrogenation upgrading generates oil (low aromatic hydrocarbon oil) and coal tar (being rich in the high aromatic oil of gluey pitch shape component).Laboratory experiment and full scale plant run verified, middle coalite tar can obtain through deep hydrofinishing the low aromatic hydrocarbons degree diesel component that cetane value was greater than for 26 (or being greater than 35), now, middle coalite tar deep hydrofinishing generates oil and has extraction effect with mixing of middle coalite tar, namely substantially Two Liquid Phases is formed: low aromatic hydrocarbons liquid phase and high aromatic hydrocarbons concentrate liquid phase, namely the low aromatic hydrocarbons migration of liquid that stable hydrocarbon consequently in middle coalite tar and rudimentary aromatic hydrocarbons generate oily place to middle coalite tar deep hydrofinishing dissolves, middle coalite tar forms the concentrated high aromatic hydrocarbons liquid phase of gluey pitch shape component after losing fractional saturation hydrocarbon and rudimentary aromatic hydrocarbons, if above-mentioned situation occurs in hydrogenation catalyst bed, due to the surface adsorption effect of catalyzer, high aromatic hydrocarbons liquid phase is tended to be positioned near the side of catalyst surface and the inner side of catalyst surface Two Liquid Phases, if when middle coalite tar deep hydrofinishing generation oil is higher with the mass ratio of middle coalite tar, floss even condenses will be there is in high aromatic hydrocarbons liquid phase, if lighting end such as gasoline or diesel oil distillate that in using, coalite tar deep hydrofinishing generates in oil extract, effect is more obvious.Therefore comprise gluey pitch shape component coal tar deep hydrogenation upgrading processes pre-hydrogenation process in, in should not using coalite tar deep hydrofinishing generate oil particularly should not use in the coalite tar deep hydrofinishing low virtue oil of lighting end wet goods that generates oil increase the means of amount of liquid phase as described pre-hydrogenation process, this point and the regulation of solvent oil process direct coal liquefaction process to hydrogen supply dissolvent oil nature same or similar.The pre-hydrogenation process of centering coalite tar hydroconversion process, if it is low aromatic hydrocarbons that the liquid phase used increases material, then poor with raw material mutual solubility, and the Two Liquid Phases that extraction effect forms " the high aromatic hydrocarbons of low aromatic hydrocarbons liquid phase one concentrates liquid phase " is formed to raw material.In fact, during ratio is suitable, coalite tar deep hydrofinishing generates diesel oil distillate and middle coalite tar hybrid extraction in transparent glass beaker of oil, also can observe apparent three-phase " upper strata low aromatic hydrocarbons liquid phase (transparency is high), lower floor height aromatic hydrocarbons liquid phase (transparency is low and have solidifying wadding suspended substance), the gluey coagulation phase of bottom pitch shape (viscosity greatly, to wall strong adhesion, mobility extreme difference) ".

And be separated theory theoretical with the colloidal solution being rich in the heavy hydrocarbon hot procedure of gluey pitch shape component is instruct below, in conjunction with in the catalyzer coking process of pre-hydrogenation process of deep hydrogenation upgrading processes of coalite tar, the constitutive property of the liquor on analysis of catalyst surface and thermal transition behavior, the hydrocracking thing of intermediate time gluey pitch shape component of selective analysis coal tar deep hydrogenation upgrading processes and the mutual solubility relation of the hydrocracking thing of lighting end, i.e. the mutual solubility relation of the middle hydrocracking thing of the different components of coal tar.Experiment and full scale plant run verified, if middle coalite tar coal-tar pitch and middle coalite tar lighting end mix reaction and synchronous averaging reaction, existing catalyst technology and Process engineering are difficult to not control molecular size not etc., the synergetic property of the pre-hydrotreating reaction process of the component of virtueization varying degree or selectivity, compared with the component of middle coalite tar coal-tar pitch, the component of middle coalite tar lighting end, because molecule its heat movement speed little is fast, in addition viscosity is less in the liquid phase, large with catalyst exposure probability, because its sulphur, oxygen, alkene structures is simply rudimentary, its desulfurization, deoxidation, olefin saturated speed is fast, aggregate performance is that hydrofining reaction speed is fast, " normal boiling point lower than 480 DEG C of lighting end weight/normal boiling point lower than 480 DEG C of last running weight " ratio K F is greater than 1 usually among adding in the full cut coal tar of low temperature, generally be greater than 2, " normal boiling point lower than 480 DEG C of lighting end molecule number/normal boiling point lower than 480 DEG C of last running molecule number " ratio K FM is greater than 2 usually, generally be greater than 4, it is high that middle coalite tar lighting end response competition ability occupies active centre probability by force, active hydrogen in a large amount of consumption liquid phase, result is reduction of the speed of reaction of the gluey pitch shape component of middle coalite tar, thus reduce the selectivity of high viscosity heavy hydrocarbon pre-hydrotreating reaction, result causes each component pre-hydrogenation process speed that fragrantization degree in pre-hydrotreating reaction process Raw oil is different unbalanced, the hydrogenation lighting speed of the aromatic component that the aromatic component that in trickle-bed reactor, usual fragrantization degree is high is lower than virtue degree is slow, that is define that " last running transforms slow, lighting end transforms fast " polarization trend, along with the intensification of pre-hydrogenation degree, gluey pitch shape component in middle coalite tar and pre-hydrogenation conversion product (can be considered as solute) thereof and middle coalite tar lighting end and the mutual solubility in advance between hydrogenation conversion product (can be considered as solvent) thereof are worse and worse, pre-hydrotreating reaction generates the Two Liquid Phases that the oily hydrocarbon ils liquid phase self formed will be tending towards being formed " low aromatic hydrocarbons liquid phase-Gao aromatic hydrocarbons concentrates liquid phase ", once catalyst for pre-hydrogenation surface forms the Two Liquid Phases of " low aromatic hydrocarbons liquid phase-Gao aromatic hydrocarbons concentrates liquid phase ", polarity is strong, the high aromatic hydrocarbons that viscosity is large concentrates liquid phase by the hydrogenation reaction working conditions on long-term covering catalyst active centre and deteriorated catalyst surface continuously, result reduces hydrogen transmission speed to form scarce hydrogen environment, reduce thermophore translational speed and form focus center, reduce catalyst surface material and substitute speed reduction catalytic efficiency, extend the acceleration coking of the heavy component residence time, the performance of full scale plant is, because the quick coking of catalyst for pre-hydrogenation bed, the consequent is the quick coking of deep hydrogenation beds, finally cause the continuous cycle of operation short, stopping work frequently makes device lose economy, security.

A kind for the treatment of process of middle coalite tar is, first delayed coking process is carried out to the last running of coalite tar or middle coalite tar in full cut, then hydro-upgrading is carried out to coking distillate, clearly, in the process furnace and coke drum of delayed coking, the following dehydrogenation reaction of intentional arrangement and coking reaction, the Direction of Reaction is:

" coke ← Carbonaceous mesophase ← bituminous matter component ← colloid ← condensed-nuclei aromatics ← polycyclic aromatic hydrocarbons ← double ring arene "

The highly energy-consuming reaction process of this to be a technique object be green coke, its essence is make enormous amount can by adding hydrogenolysis and form and then the gluey pitch shape component accounting for coal tar all wts 1/3 ~ 1/2 of hydrogenation lighting, experienced by the high temperature thermal cracking coking reaction of an efficient dehydrogenation, increase considerably coking yield, reduce yield of light oil, full scale plant shows, coke productive rate about 14 ~ 17 % by weight, conventional gas productive rate about 4 ~ 6 % by weight, seriously reduce the use value of coalite tar in full cut, add negative effect investment and negative effect energy consumption.From the Component seperation angle of macroscopic view, this technique be in fact the strategy that gluey pitch shape component be have employed to " phase transform, be convenient to be separated ", process nature is that gluey pitch shape component is considerably heated and has been changed into coke solids and conventional gas appropriate hydrocarbon gas, achieve easily and being separated of other hydrocarbon ils component, just cost is too high.

But, the coking reaction that gluey pitch shape component representated by above-mentioned obvious green coke phenomenon occurs in hot procedure, in full cut, the hydrogenation catalyst surface of the deep hydrogenation upgrading processes of coalite tar is same exists, just in order to reduce coking speed as far as possible, we wish that namely do contrary thing suppresses coking.Therefore, intuitively, coking is beneficial to the factor of condensation coking, is all the factors that should suppress as far as possible in the deep hydrogenation upgrading processes of coalite tar in full cut.

Based on above analysis, can draw the following conclusions: because the concentration of the glial component of coalite tar in full cut is usually up to 35 ~ 55 % by weight, the pre-hydrogenation process of the deep hydrogenation upgrading processes of the gluey pitch shape component of middle coalite tar, the solution that must comprise macromole associated complex is formed or is faced hydrogenolysis and forms or add the basic step that hydrogenolysis forms, consider that hydrogenation catalyst coking speed is to the critical importance of industrial operation period of hydrogenation device, this is a step of occupying leading meaning in pre-hydrogenation process, due to this step hot conditions in certain, catalyzer exists, hydrogen exists, multi-step shortening dynamic process under other symbiosis component existence of middle coalite tar, for gluey pitch shape component, there are two kinds of parallel reaction conditionss, and then specify the mutual solubility of the hydrocarbon ils liquid phase component that middle hydrocracking thing is formed, beds coking speed in final decision, these two kinds of the Direction of Reaction are:

1. namely hydrogenation reaction suppresses the reaction of coking, and direction is " bituminous matter component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons ";

2. dehydrogenation reaction and coking reaction, direction is " coke ← Carbonaceous mesophase ← bituminous matter component ← colloid ← condensed-nuclei aromatics ".

Each component in full cut in coalite tar is dissolved each other, each component that the deep hydrogenation upgrading that we expect generates in oil is also dissolved each other, but in full cut, the mutual solubility of the hydrocarbon ils liquid phase component of middle the hydrocracking thing formation of coalite tar changes with the change of hydrogenation conditions, needs to find out controlled hydrogenation conditions.

As previously mentioned, the reaction conditions improving the pre-hydrogenation process of gluey pitch shape component either shallow is the key of the pre-hydrogenation process of coalite tar deep hydrofinishing process in improving, and the pre-hydrogenation process of the existing coal tar deep hydrogenation method for modifying particularly pre-hydrogenation process of either shallow, there is gluey pitch shape component liquid-phase reaction condition poor, cause the significant drawback that coking speed is fast, catalyst efficiency is low.

Because the present inventor has proposed efficient middle low temperature pyrolysis of coal novel process, and the success or failure of middle coalite tar deep hydrofinishing process associate the utilization ratio of the main products of middle low temperature pyrolysis of coal, also indirectly decide the economy of middle low temperature pyrolytic process of coal, thus the present inventor must solve in the quick coking problem of hydrogenation catalyst particularly catalyst for pre-hydrogenation of coalite tar deep hydrofinishing process.

Because the kinetics prerequisite of the quick coking in hydrogenation catalyst surface is that Carbonaceous mesophase appears in catalyst surface liquid phase, therefore need on the one hand to take " defensive tactics " namely to reduce " Carbonaceous mesophase ← bituminous matter component ← colloid " speed of response to greatest extent, need on the one hand to take " attack tactics " namely reliably to improve " bituminous matter component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons " speed of response; In order to the pre-hydrotreating reaction effect preventing the competing reaction of light constituent from reducing gluey pitch shape component, the hydrogenation conditions that the selectivity needing to create a kind of gluey pitch shape component is high.

The present invention proposes coalite tar deep hydrogenation method for modifying in one, main purpose is the liquid-phase reaction condition of the pre-hydrogenation process of the gluey pitch shape component particularly pre-hydrogenation process of its either shallow of coalite tar in improving, macromolecule, high boiling substance is mostly based on gluey pitch shape component and conversion product thereof, its hydro-upgrading reaction process particularly pre-hydrogenation process mainly belongs to liquid phase reaction, therefore strengthening and improve this liquid reactive method is exactly the method needed, and main points are as follows:

1. the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon is used to make catalyst surface hydrocarbon ils liquid phase form the liquid solution that high viscosity heavy hydrocarbon pre-hydrotreating reaction selectivity is strong, acquisition active hydrogen ability is strong; The middle and later periods in plant running stage, along with the raising of catalyst for pre-hydrogenation bed temperature rise, liquid phase fraction in catalyst for pre-hydrogenation bed will decline, gluey pitch shape component coking speed will increase, now, increase the concentration of the hydrogen supply hydrocarbon of association response dilution hydrocarbon, increase the quantity of association response dilution hydrocarbon, to the restraining effect of catalyst for pre-hydrogenation bed coking, will embody more and more consumingly; The association response dilution hydrocarbon that usage quantity is rationally many, reduces the temperature rise of catalyst for pre-hydrogenation bed as far as possible, reduces catalyst for pre-hydrogenation deactivation rate as far as possible, reduce catalyst for pre-hydrogenation coking speed, most important to the prolongation pre-hydrogenator operate continuously cycle;

2. the pre-hydrogenation process of the deep hydrogenation upgrading processes of the gluey pitch shape component of middle coalite tar, the solution that must comprise macromole associated complex is formed or is faced hydrogenolysis and forms or add the basic step that hydrogenolysis forms, be necessary for it and sufficient liquid phase reaction time is provided, namely under the precondition of amount of hydrogen needed for hydrogen partial pressure needed for the coking of satisfied resistance catalyzer and pre-hydrotreating reaction hydrogen supply, the operational condition that the liquid phase residence time should be adopted long and low hydrogen/gasoline ratio operation;

3. control hydrogen-oil ratio to be in suitable low value and to make the hydrocarbon ils liquid phase fraction in beds be in high level, thus make liquid phase that catalyst surface dissolves high viscosity heavy hydrocarbon components such as gluey pitch shape component form the dilute solution of high viscosity heavy hydrocarbon, to keep its good high dispersiveness, mobility, to catch active hydrogen speed; The hydrogen of hydrogenation reaction consumption can divide bed immediately to supply step by step, and does not need to supply in advance;

4. improve active hydrogen supply as far as possible, namely improve the hydrogen supply hydrocarbon concentration of association response dilution hydrocarbon, improve catalyst surface and produce the velocity ratio of active hydrogen as strengthened gas-phase presulfiding hydrogen concentration thus the speed of larger catalyst active centre dissociation hydrogen sulfide;

5. use the catalyzer with highly selective response capacity as far as possible, develop the new catalyzer with highly selective response capacity.

The present invention mainly in conjunction with above-mentioned 1. ~ 4. item factor, process modification is proposed.

In the pre-hydrogenation process of gluey pitch shape component particularly its either shallow pre-hydrotreating reaction process of middle coalite tar, under the constant prerequisite of other reaction conditions, improve hydrogen-oil ratio, to the stability of hydrocarbon ils liquid phase and pre-hydrogenation target, there is following disadvantageous effect:

1. improve hydrogen-oil ratio, increase the vaporization rate of light oil, reduce hydrocarbon ils amount of liquid phase, improve the concentration of gluey pitch shape component;

2. improve hydrogen-oil ratio, increase the speed of air-flow through beds, reduce liquid phase reserve, shorten the liquid phase residence time, reduce the pre-hydrogenation depth that liquid phase particularly reduces gluey pitch shape component;

3. hydrogen-oil ratio is improved, increase the speed of air-flow through beds, enhance gas " stirring " perturbation action to liquid, add liquid phase Semi-polarity strong, the gluey pitch shape component collision that viscosity is high, associate, the probability of condensation, when hydrogenation catalyst surface forms the Two Liquid Phases of " the high aromatic hydrocarbons of low aromatic hydrocarbons liquid phase one concentrates liquid phase ", the velocity of flow missionary society of the light constituent that viscosity is little and the large heavy constituent of viscosity becomes large, under the effect of catalyst surface adsorptive power, high aromatic hydrocarbons liquid phase Semi-polarity will be aggravated strong, the gathering of the pitch coagulation phase that the gluey pitch shape component that viscosity is high is adhered to catalyst surface or catalyst surface, reduce catalyst bed layer porosity, increase pressure drop of column.

Negative impact that above-mentioned raising hydrogen-oil ratio brings mechanism or say its intensity affected, that petroleum base distillate (usual gum level is extremely low) unifining process or petroleum based heavy fuel oils be not (usually containing low boiling hydrocarbon and total aromaticity content is low, its gluey pitch shape component molecular amount is very large) not available for unifining process, this is that the particular components of middle coalite tar forms the feature determined.

In the pre-hydrogenation process of middle coalite tar, use the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon can optimize the pre-hydrotreating reaction effect of coal tar heavy fractioning, to this, present inventors have proposed patent application listed by table 1, but not pointing out to control hydrogen-oil ratio is in suitable low value and makes the hydrocarbon ils liquid phase fraction in catalyst for pre-hydrogenation bed be in high level to form particularly advantageous liquid-phase reaction condition.The hydrogenation modifying process of low temperature coal-tar pitch in the present inventor's research, be not only in the blue charcoal process generation of normal pressure lump coal destructive distillation system, the coal-tar pitch of coalite tar finds hydrocracking means, main target is for a large amount of heavy coal tar of the efficient middle low temperature pyrolysis of coal production of coal tar high yield find hydrocracking means, along with the success of the efficient middle low temperature coal solution thermal technology of coal tar high yield, the high coal tar of a large amount of coal-tar pitch content will be produced, when the time comes, the association response dilution hydrocarbon that method described in table 1 can not provide quantity to be rich in hydrogen supply hydrocarbon fully, for this reason, present inventors have proposed with the pre-hydrogenated oil of coal tar for mutual solubility good be rich in hydrogen supply hydrocarbon association response dilution hydrocarbon coal tar hydro-conversion method, in patent application listed by table 2, but do not point out to control hydrogen-oil ratio to be in suitable low value and to make the hydrocarbon ils liquid phase fraction in catalyst for pre-hydrogenation bed be in high level to form particularly advantageous pre-hydrogenation liquid-phase reaction condition yet.Up to the present, other document is not had to propose to form pre-method of hydrotreating into major objective with the hydrogenolysis that adds of the gluey pitch shape component of middle coalite tar yet.

Table 1 take coal tar lighting end hydrogenation products as the coal tar heavy oil hydrogenating conversion process of the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon

Table 2 take the pre-hydrogenated oil of coal tar heavy oil self as the coal tar heavy oil hydrogenating conversion process of the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon

For the pre-hydrogenation process particularly pre-hydrogenation process of either shallow of the deep hydrogenation upgrading processes of the coal-tar pitch of middle coalite tar, technique theory of the present invention is:

1. first aspect, uses the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon:

Use the association response dilution hydrocarbon being rich in hydrogen supply hydrocarbon, make it in the pre-hydrogenation process of liquid phase of gluey pitch shape component, serve as the liquid phase solvent of excellent property, this dilution hydrocarbon solvent preferably possesses reactive poor (namely because of little and the least possible the competing the active centre adsorption potential of catalyst surface with gluey pitch shape component and improve the selectivity of the pre-hydrotreating reaction of gluey pitch shape component of reaction probabilities, good heat-carrying capacity is possessed and temperature control rises ability) because exothermic heat of reaction amount is little, mutual solubility good (by force namely good polymerization inhibiting capacity is possessed to the dispersive ability of gluey pitch shape component), be rich in hydrogen supply hydrocarbon (providing active hydrogen ability namely to possess anti-coking performance by force), the feature of viscosity little (i.e. good fluidity), ensure that gluey pitch shape component has good dispersiveness in the liquid phase, good mobility, speed caught by higher active hydrogen, temperature of reaction average as far as possible, prevent from using the means that low aromatic hydrocarbons hydrocarbon ils is increase liquid phase to cause catalyst surface hydrocarbon ils liquid phase to form serious " a low virtue mutually high fragrant macromole concentrates phase " Two Liquid Phases simultaneously,

For the pre-hydrogenation process of the gluey pitch shape component of middle coalite tar, the association response dilution hydrocarbon of what pre-hydrotreating reaction competitive power was low be rich in hydrogen supply hydrocarbon, can prepare by following method: first method is, use and generate oil distillate oil with the pre-hydrogenated oil of the middle coalite tar lighting end of middle coalite tar pitch fractions symbiosis or its pre-hydrogenation, the pre-hydrogenation process of middle coalite tar lighting end is to prepare concentration hydrogen supply hydrocarbon high as far as possible for target, and it is usually poor in the reactivity of the pre-hydrotreating reaction process of middle coalite tar pitch fractions; Second method is, the pre-hydrotreating reaction process of middle coalite tar pitch fractions is to prepare concentration hydrogen supply hydrocarbon high as far as possible for target, the pre-hydrogenated oil or its pre-hydrogenation that recycle middle coalite tar pitch fractions generate oil distillate oil, because the pre-hydrogenation process of middle coalite tar pitch fractions belongs to unifining process, this turning oil is usually poor in the secondary reaction ability of the pre-hydrotreating reaction process of middle coalite tar pitch fractions;

2. second aspect, controls hydrogen-oil ratio and is in suitable low value:

Do not increasing association response dilution hydrocarbon quantity, under not changing the prerequisite of temperature of reaction, the liquid phase fraction of hydro carbons is improved by the vaporization rate of reduction hydro carbons, form the liquid phase dilute solution of goal response thing and gluey pitch shape component, improve the characteristic parameter " hydrogen supply hydrocarbon/goal response thing " of liquid phase, " heat-carrying thing/goal response thing ", " low viscosity thing/goal response thing ", the ratio of " liquid phase molecule hydrogen/goal response thing ", improve liquid phase solvent composition, thus strengthen the selectivity of the pre-hydrotreating reaction process of gluey pitch shape component, anti-coking, dispersed, accelerate the updating ability of catalyst surface adsorptive, control hydrogen-oil ratio and be in suitable low value, reduce the bulk flow velocity of reactant in catalyst bed sheaf space, also reduce the velocity of flow of liquid reactants, extend the reaction times, for the long course of gluey pitch shape component pre-hydrotreating reaction process particularly the pre-hydrogenation process of either shallow the sufficient kinetic reaction time is provided, be beneficial to and improve the pre-hydrogenation depth of gluey pitch shape component,

In order to control beds temperature rise, form alap average reaction temperature, suitable many dilution hydrocarbon must be used can to reduce hydrogen-oil ratio further simultaneously, constitute the dilute solution of gluey pitch shape component, improve gluey pitch shape component dispersity in the solution, be beneficial to the speed improving and obtain active hydrogen, be beneficial to the coking speed reducing catalyst surface; Under ensureing that reaction process resists the prerequisite of the necessary hydrogen pressure of coking, can operate under minimum hydrogen-oil ratio condition, such as coordinate hydrogenation protecting catalyst, Hydrodemetalation catalyst, SA hydrogen desulfurization agent, SA removal of ccr by hydrotreating catalyzer, even can implement the full liquid phase of reaction feed " Gu liquid--reaction " or the full liquid phase of saturated dissolving molecular hydrogen of reaction feed " Gu liquid--reaction " or the bubbling bed of extremely low gas phase fraction " Gu gas,--liquid--reacts ";

3. the third aspect, controls the gas phase condition of pre-hydrogenation process, makes it to improve active hydrogen supply as far as possible:

By improving the hydrogen supply hydrocarbon concentration of association response dilution hydrocarbon, or produce the velocity ratio of active hydrogen as strengthened gas-phase presulfiding hydrogen concentration thus the speed of larger catalyst active centre dissociation hydrogen sulfide by improving catalyst surface, improve active hydrogen supply, improve gluey pitch shape component pre-hydrotreating reaction and then reduce the thermal condensation speed of gluey pitch shape component;

4. fourth aspect, keeps high hydrogen partial pressure as far as possible, reduces non-hydrogen partial pressure:

In order to maintain high hydrogen partial pressure under low hydrogen/gasoline ratio condition, on the one hand, require to use highly purified hydrogen gas stream such as to use new hydrogen stream gas or highly purified recycle hydrogen as the hydrogen source of pre-hydrogenation process, on the other hand, reduce non-hydrogen gaseous component such as water vapour, normal boiling point enters pre-hydrogenation process lower than the hydrocarbon component of 200 DEG C, such as import deep hydrogenation upgrading reaction process R2 by after the gas phase separation in the source logistics of the dilution hydrocarbon of gas-liquid two-phase, this point is extremely important for the pre-hydrogenation process of middle coalite tar, because organic oxygen level of middle coalite tar is generally 3 ~ 12 % by weight, calculate by organic oxygen of 5 ~ 10 % by weight, the weight that organic oxygen in 1 ton in coalite tar is all converted into water is 56.25 ~ 112.50kg, the gaseous phase volume of standard state is 70 ~ 140 standard cubic meter, in 1 ton, the standard state liquid volume of coalite tar is by 1 cubic metre of calculating, transform the volume ratio of the gas phase standard state volume/accurate volume of raw tar liquid phase mark state generating water up to 70 ~ 140, when pre-hydrogenation process works under low hydrogen-oil ratio (such as 50 ~ 300) condition, the existence of water vapor, both hydrogen partial pressure was reduced, also increase the disadvantageous effect to catalyzer, its impact is big is surprising.

When the present invention is applied to middle coalite tar deep hydrogenation upgrading processes, for the middle coalite tar of last running content low i.e. " KF is high for light ends content/last running content ratio ", its application form can be, first middle coalite tar is separated into lighting end and last running (i.e. coal-tar pitch), then the pre-hydrogenation of coal-tar pitch is applied the present invention to, using lighting end pre-hydrotreating reaction effluent or its pre-hydrotreating reaction generation oil or its pre-hydrotreating reaction to generate oil fraction oil is dilution hydrocarbon, namely the novel middle coalite tar deep hydrogenation modifying process of the low gas phase fraction of " the strengthening heavy oil pre-hydrogenation liquid phase reaction " of " liquid phase concerted reaction type " is constituted.Lighting end described herein, last running, be commonly referred to as with normal boiling point 480 DEG C as dividing point.

When the present invention is applied to middle coalite tar deep hydrogenation upgrading processes, for the last running content height i.e. middle coalite tar of " KF is low for light ends content/last running content ratio " or middle coalite tar heavy distillate, its application form can be, be separated pre-hydrotreating reaction effluent or either shallow pre-hydrotreating reaction effluent gained hydrocarbon ils, enter pre-hydrotreating reaction process or either shallow pre-hydrotreating reaction process and serve as circulation dilution hydrocarbon, namely the novel middle coalite tar deep hydrogenation modifying process of low gas phase fraction of " strengthening heavy oil pre-hydrogenation liquid phase reaction " or the deep hydrogenation modifying process of the coal-tar pitch of middle coalite tar of " pre-hydrogenation liquid product circulating reaction type " is constituted.

When the present invention is applied to middle coalite tar hydro-upgrading process, " reaction product step-down divergence type " flow process can be formed, its application form can be, when amounts of hydrogen in the end reaction effluent R2P of the deep hydrogenation upgrading processes of central coalite tar or its distillate is less, by the pressure reducing end reaction effluent R2P, (gas-liquid separating function district is normally set, then reaction effluent R2P is separated the vapour phase formed and (comprises hydrogen, hydrogen sulfide, ammonia and Light hydrocarbon products) R2PV and liquid phase (deviate from hydrogen, hydrogen sulfide, the hydrocarbon ils primarily of heavy hydrocarbon composition of ammonia and light hydrocarbon) R2PL reduces its pressure respectively through phase buck process, then under low pressure conditions respectively or combine the hydrogen and hydrocarbon oil separating and recovery that carry out vapour phase R2PV and liquid phase R2PL, significantly to reduce construction investment, certain one-level entrance that the hydrogen that sepn process is reclaimed can enter make-up hydrogen compressor uses by returning hydrogenation reaction system after make-up hydrogen compressor supercharging.

As required, by " liquid phase concerted reaction type ", " pre-hydrogenation liquid product circulating reaction type ", " reaction product step-down divergence type " path combination, the novel middle coalite tar deep hydrogenation modifying process of the low gas phase fraction of built-up type " strengthening heavy oil pre-hydrogenation liquid phase reaction " can be formed.

Reactor or the reactor assembly of the easily long-pending solid hydrocarbon method of hydrotreating use of existing catalyst surface are below described.

The reactor of the use such as hydrocarbon hydrogenation process such as residual hydrocracking process, DCL/Direct coal liquefaction process that catalyst surface is easily long-pending solid, there is multiple known form, such as down-flow fixed bed, downflow system moving-bed, downflow system replace bed, the combination that upflow fixed bed, upflowing slight expanded-bed, upflowing moving-bed, upflowing replace bed, ebullated bed, suspension bed, bubbling bed and particular form thereof online online, and great majority have industrial application case, define comparatively fixing technical characterstic.

Gluey pitch shape component contained by petroleum base residual oil is normally with the disperse phase that supramolecular structure exists, analytical data shows that the molecular weight of gluey pitch shape group disperse phase is wherein up to several thousand to several ten thousand even the rock steady structure group of hundreds of thousands of, certainly these groups contain a large amount of condensed-nuclei aromatics unit and contain metal, sulphur, the elements such as nitrogen, the main task of its lighting process is formed at these macromole solutions, cracking is compared with few ten times of its original thing charcoal number, hundred times even small molecules of thousand times, clearly, the thermally splitting task of process is occupied an leading position, this only can not rely on hydrodemetallation (HDM), hydrogenating desulfurization, hydrodenitrification, hydrogenation aromatic saturation realizes, the hydrodemetallation (HDM) of petroleum base residual oil, hydrogenating desulfurization, hydrodenitrification, the pre-hydrogenation process nature such as hydrogenation aromatic saturation is for follow-up hydrocracking reaction prepare stock oil unifining process, otherwise the hydrocracking catalyst active centre in the down-type fixed-bed reactor of routine deposits because of metal and quick coking is caused the operational cycle too short by rapid Cover, the cycle of operation of the minimum economy of course of industrialization requirement cannot be maintained, even if employ the processes such as the hydrodemetallation (HDM) in conventional down-type fixed-bed reactor, hydrogenating desulfurization, hydrodenitrification, hydrogenation aromatic hydrocarbons is full, also higher transformation efficiency cannot be reached, because be difficult to overcome the rapid, high volume coking problem that high temperature thermal cracking process certainly leads to, this is that the thermodynamic property of process determines, in order to overcome the defect of above-mentioned fixed bed reactor system, reactor types occur upflow fixed bed, upflowing slight expanded-bed, upflowing replace bed, the strong expanded bed of upflowing and ebullated bed, upflowing limiting equation expanded bed online and suspension bed boils, downflow system replaces the various ways such as bed online.

In the hydrocracking process of petroleum base residual oil, it is that transformation efficiency that normal boiling point is less than 530 DEG C of cuts is generally 40 ~ 80% even higher that normal boiling point is greater than 530 DEG C of cut crackings, in order to reach so high cracking rate and improve speed of response, the necessary hot conditions of thermally splitting that inevitable usage degree is stronger, the quick coking of catalyst active center is inevitable, in order to by reactor bed because of metal deposition, coking makes the active catalyzer declined fast shift out and change, technician develops ebullated bed, the upflowing expanded bed reactor that these two kinds of beds ratio of expansion of suspension bed are larger, and follow-up high pressure hot separator and reactor are merged into a combination plant, the movement system of high viscosity residual oil (between reactor and hot high score) is between devices simplified greatly, the reliability of system can be improved, security, heat insulating ability, improve the homogeneity of temperature of charge in reactor, save floor space, from favourable aspect, the high conversion of the cracking of residual oil boiling bed hydrogenation, floating bed hydrocracking is that fixed-bed reactor are beyond one's reach, the cracking reaction of heat absorption is mixed with the hydrogenation reaction of heat release carry out being beneficial to reaction heat utilization, be beneficial to reduction reaction temperature rising, recycle a large amount of hot reaction and generate oil or intermediate reaction and generate oily direct heating stock oil and can reduce fuel oil preheating temperature, from unfavorable aspect, beds ratio of expansion is comparatively large, compared with fixed-bed reactor, adds the complicacy of system, reduces the stationarity of operation, increased considerably construction investment, because adding wearing and tearing and the collision of catalyzer, the loss of reason beyond the coking adding catalyzer, because bed exists the violent back-mixing of catalyzer and liquid phase, the quality product containing part fresh feed low degree of conversion product is inevitable poor, the industrialization technology of this type of technology has H-OIL technique, LC-FINING technique, all use ebullated bed reactor system, in order to optimize the boiling state with stability contorting catalyzer, be provided with turning oil circulating pump system, the collector of turning oil is placed on catalyst in reactor bed, be equivalent to one for recycle pump provides the high-temperature high-pressure separator that must be placed in high elevation location of turning oil and ebullated bed reactor combine and simplify the structure of high-temperature high-pressure separator, but in order to not affect the fluidized state of ebullated bed, the position of the collector of turning oil, size and form all must carefully designs.Compared with ebullated bed reactor system, suspended-bed reactor system, the Homogeneous phase mixing system of catalyzer and raw material also must be set, the separation system of catalyzer and hydrogenated oil must be set, the resistance to erosion ability of equipment, pipeline, valve be it is also proposed and must be required, so system is more complicated.

But, no matter hydrogenator and the catalyzer thereof of which kind of form, all must based on process goal, optimizing reaction effect, strengthen security, strengthen handiness, simplify the operation, reduce in all targets such as investment one or several carry out adaptive optimization design.The pre-hydrogenation process of the deep hydrogenation upgrading processes of coalite tar in high for gluey pitch shape component concentration, particularly for the pre-hydrogenation process of either shallow of its coal-tar pitch, its process goal has been the either shallow lighting of gluey pitch shape component, fixed bed hydrogenation Refining tests data show, at suitable high hydrogen pressure, middle high temperature, such as at the hydrogen partial pressure of 15.0MPa under the appropriateness Hydrobon catalyst of function and reaction time condition, the temperature of 250 ~ 350 DEG C, combinationally use " hydrogenation protecting agent+hydrodemetallation (HDM) agent+removal of ccr by hydrotreating agent+hydrogen desulfurization agent ", 0.3 ~ 1.5h ^-1liquid hourly space velocity condition under, use fixed bed hydrogenation reactor can complete transforming based on the lighting of liquid-phase hydrogenatin refining reaction warm in high pressure of " bituminous matter component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons ".This point, with the hydrogenating desulfurization of petroleum base residual oil or hydrocracking has more greatly or even the difference of essence in a way, the hydrogenation lighting technology (namely usually described in residual hydrocracking process) simply can not transplanting the petroleum base residual oil being rich in macromolecule gluey pitch shape component is applied to the hydrogenation lighting process of the coal-tar pitch of the middle coalite tar being rich in gluey pitch shape component.

For the pre-hydrogenation process particularly pre-hydrogenation process of either shallow of the deep hydrogenation upgrading processes of middle coalite tar or its coal-tar pitch, the form of the pre-hydrogenator of filling catalyst for pre-hydrogenation of the present invention is selected as required, can be the reactor of any one suitable form, can be known form or form newly developed.

The pre-hydrogenation process particularly pre-hydrogenation process of either shallow of the deep hydrogenation upgrading processes of the coal-tar pitch of middle coalite tar, the present invention about the theory of its reactor assembly device structure function and principle of design is:

1. unsuitable prioritizing selection ebullated bed or suspended-bed reactor system:

By and large, the thermo-cracking task in " bituminous matter component → colloid → condensed-nuclei aromatics → polycyclic aromatic hydrocarbons " hydrogenolysis course of the gluey pitch shape component in middle coalite tar is much smaller compared with the thermo-cracking task of the gluey pitch shape component of petroleum base residual oil; Should not there is system complex in prioritizing selection, service temperature is too high and expanded bed reactor system that the beds ratio of expansion of the rapid, high volume coking of excessive heat cracking process association that causes and a large amount of aerogenesis, the multinomial shortcoming such as catalyzer consumption quality product that is large, that cause because there is a large amount of back-mixing in reactor is poor, space reactor efficiency is low is high, i.e. unsuitable prioritizing selection ebullated bed or suspended-bed reactor system;

2. the whole process of the even middle coalite tar deep hydrogenation upgrading processes of pre-hydrotreating reaction process, should not use down-type fixed-bed reactor:

Owing to containing the large component of a large amount of viscosity in middle coalite tar as polycyclic aromatic hydrocarbons, condensed-nuclei aromatics, gluey pitch shape component, containing strong polar compound (the such as oxygen of inorganic elements, sulphur, the organism of nitrogen), middle coalite tar pre-hydrogenation process operation temperature is lower, and catalyst for pre-hydrogenation and degree of depth upgrading hydrogenation catalyst are porous mass, therefore the adsorptive power existed between catalyzer and high viscosity liquid component to a certain degree, because beds is stable and substantially actionless, in the beds of down-flow fixed bed pre-hydrogenator, the fluidised bed (viscous flow film) of the relative enrichment of high viscosity component can be formed at catalyst particle surface, the not smooth region of liquid-flow is there is at the connecting portion of beds catalyst particles interlacing contact, relative enrichment can be there is and form metastable low flow velocity region and dynamic stagnant area in the liquid ingredient that middle coalite tar medium viscosity is large, on the one hand, formation local is lacked hydrogen environment and accelerates condensation coking reaction, on the other hand, catalyst bed layer porosity will be reduced, increase pressure drop of column, and increase the unstable of liquid-flow in beds, reduce the stationarity of hydrogenation process,

2. the upflow fixed bed or upflowing slight expanded-bed of preferential use:

Due to the pre-hydrogenation process particularly pre-hydrogenation process of either shallow of the deep hydrogenation upgrading processes of the gluey pitch shape component of middle coalite tar, belong to catalyst for pre-hydrogenation bed or the easily coking of catalyst for pre-hydrogenation surface, the hydrogenation process of easy generation metallic compound deposition, in the middle of coalite tar deposition of solids amount can be larger when containing ash content, in order to ensure or operational cycle of extension reactor inner catalyst bed, requiring that beds has certain makes settling pass through and the ability that do not stop, namely certain particulate matter handling capacity is possessed, for this reason, can use for reference or transplant existing upflow fixed bed, upflowing slight expanded-bed, upflowing moving-bed, upflowing replaces the reactor types such as bed online, upflowing slight expanded-bed of the present invention, 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 usually less than 1.10, generally lower than 1.08, be preferably lower than 1.05.

Deep hydrogenation upgrading processes particularly its pre-hydrotreating reaction process R1 of or olefin(e) centent high or phenol content high or gum level high or asphalt content high or certain easy reactant content high hydrocarbon material F1 high for 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;

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

Processing method of the present invention has no report.

The first object of the present invention is to propose a kind of high aromatics hydrogenation process comprising the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon.

The second object of the present invention is to propose a kind of middle coalite tar method of hydrotreating comprising the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon.

The third object of the present invention is to propose a kind of method of hydrotreating comprising the coal-tar pitch of the middle coalite tar of the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon.

Summary of the invention

A kind of high aromatics hydrogenation process comprising the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon of the present invention, is characterized in that comprising following steps:

(1) at pre-hydrotreating reaction process R1, under hydrogen and catalyst for pre-hydrogenation R1C existence condition, the pre-hydrotreating reaction R1R that high aroamtic hydrocarbon raw material HDS carries out the hydrodepolymerization reaction comprising gluey pitch shape component obtains pre-hydrotreating reaction effluent R1P, and gluey pitch shape component HD completes the pre-hydrotreating reaction comprising hydrodepolymerization, aromatic hydrogenation fractional saturation at least partially;

At pre-hydrotreating reaction process R1, the hydrogen supply hydrocarbon stream SHS containing hydrogen supply hydrocarbon component S H enters pre-hydrotreating reaction process R1, and in pre-hydrotreating reaction R1R process, hydrogen supply hydrocarbon component S H contacts with hydrocarbon component HD, and the dilution hydrocarbon as association response uses; Described hydrogen supply hydrocarbon component S H refer to fractional saturation double ring arene and or the polycyclic aromatic hydrocarbons of fractional saturation;

The ratio of logistics SHS studies on asphaltene component concentration and high aroamtic hydrocarbon raw material HDS studies on asphaltene component concentration lower than 0.5, in logistics SHS in glial component content and high aroamtic hydrocarbon raw material HDS the ratio of glial component content lower than 0.5;

In logistics SHS, in hydrogen supply hydrocarbon component S H weight and logistics SHS, the ratio of conventional liquid hydrocarbon component weight exceeds the ratio at least 3% of conventional liquid hydrocarbon component weight in hydrogen supply hydrocarbon component S H weight and high aroamtic hydrocarbon raw material HDS in high aroamtic hydrocarbon raw material HDS; In logistics SHS, conventional liquid hydrocarbon component protium weight in average content exceeds the protium weight content at least 2% of high aroamtic hydrocarbon raw material HDS;

In pre-hydrotreating reaction R1R process, technic index is:

1. in the charging of catalyst for pre-hydrogenation bed, ratio KX=SH-W/HD-W, the KX of the weight rate SH-W from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-W of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS >=0.1;

In the liquid phase of catalyst for pre-hydrogenation bed, ratio KY=SH-CLW/HD-CLW, the KY of the weight rate SH-CLW from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-CLW of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS >=0.1;

2. hydrogen to oil volume ratio is less than 500;

3. the Phase velocity map of high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HDS-KL >=0.5, i.e. overall vaporization rate HDS-KV≤0.5;

The Phase velocity map of the gluey pitch shape component HD in high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HD-KL >=0.5, i.e. overall vaporization rate HD-KV≤0.5;

4. the selection index of reaction heat, the reaction heat HDS-Q based on high aroamtic hydrocarbon raw material HDS is KZ, KZ=HDS-Q/SHS-Q, KZ >=0.5 with the ratio based on the reaction heat SHS-Q of hydrogen supply hydrocarbon stream SHS;

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

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

Pre-hydrotreating reaction process R1, operational condition is generally:

(1) at pre-hydrotreating reaction process R1, in logistics SHS gum level lower than 10 % by weight, asphalt content is lower than 1 % by weight; In logistics SHS, hydrogen supply hydrocarbon component S H weight accounts for conventional liquid hydrocarbon component weight ratio higher than 6 % by weight;

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 0.1 ~ 6;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥1.0。

Pre-hydrotreating reaction process R1, operational condition is generally:

(1) at pre-hydrotreating reaction process R1, in logistics SHS, hydrogen supply hydrocarbon component S H weight accounts for conventional liquid hydrocarbon component weight ratio higher than 15 % by weight;

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 1 ~ 4;

2. hydrogen to oil volume ratio is less than 500;

3. the Phase velocity map of high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HDS-KL >=0.7, i.e. overall vaporization rate HDS-KV≤0.3;

The Phase velocity map of the gluey pitch shape component HD in high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HDS-KL >=0.7, i.e. overall vaporization rate HDS-KV≤0.3;

④KZ≥1.5。

Pre-hydrotreating reaction process R1, operational condition is preferably:

(1) at pre-hydrotreating reaction process R1, in logistics SHS, hydrogen supply hydrocarbon component S H weight accounts for conventional liquid hydrocarbon component weight ratio higher than 25 % by weight;

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.5 ~ 3; KY is 1.5 ~ 2.5;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥2。

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

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

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

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

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

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

In the present invention's processing during coalite tar, during with the pre-hydrogenated oil of middle coalite tar lighting end for dilution hydrocarbon, be divided into high aroamtic hydrocarbon raw material HDS with middle coalite tar double distilled, the pre-hydrotreating reaction process R1 of high aroamtic hydrocarbon raw material HDS, the operational condition of deep hydrogenation upgrading reaction process R2 are generally:

(1) at pre-hydrotreating reaction process R1, high aroamtic hydrocarbon raw material HDS primarily of normal boiling point higher than coalite tar fractions consisting in 465 DEG C;

Hydrogen supply hydrocarbon precursor logistics SHSBF is selected from one or more in following logistics:

1. primarily of comprising the logistics that normal boiling point is coalite tar fractions consisting in 120 ~ 460 DEG C of cuts;

2. primarily of comprising the logistics that normal boiling point is coalite tar fractions consisting in 250 ~ 460 DEG C of cuts;

3. primarily of comprising the logistics that normal boiling point is coalite tar fractions consisting in 350 ~ 460 DEG C of cuts;

4. be the logistics of coalite tar fractions consisting in 120 ~ 460 DEG C of cuts primarily of the normal boiling point after dephenolize;

The source of hydrogen supply hydrocarbon stream SHS is: be prepared as the hydroconversion reaction zone R-SHS of target with hydrogen supply hydrocarbon, hydrogen supply hydrocarbon precursor logistics SHSBF complete with hydrogen supply hydrocarbon be prepared as target hydrogenation fractional saturation reaction R-SHS-R be converted into hydrogenation reaction effluent R-SHS-P, use using the distillate of the hydrogenated oil R-SHS-P0 in hydrogenation reaction effluent R-SHS-P or hydrogenated oil R-SHS-P0 or hydrogenation reaction effluent R-SHS-P as hydrogen supply hydrocarbon stream SHS; The hydrogenation obtaining hydrogenated oil R-SHS-P0 and penetration depth hydro-upgrading reaction process R2 by being separated hydrogenation reaction effluent R-SHS-P generates gas R-SHS-PV; The distillate of hydrogenated oil R-SHS-P0 is obtained by being separated hydrogenated oil R-SHS-P0;

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

In the present invention's processing during coalite tar height aroamtic hydrocarbon raw material HDS, the logistics of hydrogen supply hydrocarbon precursor can be high aroamtic hydrocarbon raw material HDS, and now, the pre-hydrotreating reaction process R1 of high aroamtic hydrocarbon raw material HDS, the operational condition of deep hydrogenation upgrading reaction process R2 are generally:

(1) at pre-hydrotreating reaction process R1, high aroamtic hydrocarbon raw material HDS is selected from one or more in following materials:

1. primarily of normal boiling point higher than coalite tar fractions consisting in 260 DEG C;

2. primarily of normal boiling point higher than coalite tar fractions consisting in 350 DEG C;

3. primarily of normal boiling point higher than coalite tar fractions consisting in 460 DEG C;

Hydrogen supply hydrocarbon stream SHS is selected from one or more in following logistics:

1. the pre-hydrogenated oil R1P of pre-hydrotreating reaction process R1 gained, is obtained by the gas-liquid separation process of pre-hydrotreating reaction effluent R1P;

2. the distillate of the pre-hydrogenated oil R1P of pre-hydrotreating reaction process R1 gained, the sepn process being generated oily R1P0 by pre-hydrotreating reaction is obtained;

3. generate oily R1MP in the middle of the pre-hydrogenation of pre-hydrotreating reaction process R1 gained, obtained by the gas-liquid separation process of pre-hydrogenation intermediate reaction effluent R1MP;

4. generate the distillate of oily R1MP in the middle of the pre-hydrogenation of pre-hydrotreating reaction process R1 gained, the sepn process generating oily R1MP0 by pre-hydrogenation intermediate reaction obtains;

5. generate oily R2MP0 in the middle of deep hydrogenation upgrading reaction zone R2 gained deep hydrogenation upgrading, obtained by the gas-liquid separation process of deep hydrogenation upgrading intermediate reaction effluent R2MP;

6. generate the distillate of oily R2MP in the middle of deep hydrogenation upgrading reaction zone R2 gained deep hydrogenation upgrading, obtained by the sepn process generating oily R2MP in the middle of deep hydrogenation upgrading;

Now, the logistics of hydrogen supply hydrocarbon precursor is exactly high aroamtic hydrocarbon raw material HDS;

From first hydrogenation catalyst bed that high aroamtic hydrocarbon raw material HDS contacts, to the reaction interval that last the hydrogenation catalyst bed producing hydrogen supply hydrocarbon stream SHS terminates, belong to the hydroconversion reaction zone R-SHS being prepared as target with hydrogen supply hydrocarbon;

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

The present invention, at pre-hydrotreating reaction process R1, the mode of operation of pre-hydrogenator R1-SB can be upflow fixed bed reactor or upflowing slight expanded-bed reactor, and the working conditions of pre-hydrotreating reaction process R1 is:

(1) at pre-hydrotreating reaction process R1, the mode of operation of at least one pre-hydrogenator R1-SB is upflow fixed bed reactor or upflowing slight expanded-bed reactor; Charging autoreactor R1-SB bottom enters, and reaction effluent R1P autoreactor R1-SB top is flowed out; Temperature be 230 ~ 400 DEG C, pressure is 6.0 ~ 28.0MPa, hydrogen/stock oil volume ratio is less than 500, catalyst for pre-hydrogenation R1-CAT volume space velocity is 0.05 ~ 5.0hr ^-1reaction conditions under, complete pre-hydrotreating reaction and obtain pre-hydrotreating reaction effluent R1P; 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; At pre-hydrotreating reaction process R1, hydrogen/stock oil volume ratio is 20 ~ 300; Described upflowing slight expanded-bed, bed expansion ratio KBED is lower than 1.05.

At pre-hydrotreating reaction process R1, the hydrogen rich gas logistics injecting pre-hydrogenator is preferably new hydrogen.

At pre-hydrotreating reaction process R1, in pre-hydrogenator, hydrogen sulfide in gas phase volumetric concentration can be 0.1 ~ 1%, be generally 0.3 ~ 0.5%.

In the present invention's processing during coalite tar height aroamtic hydrocarbon raw material HDS, common Action Target is, is being prepared as the hydroconversion reaction zone R-SHS of target, selects as far as possible to produce the processing condition that hydrogen supply hydrocarbon is target to greatest extent with hydrogen supply hydrocarbon; In deep hydrogenation upgrading reaction effluent R2P, full cut diesel-fuel cetane number is higher than 32.

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

The present invention, separate part HPS 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 R2P0 as deep hydrogenation upgrading.

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

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.

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

Below describe characteristic of the present invention in detail.

In pre-hydrotreating reaction R1R process, technic index is:

2. hydrogen to oil volume ratio is less than 500;

Pre-hydrotreating reaction process R1, operational condition is generally:

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 0.1 ~ 6;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥1.0。

Pre-hydrotreating reaction process R1, operational condition is generally:

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 1 ~ 4;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥1.5。

Pre-hydrotreating reaction process R1, operational condition is preferably:

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.5 ~ 3; KY is 1.5 ~ 2.5;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥2。

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

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

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

The reactor that pre-hydrotreating reaction process R1 of the present invention uses, its beds mode of operation can be any suitable form, it can be the combination of two or more dissimilar reactors, can be that fixed-bed reactor and beds are fixed, can be fluidized-bed reactor; Can be downflow reactor, also can be up-flow reactor (usually needing lower hydrogen-oil ratio); Can be bubbling style reactor (usually needing lower hydrogen-oil ratio), can be the liquid phase intensified type reactor (usually needing lower hydrogen-oil ratio) of high liquid phase fraction.Fluidized-bed reactor can be ebullated bed reactor and catalyzer working order is the ebullated bed that ratio of expansion is greater than 1.3% usually, also can be suspended-bed reactor and catalyzer working order is suspension bed.

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, by the selectivity of the liquid-phase hydrogenatin reaction of the easy coking component of strengthening high boiling point, improve the liquid-phase hydrogenatin speed of response of the easy coking component of high boiling point, following effect can be obtained:

1. effectively suppress coking, effectively extend on-stream time;

2. pressure drop of column is reduced;

3. improve catalyzer liquid phase reaction efficiency, reduce catalyst levels;

4. significantly reduce recycle hydrogen consumption, significantly can reduce correlation engineering investment and energy consumption;

5. effectively the reaction heat rate of recovery is improved;

6. form excellent bitum liquid-phase hydrogenatin condition, stock oil more inferior can be processed, widened raw material range, improve raw material availability.

Embodiment one

Coal-tar middle oil character is in table 3, table 4, be separated into primarily of normal boiling point lower than 480 DEG C hydrocarbon composition weight yield be 82% lighting end and primarily of normal boiling point higher than 480 DEG C hydrocarbon composition weight yield be the coal-tar pitch of 18%, coal-tar pitch is used as high aroamtic hydrocarbon raw material HDS, and lighting end is used as hydrogen supply hydrocarbon precursor logistics SHSBF.

Hydrogen supply hydrocarbon precursor logistics SHSBF complete with hydrogen supply hydrocarbon be prepared as target hydrogenation fractional saturation reaction R-SHS-R be converted into hydrogenation reaction effluent R-SHS-P, the part by weight of the hydrogen supply hydrocarbon component S H in the conventional liq hydrocarbon in hydrogenation reaction effluent R-SHS-P is 16 ~ 18 % by weight, in logistics SHS gum level lower than 5 % by weight, asphalt content is lower than 0.2 % by weight; Use using the hydrogenated oil R-SHS-P0 in hydrogenation reaction effluent R-SHS-P as hydrogen supply hydrocarbon stream SHS; The hydrogenation obtaining hydrogenated oil R-SHS-P0 and penetration depth hydro-upgrading reaction process R2 by being separated hydrogenation reaction effluent R-SHS-P generates gas R-SHS-PV.

According to the present invention, a kind of step of processing scheme is as follows:

(1), in pre-hydrotreating reaction R1R process, technic index is:

1. in the charging of catalyst for pre-hydrogenation bed, ratio KX=SH-W/HD-W, the KX=0.78 of the weight rate SH-W from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-W of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS ~ 0.82;

In the liquid phase of catalyst for pre-hydrogenation bed, ratio KY=SH-CLW/HD-CLW, the KY=0.55 of the weight rate SH-CLW from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-CLW of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS ~ 0.58;

2. hydrogen to oil volume ratio is 300;

3. the Phase velocity map of high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HDS-KL >=0.71, i.e. overall vaporization rate HDS-KV≤0.29;

The Phase velocity map of the gluey pitch shape component HD in high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HD-KL >=0.71, i.e. overall vaporization rate HD-KV≤0.29;

4. the selection index of reaction heat, the reaction heat HDS-Q based on high aroamtic hydrocarbon raw material HDS is KZ, KZ=HDS-Q/SHS-Q, KZ=1.0 ~ 1.1 with the ratio based on the reaction heat SHS-Q of hydrogen supply hydrocarbon stream SHS;

The mode of operation of pre-hydrogenator R1-SB is upflowing slight expanded-bed reactor; Charging autoreactor R1-SB bottom enters, and reaction effluent R1P autoreactor R1-SB top is flowed out; Temperature be 295 ~ 340 DEG C, pressure is 15.0 ~ 17.0MPa, catalyst for pre-hydrogenation R1-CAT volume space velocity is 0.8 ~ 0.9hr ^-1reaction conditions under, complete pre-hydrotreating reaction and obtain pre-hydrotreating reaction effluent R1P; Described upflowing slight expanded-bed, bed expansion ratio KBED is less than 1.03;

The hydrogen rich gas logistics injecting pre-hydrogenator is preferably new hydrogen logistics, supplements time not enough with recycle hydrogen;

In pre-hydrogenator, hydrogen sulfide in gas phase volumetric concentration controls is 0.3 ~ 0.5%;

(2) the full cut diesel-fuel cetane number in deep hydrogenation upgrading reaction effluent R2P is higher than 32.

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

Table 5 is composition and the physico-chemical property of hydrogen supply hydrocarbon preparation process spent hydroprocessing catalyst.

Table 6 is composition and the physico-chemical property of the pre-hydrotreating reaction process R1 of high aroamtic hydrocarbon raw material HDS and the catalyzer of deep hydrogenation upgrading reaction process R2 use.

Table 7 be hydrocracking reaction part catalyzer composition and physico-chemical property.

Table 8 is pre-hydrotreating reaction process R1, deep hydrogenation upgrading reaction process R2, the operational condition of hydrocracking reaction process R3 and product property.

Table 3 coal tar character

Project	Circle
		Bottle density (20 DEG C), kg.m ^-3	1.0658
Boiling range, DEG C (simulation distil)
		IBP／10％／30％／50％	164／237／314／374
70％／80％／85％／89.2	435／486／542／750
		Sulphur, μ g.g ^-1	1800
Nitrogen, μ g.g ^-1	6101
		C，％	81.36
H，％	8.21
		Condensation point, DEG C	30
Carbon residue, %	9.77
		Moisture, %	4.1
Throw out, %	0.48
		Flash-point (remaining silent), DEG C	126
Heavy metal, μ g.g ^-1
		Fe／Na／Ni／Mg	108.70／5.74／1.39／56.32
Ca／V／K／Pb	362.4／0.17／16.25／11.43
		Co／Cu／Mn／Zn／Mo	0.77／0.21／4.24／6.84／0.02
Mass spectrum forms, %
		Colloid	33.5
Paraffinic hydrocarbons	11.5
		Naphthenic hydrocarbon	5.2
Monocycle/dicyclo/tri-ring/Fourth Ring	2.7／0.7／1.3／0.5
		Aromatic hydrocarbons	49.8
Monocycle/dicyclo/tri-ring/Fourth Ring/five rings	13.8／16.4／8.3／5.0／0.6
		Total thiophene/do not identify	4.4／1.3

Table 4 coal tar true boiling point cutting result

Component, %	Circle
		Water	3.07
≤170℃	4.30
		170℃～210℃	1.48
210℃～230℃	4.81
		230℃～300℃	14.93
300℃～500℃	59.28
		>500℃	12.13
∑	96.93

The composition of table 5 hydrogen supply hydrocarbon preparation process spent hydroprocessing catalyst and physico-chemical property

The composition of the catalyzer that the pre-hydrotreating reaction process R1 of the high aroamtic hydrocarbon raw material HDS of table 6 and deep hydrogenation upgrading reaction process R2 uses and physico-chemical property

The composition of table 7 hydrocracking reaction part catalyzer and physico-chemical property

The operational condition of table 8 pre-hydrotreating reaction process R1, deep hydrogenation upgrading reaction process R2, hydrocracking reaction process R3 and product property operational condition and product property table

Sequence number	Project	Embodiment
			1	The hydrogenation reaction part of hydrogen supply hydrocarbon preparation process
1.1	Reaction pressure, MPa	15.2～17.2
			1.2	Temperature of reaction, DEG C metal remover+reductor/finishing agent	260～295／295～
1.3	Hydrogen supply hydrocarbon preparation process Hydrobon catalyst volume space velocity, h ^-1	1.0～1.2
			1.4	Reactor inlet hydrogen-oil ratio, m ³n／m ³	1800
2	Pre-hydrotreating reaction process R1
			2.1	Reaction pressure, MPa	15.0～17.0
2.2	Temperature of reaction, DEG C protective material+de-carbon residue agent+sweetening agent	295～340
			3	Deep hydrogenation upgrading reaction process R2
3.1	Hydrofining agent D volume space velocity, h ^-1	0.25～0.30
			3.2	Reactor inlet hydrogen-oil ratio, m ³n／m ³	1700～1800
3.3	The nitrogen content of the naphtha fraction in deep hydrogenation upgrading reaction effluent R2P,	≯3.0
			3.4	The cetane value of the diesel oil distillate in deep hydrogenation upgrading reaction effluent R2P	≮35.0
3.5	Tail oil boiling range in deep hydrogenation upgrading reaction effluent R2P, DEG C	350～545
			4	Hydrocracking reaction process R3
4.1	Reaction pressure, MPa	15.0～17.0
			4.2	Temperature of reaction, DEG C	380～420
4.3	Hydrocracking catalyst volume space velocity, h ^-1	0.42～0.50
			4.4	Reactor inlet hydrogen-oil ratio, m ³n／m ³	1500
4.5	Hydrocracking diesel cetane-number	≮48

Embodiment two

Coal-tar middle oil character is in table 3, be separated into primarily of normal boiling point lower than 480 DEG C hydrocarbon composition weight yield be 82% lighting end and primarily of normal boiling point higher than 480 DEG C hydrocarbon composition weight yield be the coal-tar pitch of 18%, lighting end carries out deep hydrogenation upgrading separately, and coal-tar pitch is used as high aroamtic hydrocarbon raw material HDS.

Hydrogen supply hydrocarbon stream SHS is selected from the pre-hydrogenated oil R1P of pre-hydrotreating reaction process R1 gained, quantity is 5 times of high aroamtic hydrocarbon raw material HDS, obtained by the gas-liquid separation process of pre-hydrotreating reaction effluent R1P, now, the logistics of hydrogen supply hydrocarbon precursor is exactly high aroamtic hydrocarbon raw material HDS self; The part by weight of hydrogen supply hydrocarbon component S H is about 25 % by weight, in logistics SHS gum level lower than 5 % by weight, carbon residue is lower than 1.5%.

(1), in pre-hydrotreating reaction R1R process, technic index is:

1. in the charging of catalyst for pre-hydrogenation bed, ratio KX=SH-W/HD-W, the KX=1.30 of the weight rate SH-W from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-W of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS ~ 1.35;

In the liquid phase of catalyst for pre-hydrogenation bed, ratio KY=SH-CLW/HD-CLW, the KY of the weight rate SH-CLW from the hydrogen supply hydrocarbon component S H of hydrogen supply hydrocarbon stream SHS and the weight rate HD-CLW of the gluey pitch shape component HD from high aroamtic hydrocarbon raw material HDS >=1.10;

2. hydrogen to oil volume ratio is 200;

3. the Phase velocity map of high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HDS-KL >=0.77, i.e. overall vaporization rate HDS-KV≤0.23;

The Phase velocity map of the gluey pitch shape component HD in high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HD-KL >=0.77, i.e. overall vaporization rate HD-KV≤0.23;

4. the selection index of reaction heat, the reaction heat HDS-Q based on high aroamtic hydrocarbon raw material HDS is KZ, KZ=HDS-Q/SHS-Q, KZ >=2.1 with the ratio based on the reaction heat SHS-Q of hydrogen supply hydrocarbon stream SHS;

The mode of operation of pre-hydrogenator R1-SB is upflowing slight expanded-bed reactor; Charging autoreactor R1-SB bottom enters, and reaction effluent R1P autoreactor R1-SB top is flowed out; Temperature be 300 ~ 320 DEG C, pressure is 15.0 ~ 17.0MPa, catalyst for pre-hydrogenation R1-CAT volume space velocity is 0.6 ~ 0.7hr ^-1reaction conditions under, complete pre-hydrotreating reaction and obtain pre-hydrotreating reaction effluent R1P; Described upflowing slight expanded-bed, bed expansion ratio KBED is less than 1.03;

Claims

1. comprise the high aromatics hydrogenation process of the pre-hydrogenation process of low hydrogen/gasoline ratio using hydrogen supply hydrocarbon, it is characterized in that comprising following steps:

In pre-hydrotreating reaction R1R process, technic index is:

2. hydrogen to oil volume ratio is less than 500;

The Phase velocity map of the gluey pitch shape component HD in high aroamtic hydrocarbon raw material HDS is: total body fluid one after another HD-KL >=0.5, i.e. overall vaporization rate HD-KY≤0.5;

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

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 0.1 ~ 6;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥1.0。

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

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.1 ~ 6; KY is 1 ~ 4;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥1.5。

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

In pre-hydrotreating reaction R1R process, technic index is:

1. KX is 0.5 ~ 3; KY is 1.5 ~ 2.5;

2. hydrogen to oil volume ratio is less than 500;

④KZ≥2。

5. method according to claim 1 or 2 or 3 or 4, is characterized in that:

(1) high aroamtic hydrocarbon raw material HDS is selected from one or more in following materials:

1. coalite tar or its distillate;

2. coal-tar middle oil or its distillate;

3. coal-tar heavy oil or its distillate;

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

5. shale oil or its distillate;

6. ethylene cracking tar;

7. petroleum base wax oil thermal cracking tars;

6. method according to claim 1 or 2 or 3 or 4, is characterized in that:

7. method according to claim 1 or 2 or 3 or 4, is characterized in that:

(1) at pre-hydrotreating reaction process R1, the mode of operation of at least one pre-hydrogenator R1-SB is upflow fixed bed reactor or upflowing slight expanded-bed reactor; Charging autoreactor R1-SB bottom enters, and reaction effluent R1P autoreactor R1-SB top is flowed out; Temperature be 230 ~ 400 DEG C, pressure is 6.0 ~ 28.0MPa, hydrogen/stock oil volume ratio is less than 500, catalyst for pre-hydrogenation R1-CAT volume space velocity is 0.05 ~ 5.0hr ^-1reaction conditions under, complete pre-hydrotreating reaction and obtain pre-hydrotreating reaction effluent R1P; 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.

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

(1) at pre-hydrotreating reaction process R1, hydrogen/stock oil volume ratio is 20 ~ 300;

Described upflowing slight expanded-bed, bed expansion ratio KBED is lower than 1.05.

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

(1) at pre-hydrotreating reaction process R1, the mode of operation of at least one pre-hydrogenator R1-SB is upflow fixed bed reactor or upflowing slight expanded-bed reactor, charging autoreactor R1-SB bottom enters, and reaction effluent R1P autoreactor R1-SB top is flowed out; Temperature be 230 ~ 400 DEG C, pressure is 6.0 ~ 28.0MPa, hydrogen/stock oil volume ratio is less than 500: 1, catalyst for pre-hydrogenation R1-CAT volume space velocity is 0.05 ~ 5.0hr ^-1reaction conditions under, complete pre-hydrotreating reaction and obtain pre-hydrotreating reaction effluent R1P; Described upflowing slight expanded-bed, KBED is lower than 1.10.

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

11. methods according to claim 6, is characterized in that:

12., according to method described in claim 11, is characterized in that:

13. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

14., according to method described in claim 13, is characterized in that:

15., according to method described in claim 14, is characterized in that:

16. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

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

17. methods according to claim 5, is characterized in that:

18. want method described in 6 according to right, it is characterized in that:

19. want method described in 13 according to right, it is characterized in that:

20. according to claim 1 or 2 or 3 or 4 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 ~ 1%.

21. methods according to claim 5, is characterized in that:

22. want method described in 6 according to right, it is characterized in that:

23. want method described in 13 according to right, it is characterized in that:

24. according to claim 1 or 2 or 3 or 4 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 ~ 0.5%.

25. methods according to claim 5, is characterized in that:

26. want method described in 6 according to right, it is characterized in that:

27. want method described in 13 according to right, it is characterized in that:

28. methods according to claim 6, is characterized in that:

(1) at the hydroconversion reaction zone R-SHS being prepared as target with hydrogen supply hydrocarbon, select to produce the processing condition that hydrogen supply hydrocarbon is target to greatest extent;

(2) in deep hydrogenation upgrading reaction effluent R2P full cut diesel-fuel cetane number higher than 32.

29. methods according to claim 13, is characterized in that:

30. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

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

31. methods according to claim 5, is characterized in that:

32. want method described in 6 according to right, it is characterized in that:

33. want method described in 13 according to right, it is characterized in that:

34. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

35. methods according to claim 5, is characterized in that:

36. want method described in 6 according to right, it is characterized in that:

37. want method described in 13 according to right, it is characterized in that:

38. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

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

39. methods according to claim 5, is characterized in that:

40. want method described in 6 according to right, it is characterized in that:

41. want method described in 13 according to right, it is characterized in that:

42. according to claim 1 or 2 or 3 or 4 method, it is characterized in that:

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

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

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

43. methods according to claim 5, is characterized in that:

44. want method described in 6 according to right, it is characterized in that:

45. want method described in 13 according to right, it is characterized in that: