CN104119954A - Heavy raw oil treatment method - Google Patents
Heavy raw oil treatment method Download PDFInfo
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- CN104119954A CN104119954A CN201310144166.6A CN201310144166A CN104119954A CN 104119954 A CN104119954 A CN 104119954A CN 201310144166 A CN201310144166 A CN 201310144166A CN 104119954 A CN104119954 A CN 104119954A
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Abstract
The invention provides a heavy raw oil treatment method. The method is carried out in a raw oil treatment apparatus, the apparatus comprises a hydrogenation protection unit, a hydrotreatment unit and a catalytic cracking unit which are sequentially connected in series, the hydrogenation protection unit comprises a main hydrogenation protection reactor and a standby hydrogenation protection reactor which are connected in parallel, and the volume of the main hydrogenation protection reactor is greater than the volume of the standby hydrogenation protection reactor. The method is characterized in that heavy raw oil and hydrogen are introduced to the apparatus, and contact with a plurality of hydrogenation catalyst beds arranged in the apparatus to obtain hydrogenated tail oil; and the main hydrogenation protection reactor and the standby hydrogenation protection reactor are alternately used, and the online time of the main hydrogenation protection reactor is greater than the online time of the standby hydrogenation protection reactor. The method has the advantages of high yield of low carbon olefins and monocyclic aromatic hydrocarbons, and high space utilization rate of the above reactors.
Description
Technical field
The present invention relates to a kind of heavy feed stock oil treatment process.
Background technology
Low-carbon alkene and mononuclear aromatics are important petrochemical industry basic materials.Low-carbon alkene comprises ethene, propylene and butylene, and low-carbon alkene is mainly produced by steam cracking at present, and petroleum naphtha is its topmost raw material.Mononuclear aromatics mainly comprises benzene, toluene and dimethylbenzene, is mainly also at present to take petroleum naphtha by reforming method, to produce as raw material.Along with world's crude oil heaviness, make lightweight oil and mink cell focus difference in selling prices increasing, utilize mink cell focus production low-carbon alkene and the mononuclear aromatics that price is lower to have more lower cost.
Catalytic pyrolysis technology is a kind of important means of producing propylene, it is raw material that this technology be take the mink cell focuses such as decompressed wax oil, hydrogenated residue conventionally, under the effect of the stronger catalytic cracking catalyst of acidity, there is deep pyrolytic reaction, the high value added products such as gasoline that generate propylene, ethene, butylene and be rich in mononuclear aromatics, simultaneously by-product dry gas, light cycle oil, heavy cycle oil, slurry oil and coke etc.
On the other hand, fixed bed heavy-oil hydrogenation technology is rapid in development in recent years.Heavy oil refers generally to residual oil or wax oil, or other cut heavier than diesel oil.Heavy oil removes the heteroatomss such as metal, sulphur, nitrogen through hydrotreatment, and has improved after hydrogen richness, can be used as the catalytic pyrolysis raw material of high-quality.Therefore the two combination is to make take the effective means of heavy oil as raw material production low-carbon alkene and mononuclear aromatics.But in this combination process, catalytic pyrolysis will produce some byproducts as catalytic pyrolysis light cycle oil, heavy cycle oil, clarification wet goods conventionally.If these byproducts are lower as value of the product, if but these byproducts are circulated to further processing in cat-cracker, because they are rich in polycyclic aromatic hydrocarbons, low-carbon alkene and mononuclear aromatics yield that this part logistics that circulates brings are very low, and green coke amount is very large, reduced treatment capacity and the economic benefit of heavy oil catalytic pyrolysis device.
US4,713,221 disclose on conventional residual hydrogenation and catalytic cracking combined basis, the heavy cycle oil of catalytic cracking (comprising gas oil catalytic cracking and heavy oil fluid catalytic cracking) is circulated to residual hydrogenation equipment, after mixing with topped crude, carry out hydrogenation, hydrogenated residue enters catalytic cracking unit.The change that this is little, the benefit of one barrel of crude oil of the every processing in Ke Shi refinery has a net increase of 0.29 dollar.
CN1119397C discloses a kind of residual hydrocracking-catalytic cracking combination process, is that residual oil enters residual hydrocracking device together with clarified oil, under hydrogen and hydrogenation catalyst existence, carries out hydrogenation reaction; The hydrogenated residue of reaction gained enters catalytic cracking unit, under cracking catalyst exists, carries out cracking reaction, and heavy cycle oil circulates in catalytic cracking unit inside; The slurry oil of reaction gained obtains clarified oil through separator separation, is back to hydrogenation unit.
CN1165601C discloses a kind of method of residual hydrocracking and catalytically cracking heavy oil, together with to be residual oil steam thing, heavy catalytic cycle oil, optional distillate with slurry oil, enter hydrotreater, under hydrogen and hydrogenation catalyst exist, carry out hydrogenation reaction; The generation oil of reaction gained steams after petrol and diesel oil, and hydrogenated residue enters catalytic cracking unit with together with optional vacuum gas oil, under cracking catalyst exists, carries out cracking reaction; Reaction gained heavy cycle oil enters residual hydrogenation equipment, and distillation slurry oil obtains steaming thing and is back to hydrogenation unit.
CN101747935A has proposed a kind of heavy-oil hydrogenation-catalytic pyrolysis bi-directional combination technique, and the method enters into fixed bed residual hydrogenation equipment after the turning oil of catalytic pyrolysis is mixed with wax oil and residual oil.The advantage of the method is: unmanageable turning oil in catalytic pyrolysis process can be converted into propylene and light-end products on the one hand; Utilize again on the other hand the feature that is rich in polycyclic aromatic hydrocarbons in turning oil, not only reduce slag oil viscosity after being incorporated into residual oil, and it is stable to be conducive to the colloidal dispersion of the residual oil in hydrogenation process, has alleviated fixed bed residual oil hydrocatalyst coking and deactivation situation.
But aforesaid method has only utilized catalytic cracking or catalytic pyrolysis heavy cycle oil or heavier slurry oil cut to deliver to residual hydrogenation equipment and after hydrogenation, returned catalytic cracking or catalytic pyrolysis together with residual oil, and the very high light cycle oil of unresolved as much Polycyclic aromatic hydrocarbons utilizes problem.Meanwhile these methods are also brought another one problem, are exactly that catalytic cracking or catalytic pyrolysis heavy cycle oil or slurry oil contain acid solid particulate matter, i.e. catalytic cracking or catalytic cracking catalyst dust.Catalyst dust can cause and have a strong impact on residual hydrogenation.
But for fixed bed Residue Hydrotreating Technology, solid particulate matter impurity in raw material is had to strict restriction, because solid particulate matter impurity is easy to be deposited in the surface and the space between granules of catalyst of catalyzer, blocking catalyst aperture, cause catalyst deactivation, and cause bed pressure drop to raise fast, make device frequent shutdowns and catalyst changeout more.And the catalytic cracking catalyst powder inevitably containing in catalytic pyrolysis turning oil enters into the running period of serious threat device after fixed bed residual hydrogenation equipment.
For overcoming fixed-bed reactor processing poor residuum or being easy to produce pressure drop, short shortcoming of operational cycle during containing solid particulate raw material, CN1484684A is used replaceable reactor and method that can short-circuit reaction device hydrotreatment of heavy hydrocarbon fraction.Go into operation the initial stage, A, two guard reactor serial operations of B, B guard reactor is in A guard reactor downstream; When the pressure drop of A guard reactor is too high or during catalyst deactivation, rapidly this reactor is cut out, B guard reactor remains in operation, and device is not stopped work; After A guard reactor cuts out, complete catalyzer isolation, cooling, draw off old dose, load the processes such as new agent, last switchback reactive system turns round again.Now A guard reactor is in B guard reactor downstream; When the pressure drop of B guard reactor is too high or during catalyst deactivation, excision B guard reactor, A guard reactor individual operation, B guard reactor unloads agent, dress agent, comes into operation after then sealing in A guard reactor.So repeatedly can prolong operating period, but A is before B when its A, two guard reactors one of B, 1 o'clock A is after B, and high-temperature high pressure valve is numerous, and expense is higher, and complicated operation can bring risk and inconvenience to production.France Inst Francais Du Petrole has proposed interchangeable guard reactor, but similarly, its equipment and complicated operation, production risk is higher.
In hydrogenation and other field, also having a well-known protector switching method is to adopt guard reactor that two grades are large before main reactor, and two guard reactors are used in turn; First A guard reactor is online, when the pressure drop of A guard reactor is too high or during catalyst deactivation, this reactor can be cut out, makes B guard reactor online; A guard reactor carry out catalyzer isolation, cooling, draw off old dose, load the processes such as new agent.Deng the pressure drop of B guard reactor, during too high or catalyst deactivation, B guard reactor can be cut out, the last switchback reactive system of A is turned round again.Less due to this kind of form high temperature, high pressure valve, operate comparatively simply, be the guard reactor form that a lot of technique adopts.But this method is because always there being a guard reactor off-line, and guard reactor utilising efficiency only has 50%, wastes valuable space reactor.
Summary of the invention
The object of the invention is to overcome the above-mentioned defect of prior art, provide a kind of and from heavy raw oil, by hydrogenation and catalytic pyrolysis assembled highly-effective, produce low-carbon alkene and mononuclear aromatics and can make the method that device can long-term operation.
For realizing aforementioned object, the invention provides a kind of heavy feed stock oil treatment process, wherein, the method is carried out in a kind of stock oil treatment unit, described stock oil treatment unit comprises hydrogenation protecting unit, hydrotreating unit and the catalytic pyrolysis unit of series connection successively, described hydrogenation protecting unit comprises main hydrogenation protecting reactor and standby hydrogenation protecting reactor in parallel, and the volume of described main hydrogenation protecting reactor is greater than the volume of described standby hydrogenation protecting reactor; The method comprises:
Under hydrotreatment reaction conditions, heavy raw oil and hydrogen are introduced in described device, and, a plurality of hydrogenation catalyst beds of hydrotreating unit setting contact, obtained gas, hydrotreated naphtha and hydrogenation tail oil with the hydrogenation protecting unit of described device successively;
Described hydrogenation tail oil or vacuum gas oil and the mixing oil of described hydrogenation tail oil are sent in the catalytic pyrolysis unit of described device and contacted with catalytic cracking catalyst;
Wherein, in hydrogenation protecting unit, main hydrogenation protecting reactor and standby hydrogenation protecting reactor are used alternatingly, and the line duration of described main hydrogenation protecting reactor is greater than the line duration of described standby hydrogenation protecting reactor.
Compared with prior art, the present invention has following advantage:
1, adopt method provided by the invention can make heavy raw oil (as straight run heavy oil and catalytic pyrolysis light cycle oil, the recirculate mixing wet goods of wet goods of catalytic pyrolysis, described straight run heavy oil comprises residual oil and wax oil) deliver to heavy oil hydrogenation equipment, for example, by residual oil and catalytic pyrolysis heavy cycle oil, the mixing oil of optional catalytic pyrolysis light cycle oil removes cat-cracker after hydrogenation again, catalytic pyrolysis heavy cycle oil and catalytic pyrolysis light cycle oil can reduce residual oil viscosity thus, and the light cycle oil of high aromaticity, the colloidal dispersion that heavy cycle oil can more be conducive to the residual oil in hydrogenation process is stable, prevent that bituminous matter from separating out, alleviated the situation of fixed bed residual oil hydrocatalyst coking and deactivation, and for cat-cracker, owing to being rich in the catalytic pyrolysis weight turning oil of polycyclic aromatic hydrocarbons, all passed through hydrogenation, so low-carbon alkene and the raising of mononuclear aromatics productive rate, be conducive to increase economic efficiency.
2, catalytic pyrolysis heavy cycle oil and slurry oil steam and in the mink cell focuses such as thing, contain solid particulate matter, these solid particulate matters are generally catalytic cracking catalyst dust, at residual hydrogenation equipment, will cause catalyzer coking, beds to stop up, therefore can cause the particularly too fast rising of anterior beds pressure drop of beds, have a strong impact on the residual hydrogenation equipment operational cycle.And the present invention is by adopting switchable type guard reactor in parallel; can after reaching the guard reactor limit, pressure drop switch to another guard reactor in parallel; the guard reactor off-line that this pressure drop simultaneously reaches capacity also changes agent, and so repeatedly, device can continous-stable running.
3, adopt the asymmetric guard reactor varying in size; first large main hydrogenation protecting reactor comes into operation; large main hydrogenation protecting reactor switches to little stand-by protection reactor in parallel after pressure drop reaches capacity; main protection reactor off-line is also changed agent; after changing agent, cut main protection reactor; stand-by protection reactor off-line, so repeatedly.Large guard reactor line duration is long, and little guard reactor line duration is short, so space reactor utilization ratio significantly improves, and has obvious economic benefit.In addition, the interchangeable guard reactor system high pressure valve that the present invention describes than CN1484684A is few, and changeover program is simple, and operational reliability is higher, and risk is less.Because hydrogenation is generally high temperature, high-pressure reactor, therefore simple and reliable schedule of operation has very large advantage.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the process flow sheet of the heavy feed stock oil treatment in one embodiment of the present invention.
Embodiment
Below in conjunction with accompanying drawing, the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
The invention provides a kind of heavy feed stock oil treatment process, wherein, the method is carried out in a kind of stock oil treatment unit, described stock oil treatment unit comprises hydrogenation protecting unit, hydrotreating unit C and the catalytic pyrolysis cells D of series connection successively, described hydrogenation protecting unit comprises main hydrogenation protecting reactor in parallel (being guard reactor A in Fig. 1) and standby hydrogenation protecting reactor (being guard reactor B in Fig. 1), and the volume of described main hydrogenation protecting reactor is greater than the volume of described standby hydrogenation protecting reactor; The method comprises:
Under hydrotreatment reaction conditions, heavy raw oil and hydrogen are introduced in described device, and, a plurality of hydrogenation catalyst beds of hydrotreating unit setting contact, obtained gas, hydrotreated naphtha and hydrogenation tail oil with the hydrogenation protecting unit of described device successively;
Described hydrogenation tail oil or vacuum gas oil and the mixing oil of described hydrogenation tail oil are sent in the catalytic pyrolysis unit of described device and contacted with catalytic cracking catalyst;
Wherein, in hydrogenation protecting unit, main hydrogenation protecting reactor and standby hydrogenation protecting reactor are used alternatingly, and the line duration of described main hydrogenation protecting reactor is greater than the line duration of described standby hydrogenation protecting reactor.
According to the present invention, optional a wider range of the kind of described heavy raw oil, conventional mink cell focus all can adopt method of the present invention to process, for the present invention, preferred described heavy raw oil is that residual oil, wax oil, catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil, catalytic cracking slurry oil steam one or more in thing and distillate.
According to of the present invention preferred embodiment a kind of, preferred described heavy raw oil is that residual oil and catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil and catalytic cracking slurry oil steam one or more the mixing oil in thing.
According to a kind of preferred embodiment of the present invention, preferred described heavy raw oil contains residual oil and catalytic pyrolysis heavy cycle oil, and optional described heavy raw oil also contains catalytic pyrolysis light cycle oil and/or catalytic cracking slurry oil steams thing.
According to a kind of preferred embodiment of the present invention, in preferred described heavy raw oil, the mass ratio of catalytic pyrolysis heavy cycle oil and residual oil is 0.01-1:1, more preferably 0.02-0.3:1.
In the present invention, while also containing catalytic pyrolysis light cycle oil in described heavy raw oil, the mass ratio of preferred catalytic cracking light cycle oil and residual oil is 0.001-1:1, more preferably 0.03-0.5:1.
According to of the present invention another preferred embodiment, preferred described heavy raw oil is that wax oil and catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil and catalytic cracking slurry oil steam one or more the mixing oil in thing.
According to of the present invention another preferred embodiment, preferred described heavy raw oil contains wax oil and catalytic pyrolysis heavy cycle oil, optional described heavy raw oil also contains catalytic pyrolysis light cycle oil and/or catalytic cracking slurry oil steams thing.
According to another preferred embodiment of the present invention, in preferred described heavy raw oil, the mass ratio of catalytic pyrolysis heavy cycle oil and wax oil is 0.01-1:1, more preferably 0.02-0.3:1.
In the present invention, while also containing catalytic pyrolysis light cycle oil in aforementioned heavy raw oil, the mass ratio of preferred catalytic cracking light cycle oil and wax oil is 0.001-1:1, more preferably 0.03-0.5:1.
In the present invention, described catalytic pyrolysis heavy cycle oil can be the heavy cycle oil from arbitrary cat-cracker; According to of the present invention preferred embodiment a kind of, described catalytic pyrolysis heavy cycle oil can be to carry out the heavy cycle oil of the cat-cracker of catalytic pyrolysis from take hydrogenation tail oil of the present invention as raw material.
In the present invention, the boiling range of described catalytic pyrolysis heavy cycle oil and described catalytic pyrolysis light cycle oil is different and different according to the cut point of cat-cracker, cut point for example can be 350 ℃, now the boiling range of preferred described catalytic pyrolysis heavy cycle oil is 350-520 ℃, refer to catalytic cracking reaction products after distillation, the boiling range obtaining is the product of 350-520 ℃, and the boiling range of described catalytic pyrolysis light cycle oil is 180-350 ℃, refer to catalytic cracking reaction products after distillation, the boiling range obtaining is the product of 180-350 ℃.Described catalytic pyrolysis heavy cycle oil and described catalytic pyrolysis light cycle oil cut point also can be chosen to be 300 ℃, and now the boiling range of preferred described catalytic pyrolysis heavy cycle oil is 300-520 ℃, and the boiling range of described catalytic pyrolysis light cycle oil is 180-300 ℃.In general, the cut point that catalytic pyrolysis product cuts to obtain catalytic pyrolysis heavy cycle oil and catalytic pyrolysis light cycle oil can change between 260-390 ℃, concrete view apparatus and determining.
In the present invention, it can be that slurry oil from arbitrary catalytic pyrolysis or catalytic cracking unit steams thing (general slurry oil steams the 5-80 % by weight that thing accounts for the full cut of slurry oil) that described slurry oil steams thing, and described slurry oil steams thing boiling range scope and is generally 400-520 ℃.
In the present invention, described distillate is conventional distillate, for the present invention, is preferably coker gas oil, catalytic cracking light cycle oil, heavy catalytic cycle oil, deasphalted oil, vacuum gas oil and solvent treatment and extracts one or more among oil out.
In the present invention, described residual oil is preferably vacuum residuum and/or long residuum.
The method according to this invention, the operational condition in the reaction member of preferred described catalytic pyrolysis unit comprises: temperature is 470-650 ℃, liquid hourly space velocity is 0.4-10h
-1, agent-oil ratio is 3-15.
The method according to this invention, preferred described catalytic pyrolysis also comprises regeneration unit in unit, the operational condition in regeneration unit comprises: temperature is 650-800 ℃.
The method according to this invention, described catalytic cracking catalyst can be selected for the routine of this area, for the present invention, preferably in the gross weight of catalyzer, described catalytic cracking catalyst contains: zeolite 5-70 % by weight, inorganic oxide 5-95 % by weight and clay 0-70 % by weight.
The method according to this invention, wherein, described zeolite is as active ingredient, preferred described zeolite is selected from mesopore zeolite and/or large pore zeolite, and large pore zeolite accounts for the 25-100 % by weight of zeolite gross weight, preferably large pore zeolite accounts for the 50-100 % by weight of zeolite gross weight, and preferably mesopore zeolite accounts for the 0-75 % by weight of zeolite gross weight, and preferably mesopore zeolite accounts for the 0-50 % by weight of zeolite gross weight.
In the present invention, described mesopore zeolite and large pore zeolite are continued to use the definition of this area routine, i.e. the mean pore size 0.5-0.6nm of mesopore zeolite, the mean pore size 0.8-1.0nm of large pore zeolite.For example, described large pore zeolite can be selected from y-type zeolite, one or more in rare earth Y type zeolite (REY), rare earth hydrogen y-type zeolite (REHY), ultrastable Y－type zeolite (USY), extremely steady y-type zeolite of rare earth (REUSY).
Described mesopore zeolite can be selected from the zeolite with MFI structure, for example ZSM series zeolite and/or ZRP zeolite, also can carry out modification to the transition metal such as the non-metallic elements such as phosphorus and/or iron, cobalt, nickel for above-mentioned mesopore zeolite, the more detailed description of relevant ZRP is referring to US5,232,675, ZSM series zeolite is selected from the one or more of mixture among the zeolite of ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35, ZSM-38, ZSM-48 and other similar structures, the more detailed description of relevant ZSM-5 is referring to US3,702,886.
In the present invention, described inorganic oxide, as caking agent, is preferably selected from silicon-dioxide (SiO
2) and/or aluminium sesquioxide (Al
2o
3).
In the present invention, described clay, as matrix (being carrier), is preferably selected from kaolin and/or halloysite.
According to the present invention, as long as being greater than the volume of described standby hydrogenation protecting reactor, the volume of described main hydrogenation protecting reactor can realize goal of the invention.Specifically preferably, the volume ratio of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 1.01-50:1,1.1-30:1 more preferably, and more preferably 1.1-10:1, is particularly preferably 1.5-5:1.
For the number of main hydrogenation protecting reactor and standby hydrogenation protecting reactor, there is no particular limitation in the present invention; separately can be for one or more; when being a plurality of reactor; it can be in parallel or series connection; as long as cumulative volume meets above-mentioned requirements; preferably, in the present invention, the number of described main hydrogenation protecting reactor and standby hydrogenator is one.
In the present invention, the volume of reactor refers to the volume of the catalyzer of actual filling in reactor.
According to the present invention, as long as the line duration of main hydrogenation protecting reactor is greater than the space utilization efficiency that the line duration of described standby hydrogenation protecting reactor can improve reactor.Preferably, in hydrotreatment process, the ratio of the line duration of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 1.01-60:1, more preferably 1.5-20:1, more preferably 3-15:1.
A preferred embodiment of the invention, described main hydrogenation protecting reactor is in line states except the time of catalyst changeout more always.The concrete steps that described main hydrogenation protecting reactor is in line states except the time of catalyst changeout more always comprise; first heavy raw oil and hydrogen enter main hydrogenation protecting reactor after mixing; when rising to maximum operation allowable pressure drop or catalyst activity, main hydrogenation protecting reactor pressure decrease do not reach while requiring; be switched to standby hydrogenation protecting reactor; by main hydrogenation protecting reactor excision off-line; after drawing off old catalyzer and packing raw catalyst into, main hydrogenation protecting reactor is incorporated to, simultaneously by standby hydrogenation protecting reactor excision, off-line.Main hydrogenation protecting reactor does not again reach while requiring because pressure drop rises to maximum operation allowable pressure drop or catalyst activity after operation for some time; again be switched to standby hydrogenation protecting reactor operation; by main hydrogenation protecting reactor excision off-line; after drawing off old catalyzer and packing raw catalyst into, main hydrogenation protecting reactor is incorporated to, simultaneously by standby hydrogenation protecting reactor excision, off-line.So repeatedly.After coming into operation several times, standby hydrogenation protecting reactor also can produce the situation of pressure drop increase, catalyst activity reduction; when pressure drop soon reaches maximum while allowing operation pressure drop or catalyst activity not to reach to require, catalyst changeout more during standby hydrogenation protecting reactor excision off-line.
Those skilled in the art are scrutable is, the time of described more catalyst changeout comprise catalyzer isolation, cooling, draw off old dose, load time of the processes such as new agent, concrete steps and the time of these processes are known to the skilled person, do not repeat them here.
According to the present invention, according to the flow direction of described heavy raw oil, preferably in described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor, be provided with hydrogenation protecting catalyst bed and/or Hydrodemetalation catalyst bed.; described main hydrogenation protecting reactor and standby hydrogenation protecting reactor all can only be provided with hydrogenation protecting catalyst bed; also all Hydrodemetalation catalyst bed can be only provided with, also all hydrogenation protecting catalyst bed and Hydrodemetalation catalyst bed can be provided with simultaneously.Wherein, preferably be disposed with hydrogenation protecting catalyst bed and Hydrodemetalation catalyst bed, in described hydrogenation protecting catalyst bed, in the loadings of hydrogenation protecting catalyst and Hydrodemetalation catalyst bed, the loadings of Hydrodemetalation catalyst can be the selection of this area routine simultaneously.Preferably, described hydrogenation protecting catalyst is 1:0.05-20 with the admission space ratio of described Hydrodemetalation catalyst; Preferred 1:0.1-5.
The method according to this invention, described hydrotreating unit can be a set of or a set of above hydrogenation unit, every cover hydrogenation unit at least comprises a hydrogenator and a separation column, and described hydrogenator can be fixed-bed reactor, moving-burden bed reactor or ebullated bed reactor conventionally.Specifically preferably, described hydrotreating unit can comprise or be fixed bed residual hydrogenation equipment.
According to the present invention, the flow direction according to described heavy raw oil, in preferred described hydrotreating unit, be provided with Hydrodemetalation catalyst bed and/or Hydrobon catalyst bed, in preferred described hydrotreating unit, be disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed.Described Hydrobon catalyst bed comprises at least one in Hydrobon catalyst bed, removal of ccr by hydrotreating beds and hydrodenitrogenation catalyst bed.Described Hydrodemetalation catalyst bed and described Hydrobon catalyst bed can be arranged in identical or different reactor.Wherein, the number that each beds arranges and the loadings of catalyzer can be selected for the routine of this area, and to this, there is no particular limitation in the present invention.
In the present invention hydrogenation catalyst used as hydrogenation protecting catalyst, Hydrodemetalation catalyst, Hydrobon catalyst, removal of ccr by hydrotreating catalyzer can be all the catalyzer with these functions of this area routine.Usually, above-mentioned catalyzer be all take porous inorganic oxide as aluminum oxide as carrier, take group VIB and/or group VIII metal if one or more the oxide compound in W, Mo, Co and Ni is as active ingredient, optionally add other various auxiliary agents as one or more catalyzer in P, Si, F and B.After can being purchased separately various catalyzer during use, be used in combination; also can directly be purchased the complete series catalyst for hydrotreatment of residual oil that comprises above-mentioned various catalyzer, as the RG purchased from catalyzer Chang Ling branch office, RDM, RMS and RSC series weight, hydrotreating guard catalyst for residual oil, Hydrodemetalation catalyst, Hydrobon catalyst and removal of ccr by hydrotreating catalyzer.
According to the present invention, described hydrotreatment reaction conditions can be the various hydrotreatment reaction conditionss of this area routine, and preferably, described hydrotreatment reaction conditions comprises:
In hydrogenation protecting unit: temperature is 320-440 ℃, more preferably 350-420 ℃; Hydrogen dividing potential drop is 8-20MPa, more preferably 11-17MPa; Hydrogen to oil volume ratio is 300-2000, more preferably 500-1000; Liquid hourly space velocity is 0.1-5h
-1, 0.15-2h more preferably
-1.Specifically can adjust according to character and the target value of raw material;
In hydrotreating unit: temperature is 320-440 ℃, more preferably 350-420 ℃; Hydrogen dividing potential drop is 8-20MPa, more preferably 11-17MPa; Hydrogen to oil volume ratio is 300-2000, more preferably 500-1000; Liquid hourly space velocity is 0.1-2h
-1, 0.15-1h more preferably
-1.
The method according to this invention, described catalytic pyrolysis unit can be a set of or a set of above cat-cracker, preferred every covering device at least comprises a reactor, a revivifier and a separation column.Described cat-cracker can be for example riser reactor, or the combination of riser reactor and bed reactor.
Particularly, several covering devices can for example, for the arbitrary cover in fluid catalytic cracking device (heavy oil fluidized cat-cracker (RFCC)), cat-cracker (DCC), maximizing iso-paraffins cat-cracker (MIP) or be appointed in described catalytic pyrolysis unit.
The method according to this invention; preferably the method also comprises: the separated reaction product obtaining from described catalytic pyrolysis unit; obtain dry gas, liquefied gas, catalytic pyrolysis petroleum naphtha, catalytic pyrolysis light cycle oil, catalytic pyrolysis heavy cycle oil and slurry oil; described catalytic pyrolysis heavy cycle oil and/or catalytic pyrolysis light cycle oil are returned to hydrogenation protecting unit to be used as raw material; preferably by described catalytic pyrolysis heavy cycle oil, and optional catalytic pyrolysis light cycle oil is returned to hydrogenation protecting unit as raw material, use.
According to of the present invention preferred embodiment a kind of, the present invention carries out as follows: from the catalytic pyrolysis heavy cycle oil of catalytic pyrolysis cells D, catalytic pyrolysis light cycle oil and residual oil (or wax oil, what use in an embodiment is residual oil) enter hydrogenation protecting unit after mixing with hydrogen together, then enter hydrotreating unit C, under existing, hydrogenation catalyst carries out hydrotreatment reaction, separated hydrotreatment products, obtain gas, hydrotreated naphtha and hydrogenation tail oil, wherein gas and hydrotreated naphtha are drawn respectively, hydrogenation tail oil enters catalytic pyrolysis cells D with together with optional vacuum gas oil, under existing, catalytic cracking catalyst reacts, the reaction product of separated catalytic pyrolysis, obtain being rich in the dry gas of ethene, be rich in the liquefied gas of the third rare and butylene, be rich in the catalytic pyrolysis petroleum naphtha of mononuclear aromatics, catalytic pyrolysis light cycle oil, catalytic pyrolysis heavy cycle oil and slurry oil, wherein, dry gas can obtain ethene through gas delivery, liquefied gas can obtain the third rare and butylene through separation, catalytic pyrolysis petroleum naphtha can obtain benzene through separation, toluene, dimethylbenzene and other mononuclear aromatics, catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil returns delivers to hydrogenation protecting unit, optionally catalytic cracking slurry oil is distilled and will steam thing and can deliver to hydrogenation protecting unit.As previously mentioned; described hydrogenation protecting unit adopts the in parallel asymmetric guard reactor varying in size; first large main hydrogenation protecting reactor comes into operation; large main hydrogenation protecting reactor switches to little stand-by protection reactor in parallel after pressure drop reaches capacity; main protection reactor off-line is also changed agent; after changing agent, cut main protection reactor, stand-by protection reactor off-line, so repeatedly.Large guard reactor line duration is long, and little guard reactor line duration is short, so space reactor utilization ratio significantly improves.
Below, in conjunction with Fig. 1, the operation of the hydrogenation protecting reactor in parallel in stock oil treatment unit of the present invention is described in detail.
As shown in Figure 1; when stock oil treating processes starts, valve V-1 and V-2 open, and valve V-3 and V-4 close; heavy raw oil and hydrogen are introduced guard reactor A, then by pipeline, enter hydrotreating unit C(as being fixed bed hydrogenation device) react.After operation certain hour, when the pressure drop of guard reactor A reaches or approaches equipment maximum allowed pressure drop or can not continue to operate because of other reason (general provision is 0.6MPa), valve-off V-1 and V-2, and open valve V-3 and V-4 simultaneously, heavy raw oil and hydrogen enter guard reactor B, then enter hydrotreating unit C(as being fixed bed residual hydrogenation equipment) react, then the hydrogenation tail oil obtaining being sent into catalytic pyrolysis cells D (can be for example fluid catalytic cracking device) contacts with catalytic cracking catalyst, obtain catalytic pyrolysis product.Guard reactor A changes live catalyst, changes after agent completes and immediately guard reactor A is cut and excised guard reactor B(valve-off V-3 and V-4, and open valve V-1 and V-2 simultaneously).Guard reactor B is because line duration is short, more catalyst changeout.So circulation, after certain number of cycles, guard reactor B pressure drop also reaches or approaches equipment maximum allowed pressure drop (general provision is 0.6MPa) or catalyst activity does not reach requirement, catalyst changeout more when guard reactor B off-line.
Below will describe the present invention by embodiment.In the present invention, the various catalyzer of hydrotreatment used are the catalyst Co. production of Sinopec Chang Ling.
Embodiment 1
In the stock oil treatment unit that the present embodiment is used; main hydrogenation protecting reactor is a guard reactor A; standby hydrogenation protecting reactor is a guard reactor B; described hydrotreating unit C is fixed bed residual hydrogenation equipment; described catalytic pyrolysis cells D is the fixed fluidized bed cat-cracker in laboratory, as shown in Figure 1.
Wherein, in hydrogenation main protection reactor A, load successively RG-30A catalyzer 60mL, RG-30B catalyzer 60ml, RDM-32 catalyzer 60ml; In stand-by protection reactor B, load successively RG-30A catalyzer 20mL, RG-30B catalyzer 20mL and RDM-32 catalyzer 20ml; In fixed bed residual hydrocracking reactor C, load successively RDM-32 catalyzer 200mL and RMS-30 catalyzer 400mL; In fluid catalytic cracking device D reactor, load MMC-2 catalytic cracking catalyst; Above-mentioned catalyzer is produced by catalyzer Chang Ling branch office.
Take a kind of long residuum as stock oil A, a kind of catalytic pyrolysis heavy cycle oil (HCO) is the acid solid impurity content of stock oil B(83ppm), catalytic pyrolysis light cycle oil (LCO) is a stock oil C, and the character of stock oil A, stock oil B and stock oil C is as shown in table 1.Can find out that dicyclo and above aromatic hydrocarbons in stock oil B and stock oil C are very high, substantially cannot produce low-carbon alkene and mononuclear aromatics by self cracking in cat-cracker.
The mass ratio of stock oil A, stock oil B and stock oil C is 75:8:17; after the mixing oil YL-1 of stock oil A, stock oil B and stock oil C mixes with hydrogen; enter hydrogenation protecting unit and hydrotreating unit; contact with hydrogenation catalyst and carry out hydrotreatment reaction; separated its reaction product, obtains gas, hydrotreated naphtha and hydrogenation tail oil, the hydrogenation tail oil of gained; as catalytic pyrolysis raw material, enter catalytic cracking unit and react, separated its reaction product obtains corresponding product.
Wherein, hydrogenation conditions is: the inlet amount of mixing oil YL-1 is 208g/h, and protected location and processing unit term harmonization: 385 ℃ of temperature of reaction, hydrogen dividing potential drop 15.0MPa, hydrogen to oil volume ratio 1000.
Wherein, catalytic cracking reaction condition is: 580 ℃ of temperature of reaction, agent-oil ratio 10, liquid hourly space velocity 4h
-1, 660 ℃ of regeneration temperatures.
Raw material test-results is: except obtaining returning the catalytic pyrolysis heavy cycle oil (boiling range is 350-520 ℃) of hydrogenation protecting unit and catalytic pyrolysis light cycle oil, (light cycle oil cetane value is less than 20; boiling range is 180-350 ℃) outside, can obtaining high-value product (ethene+the third rare+butylene+mononuclear aromatics) total recovery and be 54.6%(, to take fresh residual oil raw material be that stock oil A quality is benchmark).
Enter heavy raw oil after 2000 hours; the pressure drop of guard reactor A approaches 0.6MPa, then opens upstream and downstream valve V-3 and the V-4 of reactor B, meanwhile closes upstream and downstream valve V-1 and the V-2 of guard reactor A; be switched to guard reactor B in parallel and operate, reaction conditions is constant.Guard reactor A changes raw catalyst, and loading catalyst kind and loadings are with identical before.Behind 150 hours of excision guard reactor A, again cut guard reactor A, excise guard reactor B simultaneously.In second operating time section; after guard reactor A operation moves 2000 hours, pressure drop approaches 0.6MPa; switch to guard reactor B; after remaining in operation 150 hours, guard reactor B pressure drop does not have obvious rising; illustrate that guard reactor B also can continue to use; even if cut guard reactor A, guard reactor B is catalyst changeout more also, first stage off-test again.
In test subordinate phase, no longer cut guard reactor A, only with guard reactor B, fixed bed residual hydrogenation equipment serial operation, to investigate the operational cycle.Continue to pass into heavy raw oil YL-1, under identical inlet amount, pressure, temperature, hydrogen flowing quantity condition, after guard reactor B turns round 300 hours, pressure drop approaches 0.6MPa, and guard reactor B turns round 600 hours to stopping work altogether from entry into service.Illustrate that 4 all after date guard reactor B of guard reactor A running need to change catalyzer one time.
In the present invention, definition guard reactor space utilization efficiency is:
Above A represents guard reactor A, and B represents guard reactor B.
The total operating time of the above-mentioned main protection reactor A of substitution is totally 8000 hours 4 cycles; in guard reactor A, the volume of catalyzer is 180ml; the total operating time of guard reactor B is totally 600 hours 4 cycles; in guard reactor B, the volume of catalyzer is 60ml, and calculating guard reactor space utilization efficiency is 71.5%.
Table 1
| A | B | C | |
| Density (20 ℃), kg/cm 3 | 997.5 | 1022 | 943.0 |
| Viscosity (100 ℃), mm 2/s | 181.3 | 10.15 | - |
| Carbon residue, % by weight | 15.1 | 1.4 | - |
| S, % by weight | 4.7 | 1.35 | 0.76 |
| N, % by weight | 0.30 | 0.24 | 0.11 |
| H, % by weight | 10.53 | 8.97 | 9.95 |
| Metal content, μ g/g | |||
| Ni | 29.3 | ||
| V | 83.0 | ||
| Dicyclo and above aromaticity content, % by weight | 84.3 | 78.1 | |
| Cetane value | <20 |
Embodiment 2
According to the method for embodiment 1, process heavy raw oil; different is; heavy raw oil is independent long residuum A; be that the catalytic pyrolysis heavy cycle oil (HCO) that obtains of catalytic pyrolysis cells D and catalytic pyrolysis light cycle oil (LCO) do not return as hydrogenation protecting unit and use as raw material; and the inlet amount of heavy raw oil A is 156g/h; the hydrogen to oil volume ratio of protected location and processing unit is 1000, and all the other conditions are all identical.
Test-results is: take stock oil A as benchmark, can obtain high-value product (ethene+the third rare+butylene+mononuclear aromatics) total recovery is 42.6%.
Comparing embodiment 1 and embodiment 2, can find out that catalytic pyrolysis heavy cycle oil (HCO) and catalytic pyrolysis light cycle oil (LCO) return as hydrogenation protecting unit as raw material freshening, can process the high-value product yield that obtain compared with one way and improve 12 percentage points.
Comparative example 1
Consistent with the flow process of embodiment 1, different, in comparative example 1, guard reactor A is identical with quantity with guard reactor B catalyst type, is RG-30A catalyzer 40mL, RG-30B catalyzer 40ml, RDM-32 catalyzer 40ml; And guard reactor A is identical with the line duration of guard reactor B; And hydrotreatment reaction conditions and catalytic cracking reaction condition are with embodiment 1.
Test-results is: except obtaining returning the catalytic pyrolysis heavy cycle oil (boiling range is 350-520 ℃) of hydrogenation protecting unit and catalytic pyrolysis light cycle oil, (light cycle oil cetane value is less than 20; boiling range is 180-350 ℃) outside, can obtaining high-value product (ethene+the third rare+butylene+mononuclear aromatics) total recovery and be 54.4%(, to take fresh residual oil raw material be that stock oil A quality is benchmark).
Enter hydrogenating materials oil after 1200 hours; the pressure drop of guard reactor A approaches 0.6MPa; then open upstream and downstream valve V-3 and the V-4 of reactor B, meanwhile upstream and downstream valve V-1 and the V-2 of off-response device A, be switched to guard reactor B in parallel and operate.Guard reactor A changes raw catalyst, and loading catalyst kind and loadings are with identical before.After guard reactor B operation moves 1200 hours, pressure drop approaches 0.6MPa, switches to guard reactor A, so repeatedly.
Guard reactor space utilization definitions of efficiency is identical with embodiment 1, and calculating guard reactor utilization ratio is 50%.
Comparative example 2
Consistent with the flow process of embodiment 1, different, comparative example 2 only adopts a guard reactor A, and catalyst loading is RG-30A catalyzer 80mL, RG-30B catalyzer 80ml, RDM-32 catalyzer 80ml, and all the other conditions are all identical.
Enter heavy raw oil after 2600 hours, the pressure drop of guard reactor A approaches 0.6MPa, reaches device transport maximum, and device is stopped work.
By the result of embodiment and comparative example, can find out and adopt method of the present invention, not only can significantly extend the residual hydrogenation equipment operational cycle, and guard reactor utilization ratio significantly improve.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (20)
1. a heavy feed stock oil treatment process, it is characterized in that, the method is carried out in a kind of stock oil treatment unit, described stock oil treatment unit comprises hydrogenation protecting unit, hydrotreating unit and the catalytic pyrolysis unit of series connection successively, described hydrogenation protecting unit comprises main hydrogenation protecting reactor and standby hydrogenation protecting reactor in parallel, and the volume of described main hydrogenation protecting reactor is greater than the volume of described standby hydrogenation protecting reactor; The method comprises:
Under hydrotreatment reaction conditions, heavy raw oil and hydrogen are introduced in described device, and, a plurality of hydrogenation catalyst beds of hydrotreating unit setting contact, obtained gas, hydrotreated naphtha and hydrogenation tail oil with the hydrogenation protecting unit of described device successively;
Described hydrogenation tail oil or vacuum gas oil and the mixing oil of described hydrogenation tail oil are sent in the catalytic pyrolysis unit of described device and contacted with catalytic cracking catalyst;
Wherein, in hydrogenation protecting unit, main hydrogenation protecting reactor and standby hydrogenation protecting reactor are used alternatingly, and the line duration of described main hydrogenation protecting reactor is greater than the line duration of described standby hydrogenation protecting reactor.
2. treatment process according to claim 1, wherein, described heavy raw oil is that residual oil, wax oil, catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil, catalytic cracking slurry oil steam one or more in thing and distillate.
3. treatment process according to claim 2, wherein, described heavy raw oil is that residual oil and catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil and catalytic cracking slurry oil steam one or more the mixing oil in thing.
4. treatment process according to claim 3, wherein, described heavy raw oil contains residual oil and catalytic pyrolysis heavy cycle oil, and the mass ratio of catalytic pyrolysis heavy cycle oil and residual oil is 0.02-0.3:1.
5. treatment process according to claim 2, wherein, described heavy raw oil is that wax oil and catalytic pyrolysis heavy cycle oil, catalytic pyrolysis light cycle oil and catalytic cracking slurry oil steam one or more the mixing oil in thing.
6. treatment process according to claim 5, wherein, described heavy raw oil contains wax oil and catalytic pyrolysis heavy cycle oil, and the mass ratio of catalytic pyrolysis heavy cycle oil and wax oil is 0.02-0.3:1.
7. according to the treatment process described in any one in claim 2-6, wherein, described catalytic pyrolysis heavy cycle oil be catalytic cracking reaction products after distillation, the boiling range obtaining is the product of 350-500 ℃.
8. according to the treatment process described in any one in claim 2-6, wherein, described distillate is one or more among coker gas oil, catalytic cracking light cycle oil, heavy catalytic cycle oil, deasphalted oil, vacuum gas oil and solvent treatment extraction oil.
9. according to the treatment process described in any one in claim 1-6, wherein, the operational condition in the reaction member of described catalytic pyrolysis unit comprises: temperature is 470-650 ℃, and liquid hourly space velocity is 0.4-10h
-1, agent-oil ratio is 3-15.
10. according to the treatment process described in any one in claim 1-6, wherein, the volume ratio of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 1.1-30:1.
11. treatment processs according to claim 10, wherein, the volume ratio of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 1.5-5:1.
12. according to the treatment process described in any one in claim 1-6, and wherein, the ratio of the line duration of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 1.5-20:1.
13. treatment processs according to claim 12, wherein, the ratio of the line duration of described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor is 3-15:1.
14. according to the treatment process described in any one in claim 1-6, and wherein, described main hydrogenation protecting reactor is in line states except the time of catalyst changeout more always.
15. according to the treatment process described in any one in claim 1-6; wherein; according to the flow direction of described heavy raw oil, in described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor, be provided with hydrogenation protecting catalyst bed and/or Hydrodemetalation catalyst bed.
16. treatment processs according to claim 15; wherein; the flow direction according to described heavy raw oil; in described main hydrogenation protecting reactor and described standby hydrogenation protecting reactor, be all disposed with hydrogenation protecting catalyst bed and Hydrodemetalation catalyst bed, and described hydrogenation protecting catalyst is 1:0.1-5 with the admission space ratio of described Hydrodemetalation catalyst.
17. according to the treatment process described in any one in claim 1-6, wherein, according to the flow direction of described heavy raw oil, is disposed with Hydrodemetalation catalyst bed and Hydrobon catalyst bed in described hydrotreating unit.
18. according to the treatment process described in any one in claim 1-6, and wherein, described hydrotreating unit comprises fixed bed residual hydrogenation equipment, and described catalytic pyrolysis unit comprises fluid catalytic cracking device.
19. according to the treatment process described in any one in claim 1-6, and wherein, described hydrotreatment reaction conditions comprises:
In hydrogenation protecting unit: temperature is 320-440 ℃, hydrogen dividing potential drop is 8-20MPa, and hydrogen to oil volume ratio is 300-2000, and liquid hourly space velocity is 0.1-5h
-1;
In hydrotreating unit: temperature is 320-440 ℃, hydrogen dividing potential drop is 8-20MPa, and hydrogen to oil volume ratio is 300-2000, and liquid hourly space velocity is 0.1-2h
-1.
20. according to the treatment process described in any one in claim 1-6; wherein; the method also comprises: the separated reaction product obtaining from described catalytic pyrolysis unit; obtain dry gas, liquefied gas, catalytic pyrolysis petroleum naphtha, catalytic pyrolysis light cycle oil, catalytic pyrolysis heavy cycle oil and slurry oil, described catalytic pyrolysis light cycle oil and/or catalytic pyrolysis heavy cycle oil are returned to hydrogenation protecting unit and as raw material, use.
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