CN104560173B - A kind of heavy oil hydrogenation conversion method - Google Patents
A kind of heavy oil hydrogenation conversion method Download PDFInfo
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- CN104560173B CN104560173B CN201310522927.7A CN201310522927A CN104560173B CN 104560173 B CN104560173 B CN 104560173B CN 201310522927 A CN201310522927 A CN 201310522927A CN 104560173 B CN104560173 B CN 104560173B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
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- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of heavy oil hydrogenation conversion method, comprises the following steps: (1) exists hydrogen, and under conditions of presence or absence faces hydrogen hot cracking catalyst, heavy oil enters the first reactor, carries out facing hydrogen heat cracking reaction；(2) product of the first reactor is separated into light distillate, heavy distillate and residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen enters the second reactor, carry out at a lower temperature facing hydrogen heat cracking reaction；(4) second reactor reaction product isolated light distillates, heavy distillate and residual oil；(5) described heavy distillate enters fixed bed reactors, contacts with hydrocracking catalyst, carries out hydrocracking reaction and obtain light oil under hydrocracking condition；Wherein the reaction temperature of the second reactor is lower than the reaction temperature of the first reactor 5～50 DEG C.Compared with prior art, the method that the present invention provides significantly improves heavy oil conversion ratio and yield of light oil, improves the lightweight rate of heavy distillate.
Description
Technical field
The present invention relates to a kind of heavy hydrocarbon oil raw material modification group technology, more precisely a kind of will face hydrogen thermal cracking,
Distillation and the integrated method converting heavy charge of fixed bed hydrogenation process.
Background technology
Along with crude oil extraction constantly become weight, market light-weight fuel oil demand is continuously increased and environmental requirement day by day
Improving, residual oil weight-lightening technology is increasingly paid close attention to by each refinery.Residual oil weight-lightening method has hot-working and catalysis processing two big classes.
CN101463267A patent discloses one and utilizes visbreaking to carry out processing heavy oil, it is achieved the side of heavy oil lighting
Method, the method be visbreaking raw material is first carried out decompression distillation obtain heavy distillate and > decompression residuum of 540 DEG C, then will heavily follow
Ring oil first carry out visbreaking then by its with > 540 DEG C of decompression residuum mix at Fractionator Bottom, mixed material carries out visbreaking again and splits
Change.The method can improve visbreaking conversion ratio, improves viscosity and the stability of visbreaking residue, but heavy oil lightweight conversion ratio is relatively
Low, only 10～30%.Patent CN101724450A discloses after a kind of hydrogen supply agent and residual oil mixing in pressure 15～40MPa, temperature
Coprocessing 0.2～the method for modifying of 5 hours under the conditions of spending 300～500 DEG C, in the method, hydrogen supply dissolvent can give coking in heavy oil
The cracking reaction of precursor provides hydrogen, prevents its coking；Inferior raw material can be processed, and coking yield is relatively low.
Hot-working has the advantage that adaptability to raw material is strong, but its residual oil cracking conversion ratio is low, and yield of light oil is low.Catalysis adds
Work utilizes catalyst degradation cracking reaction activation energy, improves cracking reaction speed, improves residual oil cracking conversion ratio and light oil is received
Rate.CN101993723A discloses a kind of modifying low-quality heavy oil method and apparatus, and it relies on catalytic cracking unit, arranges inferior heavy
Oil reforming reactor, utilizes carbon deposit reclaimable catalyst to form the modifying low-quality heavy oil technique of fluidisation state, this technique as heat carrier
Can improve Cherry P process yield of light oil, but its be only suitable for low heavy metal (Ni+V) content inferior heavy oil raw material two
Secondary processing.US5300212 discloses a kind of inferior heavy oil hydrogenation modifying process method, and the method is heavy oil feedstock, hydrogen and urges
Agent realizes converting in two reactors, concrete grammar be raw oil and disperse type catalyzer that molybdenum phosphate is precursor advanced
Enter first slurry bed system hydrogenation reactor, under the conditions of 343～482 DEG C, 50～5000psi, carry out conversion reaction, product
Second boiling bed hydrogenation reactor is entered, in 343～399 DEG C, 800～4000psi, loaded catalyst effect after separated
Under convert, product enters distillation column, obtains<524 DEG C fractions and>524 DEG C of fractions, and wherein<524 DEG C of fractions are as product
Product, > 524 DEG C of heavy distillat loop back second reactor.This process can realize the modification of inferior heavy oil, but the method first
Individual reactor uses disperse type catalyzer, second reactor to use loaded catalyst, the catalysis that first reactor is taken out of
Agent granule easily blocks duct or the active center of covering catalyst of second reactor heavy-load catalyst, causes catalysis
The inactivation of agent, affects the operation cycle of whole process.
Heavy oil architecture, form extremely complex, its different structure unit, different component lighting path and needs anti-
Answer condition different, for being easier to the conversion component such as component containing chain alkyl, cyclic alkyl structure, cracking reaction only occurs
Realize lighting；And for aromatic ring structure, especially condensed-nuclei aromatics then needs aromatic ring first saturated recracking just can realize aromatic ring
The minimizing of number, the lighting of condensed-nuclei aromatics.Therefore, if reacted under identical reaction conditions, necessarily it is difficult to reach relatively
Good modification effect.
Summary of the invention
The technical problem to be solved in the present invention is to convert character difference, on the basis of prior art for the various component of heavy oil
On, use the method volume increase light ends oil that the heavy oil of double-reaction area faces hydrogen thermal cracking and is hydrocracked combination.
A kind of heavy hydrocarbon oil hydrogenating conversion process, including, there is hydrogen in (1), presence or absence faces hydrogen thermal cracking catalysis
Under conditions of agent, heavy oil enters the first reactor, carries out facing hydrogen heat cracking reaction under cracking conditions；(2) react first
The product of device is separated into light distillate, heavy distillate and residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen enter
Second reactor, carries out facing hydrogen heat cracking reaction at a lower temperature；(4) second reactor reaction product isolated light fractions
Oil, heavy distillate and residual oil, residual oil loops back the second reactor；(5) described heavy distillate enters fixed bed reactors, with hydrogenation
Cracking catalyst contacts, and carries out hydrocracking reaction and obtain light oil under hydrocracking condition；Wherein the second reactor is anti-
Answer temperature lower than the reaction temperature of the first reactor 5～50 DEG C；Pressure ratio first reactor high 2 of the preferably second reactor～
13MPa。。
In the method that the present invention provides, the first described reactor reaction condition is: reaction temperature is 400～480 DEG C, excellent
Selecting 420～460 DEG C, reaction pressure is 0.1～20MPa, preferably 5～12MPa, and volume space velocity is 0.5～3.0h-1, preferably 0.7～
2h-1, hydrogen counterweight oil volume ratio is 0～3000Nm3/m3, preferably 300～1500Nm3/m3, catalyst charge is 0～10000
μ g/g, preferably 100～2000 μ g/g；The second described reactor reaction condition is: reaction temperature is 380～440 DEG C, preferably
400～430 DEG C, reaction pressure is 11～30MPa, preferably 12～25MPa, and volume space velocity is 0.1～2.0h-1, preferably 0.2～
0.8h-1, hydrogen is 500～4000Nm to residual oil volume ratio3/m3, preferably 800～2000Nm3/m3, catalyst charge is 2000
～150000 μ g/g, preferably 5000～60000 μ g/g；The reaction condition of described hydrocracking reactor is: reaction temperature is
370～440 DEG C, reaction pressure is 7～20MPa, and air speed is 0.5～2.0h-1, hydrogen to oil volume ratio be 500～1500Nm3/m3。
In the method that the present invention provides, the described hydrogen hot cracking catalyst that faces is: containing metal constituent element and nonmetal constituent element,
On the basis of the gross weight of catalyst, this catalyst contains the metallic element of 2-15 weight % and the nonmetal unit of 85-98 weight %
Element, wherein, on the basis of the weight of metallic element, described metallic elements more than 95 weight % is V, Ni and lanthanide series metal unit
Element and/or group VIB metallic element；On the basis of the weight of nonmetalloid, described nonmetalloids more than 95 weight % is
C and S, possibly together with a small amount of H and N, and at least part of described S deposits with the sulphided form of this metallic element with described metallic element
?.
Compared with prior art, having the beneficial effect that of the method that the present invention provides
The method that the present invention provides will be faced hydrogen thermal cracking unit, separative element and the combination of fixed bed hydrogenation Cracking Unit and will be used for
Convert heavy oils into as light ends oil, flexible operation.Facing two reactions that hydrogen thermal cracking unit employing reaction severity is different
Device, the first reactor realizes easily converting in heavy oil the conversion of component, and the second reactor realizes the difficult component that converts in heavy oil and i.e. contains
The lighting of condensed ring aromatic ring structure component, unconverted to 20～80%, first reactors of the first reactor heavy oil lightweight rate
Heavy distillat enter second reactor continue reaction, by wherein strengthening differential responses, the weight of two reactors in differential responses
The total lightweight rate of oil reaches 80～100%.Significantly improve heavy oil conversion ratio and yield of light oil.Face hydrogen thermal cracking process by
After one reactor reaction product separation, heavy distillate enters the second reactor and unconverted residual oil loops back the second reactor and can increase
Second reactor heavy distillate concentration and face hydrogen hot cracking catalyst reserve, improves the lightweight rate of heavy distillate.
Accompanying drawing explanation
The schematic flow sheet of the method for catalytic conversion of heavy oil that accompanying drawing 1 provides for the present invention；
Wherein: HR1 is the first reactor, HR2 is the second reactor, and D1, D2 are separation equipment, and HR3 is fixed bed hydrogenation
Cracking Unit；1 is the first reactor feedstocks pipeline, and 3 is the second reactor catalyst pipeline, and 4 is hydrogen gas lines, and 2,5～16 are
Material pipeline.
Accompanying drawing 2 is the SEM photograph facing hydrogen hot cracking catalyst A2；
Accompanying drawing 3 is the SEM photograph facing hydrogen hot cracking catalyst A3；
Accompanying drawing 4 is the SEM photograph facing hydrogen hot cracking catalyst A5.
Detailed description of the invention
Hereinafter the detailed description of the invention of the present invention is described in detail.It should be appreciated that described herein specifically
Embodiment is merely to illustrate and explains the present invention, is not limiting as the present invention.
The heavy oil hydrogenation conversion method that the present invention provides, including: under conditions of (1) exists hydrogen, presence or absence is faced
Under conditions of hydrogen hot cracking catalyst, heavy oil feedstock enters the first reactor, carries out facing hydrogen thermal cracking anti-under cracking conditions
Should；(2) product facing hydrogen thermal cracking the first reactor is separated into light distillate, heavy distillate and residual oil；(3) residual oil with
Face hydrogen hot cracking catalyst, hydrogen enters the second reactor, carries out facing hydrogen heat cracking reaction under lower temperature, elevated pressures；
(4) second reactor reaction product isolated light distillates, heavy distillate and residual oil, residual oil loops back the second reactor；(5)
Described heavy distillate enters fixed bed reactors and contacts with hydrocracking catalyst, is hydrocracked under hydrocracking condition
Reaction；Wherein the reaction temperature of the second reactor is lower than the reaction temperature of the first reactor 5～50 DEG C, the pressure of the second reactor
Pressure high 2～13MPa than the first reactor.
In the method that the present invention provides, described heavy oil feedstock refers to boiling range in crude oil > fraction of 500 DEG C, or density is big
In 1.0g/cm3Or the petroleum hydrocarbon oil that metal (Ni+V) content is more than 200 μ g/g, raw material obtains selected from heavy crude, crude distillation
Residue oil, catalytic cracked oil pulp, coal tar, ethylene bottom oil, shale oil, viscous crude, oil sands bitumen, fixed bed and boiling bed residual oil
The various heavier feeds produced in hydrogenation tail oil, coal liquefaction tail oil and refinery's production process.
In step (1), the operating condition of the first reactor is: reaction temperature is 400～480 DEG C, preferably 420～460 DEG C,
Reaction pressure is 0.1～20MPa, preferably 5～12MPa, and volume space velocity is 0.5～3.0h-1, preferably 0.7～2.0h-1, hydrogen pair
Fresh feed volume ratio is 0～3000, preferably 300～1500.
Step (1) can add or be added without facing hydrogen hot cracking catalyst, preferably add and face hydrogen hot cracking catalyst, urge
Agent addition is 0～10000 μ g/g, preferably 100～2000 μ g/g.The described hydrogen hot cracking catalyst that faces consists of containing 2-
V, Ni of 15 weight % and lanthanide element and/or group VIB metal and C, S of 85-98 weight % and a small amount of H and N, and
S therein exists with the sulphided form of this metallic element with metallic element, the described average particle facing hydrogen hot cracking catalyst
Footpath is 0.01～200 micron, preferably 0.5～50 micron.The described microstructure facing hydrogen hot cracking catalyst is preferably lamella
Accumulation body, minimum unit body lamella length dimension is 40nm～50nm, thickness 1nm～20nm.
Step (1) carries out pretreatment to heavy oil feedstock, it is achieved the lighting of easy Cracking Component in heavy oil system.Step (1)
Controlling heavy oil lightweight rate is 20～80%, preferably 30～70%, further preferably 40～60%.Described lightweight rate refers in raw material >
500 DEG C of fractions be converted into < mass yield of 500 DEG C of fractions, computing formula is=(500 DEG C+yield/raw material 500 DEG C in 1-product+
Content) × 100.According to the corresponding relation between feedstock property and reaction condition, (reaction temperature, stop by adjusting reaction condition
Stay the time) control heavy oil lightweight rate, the lightweight rate of heavy oil such as can be improved in raising reaction temperature and the time of staying.
In the method that the present invention provides, step (2) is that the product to the first reaction zone separates, and can be that heat is high
Point, low point of heat, cold high score, cold low point, flash distillation, air-distillation, the combination of one or more separate modes such as decompression distillation, mainly
Be be divided into light distillate, heavy distillate and residual oil, wherein said double distilled to be divided into boiling point the product of step (1) < 500 DEG C evaporate
Point, preferably boiling point < 480 DEG C of fractions.
In the method that the present invention provides, step (3), in the second reactor, at hydrogen, faces the existence of hydrogen hot cracking catalyst
In lower heavy oil, the condensed-nuclei aromatics of more difficult conversion is hydrogenated with lighting further, and the operating condition of the second reactor is: reaction temperature is
380～440 DEG C, preferably 400～430 DEG C, reaction pressure is 11～30MPa, preferably 12～25MPa, volume space velocity be 0.1～
2.0h-1, preferably 0.2～0.8h-1, hydrogen is 500～4000, preferably 800～2000 to fresh feed volume ratio.Second reaction
District's reaction temperature is lower than the first reaction zone 5～50 DEG C, the pressure high 2～13MPa of pressure ratio first reactor of the second reactor.
Adding in second reactor and face hydrogen hot cracking catalyst, the described hydrogen hot cracking catalyst that faces can be with the first reaction
In device to face hydrogen hot cracking catalyst identical or different.The described addition facing hydrogen hot cracking catalyst is relative to the second reaction
Residual oil raw material in device is 2000～150000 μ g/g, preferably 5000～60000 μ g/g.
Step (4) separates the product of the second reactor, can be hot high score, low point of heat, cold high score, cold low point, sudden strain of a muscle
The combination of one or more separate modes such as steaming, air-distillation, decompression distillation, mainly by step (3) to face hydrogen thermal cracking anti-
Answer product be divided into light distillate, heavy distillate and residual oil, wherein said double distilled be divided into boiling point < 500 DEG C of fractions, preferably boiling point <
480 DEG C of fractions, distillation range of residual oil is > 524 DEG C of fractions.Isolated residual oil loops back and continues reaction in the second reactor.
Preferably will get rid of outside isolated for step (4) a small amount of residual oil, get rid of outward amount is total residual oil the 10～6wt% of residual oil；Remaining
Residual oil loops back and continues reaction in the second reactor.
Step (5) is that the heavy distillate of isolated in step (2) and step (4) is introduced fixed bed hydrogenation cracking reaction
In device, carrying out hydrocracking reaction, load hydrocracking catalyst in fixed bed reactors, described hydrocracking catalyst is
It is made up of the metal sulfide of molecular sieve, heat-resistant inorganic oxide, and group vib and/or VIII.Hydrocracking reactor
Operating condition is: reaction temperature is 370～440 DEG C, and reaction pressure is 7～20MPa, and volume space velocity is 0.5～2.0h-1, hydrogen oil
Volume ratio is 500～1500Nm3/m3。
In the method that the present invention provides, the product of the first described reactor and the product of the second reactor separate and can be total to
Use a set of separation equipment, it is also possible to be respectively adopted different separation equipments.Preferably share same set of separation equipment.Same when using
During set separation equipment, isolating light distillate, heavy distillate and residual oil, get rid of outside residual fraction, remaining residual oil introduces the second reaction
Device carries out facing hydrogen heat cracking reaction at a lower temperature；Heavy distillate enters fixed bed reactors and carries out hydrocracking reaction.Its
In, the boiling range of light fraction is initial boiling point～200 DEG C, and the boiling range of described heavy distillat is 200 DEG C～500 DEG C, and described residual oil is
Boiling point > fraction of 500 DEG C.
When using different separation equipments, in step (2), the first reactor product is separated into light distillate, heavy distillate
And residual oil, wherein the boiling range of light distillate is: initial boiling point～200 DEG C, and the boiling range of heavy distillate is 200～420 DEG C, evaporating of residual oil
Journey is boiling point > fraction of 420 DEG C.In step (4), the second reactor product is separated into light distillate, heavy distillate and residual oil, its
The boiling range of middle light fraction is initial boiling point～200 DEG C, and the boiling range of described heavy distillat is 200 DEG C～524 DEG C, and described residual oil is boiling
Point > fraction of 524 DEG C.
In the method that the present invention provides, preferably two are faced hydrogen thermal cracking reactor and share a set of separation equipment, can realize
Reduce investment outlay on the premise of separation function.
The wherein said hydrogen hot cracking catalyst that faces faces hydrogen modifying catalyst for a kind of heavy oil, with the gross weight of catalyst is
Benchmark, this catalyst contains metallic element and the nonmetalloid of 85-98 weight % of 2-15 weight %, wherein, with metallic element
Weight on the basis of, described metallic elements more than 95 weight % is V, Ni and lanthanide element and/or group VIB metal
Element；On the basis of the weight of nonmetalloid, described nonmetalloids more than 95 weight % is C and S, and at least partly institute
State S to exist with the sulphided form of this metallic element with described metallic element.Described group VIB metallic element can be any
Group VIB metallic element, such as at least one in Cr, Mo and W, it is preferable that described group VIB metallic element is Mo and/or W,
Described lanthanide series metal is preferably at least one in La, Ce, Pr and Nd.
In the method that the present invention provides, the described hydrogen hot cracking catalyst composition that faces is preferably Mo-Ni-V-La, Mo-Ni-
V-Ce、Mo-Ni-V、W-Ni-V-Ce.On the basis of the gross weight of catalyst, in described catalyst, the content of V is 0.1-5.0 weight
The content of amount %, Ni is 0.05-4.0 weight %, and the content of lanthanide element is 0-5.0 weight %, group VIB metallic element
Content is 0-15.0 weight %, and the total content of lanthanide element and group VIB metallic element is 1-20 weight %.
The described mean diameter facing hydrogen hot cracking catalyst is 0.01～200 micron, preferably 0.5～50 micron.More excellent
The microgranular microstructure facing hydrogen hot cracking catalyst of choosing is preferably lamella packed structures, and described lamella length dimension is 40
Nanometer～50 nanometers, thickness 1 nanometer～20 nanometers.Face the employing of hydrogen hot cracking catalyst and preferably employ the little particulate catalytic of sheet
Agent, has the effect that catalyst loading is few, heavy oil conversion ratio high, distillate yield is high.
In the method that the present invention provides, the described preparation method facing hydrogen hot cracking catalyst includes: by source metal and non-
Source metal in the presence of solvent and under the conditions of vulcanization reaction with sulfurizing agent, obtain facing hydrogen hot cracking catalyst.Wherein, institute
Stating source metal is that described non-metal source is for containing containing V, Ni and lanthanide element and/or the material of group VIB metallic element
After having the material of carbon, described source metal, non-metal source to make to contact with the consumption of vulcanizing agent, gained solid product contains
The metallic element of 2-15 weight % and the nonmetalloid of 85-98 weight %, and on the basis of the weight of metallic element, 95 weight %
Above described metallic element is V, Ni and lanthanide element and/or group VIB metallic element；Weight with nonmetalloid
On the basis of amount, described nonmetalloids more than 95 weight % is C and S.
Described source metal can provide in any suitable form, as with the Organic substance of metallic element in this source metal and/
Or the form of inorganic matter provides, it is preferable that as with in oxide, inorganic salt, acylate and the organic chelate of metallic element
The form of at least one provides, and specifically, the inorganic salt of described metallic element can be nitrate, sulfate, hydrochlorate and carbon
At least one in hydrochlorate, or be the oxysalt of this metallic element, such as tungstates, molybdate, having of described metallic element
Machine hydrochlorate can be oleate, naphthenate and more specifically, such as molybdenum dialkyl-dithiophosphate, nickel carbonyl and six carbonyls
Vanadium etc., described organic chelate can be such as the polycomponent coordination compound of metal in source metal, its ligand include six teeth, eight
Tooth or ten tooth parts, these parts include but not limited to following compound: EDTA, DTPA, EDPA.
Described non-metal source can provide with the form of any material of carbon elements, as described non-metal source can be with former
In oil, heavy oil, oil sands bitumen, asphalitine, white carbon black, graphite powder, coal dust, coke and activated carbon, the form of at least one provides.
More uniform in order to make source metal and non-metal source mix, described contact is carried out the most under agitation, stirs
Mix speed 300～1200rpm, and the condition of described contact makes after contact the sulfide shape of metallic element in gained solid product
It is the granule of 5-50 nanometer sized by one-tenth, preferably 10-30 nanometer.
When described activated carbon is through the activated carbon of peracid treatment, it is possible to obtain the catalyst of more preferable catalytic effect.Excellent
Selection of land, the method for described process activated carbon includes the methods such as deionized water wash, salt acid elution and nitric acid oxidation.
Being added to of described solvent makes reaction system evenly, when non-metal source is liquid, can have concurrently simultaneously
The function of solvent, it is therefore preferred that described non-metal source can be together with solvent, jointly with crude oil, distillate, residual oil and thick
In oil, the form of at least one provides.And when non-metal source is solid-state, the addition of described solvent can also be in very wide range
Interior change, such as, described solvent can be 10-1000:1, preferably 20-200:1 with the weight ratio of metallic element in source metal,
More preferably 20-100:1
The vulcanization reaction condition and the vulcanizing agent that use this area routine can realize the present invention, it is preferable that described vulcanizing agent
For at least one in Sublimed Sulfur, Carbon bisulfide, high-sulfur heavy oil, mercaptan and dimethyl sulfide；The condition bag of described vulcanization reaction
Including, temperature is 250-400 DEG C, and pressure is 5.0-10.0MPa, and the time is 15-480 minute, stir speed (S.S.) 300～1200rpm；Enter
One step is preferably, and the condition of described vulcanization reaction includes, temperature is 300-380 DEG C, and pressure is 6.0-8.0MPa, and the time is 30-
240 minutes, most preferably 60-240 minute, stir speed (S.S.) 500～1000rpm.Wherein, described pressure is hydrogen first pressing.This is prepared
Raw material can be prepared by method and need to be aged 0～36h, preferably 1～24h.
Under preferable case, the described preparation method facing hydrogen hot cracking catalyst also includes removing in reacted product
Solvent, e.g., when described solvent is water, preferably reacted product is filtered.When described solvent is solvent naphtha, this
The method of invention the most also includes being stripped reacted product with toluene, and the purpose of extracting is to remove solvent naphtha therein
And the unreacted Organic substance of part in non-metal source.
In the method that the present invention provides, described microstructure is the preparation side facing hydrogen hot cracking catalyst that lamella is piled up
Method is: by being dissolved in organic solvent containing the organo-metallic compound of W metal, V, VI race and lanthanide series metal, be subsequently adding sulfuration
Agent, flowable carbonaceous material, and stir 10min～30min at 600rpm～1000rpm rotating speed, it is aged 12～16 hours, so
After be rapidly heated to curing temperature and carry out vulcanization reaction, conditions of vulcanization is that temperature is 350-360 DEG C, and pressure is 6.0-8.0MPa,
Time is 60-80 minute.
Below in conjunction with the accompanying drawings 1, illustrate the method that the present invention provides, but the present invention is the most therefore and by any limit
System.
The schematic flow sheet of the mink cell focus catalysis conversion method that Fig. 1 provides for the present invention, as it is shown in figure 1, heavy oil or heavy oil
Enter the first reactor HR1 through the first reactor feedstocks pipeline 1 after premixing with hydrogen, there is hydrogen, adding or be added without facing
React under conditions of hydrogen hot cracking catalyst, in the first reactor HR1, realize heavy oil easily converts the lighting of component；
The product of the first reactor enters separation equipment D1 through pipeline 2 and is separated into light distillate, heavy distillate and residual oil；Wherein,
Light distillate removes reaction system through pipeline 8 as product.Residual oil gets rid of outside pipeline 12 through pipeline 10 discharging, a small amount of residual oil, its
Recrement oil through pipeline 11 with from pipeline 3 face hydrogen hot cracking catalyst, hydrogen from pipeline 4 mixs homogeneously to enter through pipeline 5
Enter the second reactor HR2, carry out facing hydrogen heat cracking reaction in the second reactor HR2, it is achieved heavy oil more difficult conversion component i.e. contains
There is the lighting of condensed ring aromatic ring structure component；The product of the second reactor HR2 separates in pipeline 7 enters separation equipment D1
For light distillate, heavy distillate and residual oil.It is anti-that heavy distillate from separation equipment D1 enters fixed bed hydrogenation cracking through pipeline 9
Answer device HR3, depositing in the case of hydrogen, contact with hydrocracking catalyst and carry out hydrocracking reaction, hydrocracking reaction
Product, through pipeline 14 discharging, enters fractional distillation in separation equipment D2 and produces light oil.Wherein, the first reactor reaction product and second
Reactor reaction product shares a set of separation equipment D1.
Illustrate, below by embodiment, the method that the present invention provides, but the present invention is the most therefore and by any limit
System.
In embodiment and comparative example, the heavy oil feedstock of employing takes from Tahe oil plant, and its character is shown in Table 1.Can from table 1
Seeing, heavy oil feedstock density is big, and hydrogen-to-carbon ratio is low, and carbon residue is up to 25.9wt%, and asphalt content is up to 21wt%, tenor
Height, belongs to the reluctant inferior raw material of generally conventional method for modifying.
The hydrogen hot cracking catalyst that faces in embodiment uses following methods to prepare:
In autoclave, by 5.89g ammonium molybdate ((NH4)6Mo7O24·4H2O), 7.40g nickel nitrate (Ni (NO3)2·
6H2O), 1.78g vanadium oxide (V2O5), 4.8g Lanthanum (III) nitrate (La (NO3)3·6H2O), mix with 300mL water, be stirring evenly and then adding into
81.2g is successively the vulcanizing agent (Sublimed Sulfur) of the hydrochloric acid of 2mol/L and the activated carbon of nitric acid treatment and 7.8g through over-richness,
Under 300rpm rotating speed stir 30min, be aged 8h, then 300 DEG C, 7.0MPa(hydrogen first pressing), the bar of high-speed stirred (300rpm)
Vulcanizing 120min under part, product is listed in table 1 through the elementary composition analysis filtering, obtaining after drying catalyst A1, catalyst A1.Grain
Degree measurement result shows that the mean diameter of catalyst A1 is 10 μm, and tem analysis result shows, the average particle of metallic element sulfide
Footpath is 45nm.
By 43.7g molybdenum naphthenate (Mo accounts for 10.3 weight %), 30.8g aphthenic acids tungsten (W accounts for 8.78 weight %), 6.2g tetra-carbonyl
Nickel (Ni accounts for 33.73 weight %), 6.5g Vanadium hexacarbonyl. (V accounts for 23.29 weight %), 25.3g isooctoate of rare earth metal (La accounts for 4.8 weight %,
Ce accounts for 7.1 weight %), the residual oil (Kuwait's decompression residuum) of 17.7g vulcanizing agent (DMDS) and 295mL be sequentially added into the height of 500mL
Pressure still in, under 800rpm rotating speed stir 30min, be aged 14h, then stir 370 DEG C, 6.0MPa(hydrogen first pressing), high-speed stirring
Mixing and vulcanize 60min under conditions of (800rpm), product is performing centrifugal separation on, toluene extract, be vacuum dried and obtain catalyst A2, is catalyzed
The elementary composition of agent A2 is listed in table 1.Granulometry result shows that the mean diameter of catalyst A2 is 1 μm, tem analysis result table
Bright, the mean diameter of metallic element sulfide is 20nm, and accompanying drawing 2 is the stereoscan photograph of catalyst A2, shows catalyst A2
Pattern is the stratiform accumulation body of lamellar structure, and lamellar structure a length of 60～100nm, thickness is 2～10nm.
By 5.7g molybdenum dialkyldithiocarbamacompositions (Mo content 8.7%), 3.6g nickel octoate, 2.9g aphthenic acids vanadium, 2.8g
Aphthenic acids praseodymium, 100mL recycle oil, 5.6g vulcanizing agent (Sublimed Sulfur) and 88g crude oil are added sequentially in 500mL autoclave,
Stir 45min under 1000rpm rotating speed, be aged 16h, then 350 DEG C, 8.0MPa(hydrogen first pressing), high-speed stirred (1000rpm)
Under the conditions of vulcanize 80min, product obtains the elementary composition of catalyst A3, catalyst A3 be listed in table 1 through filtering, after vacuum drying.
Granulometry result shows, the mean diameter of catalyst A3 is 0.5 μm, and tem analysis result shows, putting down of metallic element sulfide
All particle diameters are 10nm, and accompanying drawing 3 is the stereoscan photograph of catalyst A3, and display catalyst A3 pattern is the stratiform heap of lamellar structure
Long-pending body, lamellar structure a length of 40～50nm, thickness is 2～10nm.
By 30.4g molybdenum dialkyl-dithiophosphate (Mo accounts for 5.7 weight %), (Ni accounts for 33.73 weights to 30.4g nickel carbonyl
Amount %), 6.5g Vanadium hexacarbonyl. (V accounts for 23.29 weight %), 28.2g cerium naphthenate (Ce accounts for 8.6 weight %), 4.9g vulcanizing agent (distillation
Sulfur), the solvent naphtha (hydrogenated diesel oil) of 200mL and 57.2g heavy oil asphalt matter (Qing Chuan 3# bitumen, C content 88.9%, H content
7.2%, S content 5.8%, N content 1.1%) it is added sequentially in the autoclave of 500mL, stir 20min, ageing under 300rpm rotating speed
4h, then 350 DEG C, 8.0MPa(hydrogen first pressing), vulcanize 210min under conditions of high-speed stirred (500rpm), product divides by centrifugation
Obtain the elementary composition of catalyst A4, catalyst A4 be listed in table 1 from the extracting of, toluene, vacuum drying.Granulometry result shows to urge
The mean diameter of agent A4 is 5 μm, and tem analysis result shows, the mean diameter of metallic element sulfide is 12nm.
By 30.4g aphthenic acids tungsten (W accounts for 8.78 weight %), 30.4g nickel carbonyl (Ni accounts for 33.73 weight %), 6.5g six carbonyl
Base vanadium (V accounts for 23.29 weight %), 28.2g cerium naphthenate (Ce accounts for 8.6 weight %), 4.9g vulcanizing agent (Sublimed Sulfur), 200mL return
Oil refining and 57.2g petroleum coke, be added sequentially in the autoclave of 500mL, stirs 20min under 500rpm rotating speed, is aged 2h, then
350 DEG C, 8.0MPa(hydrogen first pressing), vulcanize 210min under conditions of high-speed stirred (500rpm), product is performing centrifugal separation on, toluene
Extracting, vacuum drying obtain the elementary composition of catalyst A5, catalyst A5 and are listed in table 1.Granulometry result shows, catalyst is put down
All particle diameter 20 μm, the mean diameter of tem analysis result display metallic element sulfide is 50nm.What accompanying drawing 4 was catalyst A5 sweeps
Retouching electromicroscopic photograph, the pattern of display catalyst A5 is microspheroidal.
Face hydrogen hot cracking catalyst composition and be shown in Table 2.Wherein, in catalyst the content of various elements by X-ray fluorescence spectra
Method records, and is measured the valence state of element by X-ray energy spectrum, judges the existence form of metallic element in catalyst according to result；
The mean diameter of catalyst is measured by laser particle size analyzer, and the mean diameter of sulfide is by high-resolution scanning and transmission
Electronic microscope photos obtains.
The catalyst that hydrocracking process uses is the ICR-117(NiW catalyst containing molecular sieve of Chevron company).
The lighting effect of the method for catalytic conversion of heavy oil that the embodiment 1-7 explanation present invention provides.
Embodiment 1
As shown in Figure 1, heavy oil feedstock, by being pumped into preheating furnace, enters first anti-to the device flow process used after preheating
Answering device to react, the product of the first reactor enters separation equipment D1 and is separated into light distillate, heavy distillate and residual oil,
Light distillate removal response system, heavy distillate removes follow-up fixed bed hydrogenation reactor HR3, and residual oil is catalyzed with facing hydrogen thermal cracking
Agent A1, hydrogen enter the second reactor and carry out facing hydrogen heat cracking reaction, and the product of the second reactor enters separation equipment D1,
Isolating light distillate, heavy distillate and residual oil, remaining residual oil loops back the second reactor；Heavy distillate and hydrogen enter fixing
Bed reactor HR3, contacts with hydrocracking catalyst ICR-117, carries out hydrocracking reaction and generates light oil.Plant running 4
Hour post-sampling analysis measures toluene insolubles content and boiling range in fixed bed hydrogenation cracker product, according to reaction
The cracking rate of<500 DEG C of distillate yields calculate in heavy oil feedstock>500 DEG C of residual oil, toluene insolubles yield in product simulation distillation
It is defined as process coking yield.Operating condition is shown in Table 3, and reaction result is listed in table 4.Coke forming property generates toluene insoluble in oil to measure
Thing content is weighed.
Embodiment 2
The device used and flow process are with embodiment 1, except that get rid of outside the residual fraction of separation equipment D1 isolated,
Remaining residual oil and face hydrogen hot cracking catalyst A2 and enter and face hydrogen heat cracking reaction in the second reactor, operating condition is shown in Table 3, reaction
Result is listed in table 4.
Embodiment 3
The device used and flow process are with embodiment 2, except that heavy oil feedstock, hydrogen and face hydrogen hot cracking catalyst A1
Enter the first reactor after preheated to carry out facing hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 4
The device used and flow process are with embodiment 3, except that from the residual oil of separation equipment D1 with face hydrogen thermal cracking
Catalyst A3 enters and faces hydrogen heat cracking reaction in the second reactor, and operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 5
The device used and flow process are with embodiment 3, except that heavy oil feedstock, hydrogen and face hydrogen hot cracking catalyst A2
Enter the first reactor after preheated to carry out facing hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 6
The device used and flow process are with embodiment 4, except that heavy oil feedstock, hydrogen and face hydrogen hot cracking catalyst A2
Enter the first reactor after preheated to carry out facing hydrogen heat cracking reaction.Operating condition is shown in Table 3, and reaction result is listed in table 4.
Embodiment 7
The device used and flow process are with embodiment 5, except that from the residual oil of separation equipment D1 with face hydrogen thermal cracking
Catalyst A4 enters and faces hydrogen heat cracking reaction in the second reactor.Operating condition is shown in Table 3, and reaction result is listed in table 4.
The effect of heavy oil lightening method in comparative example 1-2 explanation prior art.
Catalyst B preparation method: by 10g iron naphthenate (Fe content 12%), it is former that 4g vulcanizing agent (Sublimed Sulfur) joins heavy oil
In material, being directly warming up to reaction temperature, iron naphthenate decomposes in temperature-rise period, vulcanizes, generates catalyst B, catalyst B online
Consist of Fe-20%, S-22.8%, C-57.2%.Results of grain size analysis display catalyst B mean diameter is 100 μm；In Electronic Speculum
Lower observation, catalyst B is spherical in shape, and the mean diameter of iron sulfide is～1 μm.
Comparative example 1
Use batch reactor, disperse type catalyzer B.By heavy oil feedstock and iron naphthenate (Fe content 12%), vulcanizing agent
(Sublimed Sulfur), hydrogen enter batch reactor together and react, and the separated equipment of product is divided into gas, liquid and consolidates
Body, product liquid obtains<500 DEG C distillates and>500 DEG C of unconverted heavy oil yields through gas chromatographic analysis.
Comparative example 2
Carrying out facing hydrogen heat cracking reaction by heavy oil feedstock, catalyst B, product is separated, and light fraction removal reaction is
System, heavy distillat enters follow-up hydrocracking reactor and carries out hydrocracking reaction, residual oil, fresh residual oil after primary first-order equation, urges
Agent B and hydrogen carry out second time and face hydrogen heat cracking reaction, twice product are collected, calculate slag oil cracking and turn
Rate, distillate yield and coking yield.Reaction condition and reaction result are listed in table 5.
Data from table 3-5 it can be seen that use the present invention tail oil part circulation double-reaction area heavy oil modification technique,
Can increase second reaction zone catalyst inventory, be greatly improved heavy oil conversion ratio and distillate yield, additionally heavy distillate enters to add
Hydrogen cracking unit volume increase light-weight fuel oil, embodiment 1,2 is that the most thermally treated the making of residual oil raw material easily converts component conversion realization turn
Rate 25%～40%, then convert further in second reaction zone, heavy distillate enters hydrocracking unit, finally realizes ＜
500 DEG C of product yields > 67%, > 500 DEG C of slag oil cracking conversion ratios > 63%, light oil (petrol and diesel oil) yield > 60%, toluene insolubles
Yield < 0.7%；Comparing the conventional single reaction district reaction result of comparative example 1,500 DEG C of product yields of ＜ improve 3 percentage points, >
500 DEG C of slag oil cracking conversion ratios improve 3 percentage points, and toluene insolubles yield declines 8 percentage points, and yield of light oil improves
24 percentage points.
Embodiment 3 is compared comparative example 2(and is used conventional catalyst double-reaction area thermal response), 500 DEG C of product yields of ＜ improve
10 percentage points, > 500 DEG C of slag oil cracking conversion ratios improve 10 percentage points, and light oil (petrol and diesel oil) yield improves 35
Percentage point, toluene insolubles yield declines 4 percentage points.
500 DEG C of product yields of ＜ in embodiment 4～7 > 80%, > 500 DEG C of slag oil cracking conversion ratios > 77%, light oil (vapour bavin
Oil) yield>75%,<2%, effect is superior to comparative example 1,2 to toluene insolubles yield.Table 1 heavy oil feedstock character
| Project | Numerical value |
| Density (20 DEG C)/(g cm-3) | 1.0378 |
| W (carbon residue)/% | 25.9 |
| W (element)/% | |
| C | 85.64 |
| H | 10.00 |
| S | 3.1 |
| N | 0.6 |
| W (four components)/% | |
| Saturated point | 15.8 |
| Fragrance point | 37.1 |
| Colloid | 25.7 |
| Asphalitine | 21.4 |
| W (metal)/(μ g g-1) | |
| Ca | 19.1 |
| Fe | 18.3 |
| Ni | 58 |
| V | 395 |
| Simulation distillation boiling range/DEG C | |
| Initial boiling point | 393 |
| 5% | 457 |
| 10% | 486 |
Table 2 catalyst composition data
Table 3
In table, catalyst concn is all in terms of metal.
Table 4
Table 5 comparative example experimental result data
| Comparative example 1 | Comparative example 2 | |
| Operating condition | ||
| First set reaction | ||
| Reaction temperature/DEG C | 440 | 430 |
| Reactive hydrogen first pressing/MPa | 7 | 9 |
| Air speed/h-1 | 1.0 | 1.0 |
| Hydrogen to oil volume ratio/(Nm3/m3) | 1000 | 1200 |
| Catalyst | B | B |
| Catalyst concn (total metal meter)/(μ g g-1) | 500 | 1000 |
| Second time reaction | ||
| Reaction temperature/DEG C | 410 | |
| Reaction pressure/MPa | 10 | |
| Air speed/h-1 | 0.5 | |
| Hydrogen to oil volume ratio/(Nm3/m3) | 1600 | |
| Catalyst | B | |
| Catalyst concn (total metal meter)/(μ g g-1) | 6000 | |
| 500 DEG C of product yield/% of ＜ | 64.0 | 67.6 |
| > 500 DEG C of bottoms conversion/% | 60.6 | 63.5 |
| Toluene insolubles/% | 8.21 | 4.25 |
| Product liquid distribution/% | ||
| Gasoline (C5～180 DEG C) | 9.78 | 10.42 |
| Diesel oil (180～350 DEG C) | 23.58 | 25.81 |
| Cracking tail oil (350～500 DEG C) | 30.64 | 31.37 |
Claims (12)
1. a heavy oil hydrogenation conversion method, it is characterised in that comprise the following steps:
(1) there is hydrogen, under conditions of presence or absence faces hydrogen hot cracking catalyst, heavy oil enters the first reactor, in heat
Carry out under cracking conditions facing hydrogen heat cracking reaction；(2) product of the first reactor is separated into light distillate, heavy distillate
And residual oil；(3) residual oil with face hydrogen hot cracking catalyst, hydrogen enters the second reactor, carry out at a lower temperature facing hydrogen hot tearing
Change reaction；(4) second reactor reaction product isolated light distillates, heavy distillate and residual oil；(5) described heavy distillate enters
Enter fixed bed reactors, contact with hydrocracking catalyst, under hydrocracking condition, carry out hydrocracking reaction obtain lightweight
Oil；Wherein the reaction temperature of the second reactor is lower than the reaction temperature of the first reactor 5～50 DEG C.
2. according to the method for claim 1, it is characterised in that the pressure of pressure ratio first reactor of the second described reactor
High 2～13MPa.
3. according to the method for claim 1 or 2, it is characterised in that the first described reactor operating condition is: reaction temperature is
400～480 DEG C, reaction pressure is 0.1～20MPa, and volume space velocity is 0.5～3.0h-1, hydrogen is 0 to heavy oil volume feed
～3000Nm3/m3, facing hydrogen hot cracking catalyst addition is 0～10000 μ g/g；The second described reactor reaction condition is:
Reaction temperature is 380～440 DEG C, and reaction pressure is 11～30MPa, and volume space velocity is 0.1～2.0h-1, hydrogen is to residual oil raw material
Volume ratio is 500～4000Nm3/m3, facing hydrogen hot cracking catalyst addition is 2000～150000 μ g/g；Described fixed bed
The operating condition of reactor is: reaction temperature is 370～440 DEG C, and reaction pressure is 7～20MPa, volume space velocity be 0.5～
2.0h-1, hydrogen to oil volume ratio be 500～1500Nm3/m3。
4. according to the method for claim 3, it is characterised in that the first described reactor operating condition is: reaction temperature is 420
～460 DEG C, reaction pressure is 5～12MPa, and volume space velocity is 0.7～2h-1, hydrogen to heavy oil volume feed be 300～
1500Nm3/m3, facing hydrogen hot cracking catalyst addition is 100～2000 μ g/g；The second described reactor operating condition is: anti-
Answering temperature is 400～430 DEG C, and reaction pressure is 12～25MPa, and volume space velocity is 0.2～0.8h-1, hydrogen is to residual oil raw material body
Long-pending ratio is 800～2000Nm3/m3, facing hydrogen hot cracking catalyst addition is 5000～60000 μ g/g.
5. according to the method for claim 1 or 2, it is characterised in that described face hydrogen hot cracking catalyst contain metallic element and
Nonmetalloid, on the basis of the gross weight of catalyst, this catalyst contains metallic element and the 85-98 weight of 2-15 weight %
The nonmetalloid of amount %, wherein, on the basis of the weight of metallic element, described metallic elements more than 95 weight % is V, Ni
And lanthanide element and/or group VIB metallic element；On the basis of the weight of nonmetalloid, more than 95 weight %
Described nonmetalloid is C and S, and possibly together with a small amount of H and N, and at least part of described S is first with this metal with described metallic element
The sulphided form of element exists.
6. according to the method for claim 5, it is characterised in that the described mean diameter facing hydrogen hot cracking catalyst be 0.01～
200 microns.
7. according to the method for claim 6, it is characterised in that the described mean diameter facing hydrogen hot cracking catalyst be 0.2～
50 microns.
8. according to the method for claim 6 or 7, it is characterised in that the described microstructure facing hydrogen hot cracking catalyst is sheet
Rotating fields, its length dimension is 20nm～200nm, thickness 1nm～20nm.
9. according to the method for claim 1 or 2, it is characterised in that described step (2) and step (4) use same set of point
From equipment, light distillate, heavy distillate and residual oil will be separated into from the product of step (1) and step (3).
10. according to the method for claim 9, it is characterised in that the boiling range of described light distillate is initial boiling point～200 DEG C, institute
The boiling range of the heavy distillat stated is 200 DEG C～500 DEG C, and described residual oil is boiling point > fraction of 500 DEG C.
11. according to the method for claim 1 or 2, it is characterised in that described hydrocracking catalyst contains heat resistant inorganic oxidation
Thing, molecular sieve, and group vib and VIII metal component.
12. according to the method for claim 1 or 2, it is characterised in that described heavy oil feedstock refers to boiling range in crude oil > 500 DEG C
Fraction, or density is more than 1.0g/cm3Or the petroleum hydrocarbon oil that the content of W metal and V is more than 200 μ g/g.
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| CN103328613A (en) * | 2010-12-24 | 2013-09-25 | 道达尔炼油与销售部 | Method for converting hydrocarbon feedstock comprising a shale oil by hydroconversion in an ebullating bed, fractionation by atmospheric distillation and hydrocracking |
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| US4810361A (en) * | 1987-05-18 | 1989-03-07 | Mobil Oil Corporation | Resid hydrotreating process using lanthana-alumina-aluminum phosphate catalyst |
| CN1952067A (en) * | 2005-10-19 | 2007-04-25 | 中国石油化工股份有限公司 | Two-segment hydrocracking method |
| CN101173189A (en) * | 2006-11-01 | 2008-05-07 | 中国石油化工股份有限公司 | Two-stage hydrogenation cracking method for producing industrial chemicals |
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