CN109486515A - A kind of method and system that poor oil efficiently modifies - Google Patents
A kind of method and system that poor oil efficiently modifies Download PDFInfo
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- CN109486515A CN109486515A CN201710812669.4A CN201710812669A CN109486515A CN 109486515 A CN109486515 A CN 109486515A CN 201710812669 A CN201710812669 A CN 201710812669A CN 109486515 A CN109486515 A CN 109486515A
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
Abstract
The present invention relates to a kind of method and systems that poor oil efficiently modifies, this method comprises: modification raw material is successively heat-treated, after conversion reaction, separating treatment and extraction and separation, obtains modification oil and tailings, get rid of or be recycled back to conversion reaction outside gained tailings.Method and system provided by the invention maintains system to operate for a long time in the case where outer whipping slag is as few as possible, realizes the efficient utilization of low-quality oil and catalytic cracked oil pulp.
Description
Technical field
The present invention relates to a kind of method and systems that poor oil efficiently modifies.
Background technique
In recent years, the in poor quality trend of fossil fuel is aggravated year by year.Moreover, residual oil, crude oil with poor quality, shale oil, oil-sand weight
The yield of oil and the low-rank fuels oil such as coal derived oils also cumulative year after year.The characteristics of this kind of poor oil be density is big, viscosity is big,
Hetero atom (sulphur, nitrogen, heavy metal) content is high or asphalt content is high.In addition, for this kind of poor oil and develop existing plus
That there is coke yields is high for work technique (such as delayed coking), effective utilization rate of energy is low, deficiency in economic performance, production process not ring
The problems such as guarantor.Therefore, efficient, the green modification technology for further developing this kind of poor oil, has become petrochemical industry
One of developing direction and research emphasis.
Chinese patent CN200310104918.2 discloses the method for modifying of a kind of inferior heavy, residual oil, and this method will weight, slag
Oil is first cracked through suspension bed mild hydrogenation, makes most or all of metal impurities separate out from resin and asphalt；Institute
Hydrogenation products are obtained by the changeable metal adsorption reactor operated or filling can be replaced online, adsorbing and removing floating bed hydrogenation is split
The metal impurities to dissociate in solution oil；It is other that product after demetalization is sent into residue fixed-bed hydrotreater deep hydrogenation removing
Impurity produces high-quality Rfcc Feedstock.
United States Patent (USP) US20130112593A1 discloses a kind of heavy crude, distillation residue method for transformation, and this method passes through
Solvent deasphalting, hydrotreating, distillation and gasification are combined and realize the modification of mink cell focus.But this method processes heavy oil residue
Modification oil yield only have 75%~85%, while micro- gram gram of content > 100 metal (Ni+V) in modification oil.
Summary of the invention
The object of the present invention is to provide a kind of method and system that poor oil efficiently modifies, method for modifying provided by the invention
System is maintained to operate for a long time in the case where outer whipping slag is as few as possible with system.
To achieve the goals above, the present invention provides a kind of efficient method for modifying of poor oil, this method comprises:
(1) it is heat-treated poor oil as modification raw material, obtains gas-phase product and liquid product；Wherein, described to change
Matter raw material includes the toluene at least one of asphalitine, asphaltene and preasphaltene asphalt component, the liquid product
Insoluble matter yield ≯ 0.5 weight %；
(2) conversion reaction will be carried out in conversion reactor under gained liquid product hydro condition in step (1), turned
Change product；Wherein, conversion reaction described in step (2) and step (1) middle total conversion being heat-treated are 30-70 weight %, institute
State total conversion=(modification raw material in boiling range in weight-converted product of 524 DEG C or more components boiling range in 524 DEG C or more groups
Point weight)/modification raw material in boiling range 524 DEG C or more components weight × 100 weight %；
(3) gained converted product in step (2) is subjected to separating treatment, at least obtains the first separation product；Wherein, described
In first separation product, boiling range is not more than 5 weight %, boiling range component between 350-524 DEG C in the content of 350 DEG C of following components
Content be 20-60 weight %；
(4) the first separation product of gained in step (3) is subjected in extract and separate unit extraction and separation, obtains modification oil
And tailings；
(5) conversion reaction will be carried out in tailings return step (2) obtained in step (4)；Alternatively, by step (4)
Obtained in tailings carry out outer get rid of；Alternatively, the conversion will be carried out in tailings return step (2) obtained in part steps (4)
Reaction, remainder tailings carry out outer get rid of.
The present invention also provides a kind of efficient reforming system of poor oil, which includes annealer, conversion reactor, divides
From processing unit and extract and separate unit；The annealer has feed inlet, gas-phase product outlet and liquid product outlet, described
Conversion reactor is provided with reaction mass entrance and converted product outlet, and the separation processing unit is provided with processing feed(raw material)inlet
It is exported with the first separation product, the extract and separate unit is provided with extractant entrance, extraction feed entrance, modification oil export
It is exported with tailings；The liquid product outlet of the annealer is connected with the reaction mass entrance of the conversion reactor, described
The converted product outlet of conversion reactor is connected with the processing feed(raw material)inlet of the separation processing unit, the separation processing unit
The first separation product outlet be connected with the extraction feed entrance of the extract and separate unit, the tailings of the extract and separate unit
Outlet is optionally connected with the reaction mass entrance of the conversion reactor.
Compared with prior art, the present invention has the advantage that
1, can will modification raw material high efficiency, modify to maximum for rich in saturated structures, substantially free of heavy metal and
Modification oil substantially free of asphalitine.In situations where it is preferred, the conversion ratio of modification raw material is generally higher than 90 weight %, preferably
Greater than 95 weight %, the content of heavy metal (with the total weight of nickel and vanadium) is generally less than 10 micro- gram grams in gained modification oil, excellent
Choosing is less than 1 micro- gram gram, and the content for modifying oily studies on asphaltene is generally less than 2.0 weight %, preferably smaller than 0.5 weight %.
2, method for modifying and reforming system provided by the invention have stable operation, modification is high-efficient, three waste discharge is less,
It is environmentally protective, coke yield is low, the high advantages such as low with toluene insolubles yield in modification oil of modification oil yield.
3, one aspect of the present invention can maintain conversion reactor for a long time under the premise of modifying raw material high conversion realizing
Operating reduces outer whipping slag, improves utilization of resources rate, can on the other hand by the composition of the first separation product of optimization
Prevent the light component in the first separation product less than 350 DEG C excessive, solvent slop, and then it is black to cause extraction separation process to generate
Oil, and boiling range component between 350-524 DEG C in the first separation product is maintained to prevent tailings from coming back within zone of reasonableness
Occur poor fluidity when conversion reaction and is difficult to the problem of dissolving.
4, the present invention is heat-treated poor oil and can reduce its viscosity, reduce equipment in subsequent feed unit (such as
Circulating pump) operation severity and dosing (such as material-compound tank) operation difficulty, extend the device cycle of operation；In addition, hot
Generated in-situ toluene insolubles can be used as " coke trap " of subsequent transformation unit in treatment process, so that it is single to reduce conversion
The inactivation of catalyst in member reduces catalyst usage amount, improves process economics.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Detailed description of the invention
The drawings are intended to provide a further understanding of the invention, and constitutes part of specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 includes a kind of flow diagram of specific embodiment of the method for the present invention, also includes a kind of tool of present system
The structural schematic diagram of body embodiment.
Description of symbols
1 pipeline, 2 annealer, 3 pipeline
4 pipeline, 5 pipeline, 6 pipeline
7 pipeline, 8 pipeline, 9 pipeline
10 conversion reactor, 11 pipeline, 12 high pressure separative unit
13 pipeline, 14 pipeline, 15 pipeline
16 low pressure separative unit, 17 pipeline, 18 pipeline
19 extract and separate unit, 20 pipeline, 21 pipeline
22 pipeline, 23 pipeline
Specific embodiment
Below in conjunction with attached drawing, detailed description of the preferred embodiments.It should be understood that this place is retouched
The specific embodiment stated is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
In the present invention, boiling range refers to the distillation resulting boiling spread of oil product at normal pressure (101325Pa).
In the present invention, if pressure refers both to gauge pressure without specified otherwise.
The present invention provides a kind of efficient method for modifying of poor oil, this method comprises: (1) is using poor oil as modification raw material
It is heat-treated, obtains gas-phase product and liquid product；Wherein, the modification raw material includes selected from asphalitine, asphaltene and preceding
At least one of asphaltene asphalt component, toluene insolubles yield ≯ 0.5 weight % in the liquid product；(2) by step
(1) conversion reaction is carried out in conversion reactor under gained liquid product hydro condition in, obtains converted product；Wherein, step
(2) total conversion being heat-treated in conversion reaction described in and step (1) is 30-70 weight %, the total conversion=(modification
The boiling range weight of boiling range in 524 DEG C or more components in weight-converted product of 524 DEG C or more components in raw material)/modification raw material
Weight × 100 weight %s of the middle boiling range in 524 DEG C or more components；(3) gained converted product in step (2) is carried out at separation
Reason, at least obtains the first separation product；Wherein, in first separation product, boiling range is little in the content of 350 DEG C of following components
In 5 weight %, preferably smaller than 3 weight %, boiling range 350-524 DEG C (preferably 355-500 DEG C or 380-524 DEG C, it is further excellent
Be selected as 400-500 DEG C) between the content of component be 20-60 weight %, the initial boiling point of first separation product is generally not less than
300 DEG C, preferably not less than 330 DEG C, more desirably not less than 350 DEG C；(4) the first separation product of gained in step (3) is being extracted
Extraction and separation are carried out in separative unit, obtain modification oil and tailings；It (5) will be in tailings return step (2) obtained in step (4)
Carry out the conversion reaction；Alternatively, tailings obtained in step (4) is carried out outer get rid of；Alternatively, by gained in part steps (4)
Tailings return step (2) in carry out the conversion reaction, remainder tailings carries out outer gets rid of.
The present invention as far as possible reduce tailings outside get rid of improve resource utilization in the case where, can maintain system it is long when
Between operate, poor oil raw material initially enters annealer and carries out either shallow cracking, generated in-situ toluene insoluble in heat treatment process
Object (coke) can be used as " coke trap ", to reduce the inactivation of catalyst in conversion unit, reduces catalyst usage amount, mentions
High process economics, heat treatment process reduce liquid product viscosity and can reduce the operation difficulty extension fortune of follow-up equipment
The row period, but the cracking severity that is heat-treated is too deep that system stability decline can also be caused to be unfavorable for stable system, therefore is heat-treated
Toluene insolubles yield must be strictly controlled in gained liquid product afterwards, i.e. toluene insolubles content ≯ 0.5%, wherein being heat-treated
Reaction condition may include: temperature be 350-470 DEG C, preferably 370-460 DEG C；Volume space velocity (unit volume in the unit time
Annealer handled by modify raw material volume) be 0.05-10 hours-1, preferably 0.1-8.0 hours-1。
Conversion reactor and extract and separate unit are determined whether the key that can be operated for a long time, the conversion of conversion reactor
Rate should be as high as possible in the case where system stability allows, and enters small in the first separation product in extract and separate unit
Should not be excessive in 350 DEG C of light components, otherwise can solvent slop, cause extraction separation process generate dirty oil, boiling range is in 350-524
DEG C component should be more, otherwise be easy to cause tailings to be not easy to flow and be not easy convert in conversion reactor anti-
It answers.
According to the present invention, it is heat-treated the excessively high easy green coke of total conversion with conversion reaction, thus when reducing system operating
Between, and conversion ratio is too low, is easy to keep outer whipping slag excessive and reduces modification efficiency, inventor has found by many experiments, this hair
Liquid product toluene insolubles content ≯ 0.5 weight % obtained by the bright heat treatment；The heat treatment turns with the total of conversion reaction
Rate can be 30-70 weight %, preferably 30-60 weight %, reforming system ability operation cycle president.
According to the present invention, being heat-treated in reacting quintessence is thermal conversion reaction, refers to heat under conditions of no catalyst
Treatment process；Conversion reaction is substantially to face hydrogen thermal conversion reaction, refers to and is heat-treated modification raw material under hydro condition,
And the converted product at least containing the first separation product is obtained, converted product can also be lower than first containing gas component and boiling range
The product liquid of separation product initial boiling point.The present invention condition of conversion reaction, catalyst and reactor are had no it is specifically limited, only
It wants that above-mentioned conversion ratio can be reached.
A kind of embodiment, conversion reaction are carried out in flowing bed reactor using solid-liquid suspension object as catalyst, because
This described conversion reactor can be flowing bed reactor, and flowing bed reactor is reaction raw materials and catalyst in flow regime
The lower reactor reacted, generally comprises paste state bed reactor and fluidized bed reactor, and the present invention is preferably slurry reactor
Device.
A kind of embodiment, the conversion reaction carry out under the conditions of reforming catalyst is present or absent, and described turn
Changing catalyst can be containing in Group VB metallic compound, vib metals compound and group VIII metallic compound
At least one, preferably Mo compound, W compound, Ni compound, Co compound, Fe compound, V compound and Cr chemical combination
At least one of object；The condition of the conversion reaction may include: temperature be 380-470 DEG C, preferably 400-440 DEG C, hydrogen
Partial pressure is 10-25 megapascal, preferably 13-20 megapascal, and the volume space velocity of fresh feed (referring to heat treatment gained liquid product) is
0.01-2 hours-1, preferably 0.1-1.0 hours-1, the volume ratio of hydrogen and fresh feed (referring to heat treatment gained liquid product)
It for 500-5000, preferably 800-2000, is counted by metal in the reforming catalyst and on the basis of the weight for modifying raw material, institute
The dosage for stating reforming catalyst is micro- gram gram of 10-50000, micro- gram gram of preferably 30-25000.
According to the present invention, modification raw material may include selected from the drip of at least one of asphalitine, asphaltene and preasphaltene
Green component preferably includes asphalitine and/or preasphaltene, more preferably includes asphalitine.Asphalitine refers to insoluble in modification raw material
It is dissolved in the substance of benzene or toluene in nonpolar small molecule n-alkane (such as pentane or normal heptane), asphaltene is
Refer to the Toluene Soluble in modification raw material and the insoluble substance of n-hexane, preasphaltene refer in modification raw material tetrahydrofuran it is solvable and
The substance of toluene insoluble.The modification raw material, which is preferably satisfied, is greater than 350 DEG C (preferably greater than less than 27, boiling range selected from API degree
500 DEG C, more preferably greater than 524 DEG C), asphalt content be greater than 2 weight % (preferably greater than 5 weight %, more preferably greater than 10 weights
Measure %, further preferably greater than 15 weight %) and with the content of beary metal of the total weight of nickel and vanadium be greater than 100 micro- gram grams
In one or more indexs.Specifically, the modification raw material may include spreading out selected from crude oil with poor quality, heavy oil, de-oiled asphalt, coal
At least one of oil generation, shale oil and petrochemical industry waste oil；The heavy oil refers to distillate or slag of the boiling point at 350 DEG C or more
Oil, distillate are generally referred to as the fraction product that crude oil or secondary operation oil are obtained through atmospheric distillation and rectification under vacuum, such as heavy
Diesel oil, heavy gas oil, lube cut or cracked stock etc.；Residual oil refers to that crude oil is evaporated by the tower bottom that atmospheric and vacuum distillation obtains
Air-distillation tower bottom distillate is generally known as reduced crude (generally fraction of the boiling point greater than 350 DEG C), will generally subtracted by object out
Pressure distillation the bottomsstream is known as decompression residuum (generally boiling point is greater than 500 DEG C or 524 DEG C of fraction), residual oil can for selected from
At least one of topped crude, the heavy oil of heavy oil and initial boiling point greater than 350 DEG C obtained by oil sands bitumen, topped crude refers to
When being fractionated in atmospheric and vacuum distillation technique to crude oil, from the oil of the tower bottom discharge of the tower bottom or flash column of primary distillation tower；It is bad
Matter crude oil is, for example, viscous crude, and viscous crude refers to asphalitine and gum level is higher, the higher crude oil of viscosity, generally that 20 DEG C of ground is close
Degree is greater than 0.943 gram per centimeter3, underground crude oil viscosity be greater than 50 centipoises crude oil viscous crude；Deasphalted oil refers to feedstock oil molten
In agent deasphalting unit, by contacting with solvent, the rich asphalitine that separated and dissolved, extraction tower tower bottom obtain, it is rich in aromatised fraction
Extract remainder propane de-oiled asphalt, butane de-oiled asphalt, pentane de-oiled asphalt etc. can be divided into according to the difference of solvent type；Coal
Derived oils refer to that using coal as raw material, the liquid fuel obtained by chemical process can be the coal liquefaction generated selected from coal liquefaction
At least one of the coal tar that oil and pyrolysis of coal generate；Shale oil refers to the brown by oil shale through obtaining when low temperature distillation
Sticky shape paste, irritant stink, nitrogen content are higher；The petrochemical industry waste oil can be for selected from petrochemical industry waste oil mud, petrochemical industry oil
At least one of slag and its refining product.Other poor oils well-known to those skilled in the art can also be individually or after mixing
Conversion reaction is carried out as modification raw material, the present invention repeats no more.
According to the present invention, the first separation product is generally made of the highest product of boiling range in converted product comprising step
Suddenly the tailings in (4), tailings main component are asphalitines, wherein also including some colloidal substances and fragrance necessary to keeping mobility
Grouping point further includes modification oil other than tailings in the first separation product, after being separated by extraction in the first separation product
It can be used as the good raw material of subsequent processing to be processed to obtain other oil products, the lower component of remaining boiling range can in converted product
Gaseous product (such as dry gas and liquefied gas etc.) and boiling range to separate with the first separation product, such as under standard state exist
350 DEG C of other components below.
According to the present invention, separating treatment described in step (3) is used to obtain the first separation production for meeting above-mentioned boiling range composition
Object, the present invention is to its specific embodiment and is not particularly limited, and specifically, the separating treatment in the step is commonly referred to as physics
Separation, such as extraction, liquid separation, distillation, evaporation, flash distillation and condensation etc..
A kind of specific embodiment, in step (3), the separating treatment includes step (3-1) and step (3-2):
(3-1) separates gained converted product in step (2) at a temperature of first pressure and first, obtains gas group
Point and liquid component；Preferable separate goes out the gaseous products such as hydrogen in step (3-1), and gas component is rich in hydrogen, and preferably hydrogen contains
Amount is more than 85 weight %；Such as the first pressure can be 10-25 megapascal, preferably 13-20 megapascal, survey for convenience
Amount, the first pressure refer generally to outlet pressure when gas component leaves separator, and the first temperature can be 380-470 DEG C,
It preferably 400-440 DEG C, measures for convenience, which refers generally to outlet temperature when liquid component leaves separator
Degree；The mode separated in the step can be distillation, fractionation and flash distillation etc., preferably distill, which can be in a distillation column
It carries out, gas component can be obtained from overhead, and liquid component can be obtained from destilling tower tower bottom；
(3-2) separates liquid component under second pressure and second temperature, obtain first separation product and
Second separation product；Preferable separate goes out boiling range and retains boiling range as far as possible in 350-524 in 350 DEG C of following components in step (3-2)
DEG C component；The first pressure is preferably greater than the second pressure, and the first pressure is further preferably bigger than second pressure
4-24 megapascal, more preferably big 7-19 megapascal；Specifically, the second pressure can be 0.1-5 megapascal, preferably 0.1-4 megapascal,
In order to facilitate measurement, which refers generally to outlet pressure when the second separation product leaves separator, and second temperature can
Think 150-390 DEG C, preferably 200-370 DEG C, measure for convenience, which refers generally to the first separation product and leave point
Outlet temperature when from device；Separation in the step can be to distill and/or be fractionated, preferably normal pressure or pressure fractionation, can
To be carried out in air-distillation tank or distillation under pressure tower.
A kind of optional embodiment, the separating treatment further include step (3-3) and/or step (3-4):
(3-3) cuts the second separation product of gained in step (3-2), obtains naphtha and AGO (atmospheric gas oil), should
The mode of cutting can be preferably fractionated, such as carry out in fractionating column, operating pressure can be using fractionation or distillation
0.05-2.0 megapascal, preferably 0.1-1.0 megapascal, operation temperature can be 50-350 DEG C, preferably 150-330 DEG C；And/or
(3-4) will carry out conversion reaction in gained gas component return step (2) in step (3-1), which can
Directly or through separating as circulating hydrogen to use.
According to the present invention, extraction and separation are used to separate the modification oil easy to process in the first separation product, and by tail
Slag carry out it is outer gets rid of or comes back for conversion reaction, specifically, in step (4), the extraction and separation can be in third temperature and the
It is carried out in extractant under three pressure, preferably extractant and the first separation product counter current contacting extract, and can arbitrarily extract
It takes in device and carries out, such as extraction tower；Wherein, the third pressure can be 3-12 megapascal, preferably 3.5-10 megapascal, third
Temperature can be 55-300 DEG C, and preferably 70-220 DEG C, extractant can be C3-C7Hydrocarbon, preferably C3-C5Alkane and C3-C5
At least one of alkene, further preferably C3-C4Alkane and C3-C4At least one of alkene, the extractant and described the
The weight ratio of one separation product is (1-7): 1, preferably (1.5-5): 1.Those skilled in the art can also take other routines
Extraction mode extracted, the present invention repeats no more.
According to the present invention, tailings is the highest component of boiling range in converted product, in the more high then converted product of softening point easily
Then separate more complete in the component of processing, but in order to maintain mobility and return conversion of the tailings in pipeline conveying anti-
Answer dissolubility when device, in step (4), the softening point of the tailings is preferably smaller than 150 DEG C, and more preferably less than 120 DEG C.
According to the present invention, if conversion reaction of the present invention carries out in flowing bed reactor, reforming catalyst meeting therein
As converted product carries out subsequent separation together and is retained in tailings, and with the increase and modification of catalyst charge
The accumulation of metal component in raw material, the metal in entire reforming system can be continuously increased.In order to maintain metal in reforming system
Balance needs that tailings intermittently or continually is carried out outlet, while sufficiently being used to make to modify raw material, in step (5),
It will be got rid of outside the tailings of part, the tailings got rid of outside accounts for the ratio of the modification raw material less than 10 weight %；Tailings in return step (1)
Ratio be preferably greater than 80 weight %, preferably greater than 90 weight %, more preferably greater than 95 weight %.Those skilled in the art can also
To be adjusted the ratio got rid of outside tailings according to modification raw material of different nature, the present invention is repeated no more.
As shown in Figure 1, the system includes annealer 2, turns the present invention also provides a kind of efficient reforming system of poor oil
Change reactor 10, separation processing unit and extract and separate unit 19；The annealer 2 have feed inlet, gas-phase product outlet and
Liquid product outlet, the conversion reactor 10 are provided with reaction mass entrance and converted product outlet, the separating treatment list
Member be provided with processing feed(raw material)inlet and the first separation product outlet, the extract and separate unit 19 be provided with extractant entrance,
Extraction feed entrance, modification oil export and tailings outlet；Liquid product outlet and the conversion reactor of the annealer 2
10 reaction mass entrance is connected, and the converted product outlet of the conversion reactor 10 and the processing of the separation processing unit are former
Expect that entrance is connected, the first separation product outlet of the separation processing unit and the extraction feed of the extract and separate unit 19 enter
Mouthful it is connected, the reaction mass entrance of the outlet of the tailings of the extract and separate unit 19 and the conversion reactor 10 optionally phase
Even.
System provided by the invention is for carrying out modification reaction provided by the present invention, such as shown in Figure 1, the separation
Processing unit includes high pressure separative unit 12 and low pressure separative unit 16, and the high pressure separative unit 12 is provided with gas component and goes out
Mouth, liquid component outlet and the processing feed(raw material)inlet, the low pressure separative unit 16 are provided with low pressure feed(raw material)inlet, second point
It is exported from product exit and first separation product, liquid component outlet and the low pressure point of the high pressure separative unit 12
Feed(raw material)inlet from unit 16 is connected.
According to the present invention, annealer is well-known to those skilled in the art, can be tower reactor, for example, subtract
Viscous tower etc..
According to the present invention, in order to which gas component is carried out reuse, as shown in Figure 1, the gas of the high pressure separative unit 12
Group sub-export is connected with the reaction mass entrance of the conversion reactor 10.
The present invention will be further illustrated by specific embodiment below, but the present invention is not therefore and by any
Limitation.
As shown in Figure 1, modification raw material enters annealer 2 through pipeline 1, gas-phase product and liquid product are obtained, gas phase produces
Object draws reforming system through pipeline 3, and liquid product is through pipeline 4, reforming catalyst through pipeline 5, circulating hydrogen through pipeline 6, fresh
Hydrogen is delivered in conversion reactor 10 through pipeline 9 through the mixing of pipeline 8 through pipeline 7 and tailings and carries out conversion reaction.Conversion produces
Object is delivered to high pressure separative unit 12 through pipeline 11 and carries out high pressure distillation, gas component and liquid component is separated into, then by gas
Body component is successively delivered to conversion reactor 10 through pipeline 13, pipeline 6, pipeline 9 as circulating hydrogen, or successively through pipeline 13,
Pipeline 14 is drawn to outside reforming system.Liquid component is delivered to low pressure separative unit 16 through pipeline 15 and carries out pressure drop, separation
For the second separation product and the first separation product.Second separation product is drawn through pipeline 18 to outside reforming system, and the first separation produces
Object is delivered to extract and separate unit 19 and the extractant counter current contacting from pipeline 20 through pipeline 17 and carries out extraction and separation, obtains
To modification oil and tailings.Modification oil is drawn through pipeline 21 to outside reforming system, and a part of tailings is successively through pipeline 22, pipeline 23
It gets rid of outside, rest part is successively recycled to conversion reactor 10 and modification raw material through pipeline 22, pipeline 8, pipeline 9 as modification raw material
Reaction is continued the conversion together.Alternatively, can also be by whole tailings successively through being got rid of outside pipeline 22, pipeline 23 and without following
Ring.
The present invention is illustrated using embodiment in further detail below, however, the present invention is not limited to these examples.
In the context of the present invention and it is included in embodiment and comparative example below:
The measuring method of heavy metal (with the total weight of nickel and vanadium) content is according to ASTM D5708 in oil product；
The measuring method of nitrogen content is measured according to SH/T0704-2001 method in oil product；
The measuring method of oil product studies on asphaltene content is according to SH/T 0266-92 (1998)；
Modification feed stock conversion=(rate is got rid of outside 1- tailings) × 100 weight %, tailings get rid of rate=outer whipping slag weight/outside and change
Matter raw material weight × 100 weight %；
Modify oil yield=modification oil weight/modification raw material weight × 100 weight %；
Tailings circulation ratio=circulation tailings weight/total tailings weight × 100 weight %；
Denitrification percent=(modification raw material nitrogen content-modification oil nitrogen content × modification oil yield)/modification raw material nitrogen content × 100
Weight %；
Toluene insolubles yield=toluene insolubles weight/modification raw material weight × 100 weight % in modification oil；
Tailings softening point is measured using GB/T 4507-84 method；
Special component refers to component of the boiling range between 350-524 DEG C in the first separation product.
The stable operation number of days of the operational stability of upgrading processes reforming system is evaluated.Specifically, modification
There is any one of following situation in system, then determines that it is unable to stable operation:
(1) the maximum temperature difference △ T (absolute value) of different temperatures measurement point is greater than 5 DEG C inside conversion reactor；(2) modification oil
It is rendered as black, is rendered as yellow or yellow green under normal circumstances.
Embodiment and comparative example below carries out modifying process according to the embodiment of earlier figures 1.
In embodiment and comparative example below, as modification raw material, modification raw material A and modification raw material B are decompression residuum,
Modifying raw material C is heavy crude oils of Venezuela decompression residuum, and modification raw material D is high temperature coal-tar, and modification raw material E is de-oiled asphalt, this
The property of five kinds of modification raw materials is shown in Table 1.
Embodiment 1-5
On middle- scale device, first to modification raw material be heat-treated, gained liquid product carry out conversion reaction, then into
The separating treatment of row converted product, separating treatment carry out in two fractionating columns, obtain the first separation product and the second separation produces
The actual conditions and result of object, conversion reaction and separating treatment are listed in table 2-1 and table 2-2.
Embodiment 6-8
On middle- scale device, first to modification raw material be heat-treated, gained liquid product carry out conversion reaction, then into
Row separating treatment, separating treatment carry out in two fractionating columns, obtain the first separation product and the second separation product, conversion reaction
Table 3 is listed in the actual conditions and result of separating treatment.
Embodiment 9-11
On middle- scale device, the first separation product that embodiment 2, embodiment 4 and embodiment 7 obtain is extracted respectively
Separation is taken, the actual conditions and result of extraction and separation are listed in table 4.
Embodiment 12-13
On middle- scale device, modification raw material B and modification raw material C are heat-treated first, gained liquid product is turned
Change reaction, then carry out separating treatment, separating treatment carries out in two fractionating columns, obtains the first separation product and the second separation
Product.First separation product carries out extraction and separation again, obtains modification oil and tailings.A part of tailings recycles, outside rest part
It gets rid of.Convert after the tailings of acquisition is mixed with gained liquid product after modification raw material B and modification raw material C heat treatment respectively anti-
It answers, the second separation product is separated, naphtha cut and AGO (atmospheric gas oil) are obtained.The actual conditions and result of each step arrange
In table 5-1 and table 5-2.
The result of contrast table 4, table 5-1 and table 5-2 is conducive to improve modification raw material conversion it is found that tailings is recycled
Rate and modification oil yield.
Embodiment 14
On middle- scale device, modification raw material B is heat-treated first, gained liquid product carries out conversion reaction, then
Separating treatment is carried out, separating treatment carries out in two fractionating columns, obtains the first separation product and the second separation product.First point
It carries out extraction and separation (extraction and separation condition is with embodiment 12) again from product, obtains modification oil and tailings.A part of tailings with
Conversion reaction is carried out together after gained liquid product mixing after modification raw material B heat treatment, is got rid of outside rest part tailings.Mixed raw material
Converted product successively separated in two fractionating columns, carry out extraction and separation, obtain modification oil and tailings.Simultaneously by the of acquisition
Two separation products are separated, and naphtha cut and AGO (atmospheric gas oil) are obtained.The actual conditions and result of each step are listed in table 6-1
With table 6-2.
Comparative example 1 is to comparative example 6
It is identical as the basic procedure of embodiment 14, only it is changed according to table 7-1, comparative example 6 does not use heat treatment,
Extraction and separation condition is the same as embodiment 12.
Table 7-2 is the results show that work as conversion ratio, less than 350 DEG C constituent contents of the first separation product, special group of conversion reaction
There is one when being unsatisfactory for corresponding requirements of the invention in point content, it will so that modification feed stock conversion reduces 6-12 percentage
Point, modification oil yield decline 5-16 percentage points, and toluene insolubles yield improves 1-4.6 percentage points, and due to T > 5 DEG C △
Or modification oil is rendered as black, the stable operation number of days of reforming system declines to a great extent.Comparative example 1 and 5 and embodiment are compared simultaneously
14, when heat treatment condition is improper leads to toluene insolubles yield > 0.5%, device stable operation number of days also declines to a great extent.It is right
Than embodiment 14 and comparative example 6 it can be found that catalyst usage amount can be reduced after to modification oil heat treatment.
Table 1
Table 2-1
Table 2-2
Table 3
Table 4
Table 5-1
Table 5-2
Table 6-1
Table 6-2
| Project | Embodiment 14 |
| It is heat-treated toluene insolubles yield in liquid product, weight % | 0.4 |
| Total conversion/% of heat treatment and conversion reaction | 56.4 |
| Product distribution/weight % | |
| First separation product | 67.9 |
| The boiling range of special component in first separation product/DEG C | 350-524 |
| Content/weight % of special component in first separation product | 34 |
| Less than 350 DEG C constituent content/weight % of boiling range in first separation product | 3 |
| The end point of distillation of second separation product/DEG C | 324 |
| Modify result | |
| Modify feed stock conversion/% | 94.8 |
| Modify oil yield/% | 86.7 |
| Modify oily content of beary metal/weight (micro- gram gram) | <1 |
| Modify oil asphalt matter content/weight % | <0.1 |
| Toluene insolubles yield/weight % | 0.8 |
| Stable operation number of days | > 30 days |
Table 7-1
Table 7-2
Claims (17)
1. a kind of efficient method for modifying of poor oil, this method comprises:
(1) it is heat-treated poor oil as modification raw material, obtains gas-phase product and liquid product；Wherein, the modification is former
Material includes the toluene insoluble at least one of asphalitine, asphaltene and preasphaltene asphalt component, the liquid product
Object yield ≯ 0.5 weight %；
(2) conversion reaction will be carried out in conversion reactor under gained liquid product hydro condition in step (1), obtain conversion and produce
Object；Wherein, conversion reaction described in step (2) and step (1) middle total conversion being heat-treated are 30-70 weight %, described total
Conversion ratio=(in modification raw material boiling range in weight-converted product of 524 DEG C or more components boiling range in 524 DEG C or more components
Weight)/modification raw material in boiling range 524 DEG C or more components weight × 100 weight %；
(3) gained converted product in step (2) is subjected to separating treatment, at least obtains the first separation product；Wherein, described first
In separation product, boiling range is not more than 5 weight % in the content of 350 DEG C of following components, and boiling range component between 350-524 DEG C contains
Amount is 20-60 weight %；
(4) the first separation product of gained in step (3) is subjected in extract and separate unit extraction and separation, obtains modification oil and tail
Slag；
(5) conversion reaction will be carried out in tailings return step (2) obtained in step (4)；Alternatively, by institute in step (4)
The tailings obtained carries out outer get rid of；Alternatively, by the conversion reaction is carried out in tailings return step (2) obtained in part steps (4),
Remainder tailings carries out outer get rid of.
2. method for modifying described in accordance with the claim 1, wherein the condition of the heat treatment includes: that temperature is 350-470 DEG C,
Volume space velocity is 0.05-10 hours-1。
3. method for modifying according to claim 1, in step (2), the total conversion is 30-60 weight %.
4. method for modifying according to claim 1, in step (2), the conversion reactor is flowing bed reactor；
The conversion reaction carries out under the conditions of reforming catalyst is present or absent, and the reforming catalyst contains selected from
At least one of VB race metallic compound, vib metals compound and group VIII metallic compound；
The condition of the conversion reaction includes: that temperature is 380-470 DEG C, and hydrogen partial pressure is 10-25 megapascal, fresh feed volume space velocity
It is 0.01-2 hours-1, the volume ratio of hydrogen and fresh feed is 500-5000, in terms of metal in the reforming catalyst and to change
On the basis of the weight of matter raw material, the dosage of the reforming catalyst is micro- gram gram of 10-50000.
5. method for modifying according to claim 1, in step (1), the modification raw material includes selected from crude oil with poor quality, again
At least one of oil, de-oiled asphalt, coal derived oils, shale oil and petrochemical industry waste oil.
6. method for modifying according to claim 1, the modification raw material, which meets, is greater than 350 less than 27, boiling range selected from API degree
DEG C, asphalt component content be greater than 2 weight % and with the content of beary metal of the total weight of nickel and vanadium be greater than 100 micro- gram grams in
One or more indexs.
7. method for modifying according to claim 1, in step (3), in first separation product, boiling range 350 DEG C with
The content of lower component is 25-55 weight % less than 3 weight %, the content of boiling range component between 350-524 DEG C.
8. method for modifying according to claim 1, in step (3), the separating treatment includes:
(3-1) separates gained converted product in step (2) at a temperature of first pressure and first, obtain gas component and
Liquid component；
(3-2) separates liquid component under second pressure and second temperature, obtains first separation product and second
Separation product；Wherein, the first pressure is greater than the second pressure.
9. method for modifying according to claim 8, wherein first pressure 4-24 megapascal bigger than second pressure.
10. method for modifying according to claim 8, wherein the first pressure is 10-25 megapascal, and the first temperature is
380-470℃；The second pressure is 0.1-5 megapascal, and second temperature is 150-390 DEG C.
11. method for modifying according to claim 8, wherein the separating treatment further include:
(3-3) cuts the second separation product of gained in step (3-2), obtains naphtha and AGO (atmospheric gas oil)；And/or
(3-4) will carry out conversion reaction in gained gas component return step (2) in step (3-1).
12. method for modifying according to claim 1, in step (4), the extraction and separation are in third temperature and third pressure
Under extractant in carry out；Wherein, the third pressure is 3-12 megapascal, and third temperature is 55-300 DEG C, and the extraction is molten
Agent is C3-C7The weight ratio of hydrocarbon, the extractant and first separation product is (1-7): 1.
13. method for modifying according to claim 1, in step (4), the softening point of the tailings is less than 150 DEG C.
14. method for modifying according to claim 1, in step (5), the ratio of the tailings in return step (2) is greater than 80
Weight %.
15. method for modifying according to claim 1, in step (5), will be got rid of outside the tailings of part, the tailings got rid of outside accounts for described
The ratio of raw material is modified less than 10 weight %.
16. a kind of efficient reforming system of poor oil, which includes annealer (2), conversion reactor (10), separating treatment
Unit and extract and separate unit (19)；
The annealer (2) has feed inlet, gas-phase product outlet and liquid product outlet, conversion reactor (10) setting
There are reaction mass entrance and converted product outlet, the separation processing unit is provided with processing feed(raw material)inlet and the first separation product
Outlet, the extract and separate unit (19) are provided with extractant entrance, extraction feed entrance, modification oil export and tailings and go out
Mouthful；
The liquid product outlet of the annealer (2) is connected with the reaction mass entrance of the conversion reactor (10), described
The converted product outlet of conversion reactor (10) is connected with the processing feed(raw material)inlet of the separation processing unit, the separating treatment
The first separation product outlet of unit is connected with the extraction feed entrance of the extract and separate unit (19), the extraction and separation list
The tailings outlet of first (19) is optionally connected with the reaction mass entrance of the conversion reactor (10).
17. system according to claim 16, wherein the separation processing unit includes high pressure separative unit (12) and low pressure point
From unit (16), the high pressure separative unit (12) is provided with gas component outlet, liquid component outlet and the processing raw material
Entrance, the low pressure separative unit (16) are provided with low pressure feed(raw material)inlet, the outlet of the second separation product and first separation and produce
Object outlet, the feed(raw material)inlet phase of the liquid component outlet and the low pressure separative unit (16) of the high pressure separative unit (12)
Even.
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| CN102863988A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Coal tar combined machining method |
| CN105940086A (en) * | 2013-12-17 | 2016-09-14 | Ifp 新能源公司 | Novel integrated process for treating petroleum feedstocks for the production of fuel oils having a low content of sulphur and of sediments |
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| CN102863988A (en) * | 2011-07-07 | 2013-01-09 | 中国石油化工股份有限公司 | Coal tar combined machining method |
| CN105940086A (en) * | 2013-12-17 | 2016-09-14 | Ifp 新能源公司 | Novel integrated process for treating petroleum feedstocks for the production of fuel oils having a low content of sulphur and of sediments |
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