CN109486518A - A kind of method for modifying and system of low-quality oil - Google Patents
A kind of method for modifying and system of low-quality oil Download PDFInfo
- Publication number
- CN109486518A CN109486518A CN201710814175.XA CN201710814175A CN109486518A CN 109486518 A CN109486518 A CN 109486518A CN 201710814175 A CN201710814175 A CN 201710814175A CN 109486518 A CN109486518 A CN 109486518A
- Authority
- CN
- China
- Prior art keywords
- raw material
- separation
- weight
- oil
- residue
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
-
- 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
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/04—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including solvent extraction as the refining step in the absence of hydrogen
- C10G67/0454—Solvent desasphalting
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
-
- 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
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/205—Metal content
- C10G2300/206—Asphaltenes
Abstract
The present invention relates to the method for modifying and system of a kind of low-quality oil to obtain converted product this method comprises: the low-quality oil as modification raw material is carried out conversion reaction by (1) under hydro condition in conversion reactor；(2) gained converted product in step (1) is subjected to separating treatment, at least obtains the first separation product；(3) the first separation product of gained in step (2) is subjected in extract and separate unit extraction and separation, obtains modification oil and residue；(4) conversion reaction will be carried out in residue return step (1) obtained in step (3)；Alternatively, residue obtained in step (3) is carried out outer get rid of；Alternatively, the conversion reaction will be carried out in residue return step (1) obtained in part steps (3), remainder residue carries out outer get rid of.Method for modifying provided by the invention and system, which are got rid of outside in the case that residue lacks as far as possible, maintains system to operate for a long time.
Description
Technical field
The present invention relates to the method for modifying and system of a kind of low-quality oil.
Background technique
In recent years, the low-qualityization trend of fossil fuel is aggravated year by year.Moreover, residual oil, poor oil, 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 feature of this kind of low-quality oil is that density is big, viscosity
Greatly, hetero atom (sulphur, nitrogen, heavy metal) content is high or asphalt content is high.In addition, for it is this kind of it is low-quality oil and develop show
There is a processing technology (such as delayed coking) there is coke yields that high, effective utilization rate of energy is low, deficiency in economic performance, production process
Not environmentally the problems such as.Therefore, efficient, the green modification technology for further developing this kind of low-quality oil, has become petrochemical industry
One of developing direction and research emphasis of industry.
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 the method for modifying and system of a kind of low-quality oil, method for modifying provided by the invention with
System, which is got rid of outside in the case that residue lacks as far as possible, maintains system to operate for a long time.
To achieve the goals above, the present invention provides a kind of method for modifying of low-quality oil, this method comprises:
(1) the low-quality oil as modification raw material is subjected in conversion reactor under hydro condition conversion reaction, obtained
To converted product；Wherein, the modification raw material includes selected from least one of asphalitine, asphaltene and preasphaltene pitch group
Point, the conversion ratio of the conversion reaction is 30-70 weight %, the conversion ratio of the conversion reaction=(boiling range exists in modification raw material
Weight of the boiling range in 524 DEG C or more components in weight-converted product of 524 DEG C or more components)/modification raw material in boiling range 524
DEG C or more component weight × 100 weight %；
(2) gained converted product in step (1) 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 %；
(3) the first separation product of gained in step (2) is subjected in extract and separate unit extraction and separation, obtains modification oil
And residue；
(4) conversion reaction will be carried out in residue return step (1) obtained in step (3)；Alternatively, by step (3)
Obtained in residue carry out outer get rid of；Alternatively, the conversion will be carried out in residue return step (1) obtained in part steps (3)
Reaction, remainder residue carry out outer get rid of.
The present invention also provides a kind of reforming systems of low-quality oil, which includes conversion reactor, separation processing unit
And extract and separate unit；The conversion reactor is provided with reaction mass entrance and converted product outlet, the separating treatment list
Member is provided with processing feed(raw material)inlet and the outlet of the first separation product, and the extract and separate unit is provided with extractant entrance, extraction
Take feed(raw material)inlet, modification oil export and solid discharge；Converted product outlet and the separating treatment list of the conversion reactor
The processing feed(raw material)inlet of member is connected, the outlet of the first separation product and the extract and separate unit of the separation processing unit
Extraction feed entrance is connected, the reaction mass entrance phase of the solid discharge of the extract and separate unit and the conversion reactor
Even.
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, reduction is outer to get rid of residue, 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 residue from coming back within zone of reasonableness
Occur poor fluidity when conversion reaction and is difficult to the problem of dissolving.
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 pipeline, 3 pipeline
4 pipeline, 5 pipeline, 6 pipeline
7 conversion reactor, 8 pipeline, 9 high pressure separative unit
10 pipeline, 11 pipeline, 12 pipeline
13 low pressure separative unit, 14 pipeline, 15 pipeline
16 extract and separate unit, 17 pipeline, 18 pipeline
19 pipeline, 20 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 method for modifying of low-quality oil, this method comprises: (1) will be as the low-quality of modification raw material
Oil carries out conversion reaction under hydro condition in conversion reactor, obtains converted product；Wherein, the modification raw material includes choosing
From at least one of asphalitine, asphaltene and preasphaltene asphalt component, the conversion ratio of the conversion reaction is 30-70 weight
Measure %, the conversion ratio of the conversion reaction=(boiling range evaporates in weight-converted product of 524 DEG C or more components in modification raw material
Weight of the journey in 524 DEG C or more components)/modification raw material in boiling range 524 DEG C or more components weight × 100 weight %；(2) will
Gained converted product carries out separating treatment in step (1), at least obtains the first separation product；Wherein, first separation product
In, boiling range is not more than 5 weight % in the content of 350 DEG C of following components, and preferably smaller than 3 weight %, boiling range is (excellent at 350-524 DEG C
Be selected as 355-500 DEG C or 380-524 DEG C, further preferably 400-500 DEG C) between component content be 20-60 weight %, it is excellent
It is selected as 25-55 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 excellent
Choosing is not less than 350 DEG C；(3) the first separation product of gained in step (2) is subjected in extract and separate unit extraction and separation, obtained
Modification oil and residue；(4) conversion reaction will be carried out in residue return step (1) obtained in step (3)；Alternatively, will step
Suddenly residue obtained in (3) carries out outer get rid of；Alternatively, described in being carried out in residue return step (1) obtained in part steps (3)
Conversion reaction, remainder residue carry out outer get rid of.
The present invention as far as possible reduce residue outside get rid of improve resource utilization in the case where, can maintain system it is long when
Between operate, and conversion reactor and extract and separate unit are determined whether the key that can be operated for a long time, and conversion reactor turns
Rate should be as high as possible in the case where system stability allows, and enters in the first separation product in extract and separate unit
Light component less than 350 DEG C should not be excessive, otherwise can solvent slop, cause extraction separation process generate dirty oil, boiling range is in 350-
524 DEG C of component should be more, and residue is otherwise be easy to cause to be not easy to flow and be not easy to be converted in conversion reactor
Reaction.
According to the present invention, the excessively high easy green coke of the conversion ratio of conversion reaction, so that the system duration of runs is reduced, and conversion ratio
It is too low, it is easy to make the outer residue that gets rid of excessive and reduce unit time modification efficiency, inventor has found by many experiments, of the invention
The conversion ratio of the conversion reaction can be 30-70 weight %, preferably 30-60 weight %.
According to the present invention, conversion reaction is substantially thermal conversion reaction, refers to and carries out modification raw material under hydro condition
Thermal transition, and the converted product at least containing the first separation product is obtained, converted product can also contain gas component and boiling range
Lower than the product liquid of the first separation product initial boiling point.The present invention has no spy to the condition of conversion reaction, catalyst and reactor
Different limitation, as long as 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 for modifying raw material is 0.01-2 hours-1, preferably 0.1-1.0
Hour-1, hydrogen and the volume ratio for modifying raw material are 500-5000, preferably 800-2000, with metal in the reforming catalyst
It counts and on the basis of the weight for modifying raw material, the dosage of the reforming catalyst is micro- gram gram of 10-50000, preferably 30-
25000 micro- gram grams.
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 low-quality oil well-known to those skilled in the art can also independent or mixing
Conversion reaction is carried out as modification raw material afterwards, 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 residue in (3), residue main component are asphalitines, wherein also including some colloidal substances and fragrance necessary to keeping mobility
Grouping point further includes modification oil other than residue 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 (2) 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 (2), the separating treatment includes step (2-1) and step (2-2):
(2-1) separates gained converted product in step (1) 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 (2-1), 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；
(2-2) 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 (2-2)
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 (2-3) and/or step (2-4):
(2-3) cuts the second separation product of gained in step (2-2), 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
(2-4) will carry out conversion reaction in gained gas component return step (1) in step (2-1), 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 will be residual
Slag carry out it is outer gets rid of or comes back for conversion reaction, specifically, in step (3), 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, residue 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 residue in pipeline conveying anti-
Answer dissolubility when device, in step (3), the softening point of the residue 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 residue, 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 residue intermittently or continually is carried out outlet, while sufficiently being used to make to modify raw material, in step (4),
It will be got rid of outside the residue of part, the residue got rid of outside accounts for the ratio of the modification raw material less than 10 weight %；Residue 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
It is adjusted the ratio got rid of outside residue with the modification raw material according to different metal content, the present invention repeats no more.
As shown in Figure 1, the system includes conversion reactor 7, divides the present invention also provides a kind of reforming system of low-quality oil
From processing unit and extract and separate unit 16；The conversion reactor 7 is provided with reaction mass entrance, and (reaction mass includes changing
Matter raw material, hydrogen and residue, including or do not include modifying catalyst) and converted product outlet, the separation processing unit setting
There are processing feed(raw material)inlet and the outlet of the first separation product, the extract and separate unit 16 is provided with extractant entrance, extraction original
Expect entrance, modification oil export and solid discharge；Converted product outlet and the separation processing unit of the conversion reactor 7
Processing feed(raw material)inlet is connected, the extraction of the first separation product outlet and the extract and separate unit 16 of the separation processing unit
Feed(raw material)inlet is taken to be connected, the reaction mass entrance of the solid discharge of the extract and separate unit 16 and the conversion reactor 7
Optionally it is connected.
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 9 and low pressure separative unit 13, and the high pressure separative unit 9 is provided with gas component and goes out
Mouth, liquid component outlet and the processing feed(raw material)inlet, the low pressure separative unit 13 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 9
Low pressure feed(raw material)inlet from unit 13 is connected.The high pressure separative unit and low pressure separative unit all can be distillation unit or point
Unit, such as destilling tower etc. are evaporated, the two is distinguish by operating pressure, and the operating pressure of high pressure separative unit is higher than low pressure point
From unit.
According to the present invention, in order to which gas component is carried out reuse, as shown in Figure 1, the gas group of the high pressure separative unit 9
Sub-export is connected with the reaction mass entrance of the conversion reactor 7.
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 through pipeline 1, reforming catalyst through pipeline 2, circulating hydrogen through pipeline 3, fresh hydrogen
It is delivered in conversion reactor 7 through pipeline 4 and residue through pipeline 5 and carries out conversion reaction.Converted product conveys supreme through pipeline 8
It presses separative unit 9 to carry out distillation under pressure, is separated into gas component and liquid component, then using gas component as circulating hydrogen elder generation
It is delivered to conversion reactor 7 by pipeline 10, pipeline 3, pipeline 6, or is successively drawn through pipeline 10, pipeline 11 to outside reforming system
Out.Liquid component is delivered to low pressure separative unit 13 through pipeline 12 and carries out pressure drop, is separated into the second separation product and first
Separation product.Second separation product is drawn through pipeline 15 to outside reforming system, and the first separation product is delivered to extraction through pipeline 14
Separative unit 16 and the extractant counter current contacting from pipeline 17 and carry out extraction and separation, obtain modification oil and residue.Modification
Oil is drawn through pipeline 18 to outside reforming system, and successively through getting rid of outside pipeline 19, pipeline 20, rest part is used as to be changed a part of residue
Matter raw material successively through pipeline 19, pipeline 5, pipeline 6 be recycled to conversion reactor 7 continued the conversion together with modification raw material it is anti-
It answers.Alternatively, can also be by whole residues successively through being got rid of outside pipeline 19, pipeline 20 and without circulation.
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 ASTMD5708 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- residue) × 100 weight %, residue get rid of rate=getting rid of residue weight outside/outside and change
Matter raw material weight × 100 weight %；
Modify oil yield=modification oil weight/modification raw material weight × 100%；
Toluene insolubles yield=toluene insolubles weight/modification oil weight × 100% in modification oil；
Residue 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,
Modification raw material C is that heavy crude oils of Venezuela subtracts slag, and modification raw material D is high temperature coal-tar, and modification raw material E is de-oiled asphalt, this five kinds
The property of modification raw material is shown in Table 1.
Embodiment 1-5
On middle- scale device, makes to modify raw material progress conversion reaction first, then carry out the separating treatment of converted product, point
It is carried out in two fractionating columns from processing, obtains the first separation product and the second separation product, conversion reaction and separating treatment
Actual conditions and result are listed in table 2.
Embodiment 6-8
On middle- scale device, makes to modify raw material progress conversion reaction first, then carry out separating treatment, separating treatment is two
Carried out in a fractionating column, obtain the first separation product and the second separation product, the actual conditions of conversion reaction and separating treatment and
As a result it is listed in table 3.
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, conversion reaction is carried out as raw material to modify raw material B and modification raw material C, is then carried out at separation
Reason, separating treatment carry out in two fractionating columns, obtain the first separation product and the second separation product.First separation product again into
Row extraction and separation obtain modification oil and residue.A part circulation of residue, rest part are got rid of outside.By the residue of circulation respectively with
Conversion reaction is carried out after modification raw material B and modification raw material C mixing, separating treatment, extraction and separation is successively carried out thereafter, is modified
Oil and residue.Second separation product of acquisition is separated, naphtha cut and AGO (atmospheric gas oil) are obtained.Each step it is specific
Condition and result are listed 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 residue is recycled
Rate and modification oil yield.
Embodiment 14
On middle- scale device, conversion reaction is carried out to modify raw material B as modification raw material, separating treatment is then carried out, separates
Processing carries out in two fractionating columns, obtains the first separation product and the second separation product.First separation product is extracted again
It separates (extraction and separation condition is with embodiment 12), obtains modification oil and residue.A part of residue is and fresh as recycle stock
Conversion reaction is carried out together after modification raw material B mixing, is got rid of outside rest part residue.The converted product of mixed raw material is successively at two
It separates, carries out extraction and separation (extraction and separation condition is with embodiment 12) in fractionating column, obtain modification oil and residue.It will obtain simultaneously
The second separation product separated, obtain naphtha cut and AGO (atmospheric gas oil).The actual conditions and result of each step are listed in
Table 6-1 and table 6-2.
Comparative example 1 is to comparative example 4
It is identical as the basic procedure of embodiment 14, it is only changed according to table 7-1, the same embodiment of extraction and separation condition
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 1-4.5 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.
Table 1
Table 2
Table 3
Table 4
Table 5-1
Table 5-2
Table 6-1
| Project | Embodiment 14 |
| Modify raw material | Modify raw material B+ residue |
| Residue source | Itself (embodiment 14) |
| Conversion reaction | |
| Reaction temperature/DEG C | 425 |
| Reaction pressure/megapascal | 18 |
| Reforming catalyst | Ammonium molybdate |
| Volume space velocity/hour-1 | 0.15 |
| Catalyst charge/(micro- gram gram) | 1000 |
| Hydrogen partial pressure/megapascal | 17.4 |
| The volume ratio of hydrogen and modification raw material | 1300 |
| Converted product processing | |
| First pressure/megapascal | 18 |
| First temperature/DEG C | 410 |
| Second pressure/megapascal | 1.5 |
| Second temperature/DEG C | 320 |
Table 6-2
| Project | Embodiment 14 |
| Conversion ratio/% of conversion reaction | 55.3 |
| Product distribution/weight % | |
| First separation product | 67.7 |
| 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/% | 92.6 |
| Modify oil yield/% | 86.4 |
| Modify oily content of beary metal/weight (micro- gram gram) | <1 |
| Modify oil asphalt matter content/weight % | <0.1 |
| Toluene insolubles yield/weight % | 0.9 |
| Stable operation number of days | > 30 days |
Table 7-1
Table 7-2
Claims (16)
1. a kind of method for modifying of low-quality oil, this method comprises:
(1) the low-quality oil as modification raw material is subjected in conversion reactor under hydro condition conversion reaction, is turned
Change product；Wherein, the modification raw material includes being selected from least one of asphalitine, asphaltene and preasphaltene asphalt component,
The conversion ratio of the conversion reaction is 30-70 weight %, the conversion ratio of the conversion reaction=(boiling range is 524 in modification raw material
DEG C or more weight of the boiling range in 524 DEG C or more components in weight-converted product of component) in/modification raw material boiling range 524 DEG C with
The weight of upper component × 100 weight %；
(2) gained converted product in step (1) 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 %；
(3) the first separation product of gained in step (2) is subjected in extract and separate unit extraction and separation, it is oily and residual obtains modification
Slag；
(4) conversion reaction will be carried out in residue return step (1) obtained in step (3)；Alternatively, by institute in step (3)
The residue obtained carries out outer get rid of；Alternatively, by the conversion reaction is carried out in residue return step (1) obtained in part steps (3),
Remainder residue carries out outer get rid of.
2. method for modifying according to claim 1, in step (1), the conversion ratio of the conversion reaction is 30-60 weight
Measure %.
3. method for modifying according to claim 1, in step (1), 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, and the volume for modifying raw material is empty
Speed is 0.01-2 hours-1, hydrogen and modification raw material volume ratio be 500-5000, in terms of metal in the reforming catalyst and with
On the basis of the weight for modifying raw material, the dosage of the reforming catalyst is micro- gram gram of 10-50000.
4. 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.
5. 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.
6. method for modifying according to claim 1, in step (2), 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.
7. method for modifying according to claim 1, in step (2), the separating treatment includes:
(2-1) separates gained converted product in step (1) at a temperature of first pressure and first, obtain gas component and
Liquid component；
(2-2) 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.
8. method for modifying according to claim 7, wherein first pressure 4-24 megapascal bigger than second pressure.
9. method for modifying according to claim 7, 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.
10. method for modifying according to claim 7, wherein the separating treatment further include:
(2-3) cuts the second separation product of gained in step (2-2), obtains naphtha and AGO (atmospheric gas oil)；And/or
(2-4) will carry out conversion reaction in gained gas component return step (1) in step (2-1).
11. method for modifying according to claim 1, in step (3), 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.
12. method for modifying according to claim 1, in step (3), the softening point of the residue is less than 150 DEG C.
13. method for modifying according to claim 1, in step (4), the ratio of the residue in return step (1) is greater than 80
Weight %.
14. method for modifying according to claim 1, in step (4), will be got rid of outside the residue of part, the residue got rid of outside accounts for described
The ratio of raw material is modified less than 10 weight %.
15. a kind of reforming system of low-quality oil, which includes conversion reactor (7), separation processing unit and extraction and separation
Unit (16)；
The conversion reactor (7) is provided with reaction mass entrance and converted product outlet, and the separation processing unit is provided with
Feed(raw material)inlet and the outlet of the first separation product are handled, the extract and separate unit (16) is provided with extractant entrance, extraction original
Expect entrance, modification oil export and solid discharge；
The converted product outlet of the conversion reactor (7) is connected with the processing feed(raw material)inlet of the separation processing unit, institute
The the first separation product outlet for stating separation processing unit is connected with the extraction feed entrance of the extract and separate unit (16), institute
The solid discharge for stating extract and separate unit (16) is optionally connected with the reaction mass entrance of the conversion reactor (7).
16. system according to claim 15, wherein the separation processing unit includes high pressure separative unit (9) and low pressure point
From unit (13), the high pressure separative unit (9) is provided with gas component outlet, liquid component outlet and the processing raw material and enters
Mouthful, the low pressure separative unit (13) is provided with low pressure feed(raw material)inlet, the outlet of the second separation product and first separation product
The liquid component outlet of outlet, the high pressure separative unit (9) is connected with the feed(raw material)inlet of the low pressure separative unit (13).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710814175.XA CN109486518B (en) | 2017-09-11 | 2017-09-11 | Method and system for modifying low-quality oil |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710814175.XA CN109486518B (en) | 2017-09-11 | 2017-09-11 | Method and system for modifying low-quality oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109486518A true CN109486518A (en) | 2019-03-19 |
| CN109486518B CN109486518B (en) | 2021-01-08 |
Family
ID=65688926
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710814175.XA Active CN109486518B (en) | 2017-09-11 | 2017-09-11 | Method and system for modifying low-quality oil |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109486518B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574778A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Inferior oil hydro-upgrading method and system |
| CN114058405A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Inferior oil hydroconversion reaction method and system |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102834490A (en) * | 2010-04-13 | 2012-12-19 | Ifp新能源公司 | Process for the hydroconversion of petroleum feedstocks via slurry technology allowing the recovery of metals from the catalyst and feedstock using a leaching step |
-
2017
- 2017-09-11 CN CN201710814175.XA patent/CN109486518B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102834490A (en) * | 2010-04-13 | 2012-12-19 | Ifp新能源公司 | Process for the hydroconversion of petroleum feedstocks via slurry technology allowing the recovery of metals from the catalyst and feedstock using a leaching step |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112574778A (en) * | 2019-09-27 | 2021-03-30 | 中国石油化工股份有限公司 | Inferior oil hydro-upgrading method and system |
| CN112574778B (en) * | 2019-09-27 | 2022-07-15 | 中国石油化工股份有限公司 | Inferior oil hydro-upgrading method and system |
| CN114058405A (en) * | 2020-07-30 | 2022-02-18 | 中国石油化工股份有限公司 | Inferior oil hydroconversion reaction method and system |
| CN114058405B (en) * | 2020-07-30 | 2023-09-05 | 中国石油化工股份有限公司 | Hydroconversion reaction method and system for inferior oil |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109486518B (en) | 2021-01-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105765036B (en) | By the method for transformation of the integrated heavy hydrocarbon feedstocks of selectivity cascade depitching and the recycling of de-asphalted fraction | |
| RU2759287C2 (en) | Method and system for improving quality of low-quality oil | |
| CN105602616A (en) | Hydrocarbon material hydrogenation method and combined expanded bed hydrogenation reactor | |
| RU2005117790A (en) | METHOD FOR PROCESSING HEAVY RAW MATERIALS, SUCH AS HEAVY RAW OIL AND CUBE RESIDUES | |
| US9809763B2 (en) | Process and apparatus for recovering hydrotreated hydrocarbons with two strippers | |
| CN104962307B (en) | Method for producing light oil through coal liquefaction | |
| CN111465675B (en) | Process and apparatus for recovering products of slurry hydrocracking | |
| CN104995284A (en) | Method for converting a heavy hydrocarbon feedstock incorporating selective deasphalting with recycling of the deasphalted oil | |
| US3637483A (en) | Synthetic lubricating oil stock production | |
| CN109486518A (en) | A kind of method for modifying and system of low-quality oil | |
| US10041011B2 (en) | Processes for recovering hydrocarbons from a drag stream from a slurry hydrocracker | |
| CN105567319B (en) | A kind of method for handling mink cell focus | |
| US20070227947A1 (en) | T-6604 full conversion hydroprocessing | |
| CN109486519A (en) | A kind of method for modifying and system by low-quality oil production high-knock rating gasoline | |
| WO2009014303A1 (en) | Method for producing feedstocks of high quality lube base oil from coking gas oil | |
| CN109486517A (en) | A kind of low-quality oily method for modifying that realizing metal reuse and system | |
| CN104611031A (en) | Process method for maximally producing chemical industry raw material | |
| CN106190292B (en) | A kind of method by wax tailings production environment-friendly aromatic type rubber filling oil | |
| CN109486515A (en) | A kind of method and system that poor oil efficiently modifies | |
| CN111040808B (en) | Inferior oil upgrading method and system for high-yield heavy upgraded oil | |
| CN109486521A (en) | A kind of method and system that catalytic cracked oil pulp efficiently utilizes | |
| CN114058405B (en) | Hydroconversion reaction method and system for inferior oil | |
| CN112574778B (en) | Inferior oil hydro-upgrading method and system | |
| CN109486522B (en) | Method and system for producing fuel oil, aviation kerosene and diesel oil | |
| TWI757337B (en) | A kind of modification method and modification system of low-quality oil |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |