CN108359493A - The method that catalytically cracked gasoline is modified - Google Patents
The method that catalytically cracked gasoline is modified Download PDFInfo
- Publication number
- CN108359493A CN108359493A CN201810129407.2A CN201810129407A CN108359493A CN 108359493 A CN108359493 A CN 108359493A CN 201810129407 A CN201810129407 A CN 201810129407A CN 108359493 A CN108359493 A CN 108359493A
- Authority
- CN
- China
- Prior art keywords
- oil
- extraction
- gasoline
- solvent
- fraction
- 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
-
- 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
- C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1037—Hydrocarbon fractions
-
- 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
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a kind of method modified to catalytically cracked gasoline.The method of the present invention, includes the following steps：Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；The pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；Solvent extraction is carried out to the middle fraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；At least partly described light olefin is back to and carries out carrying out backwash in the solvent-extracted system；Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.The method of the present invention does not lose octane number substantially while reducing sulfur content and olefin(e) centent.
Description
Technical field
The invention belongs to technical field of petrochemical industry, and in particular to a method of catalytically cracked gasoline is modified.
Background technology
In recent years, with the influence of the pollution problems such as haze weather caused by vehicle exhaust, requirement of the people to environmental protection
It increasingly improves, the new standard of stringent clean gasoline has been formulated in countries in the world in succession.For example, the Europe V that European Union promulgated in 2011
Motor petrol standard regulation olefin(e) centent in 18v% hereinafter, sulfur content in 10ppm hereinafter, octane number maintains 95 or more；China
In on December 23rd, 2016 promulgate state VI motor petrol standards require olefin(e) centent in 18v% hereinafter, sulfur content 10ppm with
Under, octane number is 93 or more.Therefore, what gasoline quality standard improved is mainly shown as：10ppm or less is maintained making sulfur content
While reduce and olefin(e) centent and improve octane number.
Currently, the motor petrol reconciliation pond of developed country is distributed more widely, wherein 1/3 or so is catalytically cracked gasoline, no alkene
Hydrocarbon content Reformed Gasoline accounts for 1/3 or so, and both the gasoline such as isomerization, alkylation of aromatic-free or non-olefin-containing account for 1/3 left side in addition
It is right.It is therefore possible to use the method that gasoline reconciles makes merchantable gasoline reach standard, so that the sulfur content of gasoline and alkene contain
Measure low, and octane number is high.
Catalytically cracked gasoline (i.e. FCC gasoline) is the chief component of China's motor petrol, in gasoline reconciliation Chi Zhongzhan
75% or so.Catalytically cracked gasoline has the characteristics that high alkene (30-45v%), high sulfur content (150-1000ppm).It is reported that I
The alkene of the sulphur of 85-95wt% and 95v% come from catalytically cracked gasoline in state's merchantable gasoline, are to cause China's motor petrol
It is difficult to meet the main reason for sulfur content is less than 18v% less than 10ppm, olefin(e) centent, therefore the merchantable gasoline in China is far from
The standard of state's V gasoline can be met.
China depends on hydrodesulfurization technology for the processing of catalytically cracked gasoline, which disclosure satisfy that sulfur content
Less than the requirement of 10ppm and reduction alkene, however olefin(e) centent is reduced in a manner of adding hydrogen to be saturated as alkane, to cause
The reduction of gasoline products octane number cannot not only meet the target that desulfurization drop alkene protects octane number, seriously affect enterprise in addition
Economic benefit.
Currently, main desulfurization drop alkene technique remains as hydrodesulfurization in the world, can not be kept away in hydrogenation process
Result in the saturation of a large amount of alkene with exempting from so that octane number loss is serious, to seriously affected quality of gasoline and
The economic benefit of enterprise.With the increasingly heaviness and in poor quality of raising and crude oil of environmental requirement, desulfurization drops alkene and protects octane
The problem of value, seems more prominent so that each large enterprises have to the technique for researching and developing new catalytically cracked gasoline quality upgrading.
Existing catalytically cracked gasoline sulfur reduction technology is mainly with Sinopec S-zorb, Shi Ke institute RSDS and France Prime-
G+ is representative.Wherein, S-zorb is used for full fraction catalytic gasoline desulfurization, and the sulfur content of gasoline can be controlled in 10ppm after desulfurization
Hereinafter, however the loss of distillation gasoline octane number is in 1.0-2.0 unit entirely；Catalytic gasoline is first cut into weight by RSDS technique
Extraction desulfurization alcohol is passed through in fraction, light fraction, and heavy distillat carries out selective hydrodesulfurization, in production sulfur content less than 10ppm's
Light fraction yield is 20% or so when product, is largely needed plus hydrogen, the loss of octane number of full distillation gasoline 3.0-4.0 it
Between；Prime-G+ is divided using full fraction pre-add hydrogen, weight gasoline and the technological process of heavy distillat selective hydrodesulfurization, although
Part low-sulfur light component is not necessarily to hydrotreating, however light component yield is less, largely still needs to hydrotreating, leads to full fraction vapour
The loss of octane number of oil is between 3.0-4.0.
The existing technology for reducing sulfur content of catalytic cracking gasoline is when coping with deep desulfuration requirement, generally existing hydrotreating
The problems such as ratio is big, loss of octane number is more, drop alkene and sulfur reduction is uncoordinated；Therefore, there is an urgent need to develop reduce sulfur content and
The catalytically cracked gasoline quality upgrading technology that octane number does not lose substantially while olefin(e) centent.
Invention content
The present invention provides a kind of method modified to catalytically cracked gasoline, and this method contains in reduction sulfur content and alkene
Substantially octane number is not lost while amount.
The present invention provides a kind of method modified to catalytically cracked gasoline, includes the following steps：
Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；
The pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；
Solvent extraction is carried out to the middle fraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
At least partly described light olefin is back to and carries out carrying out backwash in the solvent-extracted system；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.
The present invention does not limit catalytically cracked gasoline strictly；Specifically, the olefin(e) centent in catalytically cracked gasoline can be with
≤ 40%.In the present invention, unless otherwise specified, pressure refers to that gauge pressure, content refer to mass content.
The present invention carries out pre-add hydrogen to catalytically cracked gasoline, is used for the trechmannite compound and alkadienes in catalytically cracked gasoline
Effect forms high boiling sulfide, situations such as to avoid alkadienes from generating coking during subsequent technique, to ensure
The longtime running of heavy fractioning hydrogenation desulfurization；During pre-add hydrogen, the alkene in catalytically cracked gasoline is not saturated.
The present invention does not limit pre- hydrogenation technique strictly, for example, may be used this field routine alkali-free sweetening technique or
The pre- hydrogenation techniques of Prime-G+.
In the concrete scheme of the present invention, the pre-add hydrogen is carried out in the presence of catalyst for pre-hydrogenation；Wherein, pre-add hydrogen is urged
Agent is Ni-Mo/Al2O3(nickel molybdenum bimetallic catalyst), composition for example can be (mass content %)：Al2O3(carrier)
90.5%, Ni 6%, Mo 3.5%；Pre- hydrogenation process conditions can be：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen
Oil volume ratio is 10: 1, and reaction temperature is 110 DEG C.
In the present invention, the cutting be pre- hydrogenation catalyst cracking gasoline is cut into from low to high according to boiling range it is light, in,
Weigh three fractions；This field conventional method may be used and carry out the cutting, such as distillation cutting may be used etc..
In the concrete scheme of the present invention, the cutting temperature of the light fraction and middle fraction is 35-65 DEG C, further for
50-60℃；The middle fraction and the cutting temperature of heavy distillat are 100-160 DEG C；That is, the boiling range of middle fraction be 35-65 DEG C extremely
100-160℃。
Based on C5, C6, sulfur content is less than 10ppm, can be used as gasoline reconciliation group for the light fraction formed through above-mentioned cutting
Divide and uses；Middle fraction is based on C6-C8；Double distilled is divided into C9 or more fractions.
In the present invention, after being carried out to the light olefin that recycling obtains according to the olefin(e) centent in catalytically cracked gasoline
Continuous processing.
Specifically, the olefin(e) centent in the catalytically cracked gasoline<When 30%, all light olefins can be returned
It is back to and carries out carrying out backwash in the solvent-extracted system.
In addition, olefin(e) centent in the catalytically cracked gasoline >=30% when, can be by a part of light olefin
It is back to and carried out in the solvent-extracted system backwash, and catalytic cracking is carried out to light olefin described in another part
Freshening or selective hydrodesulfurization.Wherein, the olefin(e) centent in the catalytically cracked gasoline can be 30-40%；It comes back for
The light olefin of backwash and the volume ratio for the light olefin for carrying out catalytic cracking freshening or selective hydrodesulfurization can be (3-
4)：1.
In the present invention, solvent extraction mainly utilizes aromatic hydrocarbons and alkene, alkane and cycloalkane in fraction in solvent realization
Directional separation；The present invention does not limit solvent used by solvent extraction strictly, as long as above-mentioned directional separation can be realized
, such as diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, dimethyl sulfoxide, sulfolane, N- N-formyl morpholine Ns, N- crassitudes may be used
The double solvents that a kind of solvent or two or more combinations in ketone, polyethylene glycol, propene carbonate etc. are formed.In particular, above-mentioned
The water content of solvent preferred by weight percentage ＜ 1.0%, further preferably 0.5-0.8%.
In the concrete scheme of the present invention, solvent extraction is carried out using the double solvents of sulfolane and N-Methyl pyrrolidone
(i.e. using the double solvents as solvent), wherein volume content of the N-Methyl pyrrolidone in the double solvents are 5-
40%, it is further 5-20%.
Research shows that：When carrying out solvent extraction using above-mentioned double solvents, the alkene mass content in raffinate oil is 40-
45%, the aromatics quality content in extraction oil is 60-70%；And when sulfolane being used to carry out solvent extraction, the alkene in raffinate oil
Hydrocarbon mass content is 35-40%, and the aromatics quality content in extraction oil is 50-55%.It is indicated above that the present invention's is above-mentioned compound
The high selectivity of solvent, when carrying out solvent extraction using the double solvents, the alkene mass content in raffinate oil increases by 5 percentages
Point or so, the aromatics quality content in extraction oil increases 10-15 percentage points or so, to be conducive to aromatic hydrocarbons and alkene in middle fraction
The directional separation of hydrocarbon.
In the present invention, the usual manner that this field may be used carries out solvent extraction；Specifically, the solvent extraction can
To include：
The middle fraction is set to enter from extraction tower middle and lower part, solvent enters from extraction tower top, controls the tower top of extraction tower
Temperature is 50-105 DEG C, and column bottom temperature is 35-80 DEG C, and tower top pressure (absolute pressure) is 0.2-0.8MPa, solvent and middle fraction
Charge ratio be 1.0-5.0.
Further, the tower top temperature of extraction tower is preferably 50-70 DEG C, and tower top pressure (absolute pressure) is preferably 0.5-
The charge ratio of 0.6MPa, solvent and middle fraction are preferably controlled in 2.0-3.0.
Sulfur content in the raffinate oily (i.e. fraction in desulfurization) formed through above-mentioned solvent extraction is less than 10ppm, can conduct
Gasoline blend component uses.
In the present invention, usual manner may be used, light olefin (referred to as light alkene) recycling is carried out to extraction oil；Wherein, it returns
The light olefin of receipts includes mainly C5 alkene.
Specifically, the light olefin recycling can be carried out in recovery tower, wherein the tower top temperature of recovery tower can be controlled
Degree is 80-95 DEG C, tower top pressure 0.05-0.2MPa, and column bottom temperature is 150-180 DEG C, tower bottom pressure 0.05-0.2MPa.
In the present invention, at least partly described light olefin is back to and carried out instead in the solvent-extracted system
It washes and (is stripped), for making macromolecular alkene from displacement to raffinate oil in extraction oil, to be flowed out from extraction tower tower top.Tool
Body, the light olefin can enter from the lower part of extraction tower.At this point, middle fraction carries out multistage with solvent in extraction tower epimere
After counter current contacting, raffinate oil (fraction in desulfurization) is flowed out from tower top；Meanwhile the light olefin of recycling is contacted with solvent in bottom of tower,
It to be replaced macromolecular alkene into raffinate oil from extraction oil, and then flows out, and contains from tower top together with fraction in desulfurization
There is the sulfur-rich oil (i.e. sulfur-rich middle fraction) of sulfide, aromatic hydrocarbons, cycloolefin to be flowed out from bottom of tower.
Research shows that：In solvent extraction process, the smaller then solvent of homologous series of hydrocarbon carbon number is higher to its solubility, and carbon number is bigger
Then opposite (i.e. low-carbon alkene has the solubility of bigger in a solvent)；Light olefin is back to solvent extraction by the present invention
In be stripped, higher olefins separation displacement can be made in raffinate oil, to obtain the higher raffinate oil of olefin(e) centent and
The higher extraction oil of arene content significantly improves separating effect of the solvent to alkene and aromatic hydrocarbons.
Research shows that：After light olefin is come back for solvent extraction, the mass content of alkene is 45%- in raffinate oil
50%；When without light olefin being come back for solvent extraction, the mass content of alkene is 40%-45% in raffinate oil.It will be light
Matter alkene comes back for solvent extraction, can make 5 percentage points or so of the mass content raising of alkene in raffinate oil, alkene and virtue
The separating effect of hydrocarbon is further enhanced.
In the present invention, conventional achievable mode in the prior art may be used and carry out selective hydrodesulfurization, such as
S-zorb, RSDS, OCT-M, Prime-G may be used+, the selective desulfurizations technology such as CODS and other selective deep desulfuration skills
Any one of art or two or more combinations.
In the concrete scheme of the present invention, it is de- that the selective hydrogenation is carried out in the presence of catalyst for selectively hydrodesulfurizing
Sulphur, the present invention do not make considered critical to catalyst for selectively hydrodesulfurizing, can be the catalyst of this field routine, such as disclose
Number for the catalyst etc. disclosed in the Chinese patent of CN104673376A.
Specifically, the catalyst for selectively hydrodesulfurizing can be obtained by carrier loaded active metal components；Wherein, institute
It can be molecular sieve (such as X-type, Y types or ZSM-5 types) or metal oxide (such as alundum (Al2O3)), the activity to state carrier
Metal may include Co and Mo, and the gross mass content of Co and Mo in catalyst for selectively hydrodesulfurizing can be 5-20%.More
Further, the mass ratio of the Co and Mo of supported on carriers can be (0.2-0.8)：1.
In the present invention, the selective hydrodesulfurization can carry out in fixed bed reactors.Further, the choosing
The temperature of selecting property hydrodesulfurization is 200-305 DEG C, pressure 1.5-3.0MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio is
300-600.The desulfurization heavy distillat obtained through above-mentioned selective hydrodesulfurization, sulfur content are 10ppm hereinafter, gasoline tune can be used as
It is used with component.
Since sulfide, aromatic hydrocarbons, cycloolefin are the main components for constituting sulfur-rich oil, in chosen property hydrodesulfurization,
Sulfide is decomposed removing, and aromatic hydrocarbons is not involved in reaction, and cycloolefin adds hydrogen saturation that can improve octane number, therefore octane number does not lose.
In the present invention, the progress of pre-lift pipe reactor may be used in catalytic cracking freshening；In addition, catalytic cracking freshening can
To be carried out in the presence of catalytic cracking catalyst, catalytic cracking catalyst is specially industrial equilibrium catalyst, such as ZSM-5 molecules
Sieve, USY molecular sieve etc.；It is possible to further control 600-650 DEG C of the temperature of the catalytic cracking freshening, oil ratio 90-
110, recycle ratio 0.1-0.2.Under the above-described reaction conditions, C5/C6 alkene is totally converted substantially, is ultimately formed catalytic cracking and is returned
Oil refining.
It is possible to further be reconciled to above-mentioned light fraction, raffinate oil, catalytic cracking recycle oil and desulfurization heavy distillat.
In addition, the method for the present invention can also be combined with various octane value recovering techniques, in desulfurating and reducing olefinic hydrocarbon
While, reduce the octane number that loss of octane number even improves product.
The present invention is by forming distribution to Sulfur Content in Catalytic Cracking Gasoline, olefin(e) centent and arene content isofamily and narrow evaporating
The research of point octane Distribution value, by the catalytically cracked gasoline through pre-add hydrogen be divided into it is light, in, weigh three fractions, for each fraction
Impurity content distribution and octane Distribution value concrete condition, catalytically cracked gasoline is carried out using specific processing mode comprehensive
Modification processing, not only realize deep desulfuration, the gasoline fraction sulfur content that makes that treated deteriorates to less than 10ppm or even small
In 6ppm；Importantly, olefin(e) centent is also down to 18v% hereinafter, simultaneously by the damage control of octane number in 0.8 unit
Within, realize sulfur reduction, drop alkene and the target for not losing octane number.
Description of the drawings
Fig. 1 is the process flow chart modified to catalytically cracked gasoline of an embodiment of the present invention；
Fig. 2 is the process flow chart of another embodiment of the present invention modified to catalytically cracked gasoline；
Fig. 3 is the process flow chart of a further embodiment of the present invention modified to catalytically cracked gasoline.
Specific implementation mode
To make the object, technical solutions and advantages of the present invention clearer, the attached drawing below in conjunction with the present invention and implementation
Example, technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention
A part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not having
The every other embodiment obtained under the premise of creative work is made, shall fall within the protection scope of the present invention.
In conjunction with shown in Fig. 1 to Fig. 3, the method that the present invention modifies catalytically cracked gasoline includes the following steps：
Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；
Pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；
Centering fraction carries out solvent extraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；
Light olefin recycling is carried out to extraction oil, obtains light olefin and sulfur-rich oil；
At least partly light olefin it will be back to and carry out carrying out backwash in solvent-extracted system；
Selective hydrodesulfurization is carried out to heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.
As shown in Figure 1, the olefin(e) centent in catalytically cracked gasoline<When 30%, whole light olefins are back to progress
Backwash is carried out in solvent-extracted system.
As shown in Figures 2 and 3, when the olefin(e) centent in catalytically cracked gasoline >=30%, a part of light olefin is returned
It is back to and carried out in solvent-extracted system backwash, and catalytic cracking freshening (Fig. 2) is carried out to another part light olefin
Or selective hydrodesulfurization (Fig. 3).
Embodiment 1
As shown in Fig. 2, the method modified to catalytically cracked gasoline of the present embodiment, includes the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is shown in Table 1.
The composition of 1 catalytically cracked gasoline raw material of table
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10：1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 60 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 100 DEG C, i.e.,：The boiling range of middle fraction is 60 DEG C to 100 DEG C.
3, solvent extraction and light olefin recycling
Solvent used by solvent extraction is the double solvents of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Volume content of the alkanone in double solvents is 10%.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned double solvents from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 70 DEG C, and column bottom temperature is 45 DEG C, and tower top pressure (gauge pressure) is 0.5MPa, double solvents and middle fraction
Charge ratio be 2.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (including mainly C5 alkene) recycling, wherein control recovery tower
Tower top temperature is 88 DEG C, tower top pressure 0.07MPa, and column bottom temperature is 168 DEG C, and tower bottom pressure 0.095MPa obtains lightweight
Alkene and sulfur-rich oil.
4, backwash and catalytic cracking freshening
A part of light olefin is back in extraction tower and carries out backwash, to replace macromolecular alkene from extraction oil
Into raffinate oil.
Another part light olefin is sent to pre-lift pipe reactor (i.e. FCC apparatus) and carries out catalytic cracking freshening, wherein
The volume ratio of the light olefin and the light olefin for carrying out catalytic cracking freshening that come back for backwash is 3：1；It is urged in catalytic cracking
Catalytic cracking freshening is carried out in the presence of agent, wherein：Catalytic cracking catalyst is ZSM-5 molecular sieve；Also, control catalytic cracking
The temperature of freshening is 650 DEG C, oil ratio 90, recycle ratio 0.2, obtains catalytic cracking recycle oil, and composition is shown in Table 3.
3 catalytic cracking freshening result of table
5, selective hydrodesulfurization
First use CoSO4Solution carries out incipient impregnation, washed, dry and roasting to type ZSM 5 molecular sieve (carrier)
Afterwards, then using (NH4)6Mo7O24.4H2The aqueous solution of O is to having impregnated CoSO4The type ZSM 5 molecular sieve of solution is soaked in equal volume
Catalyst for selectively hydrodesulfurizing is made after washed, dry and roasting in stain；After testing, selective hydrodesulfurization obtained is urged
Total specific surface of agent is 168m2/ g or so, total pore volume are 0.378mL/g or so, and load capacity of the Co on carrier is about
The load capacity of 7%, Mo on carrier is about 10%, and the mass ratio of the Co and Mo of supported on carriers are 0.7：1.
In the presence of above-mentioned catalyst for selectively hydrodesulfurizing, it is de- that selective hydrogenation is carried out to above-mentioned heavy distillat and sulfur-rich oil
Sulphur, the wherein temperature of control selections hydrodesulfurization are 260 DEG C, pressure 1.8MPa, volume space velocity 3.0h-1, hydrogen oil volume
It is 500 than (i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume), obtains desulfurization heavy distillat.
6, oil product reconciles
Above-mentioned light fraction, raffinate oil, catalytic cracking recycle oil and desulfurization heavy distillat are reconciled, high-quality gasoline is obtained
Product；The composition of gasoline products is shown in Table 4.
Embodiment 2
As shown in Fig. 2, the method modified to catalytically cracked gasoline of the present embodiment, includes the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is same as Example 1.
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10: 1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 50 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 130 DEG C, i.e.,：The boiling range of middle fraction is 50 DEG C to 130 DEG C.
3, solvent extraction and light olefin recycling
Solvent used by solvent extraction is the double solvents of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Volume content of the alkanone in double solvents is 5%.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned double solvents from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 50 DEG C, and column bottom temperature is 35 DEG C, and tower top pressure (gauge pressure) is 0.6MPa, double solvents and middle fraction
Charge ratio be 3.0, obtain rich in alkene raffinate oil and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (including mainly C5 alkene) recycling, wherein control recovery tower
Tower top temperature is 80 DEG C, tower top pressure 0.05MPa, and column bottom temperature is 150 DEG C, and tower bottom pressure 0.08MPa obtains lightweight alkene
Hydrocarbon and sulfur-rich oil.
4, backwash and catalytic cracking freshening
A part of light olefin is back in extraction tower and carries out backwash, to replace macromolecular alkene from extraction oil
Into raffinate oil.
Another part light olefin is sent to pre-lift pipe reactor and carries out catalytic cracking freshening, wherein coming back for backwash
Light olefin with carry out catalytic cracking freshening light olefin volume ratio be 4：1；In the presence of catalytic cracking catalyst into
Row catalytic cracking freshening, wherein：Catalytic cracking catalyst is USY molecular sieve；Also, the temperature for controlling catalytic cracking freshening is
625 DEG C, oil ratio 100, recycle ratio 0.15 obtains catalytic cracking recycle oil.
5, selective hydrodesulfurization
Catalyst for selectively hydrodesulfurizing is prepared according to 1 method of embodiment, unlike, loads of the control Co on carrier
Amount is about that load capacity of 4%, the Mo on carrier is about 10%, and the mass ratio of the Co and Mo of supported on carriers are 0.4：1.
In the presence of above-mentioned catalyst for selectively hydrodesulfurizing, it is de- that selective hydrogenation is carried out to above-mentioned heavy distillat and sulfur-rich oil
Sulphur, the wherein temperature of control selections hydrodesulfurization are 300 DEG C, pressure 2.5MPa, volume space velocity 2.0h-1, hydrogen oil volume
It is 400 than (i.e. hydrogen volume and the ratio between heavy distillat and sulfur-rich oily total volume), obtains desulfurization heavy distillat.
6, oil product reconciles
Above-mentioned light fraction, raffinate oil, catalytic cracking recycle oil and desulfurization heavy distillat are reconciled, high-quality gasoline is obtained
Product；The composition of gasoline products is shown in Table 4.
Embodiment 3
As shown in figure 3, the method modified to catalytically cracked gasoline of the present embodiment, includes the following steps：
1, pre-add hydrogen
The composition of the catalytically cracked gasoline raw material of the present embodiment is same as Example 1.
In the presence of catalyst for pre-hydrogenation, pre-add hydrogen is carried out to above-mentioned catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking
Gasoline；Wherein, catalyst for pre-hydrogenation Ni-Mo/Al2O3, consisting of (mass content %)：Al2O390.5%, Ni 6%,
Mo 3.5%；Pre- hydrogenation process conditions are：Hydrogen partial pressure is 2.2MPa, volume space velocity 3.0h-1, hydrogen to oil volume ratio 10：1, instead
It is 110 DEG C to answer temperature.
After above-mentioned pre-add hydrogen, the trechmannite compound in catalytically cracked gasoline acts on forming high boiling vulcanization with alkadienes
Object, alkene are not saturated.
2, it cuts
Above-mentioned pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat, wherein gently, middle fraction cuts
It is 50 DEG C to cut temperature, in, the cutting temperature of heavy distillat be 160 DEG C, i.e.,：The boiling range of middle fraction is 50 DEG C to 160 DEG C.
3, solvent extraction and light olefin recycling
Solvent used by solvent extraction is the double solvents of sulfolane and N-Methyl pyrrolidone, wherein N- methylpyrroles
Volume content of the alkanone in double solvents is 20%.
Make among the above fraction from extraction tower middle and lower part enter, above-mentioned double solvents from extraction tower top enter, wherein controlling
The tower top temperature of extraction tower is 105 DEG C, and column bottom temperature is 80 DEG C, and tower top pressure (gauge pressure) is 0.4MPa, and double solvents is evaporated in
The charge ratio divided is 3.0, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons.
Extraction oil is sent into recovery tower and carries out light olefin (predominantly C5 alkene) recycling, wherein the tower of control recovery tower
It is 95 DEG C, tower top pressure 0.08MPa to push up temperature, and column bottom temperature is 180 DEG C, and tower bottom pressure 0.09MPa obtains light olefin
With sulfur-rich oil.
4, backwash
A part of light olefin is back in extraction tower and carries out backwash, to replace macromolecular alkene from extraction oil
Into raffinate oil.
By another part light olefin with it is sulfur-rich oil and heavy distillat merge after carry out selective hydrodesulfurization, wherein return into
The volume ratio of the light olefin of row backwash and the light olefin for carrying out selective hydrodesulfurization is 3：1.
5, selective hydrodesulfurization
Selective hydrodesulfurization is carried out using the catalyst for selectively hydrodesulfurizing of embodiment 1.
In the presence of catalyst for selectively hydrodesulfurizing, to above-mentioned heavy distillat, it is sulfur-rich oil and another part light olefin into
Row selective hydrodesulfurization, the wherein temperature of control selections hydrodesulfurization are 250 DEG C, and pressure 2.0MPa, volume space velocity are
3.0h-1, hydrogen to oil volume ratio (i.e. the ratio between hydrogen volume and heavy distillat, sulfur-rich oil and another part light olefin total volume) be 300,
Obtain desulfurization heavy distillat.
6, oil product reconciles
Above-mentioned light fraction, raffinate oil and desulfurization heavy distillat are reconciled, high-quality gasoline product is obtained；Gasoline products
Composition is shown in Table 4.
The composition of 4 gasoline products of table
As shown in Table 4：
After aforesaid way using the present invention carries out modification processing comprehensively to catalytically cracked gasoline, the sulfur content of gasoline products
Drop to 6ppm or less；In particular, the olefin(e) centent in gasoline products is reduced to 18v% hereinafter, the loss control of octane number simultaneously
System realizes depth sulfur reduction, drop alkene and the target for not losing octane number substantially within 0.8 unit.
Finally it should be noted that：The above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；To the greatest extent
Present invention has been described in detail with reference to the aforementioned embodiments for pipe, it will be understood by those of ordinary skill in the art that：Its according to
So can with technical scheme described in the above embodiments is modified, either to which part or all technical features into
Row equivalent replacement；And these modifications or replacements, various embodiments of the present invention technology that it does not separate the essence of the corresponding technical solution
The range of scheme.
Claims (10)
1. a kind of method modified to catalytically cracked gasoline, which is characterized in that include the following steps：
Pre-add hydrogen is carried out to catalytically cracked gasoline, obtains pre- hydrogenation catalyst cracking gasoline；
The pre- hydrogenation catalyst cracking gasoline is cut into light fraction, middle fraction and heavy distillat；
Solvent extraction is carried out to the middle fraction, obtains the raffinate oil rich in alkene and the extraction oil rich in aromatic hydrocarbons；
Light olefin recycling is carried out to the extraction oil, obtains light olefin and sulfur-rich oil；
At least partly described light olefin is back to and carries out carrying out backwash in the solvent-extracted system；
Selective hydrodesulfurization is carried out to the heavy distillat and sulfur-rich oil, obtains desulfurization heavy distillat.
2. according to the method described in claim 1, it is characterized in that, olefin(e) centent >=30% in the catalytically cracked gasoline
When, a part of light olefin is back to and carries out carrying out backwash in the solvent-extracted system, and to another part
The light olefin carries out catalytic cracking freshening or the selective hydrodesulfurization.
3. method according to claim 1 or 2, which is characterized in that the cutting temperature of the light fraction and middle fraction is 35-
65 DEG C, the cutting temperature of the middle fraction and heavy distillat is 100-160 DEG C.
4. method according to claim 1 or 2, which is characterized in that the solvent extraction is using diethylene glycol (DEG), triethylene glycol, four
At least one in glycol, dimethyl sulfoxide, sulfolane, N- N-formyl morpholine Ns, N-Methyl pyrrolidone, polyethylene glycol and propene carbonate
Kind solvent carries out.
5. according to the method described in claim 4, it is characterized in that, the solvent extraction uses sulfolane and N- crassitudes
The double solvents of ketone carries out, and wherein volume content of the N-Methyl pyrrolidone in the double solvents is 5-40%.
6. method according to claim 1 or 2, which is characterized in that the solvent extraction includes：
The middle fraction is set to enter from extraction tower middle and lower part, solvent enters from extraction tower top, controls the tower top temperature of extraction tower
It it is 50-105 DEG C, column bottom temperature is 35-80 DEG C, tower top pressure 0.2-0.8MPa, and the charge ratio of solvent and middle fraction is 1.0-
5.0。
7. method according to claim 1 or 2, which is characterized in that carry out the light olefin recycling in recovery tower, control
The tower top temperature of recovery tower processed is 80-95 DEG C, tower top pressure 0.05-0.2MPa, and column bottom temperature is 150-180 DEG C, bottom of tower pressure
Power is 0.05-0.2MPa.
8. method according to claim 1 or 2, which is characterized in that carried out in the presence of catalyst for selectively hydrodesulfurizing
The selective hydrodesulfurization, the catalyst for selectively hydrodesulfurizing are obtained by carrier loaded active metal components；Wherein, institute
It is molecular sieve or metal oxide to state carrier, and the active metal includes Co and Mo, and Co and Mo is urged in selective hydrodesulfurization
Gross mass content in agent is 5-20%.
9. method according to claim 1 or 2, which is characterized in that the temperature of the selective hydrodesulfurization is 200-305
DEG C, pressure 1.5-3.0MPa, volume space velocity 1-5h-1, hydrogen to oil volume ratio 300-600.
10. according to the method described in claim 2, it is characterized in that, carrying out the catalysis in the presence of catalytic cracking catalyst
Cracking freshening wherein the catalytic cracking catalyst is ZSM-5 molecular sieve or USY molecular sieve, and controls the catalytic cracking
The temperature of freshening is 600-650 DEG C, oil ratio 90-110, recycle ratio 0.1-0.2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810129407.2A CN108359493B (en) | 2018-02-08 | 2018-02-08 | Method for modifying catalytic cracking gasoline |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810129407.2A CN108359493B (en) | 2018-02-08 | 2018-02-08 | Method for modifying catalytic cracking gasoline |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108359493A true CN108359493A (en) | 2018-08-03 |
| CN108359493B CN108359493B (en) | 2020-05-26 |
Family
ID=63005075
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810129407.2A Active CN108359493B (en) | 2018-02-08 | 2018-02-08 | Method for modifying catalytic cracking gasoline |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108359493B (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104673363A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for improving octane value of catalytic gasoline |
| CN105296000A (en) * | 2015-09-30 | 2016-02-03 | 中国石油大学(北京) | Coupling method of catalytic cracking gasoline desulfurization |
| CN105647581A (en) * | 2014-11-12 | 2016-06-08 | 中国石油天然气股份有限公司 | Catalytic gasoline hydrogenation method |
| CN106381168A (en) * | 2016-11-16 | 2017-02-08 | 郝智敏 | Catalytic gasoline desulfurization method capable of satisfying maximum light gasoline etherification olefin reduction demands |
| CN106520198A (en) * | 2016-11-16 | 2017-03-22 | 郝智敏 | Catalytic gasoline desulphurization method with olefin selective removing function |
-
2018
- 2018-02-08 CN CN201810129407.2A patent/CN108359493B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105647581A (en) * | 2014-11-12 | 2016-06-08 | 中国石油天然气股份有限公司 | Catalytic gasoline hydrogenation method |
| CN104673363A (en) * | 2015-02-04 | 2015-06-03 | 中国石油大学(北京) | Method for improving octane value of catalytic gasoline |
| CN105296000A (en) * | 2015-09-30 | 2016-02-03 | 中国石油大学(北京) | Coupling method of catalytic cracking gasoline desulfurization |
| CN106381168A (en) * | 2016-11-16 | 2017-02-08 | 郝智敏 | Catalytic gasoline desulfurization method capable of satisfying maximum light gasoline etherification olefin reduction demands |
| CN106520198A (en) * | 2016-11-16 | 2017-03-22 | 郝智敏 | Catalytic gasoline desulphurization method with olefin selective removing function |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108359493B (en) | 2020-05-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105296000A (en) | Coupling method of catalytic cracking gasoline desulfurization | |
| CN105238441B (en) | A kind of method that deep desulfuration is carried out to gasoline | |
| CN102337153B (en) | Hydrotreating method for gasoline distillate | |
| CN108485702B (en) | Method for maximizing aromatic hydrocarbon production by utilizing catalytic cracking gasoline | |
| CN101275084A (en) | Method for reducing sulfur content of catalytically cracked gasoline | |
| CN105255515B (en) | Combination method for producing ultralow sulphur gasoline | |
| DE60221990T2 (en) | Multi-stage method for removing sulfur from fuel components for use in vehicles | |
| CN102399585B (en) | Method for producing sweet gasoline | |
| CN108329944B (en) | Method for co-producing desulfurized low-olefin gasoline and chemical products by using catalytic cracking gasoline | |
| CN108424787B (en) | Method for upgrading quality of high-olefin catalytic cracking gasoline | |
| CN108359495A (en) | The method that high Olefinic catalytic cracking gasoline is modified | |
| KR100980324B1 (en) | A process for reducing sulfur and olefin contents in gasoline | |
| CN106635156B (en) | A kind of method of Deep Desulfurization of FCC Gasoline | |
| CN108315049B (en) | Method for producing aromatic hydrocarbon by using catalytic cracking gasoline | |
| CN104726132A (en) | Process For The Hydrodesulphurization Of Hydrocarbon Cuts | |
| KR101009469B1 (en) | A hydrogenation process for removing mercaptan from gasoline | |
| CN1224675C (en) | Method for producing sweet gasoline | |
| CN108359493A (en) | The method that catalytically cracked gasoline is modified | |
| CN108456552B (en) | Method for producing chemical products by using catalytic cracking gasoline | |
| CN105176581B (en) | A kind of deep desulfurization of gasoline method | |
| CN108315053A (en) | The method that quality upgrading is carried out to catalytically cracked gasoline | |
| CN106554813B (en) | The high-knock rating gasoline production technology of low sulfur, low olefin | |
| CN108018079B (en) | Method for reducing sulfur content of gasoline | |
| CN108359494B (en) | Method for maximally producing chemical products by using catalytic cracking gasoline | |
| CN100510018C (en) | Method for improving quality of gasolene through hydrogenation |
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 |