CN104560164B - A kind of hydrogenation modification method producing high octane gasoline component or BTX raw material - Google Patents
A kind of hydrogenation modification method producing high octane gasoline component or BTX raw material Download PDFInfo
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- CN104560164B CN104560164B CN201310520012.2A CN201310520012A CN104560164B CN 104560164 B CN104560164 B CN 104560164B CN 201310520012 A CN201310520012 A CN 201310520012A CN 104560164 B CN104560164 B CN 104560164B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- 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
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/02—Gasoline
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- 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
A kind of hydrogenation modification method producing high octane gasoline component or BTX raw material.The method enters hydrofining reaction district after being mixed with hydrogen-rich gas by poor ignition quality fuel, contact with Hydrobon catalyst, react, the reaction effluent in hydrofining reaction district separates facility entrance hydro-upgrading reaction zone in the middle of any, successively with the first catalyst for hydro-upgrading, the second catalyst for hydro-upgrading haptoreaction, hydro-upgrading reaction zone effluent obtains hydrogen-rich gas and product liquid after being cooled and separated.Use the method that the present invention provides, with poor-quality diesel-oil by cut fraction as raw material, the content of BTX can be produced in high-knock rating gasoline, and high-knock rating gasoline fraction up to more than 40%.
Description
Technical field
The present invention relates to a kind of by poor ignition quality fuel production high octane gasoline component or the hydro-upgrading side of BTX raw material
Method.
Background technology
Along with crude oil heaviness, the aggravation of in poor quality process, the quality worse becoming of catalytic cracking diesel oil, yield gradually increases
Add.In recent years, in order to improve yield of light oil, in refinery, working ability and the working depth of catalytic cracking unit constantly carry
Height, further results in the increase of catalytic cracking diesel oil yield, degradation.This part poor quality catalytic cracking diesel have density high,
The feature that arene content is high, Cetane number is low.It addition, be the yield improving vehicle fuel, the numerous and confused reconstructed coal in part oil refining enterprise
Tar or coal direct liquefaction oil, wherein the diesel oil distillate of part coal tar or coal direct liquefaction oil also has density height, aromatic hydrocarbons contains
The feature that amount is high, Cetane number is low.
To above-mentioned poor ignition quality fuel component, conventional manufacturing process includes hydrofinishing and is hydrocracked.Use hydrofinishing
Although technique can effectively remove the impurity such as the sulfur in diesel oil, nitrogen, and can be with fractional saturation aromatic hydrocarbons, but diesel product hexadecane
Value increase rate is limited, and diesel oil density also changes not quite.Although hydrocracking process can produce Petroleum and height to greatest extent
The diesel product of quality, but the naphtha cut octane number produced is relatively low.
The problem run into during utilizing according to current above-mentioned poor ignition quality fuel component hydrogenation, domestic and international each oil refining enterprise is numerous and confused
Exploitation correlation technique, during with above-mentioned poor ignition quality fuel component for raw material production high value added product, improves its hydrogenation profit
By the economy of process.It addition, from the point of view of China's gasoline pool is constituted, catalytic gasoline proportion relatively up to 78%, cause gasoline
Alkene is high with sulfur content, arene content is low, octane number is relative on the low side.If making full use of aromatic hydrocarbons in above-mentioned poor ignition quality fuel component to contain
Measure high feature, the antiknock component being translated in gasoline fraction, then can alleviate gasoline pool alkene to a certain extent
The problem that content is high, octane number is the most on the low side.
US7,384,542B1 discloses a kind of method producing low-sulfur diesel-oil and high-knock rating gasoline.This patent is by straight run
Diesel oil and/or light wax tailings (LCGO) enter hydrodesulfurization, hydrodenitrogeneration reaction zone, and catalytic cracking diesel oil (LCO) enters and adds
Hydrogen cracking reaction district, two reaction zones product mixing after enter cold high score, cold low point, subsequently into fractionating system isolated
Antiknock component and low-sulfur diesel-oil.In this invention, hydrocracking reaction district uses amorphous or adding containing low molecule sieve level
Hydrogen Cracking catalyst.This invention can process straight-run diesel oil and/or LCGO, and the part 149～LCO of 343 DEG C, obtain 88～
193 DEG C of heavy naphtha fraction octane numbers 87, > 193 DEG C of sulphur content of diesel fraction are less than 10ppm, Cetane lndex 46.
US20100116712 discloses a kind of mild hydrogenation process and be hydrocracked production low-sulfur diesel-oil and high-octane rating
The method of Petroleum.The method includes a mild hydrogenation processing section and the section of being hydrocracked, and mild hydrogenation processes raw material at least
Comprise the above aromatic hydrocarbons of dicyclo of 40%, contain up to the mononuclear aromatics of 40%, this raw material through mild hydrogenation process after, organic nitrogen content
Needs take off to 20ppm～100ppm.Mild hydrogenation processing section reaction temperature 316 DEG C～426 DEG C, hydrogen dividing potential drop 6.2MPa～
8.3MPa, volume space velocity 0.5h during liquid-1～3h-1.Mild hydrocracking section reaction temperature 316 DEG C～426 DEG C, hydrogen dividing potential drop
6.2MPa～8.3MPa, volume space velocity 0.5h during liquid-1～3h-1, hydrogen-oil ratio 840Nm3/m3～2530Nm3/m3.The method produces
To heavy naphtha do 149 DEG C～204 DEG C, research octane number (RON) more than 85.The method is thought, refined oil organic nitrogen content by
When 20ppm improves to 60ppm, produce the gasoline blend component research octane number (RON) obtained and can improve 7 units.
US4,985,134 discloses a kind of technique producing high-knock rating gasoline.This invention raw material boiling spread is 150
～the light component in the LCO of 327 DEG C, i.e. catalytic cracking light cycle oil.The hydrocracking catalyst used contains Y type molecule
Sieve, USY molecular sieve or dealuminzation Y type molecular sieve.Additionally, more than gasoline fraction less than 232 DEG C or less than 260 DEG C in fractionated products oil
Midbarrel be back to hydrocracking reactor entrance or be back to catalytic cracking reaction zone.
Summary of the invention
It is an object of the invention to improve a kind of by the poor ignition quality fuel raw material production high octane gasoline component of high arene content
Or the method for BTX raw material.Specifically, the present invention is to provide a kind of modifying catalyst combination loading method, mainly solves existing
Technology produces high octane gasoline component or the purpose product yield such as benzene,toluene,xylene is on the low side during BTX raw material problem.
The method that the present invention provides is: poor ignition quality fuel enters hydrofining reaction district, with hydrogenation after mixing with hydrogen-rich gas
Catalyst for refining contact, reaction, the reaction effluent in hydrofining reaction district changes without any middle facility entrance hydrogenation that separates
Qualitative response district, successively with the first catalyst for hydro-upgrading, the second catalyst for hydro-upgrading haptoreaction, hydro-upgrading reaction zone is flowed
Go out and after thing is cooled and separated, obtain hydrogen-rich gas and product liquid.
Wherein, organic nitrogen content need to be taken off to 20 below μ g/g by hydrofining reaction district, simultaneously facilitates the above aromatic hydrocarbons of dicyclo
Being hydrogenated with saturated, it is to avoid the excessive hydrogenation of mononuclear aromatics is saturated, in refined oil, total arene content is more than 60 mass %, wherein monocycle
Arene content more than 45 mass %, preferably total arene content more than 65 mass %, preferably mononuclear aromatics content 50 mass % with
On.
A kind of Hydrobon catalyst with excellent nitrogen removal performance, this catalyst load in described hydrofining reaction district
The hydrogenation of aromatic hydrocarbons above to dicyclo is saturated has preferable selectivity, but satisfies the hydrogenation of the mononuclear aromatics such as alkylbenzene, naphthane
And poor-performing.The present invention have employed the technological parameter matched with catalyst for refining performance, further promote dicyclo with
Upper aromatic hydrocarbons is saturated, is prevented effectively from the mononuclear aromatics such as alkylbenzene, naphthane simultaneously and is hydrogenated with saturated further.In conventional hydro modification essence
Reaction zone processed, compared with poor ignition quality fuel raw material, the refining reaction district total arene content of product liquid is greatly lowered.In the present invention,
By using this catalyst for refining and suitable technological parameter, the loss of total arene content of refining reaction district product can be dropped
As little as less than 10%, refining reaction district product liquid organic nitrogen content can be reduced to 20 below μ g/g simultaneously.
Described hydro-upgrading reaction zone filling at least two modifying catalyst, the i.e. first modifying catalyst and the second modification
Catalyst, two kinds of modifying catalysts have different functions, are seated in hydro-upgrading reaction zone in certain sequence with ratio.Described
The first catalyst for hydro-upgrading there is excellent selective opening cracking function and have certain alkyl side chain cracking function concurrently,
It is seated in top, hydro-upgrading reaction zone by a certain percentage, can isomery, selective opening cracking tetrahydronaphthalene monocycle effectively
Aromatic hydrocarbons.The second described catalyst for hydro-upgrading has excellent alkyl side chain cracking function, is seated in hydrogenation by a certain percentage
Modification bottom, reaction zone, can be the benzene in gasoline component, first by alkyl benzene mononuclear aromatics cracking in diesel component effectively
The high octane gasoline component such as benzene, dimethylbenzene.Two kinds of modifying catalysts are owing to having loaded the metal kind matched with acidic components
Class and tenor, the mononuclear aromatics that effectively prevent gasoline component is hydrogenated with saturated further.
Poor ignition quality fuel boiling spread of the present invention is 165～400 DEG C, and total arene content is higher than 60 mass %, the most always
Arene content is higher than 65 mass %.Described poor ignition quality fuel evaporates selected from catalytic cracking light cycle oil, the diesel oil of coal direct liquefaction oil
Point, the miscella of one or more in the diesel oil distillate of coal tar, or one or more miscella above-mentioned is straight with cycloalkyl
Evaporate the miscella of diesel oil, coker gas oil.
Described hydrofining reaction district process conditions are: hydrogen dividing potential drop 3.5MPa～10.0MPa, reaction temperature 300 DEG C～
450 DEG C, hydrogen to oil volume ratio 400～2500Nm3/m3, volume space velocity 0.2h during liquid-1～6.0h-1.When poor ignition quality fuel raw material nitrogen content
Not higher than during 700 μ g/g, the most individual process conditions are: hydrogen dividing potential drop 4.5MPa～7.5MPa, reaction temperature 330 DEG C～400 DEG C, hydrogen
Oil volume ratio 800～1800Nm3/m3, liquid volume air speed 2.0h-1～3.5h-1.When poor ignition quality fuel raw material nitrogen content is not less than
During 700 μ g/g, the most individual process conditions are: hydrogen dividing potential drop 5.5MPa～8.0MPa, reaction temperature 330 DEG C～410 DEG C, hydrogen oil volume
Ratio 800～1800Nm3/m3, liquid volume air speed 1.5h-1～3.0h-1。
Described hydro-upgrading reaction zone process conditions are: hydrogen dividing potential drop 3.5MPa～10.0MPa, reaction temperature 300 DEG C～
450 DEG C, hydrogen to oil volume ratio 400～2500Nm3/m3, volume space velocity 0.2h during liquid-1～6.0h-1.When poor ignition quality fuel raw material nitrogen content
Not higher than during 700 μ g/g, the most individual process conditions are: hydrogen dividing potential drop 4.5MPa～7.5MPa, reaction temperature 380 DEG C～430 DEG C, hydrogen
Oil volume ratio 800～1800Nm3/m3, liquid volume air speed 0.8h-1～2.5h-1.When poor ignition quality fuel raw material nitrogen content is not less than
During 700 μ g/g, the most individual process conditions are: hydrogen dividing potential drop 5.5MPa～8.0MPa, reaction temperature 380 DEG C～430 DEG C, hydrogen oil volume
Ratio 800～1800Nm3/m3, liquid volume air speed 0.8h-1～2.5h-1。
In terms of the filling cumulative volume of the first modifying catalyst and the second modifying catalyst, the first described modifying catalyst dress
Fill out volume and account for the 1%～99% of total fill able volume, the second described modifying catalyst admission space account for total fill able volume 1%～
99%.If poor ignition quality fuel weight carbon residue or tenor are higher, for preventing the pressure drop of beds from reaching too quickly to limit
Value, can load respectively at the first Hydrobon catalyst bed top and account for hydrofinishing agent volume total amount 5～the hydrogenation protecting of 20%
Agent, to protect major catalyst, to avoid the quick coking of bed.Protective agent is by 1.0～5.0 weight % nickel oxide, 5.5～10.0 heavy % oxidation
Molybdenum and the gamma-aluminium oxide carrier composition with diplopore distribution of surplus.
Described Hydrobon catalyst contains carrier and at least one is selected from group vib selected from VIII with at least one
Metal component.Described carrier contains silica alumina, and this silica alumina is by boehmite and silicon-containing compound
Compositions fired obtain, wherein, described boehmite is the boehmite including at least one 1.1≤n≤2.5
P1；Wherein n=D (031)/D (120), described D (031) represent crystalline substance representated by 031 peak in the XRD spectra of boehmite crystal grain
The crystallite dimension in face, D (120) represents the crystallite dimension of crystal face representated by 120 peaks in the XRD spectra of boehmite crystal grain,
Described 031 peak refers to that in XRD spectra, 2 θ are the peak of 34-43 °, and described 120 peaks refer to that in XRD spectra, 2 θ are the peak of 23-33 °, D=K
λ/(Bcos θ), K are Scherrer constant, and λ is the diffraction wavelength of target type material, and B is the half-peak breadth of diffraction maximum, and 2 θ are diffraction maximum
Position.Described Hydrobon catalyst, in terms of oxide, boehmite intends thin water aluminum in the compositions of silicon-containing compound
The content of stone is 75～97 weight %, effective 80～95 weight %, and the content of silicon-containing compound is 3～25 weight %, preferably 5～20
Weight %.The compositions of described boehmite and silicon-containing compound contains the boehmite P2 of 0.8 ＜ n ＜ 1.1, excellent
Select the boehmite P2 of 0.85 ＜ n ＜ 1.05, count and on the basis of boehmite total amount by oxide, the content of described P2
It is not more than 70 weight %, preferably no greater than 50 weight %.Counting and on the basis of described catalyst by oxide, described catalyst contains
The group VIII metal component of 1～10 weight %, preferably 1.5～5 weight %, the group vib metal component of 5～35 weight %, preferably 6～
30 weight %.Described catalyst contains at least one auxiliary agent in phosphorus or fluorine, counts and on the basis of catalyst by element, institute
State the content of auxiliary agent less than 10 weight %.
The first described modifying catalyst is that one is supported on complex carrier, containing VIII and at least one group vib
The non-precious metal catalyst of metal component.This catalyst contains carrier and at least one is selected from at least one selected from VIII
The metal component of group vib.Described carrier contains the y-type zeolite containing MoNi and alumina component, the described y-type zeolite containing MoNi
Obtained by a kind of y-type zeolite modified through MoNi, count and on the basis of the butt of described zeolite by oxide, described MoNi
Y-type zeolite in the content of MoNi addO-on therapy be 1-50 weight %, preferably 1-40 weight %.On the basis of described carrier, described
In carrier, the content of MoNiY is 0.5-95 weight %, preferably 1-80 weight %, and the content of aluminium oxide is 5-99.5 weight %, preferably
20-99 weight %.On the basis of described catalyst, carrier weight % Han 50-90, preferably 60-85 weight %；Group VIII metal component
Containing 1-10 weight %, preferably 1.5-6 weight %；Group vib metal weight % Han 5-40%, preferably 10-35.With described catalyst as base
Standard, described catalyst preferably comprises the carrier of 60-85 weight %, the nickel oxide of 1.5-6 weight %, the tungsten oxide of 10-35 weight %.
Described catalyst contains the Organic substance of one or more in Organic Alcohol, organic acid, organic amine, described organic compound with
The group VIII counted with oxide and the mol ratio of vib metals component sum are as 0.03-2.Described Organic Alcohol is selected from second two
Alcohol, glycerol, Polyethylene Glycol (molecular weight is 200-1500), diethylene glycol, butanediol, organic acid selected from acetic acid, maleic acid,
Oxalic acid, aminotriacetic acid, 1,2-CDTA, citric acid, tartaric acid, malic acid, machine amine selected from ethylenediamine,
EDTA and ammonium salt thereof, described organic compound and the group VIII in terms of oxide and vib metals component sum mole
Ratio is 0.08-1.5.
The second described modifying catalyst is the VIII base metal and/or group vib non-noble being supported on complex carrier
Metallic catalyst.Described catalyst contains the carrier of 50-90 weight %, the group VIII metal component of 1-10 weight % and 5-40 weight
The group vib metal component of amount %.On the basis of described catalyst, preferably comprise the carrier of 60-85 weight %, 1.5-6.0 weight %
Group VIII metal component, the group vib metal component of 10-35 weight %.On the basis of carrier, the content of aluminium oxide in described carrier
For 5-99.5 weight %, preferably 20-99 weight %, the content of solid acid component is 0.5-95 weight %, preferably 1-80 weight %.Described
One or more in silica alumina and molecular sieve of solid acid component.Described molecular sieve can be to have macropore knot
The zeolite of structure, can be the zeolite with central hole structure, it is also possible to be one or more of zeolite with small structure.Described
Molecular sieve can be one or more in y-type zeolite, Beta zeolite, ZSM-5 zeolite.
After the first described catalyst for hydro-upgrading and the combination of the second catalyst for hydro-upgrading, tetrahydronaphthalene mononuclear aromatics exists
Carry out isomery and selective opening cracking reaction on first catalyst for hydro-upgrading, generate alkyl benzene mononuclear aromatics, give birth to simultaneously
Becoming the aromatic hydrocarbons in the gasoline components such as part benzene,toluene,xylene, remaining unconverted alkyl benzene mononuclear aromatics is at the second hydrogenation
The enterprising step of modifying catalyst carries out dealkylation, continues to generate the aromatic hydrocarbons in the gasoline components such as benzene,toluene,xylene.Logical
Cross the modifying catalyst combination that two kinds are had different cracking activity and hydrogenation activity, be effectively increased benzene,toluene,xylene etc.
The yield of purpose product, simultaneously, it is to avoid the mononuclear aromatics of the little molecule such as benzene, toluene is hydrogenated with saturated further, is significantly carrying
The octane number of gasoline products is improved while high yield of gasoline.
Advantages of the present invention:
(1) present invention uses once by flow process, including hydrofining reaction district and hydro-upgrading reaction zone, is wherein hydrogenated with
Modification reaction zone includes the combination loading of at least two modifying catalyst.By by two kinds of different carriers, different metal load capacity,
The modifying catalyst of different performance is combined, and can be effectively improved the productivity of the purpose products such as benzene,toluene,xylene, improves
Reaction efficiency.
(2) hydrofining reaction district uses the refining catalytic that nitrogen removal performance is good, the saturated performance of the above aromatic hydrogenation of dicyclo is good
Agent and the process conditions matched with catalyst performance, can be effectively retained the above aromatic hydrocarbons of monocycle in hydrofinishing section, with former
Material oil phase ratio, the loss of refined oil total arene content can be reduced to less than 10%.
(3) using at least two modifying catalyst combination loading in the present invention, the first modifying catalyst is to tetrahydronaphthalene list
The selective opening cracking of PAH has good selectivity, has part concurrently to alkyl benzene mononuclear aromatics side chain cracking simultaneously
Performance, the second modifying catalyst the side chain cracking of alkyl benzene mononuclear aromatics is had excellence selectivity.By above-mentioned extremely
The combination loading of few two kinds of modifying catalysts, promotes the selective opening cracking of mononuclear aromatics, the function of alkyl side chain cracking,
Substantially increase the yield of purpose product.
(4) method using the present invention to provide, with poor-quality diesel-oil by cut fraction as raw material, can produce yield more than 40%, sulfur content
Less than 10 μ g/g, the gasoline fraction of research octane number (RON) more than 95.
Accompanying drawing explanation
Accompanying drawing is the schematic flow sheet that the present invention provides method.
Detailed description of the invention
Below in conjunction with the accompanying drawings method provided by the present invention is further detailed.Accompanying drawing is that the present invention uses once
By the schematic diagram of flow process, eliminating much equipment in figure, such as pump, heat exchanger, compressor etc., but this is to ordinary skill
Personnel are known.
As it is shown in figure 1, the method flow that the present invention provides is described in detail as follows: from the poor ignition quality fuel of pipeline 1 through former
Material oil pump 2, pipeline 11, enter hydrofining reaction district 3 after mixing from the hydrogen-rich gas of pipeline 24 and the new hydrogen of pipeline 10,
Contact with protective agent, Hydrobon catalyst, react.The reaction effluent in hydrofining reaction district 3 separates in the middle of any
Hydro-upgrading reaction zone 4 is entered through pipeline 12, contact with the first catalyst for hydro-upgrading, the second catalyst for hydro-upgrading successively,
Reaction, carries out the reaction such as selective opening cracking, alkyl side chain cracking.The reaction effluent of hydro-upgrading reaction zone 4 is through pipeline
13 enter cold high pressure separator 5 carries out gas-liquid separation.The acid water that cold high pressure separator 5 obtains is extracted out by pipeline 15, obtains
Hydrogen-rich gas enters the pressurized Posterior circle of circulating hydrogen compressor 9 through pipeline 16 and utilizes.The product liquid that cold high pressure separator 5 obtains
Entering cold low separator 6 through pipeline 14 and carry out gas-liquid separation further, the acid water of isolated is extracted out through pipeline 18, separates
The gas obtained is through pipeline 19 discharger, and the product liquid of isolated enters fractionating column 7 through pipeline 17 and carries out component cutting.
Overhead stream enters return tank of top of the tower 8, and the lighter hydrocarbons of isolated are extracted out through pipeline 20, and the light naphthar of isolated is through pipeline 21
Extract out.The heavy naphtha of fractionating column 7 isolated is extracted out through pipeline 22, and tower base stream is extracted out through pipeline 23.
The present invention will be further described by the following examples, but not thereby limiting the invention.
The product designation RG series protective agent of protective agent A, the product designation of Hydrobon catalyst B in embodiment
Product designation RHC-100 of RN-411, the first catalyst for hydro-upgrading C and the second catalyst for hydro-upgrading D, above-mentioned by
State's petrochemical industry limited company catalyst Chang Ling branch company produces.
Solid acid component in second catalyst for hydro-upgrading carrier is ZSM-5, the composition of the second catalyst for hydro-upgrading
For, on the basis of described catalyst, the content of ZSM-5 is 70 weight %, and in terms of oxide, the content of Co is 2 weight %, and Mo contains
Amount is 8 weight %, and surplus is aluminium oxide.
Raw oil E and F used in embodiment is all from using the catalytic cracking unit of MIP technology, its nature and characteristic to arrange
In table 1.
From table 1 it follows that the total arene content of raw oil E is up to 88.0%, wherein the above arene content of dicyclo reaches
69.0%, nitrogen content 523 μ g/g；The nitrogen content of raw oil F is up to 1300 μ g/g, and total arene content is up to 86.9 mass %, wherein
The above aromatic hydrocarbons of dicyclo reaches 58.2 mass %, and the actual measurement Cetane number of two kinds of raw oils is respectively less than 20, is typical catalysis bavin inferior
Oil raw material.
Embodiment 1
Raw oil E enters hydrofining reaction district together with hydrogen, contacts with protective agent A, Hydrobon catalyst B, instead
Should, the reaction effluent in hydrofining reaction district is segregated into hydro-upgrading reaction zone, adding with first successively without any centre
Hydrogen modifying catalyst C, the second catalyst for hydro-upgrading D contact, reaction.The reaction effluent of hydro-upgrading reaction zone sequentially enters
Cold high pressure separator, cold low separator, fractionating column etc. separate facility, are cooled and separated, obtain light naphthar, weight after fractional distillation
Petroleum and diesel oil distillate.Wherein diesel oil distillate can be as desired as low-sulfur diesel-oil blend component or return hydrofining reaction
District or hydro-upgrading reaction zone continue to produce high-knock rating gasoline blend component or BTX raw material.Reaction condition is as shown in table 2, produces
Product yield and character are as shown in table 3.
From table 3 it can be seen that gasoline fraction yield 43.5 mass %, sulfur content 3.0 μ g/g, gasoline fraction organon octane
Value 97.2, motor octane number 84.3, arene content 70.0 mass %, BTX content 42.0%.
Embodiment 2
Raw oil E enters hydrofining reaction district together with hydrogen, contacts with protective agent A, Hydrobon catalyst B, instead
Should, the reaction effluent in hydrofining reaction district is segregated into hydro-upgrading reaction zone, adding with first successively without any centre
Hydrogen modifying catalyst C, the second catalyst for hydro-upgrading D contact, reaction.The reaction effluent of hydro-upgrading reaction zone sequentially enters
Cold high pressure separator, cold low separator, fractionating column etc. separate facility, are cooled and separated, obtain light naphthar, weight after fractional distillation
Petroleum and diesel oil distillate.Wherein diesel oil distillate can be as desired as low-sulfur diesel-oil blend component or return hydrofining reaction
District or hydro-upgrading reaction zone continue to produce high-knock rating gasoline blend component or BTX raw material.Reaction condition is as shown in table 2, produces
Product yield and character are as shown in table 3.
From table 3 it can be seen that gasoline fraction yield 55.0 mass %, sulfur content 2.0 μ g/g, gasoline fraction organon octane
Value 96.3, motor octane number 83.4, arene content 66.0 mass %, BTX content 40.0%.
Embodiment 3
Raw oil F enters hydrofining reaction district together with hydrogen, contacts with protective agent A, Hydrobon catalyst B, instead
Should, the reaction effluent in hydrofining reaction district is segregated into hydro-upgrading reaction zone, adding with first successively without any centre
Hydrogen modifying catalyst C, the second catalyst for hydro-upgrading D contact, reaction.The reaction effluent of hydro-upgrading reaction zone sequentially enters
Cold high pressure separator, cold low separator, fractionating column etc. separate facility, are cooled and separated, obtain light naphthar, weight after fractional distillation
Petroleum and diesel oil distillate.Wherein diesel oil distillate can be as desired as low-sulfur diesel-oil blend component or return hydrofining reaction
District or hydro-upgrading reaction zone continue to produce high-knock rating gasoline blend component or BTX raw material.Reaction condition is as shown in table 2, produces
Product yield and character are as shown in table 3.
From table 3 it can be seen that gasoline fraction yield 54.4 mass %, sulfur content 8.0 μ g/g, gasoline fraction organon octane
Value 94.2, motor octane number 82.1, arene content 60.5 mass %, BTX content 37.0%.
Table 1
| Raw oil | E | F |
| Density (20 DEG C), g/cm3 | 0.9632 | 0.9566 |
| Bromine valency, gBr/100g | - | 6.0 |
| Sulfur, μ g/g | 7200 | 9500 |
| Nitrogen, μ g/g | 523 | 1300 |
| Cetane lndex | 19.3 | 20.7 |
| Actual measurement Cetane number | 15.4 | <19.3 |
| Total arene content, quality % | 88.0 | 86.9 |
| The above arene content of dicyclo, quality % | 69.0 | 58.2 |
| Boiling range (ASTM D-86), DEG C | ||
| Initial boiling point | 199 | 201 |
| 10% | 233 | 228 |
| 30% | 254 | 255 |
| 50% | 274 | 274 |
| 70% | 301 | 302 |
| 90% | 328 | 333 |
| The end point of distillation | 347 | 354 |
Table 2
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Hydrofining reaction district: | |||
| Hydrogen dividing potential drop, MPa | 5.0 | 6.4 | 7.0 |
| Reaction temperature, DEG C | 370 | 370 | 380 |
| Volume space velocity, h-1 | 2.5 | 2.0 | 2.3 |
| Hydrogen to oil volume ratio, Nm3/m3 | 1100 | 1300 | 1500 |
| Hydro-upgrading reaction zone: | |||
| Hydrogen dividing potential drop, MPa | 5.0 | 6.4 | 7.0 |
| Reaction temperature, DEG C | 400 | 400 | 410 |
| Volume space velocity, h-1 | 1.2 | 1.5 | 1.3 |
| Hydrogen to oil volume ratio, Nm3/m3 | 1100 | 1300 | 1500 |
Table 3
| Embodiment 1 | Embodiment 2 | Embodiment 3 | |
| Light naphthar: | |||
| Yield, % | 8.1 | 9.3 | 8.5 |
| Density (20 DEG C), g/cm3 | 0.6350 | 0.6270 | 0.6300 |
| Boiling range ASTM D-86, DEG C | |||
| IBP—FBP | 37-67 | 35-65 | 36-65 |
| Gasoline fraction character: | |||
| Yield, % | 43.5 | 55.0 | 54.4 |
| Density (20 DEG C), g/cm3 | 0.832 | 0.827 | 0.822 |
| Sulfur content, μ g/g | 3.0 | 2.0 | 8.0 |
| Research octane number (RON) | 97.2 | 96.3 | 94.2 |
| Motor octane number | 84.3 | 83.4 | 82.1 |
| PONA arene content, % | 70.0 | 66.0 | 60.5 |
| BTX content, % | 42.0 | 40.0 | 37.0 |
| Boiling range ASTM D-86, DEG C | |||
| IBP～FBP | 65～204 | 67～205 | 63～205 |
Claims (16)
1. the hydrogenation modification method producing high octane gasoline component or BTX raw material, it is characterised in that poor ignition quality fuel is with rich
Enter hydrofining reaction district after hydrogen mixing, contact with Hydrobon catalyst, react, the reaction in hydrofining reaction district
Effluent separates facility entrance hydro-upgrading reaction zone in the middle of any, urges with the first modifying catalyst, the second modification successively
Agent haptoreaction, hydro-upgrading reaction zone effluent obtains hydrogen-rich gas and product liquid, described after being cooled and separated
One modifying catalyst contain carrier and at least one selected from VIII and at least one is selected from the metal component of group vib, described load
Body contains the y-type zeolite containing MoNi and alumina component；The described y-type zeolite containing MoNi is by a kind of Y modified through MoNi
Type zeolite obtains, and counts and on the basis of the butt of described zeolite by oxide, MoNi interpolation group in the y-type zeolite of described MoNi
The content divided is 1-50 weight %；The first described modifying catalyst consists of: on the basis of described carrier, contains in described carrier
The content of the y-type zeolite of MoNi is 0.5-95 weight %, and the content of aluminium oxide is 5-99.5 weight %, with described catalyst as base
Standard, carrier weight % Han 50-90, group VIII metal component weight % Han 1-10, group vib metal contains 5-40%；Described poor quality
Diesel boiling range is 165～400 DEG C, and total arene content is higher than 60 mass %.
The most in accordance with the method for claim 1, it is characterised in that described hydrofining reaction district organic nitrogen content need to be taken off to
20 below μ g/g, simultaneously in refined oil total arene content more than 60 mass %, wherein mononuclear aromatics content 45 mass % with
On.
The most in accordance with the method for claim 2, it is characterised in that in refined oil, total arene content is more than 65 mass %, its
Middle mononuclear aromatics content is more than 50 mass %.
The most in accordance with the method for claim 1, it is characterised in that described poor ignition quality fuel selected from catalytic cracking light cycle oil,
The diesel oil distillate of coal direct liquefaction oil, coal tar diesel oil distillate in the miscella of one or more, or above-mentioned one or several
The miscella planted and cycloalkyl straight-run diesel oil, the miscella of coker gas oil.
The most in accordance with the method for claim 1, it is characterised in that described hydrofining reaction district process conditions are: hydrogen divides
Pressure 3.5MPa～10.0MPa, reaction temperature 300 DEG C～450 DEG C, hydrogen to oil volume ratio 400～2500Nm3/m3, volume space velocity during liquid
0.2h-1～6.0h-1。
The most in accordance with the method for claim 5, it is characterised in that when poor ignition quality fuel raw material nitrogen content is not higher than 700 μ g/g,
Hydrofining reaction district process conditions are: hydrogen dividing potential drop 4.5MPa～7.5MPa, reaction temperature 330 DEG C～400 DEG C, hydrogen to oil volume ratio
800～1800Nm3/m3, liquid volume air speed 2.0h-1～3.5h-1；When poor ignition quality fuel raw material nitrogen content is not less than 700 μ g/g,
Described hydrofining reaction district process conditions are: hydrogen dividing potential drop 5.5MPa～8.0MPa, reaction temperature 330 DEG C～410 DEG C, hydrogen oil
Volume ratio 800～1800Nm3/m3, liquid volume air speed 1.5h-1～3.0h-1。
The most in accordance with the method for claim 1, it is characterised in that described hydro-upgrading reaction zone process conditions are: hydrogen divides
Pressure 3.5MPa～10.0MPa, reaction temperature 300 DEG C～450 DEG C, hydrogen to oil volume ratio 400～2500Nm3/m3, volume space velocity during liquid
0.2h-1～6.0h-1。
The most in accordance with the method for claim 7, it is characterised in that when poor ignition quality fuel raw material nitrogen content is not higher than 700 μ g/g,
Described hydro-upgrading reaction zone process conditions are: hydrogen dividing potential drop 4.5MPa～7.5MPa, reaction temperature 380 DEG C～430 DEG C, hydrogen oil
Volume ratio 800～1800Nm3/m3, liquid volume air speed 0.8h-1～2.5h-1；When poor ignition quality fuel raw material nitrogen content is not less than 700 μ
During g/g, described hydro-upgrading reaction zone process conditions are: hydrogen dividing potential drop 5.5MPa～8.0MPa, reaction temperature 380 DEG C～430
DEG C, hydrogen to oil volume ratio 800～1800Nm3/m3, liquid volume air speed 0.8h-1～2.5h-1。
The most in accordance with the method for claim 1, it is characterised in that with the first modifying catalyst and the dress of the second modifying catalyst
Filling out cumulative volume meter, the first described modifying catalyst admission space accounts for the 1%～99% of total fill able volume, the second described modification
Catalyst packing volume accounts for the 1%～99% of total fill able volume.
The most in accordance with the method for claim 1, it is characterised in that described Hydrobon catalyst contains carrier and at least
A kind of metal component being selected from group vib with at least one selected from VIII, described carrier contains silica alumina, this oxidation
Silicon aluminium oxide is obtained by boehmite is fired with the compositions of silicon-containing compound, and wherein, described boehmite is bag
Include the boehmite P1 of at least one 1.1≤n≤2.5；Wherein n=D (031)/D (120), described D (031) represent the thin water of plan
The crystallite dimension of crystal face representated by 031 peak in the XRD spectra of aluminum stone crystal grain, D (120) represents the XRD of boehmite crystal grain
The crystallite dimension of crystal face representated by 120 peaks in spectrogram, described 031 peak refers to that in XRD spectra, 2 θ are the peak of 34-43 °, described
120 peaks refer to that in XRD spectra, 2 θ are the peak of 23-33 °, and D=K λ/(Bcos θ), K are Scherrer constant, and λ is target type material
Diffraction wavelength, B is the half-peak breadth of diffraction maximum, and 2 θ are the position of diffraction maximum.
11. in accordance with the method for claim 10, it is characterised in that described Hydrobon catalyst, in terms of oxide, intends thin
Diaspore is 75～97 weight % with the content of boehmite in the compositions of silicon-containing compound, and the content of silicon-containing compound is
3～25 weight %.
12. in accordance with the method for claim 1, it is characterised in that consisting of of described Hydrobon catalyst, with oxide
Counting and on the basis of described Hydrobon catalyst, described Hydrobon catalyst contains the group VIII metal of 1～10 weight %
Component, the group vib metal component of 5～35 weight %, described Hydrobon catalyst contains at least one in phosphorus or fluorine
Auxiliary agent, counts and on the basis of catalyst by element, and the content of described auxiliary agent is less than 10 weight %.
13. in accordance with the method for claim 1, it is characterised in that the first described modifying catalyst consists of: urge with described
On the basis of agent, described catalyst preferably comprises the carrier of 60-85 weight %, the nickel oxide of 1.5-6 weight %, 10-35 weight
The tungsten oxide of amount %.
14. in accordance with the method for claim 1, it is characterised in that the second described modifying catalyst is to be supported on compound load
VIII base metal on body and/or group vib non-precious metal catalyst；Described catalyst contains the carrier of 50-90 weight %,
The group VIII metal component of 1-10 weight % and the group vib metal component of 5-40 weight %；On the basis of carrier, in described carrier
The content of aluminium oxide is 5-99.5 weight %, and the content of solid acid component is 0.5-95 weight %.
15. in accordance with the method for claim 14, it is characterised in that described solid acid component selected from silica-alumina and
One or more in molecular sieve, described molecular sieve is the zeolite with macroporous structure, or has the zeolite of central hole structure, or
It is one or more of zeolite with small structure.
16. in accordance with the method for claim 15, it is characterised in that described molecular sieve selected from y-type zeolite, Beta zeolite,
One or more in ZSM-5 zeolite.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299759B1 (en) * | 1998-02-13 | 2001-10-09 | Mobil Oil Corporation | Hydroprocessing reactor and process with gas and liquid quench |
| CN1597863A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN102465023A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrogenation modification method for coking gasoline and diesel distillates |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6299759B1 (en) * | 1998-02-13 | 2001-10-09 | Mobil Oil Corporation | Hydroprocessing reactor and process with gas and liquid quench |
| CN1597863A (en) * | 2003-09-15 | 2005-03-23 | 中国石油化工股份有限公司 | Process for hydrogenating modifying faulty gasoline |
| CN102465023A (en) * | 2010-11-05 | 2012-05-23 | 中国石油化工股份有限公司 | Hydrogenation modification method for coking gasoline and diesel distillates |
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