CN109423336A - A kind of method for hydrogen cracking - Google Patents
A kind of method for hydrogen cracking Download PDFInfo
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- CN109423336A CN109423336A CN201710771942.3A CN201710771942A CN109423336A CN 109423336 A CN109423336 A CN 109423336A CN 201710771942 A CN201710771942 A CN 201710771942A CN 109423336 A CN109423336 A CN 109423336A
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- catalyst
- molecular sieve
- hydrocracking
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
-
- 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
- C10G2300/1048—Middle distillates
-
- 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
- C10G2300/1048—Middle distillates
- C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
-
- 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
- C10G2300/1048—Middle distillates
- C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
-
- 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
- C10G2400/04—Diesel oil
Abstract
The invention discloses a kind of method for hydrogen cracking, including following content: (1) diesel raw material is mixed with hydrogen is introduced into hydrofining reactor progress desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction；(2) step (1) effluent enters hydrocracking reactor, hydrocracking reactor contains at least two catalyst bed, and the hydrocracking catalyst containing modified Y molecular sieve in each catalyst bed is incremented by along logistics direction molecular sieve content, catalyst average pore size is successively decreased；(3) hydrocracking reactor effluent is separated into gas phase and liquid phase, and gas phase is recycled, and liquid phase enters fractionating column, and fractionation obtains naphtha, boat coal, diesel oil and tail oil.This method is reasonably combined using diesel oil as raw material by the hydrocracking catalyst of different function, and the heavy naphtha of Gao Fangqian is increased production, and improves boat coal and diesel product quality.
Description
Technical field
The present invention relates to a kind of method for hydrogen cracking, and specifically using diesel oil as raw material, especially straight-run diesel oil is produced
The method for hydrogen cracking of high-quality clean fuel.
Background technique
Hydrocracking technology has strong adaptability to raw material, production operation and the big, good product quality of products scheme flexibility etc.
Various heavy inferiors can be fed high-quality jet fuel, diesel oil, the lube basestocks for being converted into market in urgent need by feature
And chemical industry naphtha and tail oil preparing ethylene by steam cracking raw material, it has also become modern times oil refining and petro chemical industry are most important heavy
One of oily deep processing technique, at home and abroad obtains increasingly extensive application.With the reduction that the current Diesel Market in China needs,
Diesel yield is reduced, volume increase industrial chemicals has become the important means that Petrochemical Enterprises are increased economic efficiency.
CN200610008413.X discloses a kind of combined hydrocracking method, and this method is first by catalytic cracking bavin inferior
Oil carries out hydrotreating, and the raw materials such as crackate and VGO are mixed into the second hydrocracking reaction area, is then demultiplex out various light
Matter product and hydrogenation tail oil, although this method can effectively improve heavy naphtha virtue and dive and tail oil BMCI value, but will affect centre and evaporate
Divide oil quality, increases production low value-added diesel product.
CN200510068180.8 discloses a kind of method for hydrogen cracking of mass production of chemical materials, and this method will
Feedstock oil, hydrogen after heating enter the first reaction zone and successively contact with Hydrobon catalyst, hydrocracking catalyst, react
Logistics is recycled, liquid is then fractionated and obtains light naphthar, scheelite brain after Oil-gas Separation after the compression of gained hydrogen-rich gas
Oil, diesel oil distillate, tail oil fraction, wherein diesel oil distillate mixes after being pressurized with recycle hydrogen, then contacts with hydrocracking catalyst,
The step reaction stream is mixed into upper step reaction stream to be separated and fractionating system, although this method can effectively improve industrial chemicals
Yield, but process flow is complicated, and equipment investment is high, and device operation difficulty is big.
CN201110284518.9 discloses a kind of method for hydrogen cracking of selective increasing of aviation kerosene yield, and this method is by raw material
Oil successively carries out hydrofining reaction and hydrocracking reaction, after reaction effluent is cooled and separated, gained after mixing with hydrogen
10%~100% heavy diesel fuel fraction the reaction was continued back to head tank, this part fraction aromatic hydrocarbons is lower with naphthene content, is to select
The appropriate fractions of selecting property increasing of aviation kerosene yield fraction.Although this method can achieve the effect that increasing of aviation kerosene yield, this part recycle oil only has
Seldom cracking reaction occurs for a part, and volume increase industrial chemicals effect is unobvious.
CN200610008420.X discloses a kind of method for hydrogen cracking for producing industrial chemicals, and poor quality is catalyzed by this method
Cracked diesel oil mixes in proportion with heavy hydrogenated cracked stock, then carries out hydrotreating and is hydrocracked, is operated by control
Condition makes the yield of heavy naphtha reach 40wt% or so, while protecting tail oil yield is 20wt% or so, although this method can be with
Increase production industrial chemicals, but is affected to midbarrel product property.
CN200610008416.3 discloses a kind of parallel hydrocracking method, and this method is by heavy distillate and poor quality
Catalytic cracking diesel oil is hydrocracked respectively, carries out gas-liquid separation after resulting crackate mixing, resulting liquid phase is fractionated
To light naphthar, heavy naphtha, boat coal, diesel oil and tail oil, the effective conversion catalyst diesel oil of this method, but equipment investment is higher, behaviour
It is big to make difficulty.
CN200610008417.8 discloses a kind of method for hydrogen cracking of intermediate oil circulation, and this method urges poor quality
It after bavin is mixed with heavy hydrogenated cracked stock, is hydrocracked first, gained intermediate oil carries out secondary hydrogenation cracking, obtains
To the tail oil of Gao Fangqian heavy naphtha and low BMCI value, this method equipment investment is high, light hydrocarbon yield complicated for operation, low value-added
It is higher.
CN201210440422.1 discloses a kind of method of hydrotreating being hydrocracked with hydrogenation dearomatization combination, and this method will be bad
Matter urges bavin and hydrogen to carry out hydrofinishing in a manner of gas-liquid counter current；Purification generates oil and carries out adding hydrogen in the presence of noble metal catalyst
De- arylation reaction；Wax oil and hydrogen carry out being hydrocracked pretreatment reaction, are hydrocracked pretreatment effluent and hydrogenation dearomatization flows out
After object mixing, hydrocracking reaction is carried out；It is hydrocracked effluent to be separated and be fractionated, obtains different fractions product；Wherein split
To change tail oil and is recycled to hydrogenation dearomatization reactor, although this method can solve the limited problem of catalytic diesel oil treating capacity, but also
Light oil yield can be increased substantially, and improves product quality, but equipment investment is high, device is complicated for operation.
CN200610008418.2 discloses a kind of two-segment hydrocracking method, this method using two-stage reforming method come
Processing poor quality urges bavin, and the poor quality that especially catalytic hydrogen transfer process obtains urges bavin.The present invention urges bavin property very poor, and 20 DEG C of density are
0.90g/ml or more, aromatic hydrocarbons are greater than 60wt%, and Cetane number is less than 30.Poor quality is urged bavin to mix with heavy cracked raw material by the present invention
And hydrotreating is carried out, after removing generates the impurity such as sulphur, the nitrogen in oil and separated, then it is hydrocracked, this method
Work raw material yield is limited, and is affected to intermediate oil product quality.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of method for hydrogen cracking, and this method passes through using diesel oil as raw material
The hydrocracking catalyst of different function reasonably combines, and increases production the heavy naphtha of Gao Fangqian, improves boat coal and diesel product matter
Amount.
Method for hydrogen cracking of the invention, including following content:
(1) diesel raw material is mixed with hydrogen is introduced into hydrofining reactor progress desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction；
(2) step (1) effluent enters hydrocracking reactor, and hydrocracking reactor contains at least two catalyst bed,
The hydrocracking catalyst containing modified Y molecular sieve in each catalyst bed is incremented by along logistics direction molecular sieve content, is catalyzed
Agent average pore size is successively decreased；
(3) hydrocracking reactor effluent is separated into gas phase and liquid phase, and gas phase is recycled, and liquid phase enters fractionating column, is fractionated
Obtain naphtha, boat coal, diesel oil and tail oil.
In the method for the present invention, diesel raw material is generally straight-run diesel oil, coker gas oil and catalytic diesel oil, catalytic diesel oil density one
As be 0.92 ~ 0.96g/cm3, arene content is 60% ~ 80%, and Cetane number is 15 ~ 25, and the impurity contents such as sulphur, nitrogen are high.
In the method for the present invention, the Hydrobon catalyst of filling this field routine in hydrofining reactor, described adds
Hydrogen catalyst for refining includes carrier and hydrogenation active metals；Wherein carrier is inorganic refractory oxide, is selected generally from aluminium oxide, nothing
One or more of sizing sial, silica or titanium oxide etc.；Hydrogenation active metals include Section VI B and/or VIII group gold
Belong to component, wherein group VIB is selected from tungsten and/or molybdenum, is calculated as 10%~35%, preferably 15%~30% with oxide, group VIII
Selected from nickel and/or cobalt, 1%~7%, preferably 1.5%~6% is calculated as with oxide.Carrier is inorganic refractory oxide, is selected generally from
Aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc..The Hydrobon catalyst can choose conventional hydrocracking
Pretreatment catalyst wherein conventional hydrocracking pretreatment catalyst can choose existing various commercial catalysts, such as is comforted
Along Petroleum Chemical Engineering Institute (FRIPP) develop 3936,3996, FF-16, FF-26, FF-36, FF-46, FF-56 etc. add
Hydrogen handles catalyst；Also it can according to need and prepared by the common sense of this field.
In the method for the present invention, the reaction condition in hydrofining reactor is general are as follows: reaction pressure 5.0~35.0MPa, it is excellent
Select 6.0~19.0MPa；Average reaction temperature is 200~480 DEG C, preferably 270~450 DEG C；Volume space velocity is 0.1~15.0h-1,
It is preferred that 0.2~3.0h-1；Hydrogen to oil volume ratio is 100:1~2500:1, preferably 400:1~2000:1.
In the method for the present invention, hydrocracking operation condition includes: 5.0~35.0MPa of reaction pressure, preferably 6.0~
19.0MPa；Average reaction temperature is 200 DEG C~480 DEG C, preferably 270 DEG C~450 DEG C；Volume space velocity is 0.1~15.0h-1, excellent
Select 0.2~3.0h-1；Hydrogen to oil volume ratio is 100:1~2500:1, preferably 400:1~2000:1.
In the method for the present invention, the admission space ratio of catalyst is 1:5 ~ 5:1, preferably 1:2 ~ 2:1 in adjacent two bed.
In the method for the present invention, the hydrocracking catalyst containing modified Y molecular sieve, including active metal component and load
Body, active component content are calculated as 5wt% ~ 40wt% with oxide, and surplus is carrier；Active metal component be selected from group VIII and/
Or one or more of vib metals, wherein group VIII metal is generally Co and/or Ni, and vib metals are generally
Mo and/or W, carrier are amorphous silicon aluminium and/or aluminium oxide containing modified Y molecular sieve.It is highly preferred that the group VIII gold
Belonging to content of the element in terms of metal oxide is 2%~15%, and content of the vib metals element in terms of metal oxide is
10%~30%.
The first catalyst bed is followed successively by N catalyst bed along Flow of Goods and Materials direction, and wherein N is preferably 2 ~ 4；First
The hydrocracking catalyst containing modified Y molecular sieve in catalyst bed has the property that the content of modified Y molecular sieve is
5wt% ~ 30wt%, preferably 15wt% ~ 25wt%, the average pore size of catalyst are 5-20nm, preferably 7 ~ 11nm；Adjacent catalyst bed
In layer, the average pore size of overlying catalyst is 0.5 ~ 5nm higher than the average pore size of lower catalyst agent, preferably 1 ~ 2nm, overlying catalyst
In modified Y molecular sieve content it is 10wt% ~ 30wt% lower than the modified Y molecular sieve content in lower catalyst agent.It is preferred that the second bed
In catalyst in modified Y molecular sieve content be 20wt% ~ 60wt%, preferably 30wt% ~ 40wt%, the average hole of catalyst
Diameter is 3-15nm, preferably 5 ~ 9nm.
In the method for the present invention, the hydrocracking catalyst containing modified Y molecular sieve is using commercial goods or by existing
It is prepared by technology.General preparation method are as follows: Y molecular sieve, amorphous silicon aluminium and/or aluminium oxide are uniformly mixed, dilute nitre is added
Rear extruded moulding is slurried in acid, obtains the carrier containing Y molecular sieve through drying, roasting.Using containing group VIII and/or group VIB gold
The maceration extract of category impregnates the carrier containing Y molecular sieve, and the carrier after dipping obtains hydrocracking catalyst through drying, roasting
Agent.The liquid-solid ratio that maceration extract containing group VIII and/or vib metals impregnates when impregnating to carrier is 1.5:1 ~ 3:1.
The content of group vib metallic compound is calculated as 20 ~ 60g/100ml, group VIII metallic compound by corresponding oxide in maceration extract
Content be calculated as 3 ~ 20g/100ml by corresponding oxide, in maceration extract the concentration of metallic compound can be needed according to product into
The corresponding adjustment of row.The drying condition after dipping are as follows: 2 ~ 8 hours dry at 90 ~ 150 DEG C；Roasting condition are as follows: 400 ~
It is roasted 1 ~ 5 hour at 700 DEG C.
In the method for the present invention, the modified Y molecular sieve property is as follows, 500 ~ 800m of specific surface area2/ g, Kong Rong 0.4 ~
0.6ml/g, wherein the secondary pore of 2 ~ 7nm holds 40% or more accounting, meleic acid amount 0.6 ~ 1.2mmol/g, Na2O mass content is less than
0.15%, SiO2/Al2O3Molar ratio 8 ~ 40,2.430 ~ 2.445nm of lattice constant, crystallinity 80% ~ 100%, the secondary pore of 2 ~ 7nm
The product for holding accounting syncrystallization degree is 38% ~ 60%.The modified Y molecular sieve can be according to state of the art system
It is standby.
The present invention provides a kind of preparation method of modified Y molecular sieve, includes the following steps:
(1) Ammonium Salt Ionic is carried out in ammonium salt solution using NaY zeolite as original powder to exchange to Na2O weight content is less than 3.5%；
It (2) is 500 ~ 620 DEG C in temperature to the Y molecular sieve after ammonium obtained in step (1) exchange, pressure is 0.01 ~ 0.3MPa,
Handling the time is 1.0 ~ 4.0 hours；
(3) the hydro-thermal process Y molecular sieve that step (2) obtains carries out sodium ion exchange in sodium salt solution；
(4) after the Y molecular sieve for obtaining step (3) carries out the processing of ammonium fluosilicate dealumination complement silicon, after filtering, drying, roasting
To final Modified Zeolite Y.
The preparation of above-mentioned modified Y molecular sieve, Ammonium Salt Ionic exchange process described in step (1) are as follows: being original with NaY zeolite
Material is in ammonium salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, exchanges 1 ~ 3 hour, and exchange times are 1 ~ 2 time, are handed over
NaY zeolite after changing, Na2O content 1.3 ~ 2.8%；Wherein the silica alumina ratio of NaY zeolite raw material is 3 ~ 6, and sodium oxide molybdena quality percentage contains
Amount 6% ~ 7%；Ammonium salt is one or more of ammonium chloride, ammonium nitrate, ammonium sulfate, ammonium acetate or ammonium oxalate, and ammonium salt aqueous solution is dense
Spend 0.3 ~ 6.0mol/L, preferably 1.0 ~ 3.0 mol/L.
The preparation of above-mentioned modified Y molecular sieve, sodium salt ion exchange process described in step (3) are as follows: with water in step (2)
Hot Y molecular sieve is raw material in sodium-salt aqueous solution, at 60 ~ 120 DEG C, at preferably 60 ~ 90 DEG C, is exchanged 1 ~ 3 hour, exchange times are
1 ~ 4 time, the NaY zeolite after being exchanged, Na2O mass content is not less than 3.0%；Sodium salt be sodium chloride, sodium nitrate, sodium sulphate,
One or more of sodium citrate, sodium oxalate, sodium-salt aqueous solution 0.3 ~ 6.0mol/L of concentration, preferably 1.0 ~ 3.0 mol/L.It is excellent
It is selected in the removing for adding the non-framework aluminum that glycerine promotes hydrothermal treatment process to generate in sodium salt solution and improves sodium salt exchange effect
Rate, glycerol concentration is 0.1 ~ 2.0 in sodium salt solution, preferably 0.1-0.5 mol/L.
The preparation of above-mentioned modified Y molecular sieve, the processing of dealumination complement silicon described in step (4) is known to those skilled in the art
Method, mass ratio can be consolidated according to liquid using conventional ammonium fluosilicate dealumination complement silicon method, the Y molecular sieve that step (3) is obtained
3:1 ~ 20:1, preferably 5:1 ~ 10:1 are mixed with ammonium fluosilicate aqueous solution, and wherein ammonium fluosilicate concentration is in ammonium fluosilicate solution
0.01 ~ 1.0mol/L, preferably 0.1 ~ 0.8 mol/L are handled 0.5 ~ 6 hour in 50 ~ 100 DEG C.
The preparation of above-mentioned modified Y molecular sieve, during the ammonium fluosilicate dealumination complement silicon in step (4), ammonium fluosilicate solution
In can to add the inorganic acids such as nitric acid, hydrochloric acid, acetic acid, citric acid, oxalic acid or organic acid non-in molecular sieve preferably to remove
The concentration of framework aluminum, inorganic acid and/or organic acid is with H+It is calculated as 0.1 ~ 0.7mol/L, preferably 0.2 ~ 0.5mol/L.
The preparation process of above-mentioned modified Y molecular sieve by exchanging NaY original powder ammonia to reduce molecular sieve Na content, mentions first
High hydro-thermal process efficiency, and reduce hydrothermal treatment process skeleton extent of the destruction.Y molecular sieve after hydro-thermal process by supplement Na from
Son promotes the dealumination complement silicon of subsequent ammonium fluosilicate treatment process to react and carries out.Therefore, while hydro-thermal process and fluosilicic acid being improved
The reaction efficiency of ammonium, modified Y molecular sieve remain hydrothermal treatment process secondary pore and hold big and ammonium fluosilicate treatment process in depth
Spend dealuminzation and the high feature of skeleton crystal degree.
Above-mentioned modified Y molecular sieve is preferably carried out processing after step (4): under agitation, by Y type molecule
Sieve is added in the pressure vessel equipped with organic alkali solution, and system is closed, is boosted to 0.2 ~ 1.0MPa, is then heated to 50
~ 90 DEG C, constant temperature is handled 0.5 ~ 3 hour, and release, suction filtration, drying and roasting obtain modified Y molecular sieve；The addition of Y type molecular sieve
Amount is 1:5 ~ 20 with the water quality ratio in organic alkali solution.The organic base is tetraethyl ammonium hydroxide, tetrapropyl hydroxide
One or more of ammonium or tetrabutylammonium hydroxide, the concentration of organic alkali solution are 0.05 ~ 0.35mol/L.Boosting using to
Compressed air, nitrogen or inert gas etc. are passed through in pressure vessel to realize.Filter to pH value less than 9, drying condition be 80 ~
It is 6 ~ 24 hours dry under the conditions of 120 DEG C.Roasting condition is to roast 2 ~ 8 hours under the conditions of 450 ~ 650 DEG C.
High pressure alkali process is carried out to Y type molecular sieve in organic alkali solution, the duct that organic base had both been filled with molecular sieve is same
When also play destruction to molecular sieve structure limited extent, destroy to this method limited extent original 4nm in molecular sieve
The mesoporous hole wall of left and right extends through the mesoporous pore structure for foring 8 ~ 9nm or so, while organic base during this
In organic group protect the microcellular structure of molecular sieve.The silica alumina ratio of molecular sieve is reduced during alkali process simultaneously, greatly
The acid amount of molecular sieve, therefore the catalytic activity and diffusion that the molecular sieve of this method preparation has had are improved greatly, are adding hydrogen
It can be with preferential conversion condensed ring macromolecular in cracking process.
In the prior art, H-G hydrocracking device mainly produces Gao Fangqian heavy naphtha, 3# jet fuel blend component
With good diesel oil blending component, in hydrocracking process, since macromolecular polycyclic aromatic hydrocarbon polarity is big, it is easier to be adsorbed on and urge
Agent surface occurs cracking reaction and generates mononuclear aromatics, and the more difficult generation aromatic hydrocarbons of mononuclear aromatics is saturated and ring-opening reaction, and this portion
Divide unconverted mononuclear aromatics to be enriched in boat coal and diesel oil distillate, the flammability of boat coal and diesel product is influenced, especially in original
When expecting that property is poor, operating condition is more harsh, influence combustible on boat coal and diesel product is become apparent.By adding hydrogen
The cracker upper bed layer filling hydrocracking catalyst that aperture is larger and lytic activity is moderate, first to polycyclic in raw material
Aromatic hydrocarbons carries out plus hydrogen is saturated and ring-opening reaction, so that it is converted into the mononuclear aromatics with side chain, since this part mononuclear aromatics is more difficult
Conversion can not only reduce macromolecular polycyclic aromatic hydrocarbon and enter in catalyst duct and preferentially send out by reducing catalyst average pore size
Raw reaction reduces influence of the competitive Adsorption to mononuclear aromatics cracking reaction, can also increase stop of the reactant in catalyst
Time, then content is sieved by increasing small-bore catalyst molecule, make the mononuclear aromatics of the more difficult conversion in this part that disconnected side chain occur
Cracking reaction generates mononuclear aromatics and alkane, the aromatic hydrocarbons in navigate coal and diesel component effectively can be converted to weight in this way
Naphtha component, and alkane is retained in boat coal and diesel component, it can both increase production the heavy naphtha of Gao Fangqian in this way, also
Boat coal and diesel product quality can be improved.
Detailed description of the invention
Fig. 1 is a kind of principle process schematic diagram of present invention process method.
Specific embodiment
The technical characterstic of the method for the present invention is further described by embodiment in next step, but following embodiment cannot limit this
Invention.% is such as mass percentage without special marking in Examples and Comparative Examples.The wherein hydrocracking catalyst I
It is commercial goods with hydrocracking catalyst II, property is shown in Table 1.
For two catalyst beds are set, the process flow of the method for the present invention is illustrated: feedstock oil 1 and hydrogen
2 are mixed into hydrofining reactor 3, and effluent 4 enters hydrocracking reactor 5 and successively passes through upper and lower two catalyst beds
Layer carries out hydrocracking reaction, and cracking reaction effluent 6 enters separator 7, and isolated gas 8 is recycled, liquid 9
It enters fractionating column 10 to be separated, isolated gas 11, gasoline 12, boat coal 13 and diesel oil 14.
Embodiment 1
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium chloride for being 2.5mol/L with concentration is according to liquid-solid ratio 5:1
Mixing, 85 DEG C exchange 2 hours, repeat this process 2 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 1.3%；
(2) 530 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 1.5 hours under 0.15Mpa；
(3) Y molecular sieve that step (2) obtains is mixed with the sodium nitrate that concentration is 1.5mol/L according to liquid-solid ratio 5:1,80 DEG C of friendships
It changes 1 hour, repeats this process 2 times, Na content is calculated as 3.6% with Na2O in the Y molecular sieve after exchange；
(4) step (3) resulting molecular sieve is mixed with the ammonium fluosilicate solution that concentration is 0.5mol/L according to liquid-solid ratio 5:1 and is beaten
Slurry, 95 DEG C are handled 2 hours；
(5) through step (6) ammonium fluosilicate treated Y molecular sieve, 120 DEG C of dryings, 2 hours acquisition molecular sieves, number Y-2, property
Matter is shown in Table 1.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: it is molten to configure 1000ml dipping after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Liquid, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, and solution is compiled
Number RY-2；
(2) it takes Y-2 40g to mix with 60g macroporous aluminium oxide, 4g/100ml dust technology is added mixes in a mixer and roll to can
Shape is squeezed out, extruded moulding obtains carrier T-2 on banded extruder；
(3) it takes T-2 60g that 120ml RY-2 maceration extract is added to impregnate 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings 3 are small
When, obtain hydrocracking catalyst, number Cat-1, average pore size 8.5nm.
Embodiment 2
(1) the NaY molecular sieve original powder 200g for taking laboratory to prepare, the ammonium nitrate for being 1.6mol/L with concentration is according to liquid-solid ratio 3:1
Mixing, 80 DEG C exchange 2 hours, repeat this process 2 times, and Na content is in the Y molecular sieve after exchange with Na2O is calculated as 2.0%；
(2) 550 DEG C of Y molecular sieve that step (1) is obtained, hydro-thermal process 2 hours under 0.2MPa；
(3) the Y molecular sieve mixing for containing sodium nitrate and glycerine being respectively 3.0mol/L and 0.2mol/L that step (2) is obtained
Solution is mixed according to liquid-solid ratio 5:1, and 80 DEG C exchange 1 hour, is repeated this process 2 times, in the Y molecular sieve after exchange Na content with
Na2O is calculated as 5.3%；
(4) step (3) resulting molecular sieve is mixed with the ammonium fluosilicate solution that concentration is 0.7mol/L according to liquid-solid ratio 10:1 and is beaten
Slurry, 85 DEG C are handled 2 hours；
(5) through step (4) ammonium fluosilicate treated Y molecular sieve, 120 DEG C drying 2 hours, obtain molecular sieve, number Y-3,
Property is shown in Table 1.
Hydrocracking catalyst preparation process:
(1) it configures W-Ni dipping solution: it is molten to configure 1000ml dipping after taking ammonium metatungstate 480g and nickel nitrate 480g to be dissolved in water
Liquid, active metal is with WO in gained dipping solution3Calculating with NiO content meter is respectively 40g/100ml and 12g/100ml, and solution is compiled
Number RY-3；
(2) it takes Y-3 50g to mix with 50g macroporous aluminium oxide, 4g/100ml dust technology is added mixes in a mixer and roll to can
Shape is squeezed out, extruded moulding obtains carrier T-3 on banded extruder；
(3) it takes T-3 60g that 120ml RY-3 maceration extract is added to impregnate 2 hours, then 120 DEG C drying 4 hours, 500 DEG C of roastings 3 are small
When, obtain hydrocracking catalyst, number Cat-2, average pore size 7.4nm.
Embodiment 3
It with embodiment 1, only after obtaining Y-2, is being handled as follows: under agitation, by Y molecular sieve and tetrapropyl
Ammonia is mixed in a high pressure reaction kettle, is passed through nitrogen control system pressure in 0.4MPa, is then heated to 70
DEG C, continuing constant temperature and stirs 1 hour, release is cooling, filters to pH value less than 9, and it is 12 hours dry under the conditions of 125 DEG C, 500
DEG C roasting 3 hours, obtain modified Y molecular sieve.The concentration of tetrapropylammonium hydroxide solution is 0.12mol/L, Y molecular sieve and solution
The mass ratio of middle water is 1:9.
The main physico-chemical property of 1 hydrocracking catalyst of table.
Embodiment 3
Using straight-run diesel oil as raw material, hydrocracking reactor upper bed layer loading catalyst, lower bed layer loading catalyst, catalysis
Agent admission space ratio is 1:1.
Embodiment 4
Using straight-run diesel oil as raw material, hydrocracking reactor upper bed layer loading catalyst Cat-1, lower bed layer loading catalyst,
Catalyst packing volume ratio is 1:1.
Embodiment 5
Using straight-run diesel oil as raw material, hydrocracking reactor upper bed layer loading catalyst Cat-2, lower bed layer loading catalyst,
Catalyst packing volume ratio is 1:1.
Embodiment 6
With embodiment 4, only upper bed layer loading catalyst Cat-3.
Comparative example 1
Using straight-run diesel oil as raw material, hydrocracking reactor loading catalyst。
The main character of 2 feedstock oil of table
3 technological condition of table and product distribution
4 heavy naphtha main character of table
The main character of 5 jet fuel of table
6 > 260 DEG C of diesel oil main characters of table
Diesel raw material can produce good catalytic reforming raw material, 3# by this technology it can be seen from Examples and Comparative Examples
Jet fuel blend component and good diesel oil blending component, and diesel component is also used as steam cracking to ethylene raw,
Plant investment is at low cost, easy to operate.
Claims (10)
1. a kind of method for hydrogen cracking, including following content: (1) diesel raw material mixes with hydrogen and is introduced into hydrofining reactor
Carry out desulfurization, denitrogenation and aromatic hydrocarbons saturated reaction；(2) step (1) effluent enters hydrocracking reactor, hydrocracking reactor
Catalyst bed is contained at least two, the hydrocracking catalyst containing modified Y molecular sieve in each catalyst bed is along logistics
Direction molecular sieve content is incremented by, catalyst average pore size is successively decreased；(3) hydrocracking reactor effluent is separated into gas phase and liquid
Phase, gas phase are recycled, and liquid phase enters fractionating column, and fractionation obtains naphtha, boat coal, diesel oil and tail oil.
2. according to the method for claim 1, it is characterised in that: diesel raw material is straight-run diesel oil, coker gas oil and catalysis bavin
One or more of oil, density are 0.92 ~ 0.96g/cm3, arene content is 60% ~ 80%, and Cetane number is 15 ~ 25.
3. according to the method for claim 1, it is characterised in that: the reaction condition in hydrofining reactor are as follows: reaction pressure
5.0~35.0MPa of power；Average reaction temperature is 200~480 DEG C；Volume space velocity is 0.1~15.0h-1；Hydrogen to oil volume ratio is
100:1~2500:1.
4. according to the method for claim 1, it is characterised in that: hydrocracking operation condition are as follows: reaction pressure 5.0~
35.0MPa, average reaction temperature are that 200 DEG C~480 DEG C volume space velocities are 0.1~15.0h-1, hydrogen to oil volume ratio be 100:1~
2500:1.
5. according to the method for claim 1, it is characterised in that: in hydrocracking reactor, catalyst in adjacent two bed
Admission space ratio be 1:5 ~ 5:1, preferably 1:2 ~ 2:1.
6. according to the method for claim 1, it is characterised in that: the hydrocracking catalyst containing modified Y molecular sieve, packet
Active metal component and carrier are included, active metal component is selected from one or more of group VIII and/or vib metals,
Carrier is amorphous silicon aluminium and/or aluminium oxide containing modified Y molecular sieve；The modified Y molecular sieve property is as follows, specific surface area
500~800m20.4 ~ 0.6ml/g of/g, Kong Rong, wherein secondary pore 40% or more the accounting of appearance of 2 ~ 7nm, meleic acid amount 0.6 ~
1.2mmol/g, Na2O mass content is less than 0.15%, SiO2/Al2O3Molar ratio 8 ~ 40,2.430 ~ 2.445nm of lattice constant, knot
Brilliant degree 80% ~ 100%, it is 38% ~ 60% that the secondary pore of 2 ~ 7nm, which holds accounting and the product of crystallinity,.
7. according to the method for claim 1, it is characterised in that: in hydrocracking reactor, successively along Flow of Goods and Materials direction
For the first catalyst bed to N catalyst bed；The hydrocracking catalyst containing modified Y molecular sieve in first catalyst bed
Agent has the property that the content of modified Y molecular sieve is 5wt% ~ 30wt%, and the average pore size of catalyst is 5-20nm；It is adjacent to urge
In agent bed, the average pore size of overlying catalyst is 0.5 ~ 5nm higher than the average pore size of lower catalyst agent, in overlying catalyst
Modified Y molecular sieve content is 10wt% ~ 30wt% lower than the modified Y molecular sieve content in lower catalyst agent.
8. according to the method for claim 7, it is characterised in that: in hydrocracking reactor, along Flow of Goods and Materials direction second
The content of the modified Y molecular sieve in catalyst in bed is 20wt% ~ 60wt%, and the average pore size of catalyst is 3-15nm.
9. according to the method for claim 7, it is characterised in that: the modified Y molecular sieve in catalyst in the second bed
Content is 30wt% ~ 40wt%, and the average pore size of catalyst is 5 ~ 9nm.
10. according to the method for claim 7, it is characterised in that: in hydrocracking reactor, successively along Flow of Goods and Materials direction
For the first catalyst bed to N catalyst bed, wherein N is 2 ~ 4；In first catalyst bed containing modified Y molecular sieve
Hydrocracking catalyst has the property that the content of modified Y molecular sieve is 15wt% ~ 25wt%, and the average pore size of catalyst is
7~11nm；In adjacent catalyst bed, the average pore size of overlying catalyst is 1 ~ 2nm higher than the average pore size of lower catalyst agent, on
Modified Y molecular sieve content in layer catalyst is 10wt% ~ 30wt% lower than the modified Y molecular sieve content in lower catalyst agent.
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| CN112745922A (en) * | 2019-10-30 | 2021-05-04 | 中国石油化工股份有限公司 | Hydrocracking method for poor-quality diesel raw material |
| CN113136243A (en) * | 2020-01-19 | 2021-07-20 | 中国石油化工股份有限公司 | Hydrocracking-catalytic cracking combined process |
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