CN108690659A - A kind of method of diesel oil selective hydrogenation - Google Patents
A kind of method of diesel oil selective hydrogenation Download PDFInfo
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- CN108690659A CN108690659A CN201710218808.0A CN201710218808A CN108690659A CN 108690659 A CN108690659 A CN 108690659A CN 201710218808 A CN201710218808 A CN 201710218808A CN 108690659 A CN108690659 A CN 108690659A
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
- 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
Abstract
A kind of method of diesel oil selective hydrogenation, including diesel raw material oil is mixed with hydrogen, it is contacted with Hydrobon catalyst in the first reaction zone, under hydrogenation process conditions, carries out hydrodesulfurization, hydrodenitrogeneration and the reaction of selective hydrogenation Porous deproteinized bone;The reaction effluent of first reaction zone is separated into reaction effluent I and reaction effluent II through separator, the reaction effluent II enters second reaction zone and is contacted with Hydrobon catalyst, under hydrogenation process conditions, further carry out hydrodesulfurization, hydrodenitrogeneration and the reaction of selective hydrogenation Porous deproteinized bone, obtain reaction effluent III, after reaction effluent I and reaction effluent III is mixed, hydrogenated oil is obtained by separation, on the basis of diesel raw material oil, polycyclic aromatic hydrocarbon saturation factor is 95% or more in the hydrogenated oil, and mononuclear aromatics is selectively 85% or more.Method provided by the invention for catalytic cracking or be hydrocracked production high-knock rating gasoline or BTX components provide good raw material, while reduce hydrogenation process hydrogen consumption, be conducive to improve process economics.
Description
Technical field
The present invention relates to one kind in the presence of hydrogen, and the method for refining hydrocarbon ils is more specifically a kind of diesel oil
The method of selective hydrogenation.
Background technology
Ratio of the catalytic cracking diesel oil in China's diesel product is higher, accounts for about the 1/3 of commercial Dissel oil.With crude oil poor quality
Change and heaviness is aggravated, the quality of catalytic cracking diesel oil fraction is increasingly worse, is mainly shown as sulphur, nitrogen, arene content height, 16
Alkane value is low, stability is poor.In recent years, with the catalytic cracking technology of high severity catalytic cracking technology such as maximizing iso-paraffins
(MIP) extensive use, arene content especially polycyclic aromatic hydrocarbon content further increases in MIP catalytic diesel oils, Cetane number into
One step reduces.And with the continuous enhancing of environmental consciousness, country requires constantly upgrading, refinery enterprise to the cleaning quality of ordinary diesel oil
The cost for the diesel oil that industry production meets quality standard is continuously increased, while the market demand of diesel oil is decreased obviously, and diesel oil surplus is asked
Topic highlights.With this, poor ignition quality fuel, which is processed into high value added product, seems necessary.
For the characteristic of light cycle oil (LCO) high arene content, by controlling aromatic hydrocarbons path for transformation, by macromolecular in LCO
Aromatic hydrocarbons is converted into the small molecules aromatic hydrocarbons such as benzene,toluene,xylene (BTX) and is maintained in gasoline fraction, and final production obtains Gaoxin
Alkane value gasoline component or BTX are the efficient utilization ways of ideal LCO.High-knock rating gasoline is produced by raw material of LCO
Component or aromatic hydrocarbons field, foreign technology include mainly LCO-Unicracking and LCO-X technologies, the Criterion of UOP exploitations
The one-stage serial hydrocracking technology and SYN series of diesel fuel hydrogenation modifying process technology of catalyst Co. exploitation, IFP exploitations
Flexible hydrocracking process.Domestic technique includes mainly that the LCO of RIPP exploitations is hydrocracked production high-knock rating gasoline (RLG)
The LCO of technology, the FD2G technologies of FRIPP exploitations and RIPP exploitations adds hydrogen-catalyzed combination technology production high-knock rating gasoline
(LTAG) technology.
CN 1422327A disclose a kind of hydrogenation-catalytic cracking combined method by LCO producing more propylenes.This method be by
Catalytically cracked material passes through first set catalytic cracking unit, by the isolated gas of obtained product, naphtha, diesel oil and again
Component.Recycle oil is entered into second set of catalytic cracking unit as raw material after hydrotreating, improves productivity of propylene.The invention
It is required that decahydronaphthalenes content in hydrogen recycle oil is added to maximize, and total arene content is less than 5% (weight), holds in catalytic cracking process
Open loop cracking reaction easily occurs, produces propylene.
US6900365, which is disclosed, a kind of to be passed through hydro-dealkylation/reformation by LCO and produces BTX or high octane gasoline component
Method.This method first by LCO hydrotreatings, obtains sulfur content, nitrogen content is less than the intermediate product of 1 μ g/g, then will be in this
Between product as hydro-dealkylation/reformer feed, by dealkylation reaction/reforming reaction obtain high octane gasoline component or
BTX.The main purpose of hydrotreating unit is the impurity such as removing sulphur, nitrogen in this method, prevents subsequent catalyst poisoning.
US6900365, which is disclosed, a kind of to be passed through hydro-dealkylation/reformation by LCO and produces BTX or high octane gasoline component
Method.This method first by LCO hydrotreatings, obtains sulfur content, nitrogen content is less than the intermediate product of 1 μ g/g, then will be in this
Between product as hydro-dealkylation/reformer feed, by dealkylation reaction/reforming reaction obtain high octane gasoline component or
BTX.The main purpose of hydrotreating unit is the impurity such as removing sulphur, nitrogen in this method, prevents subsequent catalyst poisoning.
Invention content
The monocycle virtue that the technical problem to be solved by the present invention is to high aromatics diesel raw materials in conventional hydro subtractive process
The problem of hydrocarbon-selective difference.
No matter with high aromatics diesel raw material production high octane gasoline component is hydrocracked, or with high aromatics diesel raw material
Add hydrogen-catalytic cracking combination production high octane gasoline component or aromatic hydrocarbons, be all first by high aromatics diesel raw material hydrofinishing,
Then as being hydrocracked or the charging of catalytic cracking, the purpose of hydrofinishing is exactly will be polycyclic in high aromatics diesel raw material
Arenes selectivity is hydrogenated to mononuclear aromatics.
Aromatic hydrocarbons includes mainly mononuclear aromatics, double ring arene and the above aromatic hydrocarbons of tricyclic in high aromatics diesel raw material, wherein bicyclic
Aromatic hydrocarbons and the above aromatic hydrocarbons of tricyclic account for the major part of total arene content.Aromatic hydrogenation is reversible reaction, double by dynamics and thermodynamics
It controls again, compared with low reaction temperatures section, aromatic hydrogenation saturated reaction is mainly by dynamics Controlling, in higher reaction temperatures area
Between, aromatic hydrogenation saturated reaction is mainly by balance controlled.Reaction process parameter generates aromatic hydrogenation complicated influence.One side
Face improves temperature in dynamics Controlling area and is conducive to improve reaction rate;It on the other hand, will after temperature improves to a certain extent
Lead to the limitation of thermodynamical equilibrium.In the prior art, in unifining process, whether not using mononuclear aromatics as main mesh
Product is marked, or using mononuclear aromatics as key targets, the problem of aromatic hydrocarbons supersaturation all occurs, leads to final monocycle
The problem of arene content decline, i.e. mononuclear aromatics poor selectivity, while there is also hydrogen to consume the problems such as increasing.
In the present invention, polycyclic aromatic hydrocarbon refers to the general name of double ring arene and the above aromatic hydrocarbons of tricyclic (including thrcylic aromatic hydrocarbon).
The present inventor further furthers investigate discovery, and first ring of polycyclic aromatic hydrocarbon adds hydrogen saturated reaction usually to compare
Mononuclear aromatics adds hydrogen saturated reaction rate constant big, that is to say, that first ring of polycyclic aromatic hydrocarbon adds hydrogen to add hydrogen compared with mononuclear aromatics
Saturation is easy.In order to improve the saturation factor of polycyclic aromatic hydrocarbon, need to properly increase reaction severity, including improve reaction temperature, but
It is to improve reaction temperature, and can make mononuclear aromatics that hydrogen be added to be saturated, if further increasing reaction temperature, aromatic hydrogenation saturation is anti-
It should can enter balance controlled region, the saturation factor of polycyclic aromatic hydrocarbon can decline instead.The present inventor is obtained by research
The selectivity of mononuclear aromatics and the saturation factor relational graph of polycyclic aromatic hydrocarbon, referring to attached drawing 2.Under lower reaction temperature, with
The raising of reaction temperature, polycyclic aromatic hydrocarbon saturation factor increase, and the polycyclic aromatic hydrocarbon being saturated is completely converted into mononuclear aromatics, at this time monocycle
The selectivity of aromatic hydrocarbons is 100%, when reaction temperature rises to certain value, continues to improve reaction temperature, polycyclic aromatic hydrocarbon saturation factor after
It is continuous to rise, but the reaction for adding hydrogen saturation to be converted into cycloalkane of mononuclear aromatics takes place at this time, the selectivity of mononuclear aromatics is opened
Begin to decline, when reaction temperature reaches dynamics Controlling critical value, polycyclic aromatic hydrocarbon saturation factor reaches maximum value, mononuclear aromatics at this time
Selectivity reaches minimum, continues to improve reaction temperature, aromatic hydrogenation saturated reaction enters balance controlled region, in thermodynamics
Reaction temperature is improved in control area, and polycyclic aromatic hydrocarbon saturation factor declines, and mononuclear aromatics selectively rises.
Based on the studies above, the technical problem to be solved by the present invention is to high aromatics diesel raw materials to be refined in conventional hydro
The problem of mononuclear aromatics poor selectivity in journey.The present invention provides a kind of methods of diesel oil selective hydrogenation, including by diesel oil
Feedstock oil is mixed with hydrogen, is contacted with Hydrobon catalyst in the first reaction zone, under hydrogenation process conditions, carries out plus hydrogen is de-
Sulphur, hydrodenitrogeneration and the reaction of selective hydrogenation Porous deproteinized bone;The reaction effluent of first reaction zone is separated into reaction stream through separator
Go out object I and reaction effluent II, the reaction effluent II enters second reaction zone and contacted with Hydrobon catalyst, is adding hydrogen
Under process conditions, hydrodesulfurization, hydrodenitrogeneration and the reaction of selective hydrogenation Porous deproteinized bone are further carried out, reaction effluent is obtained
After III, reaction effluent I and reaction effluent III are mixed, hydrogenated oil is obtained by separation, using diesel raw material oil as base
Standard, polycyclic aromatic hydrocarbon saturation factor is 95% or more in the hydrogenated oil, and mononuclear aromatics is selectively 85% or more.
The present invention in order to improve the saturation factor of polycyclic aromatic hydrocarbon, and inhibit mononuclear aromatics plus hydrogen saturation, the present invention pass through two
A reaction zone is realized.In the first reaction zone, under process conditions appropriate, the selective hydrogenation that part polycyclic aromatic hydrocarbon occurs is full
With the reaction for being converted into mononuclear aromatics, in the first reaction zone, since reaction condition compares mitigation, polycyclic aromatic hydrocarbon adds hydrogen to be totally converted
Add hydrogen saturated reaction without mononuclear aromatics for mononuclear aromatics;First reaction zone product is fractionated, main purpose is
Mononuclear aromatics is detached with polycyclic aromatic hydrocarbon, the higher fraction of polycyclic aromatic hydrocarbon content goes successively to second reaction zone, in work appropriate
Under the conditions of skill, the further polycyclic aromatic hydrocarbon that occurs adds hydrogen saturated reaction, and control mononuclear aromatics plus hydrogen saturated reaction.Pass through two
The reaction and separator that a reaction zone is occurred are converted into mononuclear aromatics to realize that polycyclic aromatic hydrocarbon selective hydrogenation is saturated, and use up
The possible reaction for adding hydrogen saturation to be converted into cycloalkane for inhibiting mononuclear aromatics.
It is preferred that the polycyclic aromatic hydrocarbon saturation factor of liquid material is 60%~75% in the reaction effluent of the first reaction zone, it is single
Cyclophane hydrocarbon-selective is more than 98%.Further preferably, the polycyclic aromatic hydrocarbon of liquid material is full in the reaction effluent of the first reaction zone
It is 65%~72% with rate.
In the present invention, polycyclic aromatic hydrocarbon saturation factor and mononuclear aromatics are selectively defined as follows:
Polycyclic aromatic hydrocarbon saturation factor=(Adf-Adp)/Adf* 100%
Mononuclear aromatics selectivity=(Amp-Amf)/(Adf-Adp) * 100%
In formula:AdfPolycyclic aromatic hydrocarbon content in-raw material, quality %
AdpPolycyclic aromatic hydrocarbon content in-product, quality %
AmpMononuclear aromatics content in-product, quality %
AmfMononuclear aromatics content in-raw material, quality %
" polycyclic aromatic hydrocarbon content " of the present invention refers to the mass spectrum obtained with mass spectrography (analysis method SH/T-0606)
Mass fraction the sum of of the bicyclic above aromatic hydrocarbons including double ring arene itself in composition data.
" mononuclear aromatics content " of the present invention refers to the mass spectrum obtained with mass spectrography (analysis method SH/T-0606)
The mass fraction of mononuclear aromatics in composition data.
For the present invention by process optimization, the control of technological parameter and the use of mating catalyst, control plus hydrogen are deep
Degree promotes polycyclic aromatic hydrocarbon saturation to be converted into mononuclear aromatics, and avoids mononuclear aromatics that hydrogen saturation is further added to be cycloalkane as possible,
While reducing the impurity contents such as diesel oil sulphur, nitrogen, bicyclic and the above aromatic hydrocarbons of tricyclic content is reduced, and increase containing for mononuclear aromatics
Amount.That is, being rich in mononuclear aromatics in the hydrogenated oil of the present invention.The hydrogenated oil again by being hydrocracked or
Catalytic cracking reaction converts mononuclear aromatics open loop cracking to high octane gasoline component or production BTX.
The boiling spread of the diesel raw material oil is 150~400 DEG C, 60~90 mass % of total arene content, wherein more
40~80 mass % of cyclic aromatics content.It is preferred that the diesel raw material oil is selected from catalytic cracking light cycle oil, catalytic cracking follows again
Ring oil, the straight-run diesel oil of naphthene base crude, the coker gas oil of naphthene base crude, the diesel oil distillate of coal direct liquefaction oil, coal tar
One or more of diesel oil distillate.
It is preferred that the process conditions of the first heretofore described reaction zone are:3~12MPa of hydrogen partial pressure, reaction temperature 240
~400 DEG C, 400~1200Nm of hydrogen to oil volume ratio3/m3, 0.5~4.0h of volume space velocity when liquid-1.Further preferably, the first reaction
Area's hydrogenation process conditions are 4~10MPa of hydrogen partial pressure, 240~360 DEG C of reaction temperature, 500~1000Nm of hydrogen to oil volume ratio3/m3, liquid
When volume space velocity 0.5~2.0h-1。
It is preferred that the process conditions of heretofore described second reaction zone are:3~10MPa of hydrogen partial pressure, reaction temperature 260
~420 DEG C, 400~1200Nm of hydrogen to oil volume ratio3/m3, 0.3~4.0h of volume space velocity when liquid-1.Further preferably, second adds hydrogen
Reaction zone process conditions are:4~8MPa of hydrogen partial pressure, 260~380 DEG C of reaction temperature, 500~1000Nm of hydrogen to oil volume ratio3/m3, liquid
When volume space velocity 0.5~1.5h-1。
In the present invention, it is preferable that the temperature of separator is 230 DEG C~280 DEG C, and the temperature of further preferred separator is
240 DEG C~260 DEG C.The main purpose of separation is as far as possible to stay in mononuclear aromatics in reaction effluent I, and polycyclic aromatic hydrocarbon is stayed
In reaction effluent II, the reaction effluent II rich in polycyclic aromatic hydrocarbon enters the choosing that second reaction zone continues polycyclic aromatic hydrocarbon
Selecting property adds hydrogen saturated reaction, obtains reaction effluent III, after reaction effluent I and reaction effluent III mixing, by separation
Obtain hydrogenated oil.
Hydrobon catalyst can be the same or different used in first reaction zone of the present invention and second reaction zone.
Hydrobon catalyst of the present invention is non-supported hydrogenation catalyst for refining, or is load hydrogenation essence
Catalyst processed.
Contain carrier in one of which preferred embodiment of the present invention, in Hydrobon catalyst and is supported on the load
Hydrogenation metal active component on body;On the basis of the total weight of the Hydrobon catalyst, in terms of oxide, hydrogenation metal
The content of active component is 15~60 weight %, preferably 20~50 weight %.
The hydrogenation metal active component is that at least one vib metals element that is selected from is selected from Section VIII at least one
Race's metallic element, the vib metals element are preferably molybdenum and/or tungsten, the group VIII metallic element be preferably cobalt and/
Or nickel;The carrier be selected from gama-alumina, silica, aluminium oxide-silicon oxide, titanium oxide, magnesia, silica-magnesias,
Silica-zirconia, silica thoria, silica-berylias, silica-titania, silica-zirconia, titanium oxide-
Zirconium oxide, silica-alumina thoria, silica-alumina-titania, silicaalumina-magnesia and oxidation
It is one or more in silicon-aluminium oxide-zirconium oxide.
In one of which preferred embodiment of the present invention, the Hydrobon catalyst uses Sinopec petrochemical industry
Commercial grades catalyst RS-2000, RN-32L, RL-2 etc. of scientific research exploitation.
In one of which preferred embodiment of the present invention, the Hydrobon catalyst is prepared by following preparation methods
It obtains, the preparation method includes:
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, so
After be dried, roast, obtain semi-finished product catalyst, the roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Carbon content is 0.03-0.5 weight % in semi-finished product catalyst;
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is soaked
Then stain is dried and without roasting.
In the present invention, it is preferred to Hydrobon catalyst be two step preparation catalysts, first step dipping and the
Two dippings are respectively used to introduce hydrogenation metal active component and organic complexing agent, and organic network is added in first step dipping process
Mixture is simultaneously run through roasting and is converted into charcoal, can not only improve the activity of catalyst, and can effectively keep for a long time
The high activity of catalyst, to greatly improve the service life of catalyst.Speculate that its reason may be because the first step impregnated
The organic complexing agent being added in journey, the presence of organic complexing agent hinder the aggregation of active metal in roasting process, make its dispersion
More uniformly;Meanwhile roasting can make metallic compound be converted into metal oxide after first step dipping, make organic complexing agent
It is converted into charcoal, to keep the combination between active metal and carrier more secured, improves the activity and stability of catalyst.And
The organic complexing agent being added in second step dipping process is covered in catalyst surface, and active metal can be effectively prevent to vulcanize
Aggregation in the process improves metal dispersity, is more advantageous to be formed with higher active II class activity phase and be formed more
Activated centre, to the further very high activity of catalyst.Therefore, the technology can effectively solve conventional impregnation method with it is existing
The technological deficiency of infusion process is complexed.
Preferably, the preparation side of Hydrobon catalyst provided by the invention mainly includes the following steps that:
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, so
After be dried, roast, obtain semi-finished product catalyst, the roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Preferably, carbon content is 0.04~0.4 weight % in semi-finished product catalyst.
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is soaked
Then stain is dried and without roasting.
In the present invention, it can be obtained by controlling the intake of calcination temperature and imflammable gas in roasting condition
Above-mentioned carbon content, the imflammable gas can be various oxygen contents be not less than 20 volume % gas, as air, oxygen with
And it is one or more in their mixed gas.
The intake of the imflammable gas was not less than for 0.2 liter/gram hour.The imflammable gas is passed through, a side
Face meets the condition of burning so that the salt of active metal component is converted into oxide, and organic complexing agent is made to be converted into charcoal;Another party
Face can also emit carbon dioxide that burning is formed and water and other compositions, be caused on a catalyst pair to avoid deposition
The vacancy of active phase hinders.
Under preferable case, the intake of imflammable gas is 0.2~20 liter/(gram hour), preferably 0.3~10 liter/
(gram hour)." gram " herein indicates the weight of carrier.
In accordance with the present invention it is preferred that the temperature of step (1) described roasting is 350~500 DEG C, preferably 360~450 DEG C,
The time of roasting is 0.5~8h, preferably 1~6h.It controls calcination temperature and can guarantee organic complexing agent energy within the above range
Charcoal is formed on carrier with above-mentioned content range, obtains semi-finished product catalyst.
In accordance with the present invention it is preferred that step (1) organic complexing agent with the molar ratio of metal active constituent be 0.03
~2:1, preferably 0.08~1.5:1.
In accordance with the present invention it is preferred that step (1) and the molar ratio of step (2) organic complexing agent are 1:0.25~4, preferably
It is 1:0.5~2.
In the present invention, organic complexing agent described in step (1) and step (2) may be the same or different, preferably
Ground, the organic complexing agent are one or more in oxygen-containing and/or itrogenous organic substance.
The oxygen containing organic matter is one or more in Organic Alcohol, organic acid.
The Organic Alcohol is preferably the polyalcohol of binary or more, still more preferably for the polyalcohol of carbon atom number 2-6 or
Its oligomer or polymer, as one or more in ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol.It is described
The molecular weight of polyethylene glycol is preferably 200~1500.
The organic acid is preferably C2-C7The compound containing one or more COOH groups, be specifically as follows acetic acid, horse
Come one or more in sour, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acids, citric acid, tartaric acid, malic acid.
The nitrogenous organic matter is preferably selected from one or more in organic amine, organic ammonium salt.
The organic amine is preferably C2-C7The compound containing one or more NH groups, can be primary amine, secondary amine or uncle
Amine, particularly preferably ethylenediamine.
The organic ammonium salt is preferably EDTA.
Specifically, the organic complexing agent specifically preferred according to the invention is ethylene glycol, glycerine, (molecular weight is excellent for polyethylene glycol
Be selected as 200-1500), diethylene glycol, butanediol, acetic acid, maleic acid, oxalic acid, aminotriacetic acid, 1,2- cyclohexane diamine tetrems
It is one or more in acid, citric acid, tartaric acid, malic acid, ethylenediamine and EDTA.
Preferably, organic complexing agent described in step (1) is one or more in organic acid, it is highly preferred that step
(1) organic complexing agent is selected from C2-C7Organic acid in it is one or more.Using organic acid as organic network of step (1)
Mixture can be obtained with higher active hydrogenation catalyst.
There is no particular limitation to the drying condition by the present invention, can be various drying conditions commonly used in the art, step
Suddenly drying condition described in (1) and step (2) may be the same or different.
Preferably, step (1) described drying temperature is 100~250 DEG C, and the time is 1~12h.
Preferably, step (2) described drying temperature is 100~200 DEG C, and the time is 1~12h.
In accordance with the present invention it is preferred that with elemental metal, a concentration of the 0.2 of the water soluble salt of hydrogenation metal active component
~8mol/L, preferably 0.2~5mol/L are still more preferably 0.2~2mol/L.A concentration of various hydrogenation metals herein
The respective concentration of water soluble salt rather than total concentration of active component.
In accordance with the present invention it is preferred that the compound of the element containing vib metals can be selected from ammonium molybdate, ammonium paramolybdate, partially
It is one or more in ammonium tungstate, molybdenum oxide and tungsten oxide.
Preferably, the compound of the metallic element containing group VIII is selected from the oxalates of group VIII metal, group VIII gold
The nitrate of category, the sulfate of group VIII metal, the acetate of group VIII metal, the chloride of group VIII metal,
The carbonate of group VIII metal, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, group VIII gold
The water-soluble oxygen of the phosphate of category, the molybdate of group VIII metal, the tungstates of group VIII metal and group VIII metal
It is one or more in compound.
Further preferably, the compound of the metallic element containing group VIII can be selected from but not limited to nickel nitrate, nickel sulfate, vinegar
It is one or more in sour nickel, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride.
According to the present invention, the mode of loading of the hydrogenation metal active component is not particularly limited.
In accordance with the present invention it is preferred that the load of the hydrogenation metal active component is that hydrogenation metal is lived by infusion process
Property component loads on carrier.
In accordance with the present invention it is preferred that the carrier is selected from aluminium oxide, silica, aluminium oxide-silicon oxide, titanium oxide, oxidation
Magnesium, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-titania, oxidation
Silicon-zirconium oxide, titania-zirconia, silica-alumina thoria, silica-alumina-titania, silica-oxidation
One or more in aluminium-magnesia and silica-alumina, zirconia, wherein aluminium oxide is more preferably a kind of hydration
The aluminium oxide obtained after the roasting of aluminium oxide (aluminium hydroxide) glue compound.
Advantages of the present invention:
(1) method provided by the invention is used, the diesel raw material oil of high arene content can be handled, with prior art phase
Than with high mononuclear aromatics selectivity while keeping high polycyclic aromatic hydrocarbon saturation factor, polycyclic aromatic hydrocarbon saturation factor is up to 95%
When above, mononuclear aromatics is selective up to 85% or more.
(2) method provided by the invention handles the poor ignition quality fuel feedstock oil of high arene content by two reaction zones, polycyclic
For the removal efficiency of aromatic hydrocarbons at 95% or more, the removal efficiency of total aromatic hydrocarbons is below 11%, it will be apparent that the content of mononuclear aromatics is remained,
Good raw material is provided for production BTX components or high-knock rating gasoline.
(3) method provided by the invention effectively reduces hydrogenation process hydrogen consumption, improves hydrogen utilization efficiency, reduce
Processing cost improves process economics.
Description of the drawings
Fig. 1 is the flow diagram of the method one of which embodiment of diesel oil selective hydrogenation provided by the invention.
Fig. 2 is the selectivity of mononuclear aromatics and the saturation factor relational graph of polycyclic aromatic hydrocarbon
Specific implementation mode
Method provided by the present invention is further detailed below in conjunction with the accompanying drawings, but does not therefore limit this hair
It is bright.
Fig. 1 is the flow diagram of the method provided by the present invention one of which embodiment.As shown in Figure 1, diesel raw material passes through
Pipeline 1 enters pump 2, is mixed with the hydrogen from pipeline 37 after boosting, through the entrance First Heat Exchanger 4 of pipeline 3, and from pipeline 22
Material-heat-exchanging after through pipeline 5 enter the second heat exchanger 6, it is anti-with entering first through pipeline 7 after the material-heat-exchanging from pipeline 19
Device 8 is answered, is contacted with Hydrobon catalyst and carries out hydrodesulfurization, hydrodenitrogeneration, aromatic hydrogenation saturated reaction.First reactor 8
Effluent enters separator 10 through pipeline 9, through obtaining the reaction effluent I rich in mononuclear aromatics at the top of separator, from separation
Device bottom obtains the reaction effluent II rich in polycyclic aromatic hydrocarbon.Reaction effluent I enters air cooler 12 through pipeline 11, through pipeline 13
Into water cooler 14, mixed with the material from pipeline 27 through pipeline 15.Reaction effluent II is through pipeline 16, and from pipeline 39
Material mixing after through pipeline 17 enter heating furnace 18 heat after, through pipeline 19 enter heat exchanger 6, with the material from pipeline 5
Enter second reactor 21 through pipeline 20 after heat exchange, further progress polycyclic aromatic hydrocarbon is contacted with Hydrobon catalyst adds hydrogen
Saturated reaction.After the first reactor effluent enters heat exchanger 4, with the material-heat-exchanging from pipeline 3 through pipeline 22, through pipeline 23
Into air cooler 24, enter water cooler 26 through pipeline 25, through pipeline 27, after being mixed with the logistics from pipeline 15 through pipeline 28 into
Enter high-pressure separator 29.After high-pressure separator 29 carries out gas-liquid separation, the hydrogen-rich gas at top enters recycle hydrogen through pipeline 30
Compressor 31 boosts, the H after boosting2It is divided into four strands through pipeline 32, the first stock-traders' know-how pipeline 33, with the supplement from pipeline 36
It is mixed with 2 outlet materials of pump through pipeline 37 after hydrogen mixing;Cold hydrogen of the second stock-traders' know-how pipeline 34 as first reactor 8;Third stock
Through pipeline 35, mixed with the material from pipeline 16 through pipeline 39 after being mixed with the supplement hydrogen from pipeline 38;4th stock-traders' know-how pipe
Cold hydrogen of the line 40 as second reactor 21.The stream passes via line 41 obtained from 29 bottom of high-pressure separator enters low pressure separator
42, Oil-gas Separation is further carried out, the stream passes via line 43 obtained from 42 bottom of low pressure separator enters stabilizer 44, tower top
Light hydrocarbon gas extracted out by pipeline 45, naphtha from pipeline 46 extract out, tower bottom product through pipeline 47 flow out, be hydrogenated to
Oil.
The following examples will be further described method provided by the invention, but therefore not limit this hair
It is bright.
The trade names of Hydrobon catalyst A, B used in comparative example and embodiment are RN-32L, RL-2 respectively,
It is produced by Chang Ling branch company of Sinopec catalyst Co., Ltd.
The preparation method of Hydrobon catalyst C used in embodiment is as follows:
It weighs 30 grams of nickel nitrates, 45 grams of ammonium metatungstates and 15 grams of oxalic acid respectively to be put into 140 grams of deionized waters, stirring and dissolving
Clear solution is obtained, 200 grams of silica supports are impregnated using the above-mentioned solution of saturation infusion process, dip time is 2 hours, so
Afterwards, 2 hours dry at 120 DEG C, then it is roasted in the state of being passed through air stream, calcination temperature is 450 DEG C, the time
It is 4 hours, gas agent ratio is 0.3 liter/(gram hour), obtain semi-finished product catalyst, the carbon content of semi-finished product catalyst is 0.1
Weight %;10 grams of diethylene glycol (DEG)s are put into 150 grams of deionized waters, clear solution is stirred to get, using saturation infusion process with above-mentioned molten
Liquid pre-impregnated semi-finished product catalyst, dip time are 2 hours, and then, at 120 DEG C, dry 6 hours, obtain Hydrobon catalyst
C.On the basis of the total amount of C, in terms of oxide, NiO contents are 3.3 heavy %, WO3Content is 15.1 heavy %.
To give full play to the hydrodesulfurization performance of catalyst, above-mentioned Hydrobon catalyst is both needed to before contacting formal raw material
Carry out presulfurization processing.In comparative example and embodiment set forth below, the method for pre-sulphuration of each Hydrobon catalyst is identical.
Comparative example 1
Feedstock oil D is mixed into hydrofining reactor with hydrogen, is contacted with Hydrobon catalyst A, hydrogenation reaction item
Part and product property are as shown in table 2, and the saturation factor of polycyclic aromatic hydrocarbon is 84.38% in hydrogenated oil as can be seen from Table 2, total virtue
The saturation factor of hydrocarbon is 18.22%, and the selectivity of mononuclear aromatics is 67.97%.
Comparative example 2
Feedstock oil D is mixed into hydrofining reactor with hydrogen, is contacted with Hydrobon catalyst A, hydrogenation reaction item
Part and product property are as shown in table 2, and the saturation factor of polycyclic aromatic hydrocarbon is 94.49% in hydrogenated oil as can be seen from Table 2, total virtue
The saturation factor of hydrocarbon is 46.72%, and the selectivity of mononuclear aromatics is 26.65%.
Compared with comparative example 1, it can be seen that in the case where other conditions remain unchanged, in dynamics Controlling region, instead
Temperature is answered to increase, polycyclic aromatic hydrocarbon saturation factor rises, and mononuclear aromatics selectively declines.
Embodiment 1
Using flow shown in Fig. 1 to feedstock oil D processing.Feedstock oil D and hydrogen are mixed into the first reaction zone, and add
Hydrogen catalyst for refining A is contacted, the polycyclic aromatic hydrocarbon saturation factor 70% of liquid material, mononuclear aromatics in the first reaction zone reaction effluent
Selectivity 98.3%.The reaction effluent of first reaction zone isolated reaction effluent I and reaction effluent in the separator
The temperature of II, separator are 260 DEG C, and the mass ratio of reaction effluent I and reaction effluent II is 60:40.Reaction outflow
Object II is mixed into second reaction zone with hydrogen, is contacted with Hydrobon catalyst A, further carries out hydrofining reaction, obtain
Through isolated hydrogenated oil after being mixed to reaction effluent III, reaction effluent III with reaction effluent I.Two reactions
It is as shown in table 2 that the hydrogenation conditions in area and final gained are hydrogenated to oil nature.
The saturation factor of polycyclic aromatic hydrocarbon is 95.4% in hydrogenated oil as can be seen from Table 2, and the saturation factor of total aromatic hydrocarbons is
9.54%, the selectivity of mononuclear aromatics is 85.16%.
Embodiment 2
Using technique shown in Fig. 1 to feedstock oil D processing.Feedstock oil D and hydrogen are mixed into the first reaction zone, and add
Hydrogen catalyst for refining C contact, polycyclic aromatic hydrocarbon saturation factor 65%, mononuclear aromatics in liquid material in the first reaction zone reaction effluent
Selectivity 100%.The reaction effluent of first reaction zone isolated reaction effluent I and reaction effluent in the separator
The temperature of II, separator are 250 DEG C, and the mass ratio of reaction effluent I and reaction effluent II is 50:50.Reaction outflow
Object II is mixed into second reaction zone with hydrogen, is contacted with Hydrobon catalyst C, further carries out hydrofining reaction, obtain
Through isolated hydrogenated oil after being mixed to reaction effluent III, reaction effluent III with reaction effluent I.Two reactions
It is as shown in table 2 that the hydrogenation conditions in area and final gained are hydrogenated to oil nature.
The saturation factor of polycyclic aromatic hydrocarbon is 95.96% in hydrogenated oil as can be seen from Table 2, and the saturation factor of total aromatic hydrocarbons is
9.29%, the selectivity of mononuclear aromatics is 85.63%.
Embodiment 3
Using flow shown in Fig. 1 to feedstock oil D processing.Feedstock oil D and hydrogen are mixed into the first reaction zone, and add
Hydrogen catalyst for refining C is contacted, the polycyclic aromatic hydrocarbon saturation factor 68% of liquid material, mononuclear aromatics in the first reaction zone reaction effluent
Selectivity 100%.The reaction effluent of first reaction zone isolated reaction effluent I and reaction effluent in the separator
The temperature of II, separator are 260 DEG C, and the mass ratio of reaction effluent I and reaction effluent II is 60:40.Reaction outflow
Object II is mixed into second reaction zone with hydrogen, is contacted with Hydrobon catalyst C, further carries out hydrofining reaction, obtain
Through isolated hydrogenated oil after being mixed to reaction effluent III, reaction effluent III with reaction effluent I.Two reactions
It is as shown in table 2 that the hydrogenation conditions in area and final gained are hydrogenated to oil nature.
The saturation factor of polycyclic aromatic hydrocarbon is 96.32% in hydrogenated oil as can be seen from Table 2, and the saturation factor of total aromatic hydrocarbons is
9.54%, the selectivity of mononuclear aromatics is 85.31%.
Embodiment 4
Using flow shown in Fig. 1 to feedstock oil E processing.Feedstock oil E and hydrogen are mixed into the first reaction zone, and add
Hydrogen catalyst for refining B is contacted, the polycyclic aromatic hydrocarbon saturation factor 70% of liquid material, mononuclear aromatics in the first reaction zone reaction effluent
Selectivity 99%.The reaction effluent of first reaction zone isolated reaction effluent I and reaction effluent II in the separator,
The temperature of separator is 260 DEG C, and the mass ratio of reaction effluent I and reaction effluent II is 50:50.Reaction effluent II
It is mixed into second reaction zone with hydrogen, is contacted with Hydrobon catalyst B, hydrofining reaction is further carried out, is obtained anti-
Through isolated hydrogenated oil after answering effluent III, reaction effluent III to be mixed with reaction effluent I.Two reaction zones
It is as shown in table 2 that hydrogenation conditions and final gained are hydrogenated to oil nature.
The saturation factor of polycyclic aromatic hydrocarbon is 95.17% in hydrofinishing product as can be seen from Table 2, and the saturation factor of total aromatic hydrocarbons is
9.11%, the selectivity of mononuclear aromatics is 86.23%.
Embodiment 5
Using flow shown in Fig. 1 to feedstock oil F processing.Feedstock oil F and hydrogen are mixed into the first reaction zone, and add
Hydrogen catalyst for refining C is contacted, the polycyclic aromatic hydrocarbon saturation factor 70% of liquid material, mononuclear aromatics in the first reaction zone reaction effluent
Selectivity 98.5%.The reaction effluent of first reaction zone isolated reaction effluent I and reaction effluent in the separator
The temperature of II, separator are 260 DEG C, and the mass ratio of reaction effluent I and reaction effluent II is 40:60.Reaction outflow
Object II is mixed into second reaction zone with hydrogen, is contacted with Hydrobon catalyst C, further carries out hydrofining reaction, obtain
Through isolated hydrogenated oil after being mixed to reaction effluent III, reaction effluent III with reaction effluent I.Two reactions
It is as shown in table 2 that the hydrogenation conditions in area and final gained are hydrogenated to oil nature.
The saturation factor of polycyclic aromatic hydrocarbon is 95.59% in hydrofinishing product as can be seen from Table 2, and the saturation factor of total aromatic hydrocarbons is
10.73%, the selectivity of mononuclear aromatics is 85.38%.
Table 1
| Feedstock oil | D | E | F |
| Density (20 DEG C)/(g/cm3) | 0.9347 | 0.9400 | 0.9650 |
| Sulfur content/(μ g/g) | 2300 | 4000 | 7500 |
| Nitrogen content/(μ g/g) | 450 | 950 | 550 |
| Total aromatic hydrocarbons/% | 80.7 | 82.6 | 88.0 |
| Mononuclear aromatics content, quality/% | 26.3 | 25.0 | 20.0 |
| Polycyclic aromatic hydrocarbon content, quality/% | 54.4 | 57.6 | 68.0 |
| Boiling range (ASTM D-86)/DEG C | |||
| Initial boiling point | 186 | 213 | 250 |
| 50% | 251 | 290 | 314 |
| The end point of distillation | 330 | 360 | 371 |
Table 2
Claims (15)
1. a kind of method of diesel oil selective hydrogenation, including diesel raw material oil is mixed with hydrogen, in the first reaction zone and plus hydrogen
Catalyst for refining contacts, and under hydrogenation process conditions, carries out hydrodesulfurization, hydrodenitrogeneration and the reaction of selective hydrogenation Porous deproteinized bone;
The reaction effluent of first reaction zone is separated into reaction effluent I and reaction effluent II, the reaction effluent through separator
II enters second reaction zone and is contacted with Hydrobon catalyst, under hydrogenation process conditions, further carries out hydrodesulfurization plus hydrogen
Denitrogenation and the reaction of selective hydrogenation Porous deproteinized bone obtain reaction effluent III, reaction effluent I and reaction effluent III mixing
Afterwards, hydrogenated oil is obtained by separation, on the basis of diesel raw material oil, polycyclic aromatic hydrocarbon saturation factor is in the hydrogenated oil
95% or more, mononuclear aromatics is selectively 85% or more.
2. according to the method for claim 1, the polycyclic aromatic hydrocarbon of liquid material is saturated in the reaction effluent of the first reaction zone
Rate is 60%~75%, and mononuclear aromatics is selectively more than 98%.
3. according to method as claimed in claim 1 or 2, the polycyclic aromatic hydrocarbon of liquid material is full in the reaction effluent of the first reaction zone
It is 65%~72% with rate.
4. according to the method for claim 1, which is characterized in that the temperature of separator is 230 DEG C~280 DEG C, preferred point
Temperature from device is 240 DEG C~260 DEG C.
5. according to method as claimed in claim 1 or 2, which is characterized in that the boiling spread of the diesel raw material oil be 150~
400 DEG C, 60~90 mass % of total arene content, wherein 40~80 mass % of polycyclic aromatic hydrocarbon content.
6. according to method as claimed in claim 1 or 2, which is characterized in that the diesel raw material oil is gently followed selected from catalytic cracking
Ring oil, heavy catalytic cycle oil, the straight-run diesel oil of naphthene base crude, the coker gas oil of naphthene base crude, coal direct liquefaction oil
Diesel oil distillate, coal tar one or more of diesel oil distillate.
7. according to the method for claim 1, which is characterized in that the hydrogenation conditions of first reaction zone are:Hydrogen
Divide 3~12MPa, 240~400 DEG C of reaction temperature, 400~1200Nm of hydrogen to oil volume ratio3/m3, volume space velocity 0.5 when liquid~
4.0h-1;
The hydrogenation conditions of the second reaction zone are:3~10MPa of hydrogen partial pressure, 260~420 DEG C of reaction temperature, hydrogen oil body
400~1200Nm of product ratio3/m3, 0.3~4.0h of volume space velocity when liquid-1。
8. according to the method for claim 1, which is characterized in that the hydrogenation conditions of first reaction zone are:Hydrogen
Divide 4~10MPa, 240~360 DEG C of reaction temperature, 500~1000Nm of hydrogen to oil volume ratio3/m3, volume space velocity 0.5 when liquid~
2.0h-1;
The hydrogenation conditions of the second reaction zone are:4~8MPa of hydrogen partial pressure, 260~380 DEG C of reaction temperature, hydrogen oil body
500~1000Nm of product ratio3/m3, 0.5~1.5h of volume space velocity when liquid-1。
9. according to method of claim 1, which is characterized in that contain carrier in Hydrobon catalyst and be supported on the carrier
On hydrogenation metal active component;On the basis of the total weight of the Hydrobon catalyst, in terms of oxide, hydrogenation metal is lived
Property component content be 15~60 weight %, preferably 20~50 weight %.
10. according to the method for claim 9, which is characterized in that the hydrogenation metal active component is at least one selected from Section VI B
Race's metallic element and at least one are selected from group VIII metallic element, and the vib metals element is selected from molybdenum and/or tungsten, institute
It states group VIII metallic element and is selected from cobalt and/or nickel;The carrier is selected from gama-alumina, silica, aluminium oxide-silicon oxide, oxygen
Change titanium, magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, silica-oxygen
Change titanium, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-titania, oxygen
It is one or more in SiClx-alumina-silica magnesium and silica-alumina, zirconia.
11. according to the method for claim 1, which is characterized in that the Hydrobon catalyst preparation method includes:
(1) water soluble salt of hydrogenation metal active component and organic complexing agent are loaded on carrier using infusion process, then into
Row is dry, roasting, obtains semi-finished product catalyst, and the roasting condition makes on the basis of the total amount of semi-finished product catalyst, half at
Carbon content is 0.03-0.5 weight % in product catalyst;
(2) to contain the solution of organic complexing agent as maceration extract, semi-finished product catalyst obtained by step (1) is impregnated, so
After be dried and without roasting.
12. according to the method for claim 11, which is characterized in that institute in (1) the step of the preparation method of Hydrobon catalyst
State roasting carried out under conditions of being passed through gas, and roast temperature be 350~500 DEG C, preferably 360~450 DEG C, roasting
Time is 0.5~8h, preferably 1~6h, the intake of gas is 0.2~20 liter/(gram hour), preferably 0.3~10 liter/
(gram hour).
13. according to the method for claim 11, which is characterized in that the step of the preparation method of Hydrobon catalyst in (1), have
The molar ratio of machine complexing agent and metal active constituent is 0.03~2:1, preferably 0.08~1.5:1.
14. according to the method for claim 11, which is characterized in that (1) is described the step of the preparation method of Hydrobon catalyst
Organic complexing agent and step (2) described organic complexing agent are identical or different, and the organic complexing agent is selected from oxygen-containing and/or nitrogenous
One or more in organic matter, the oxygen containing organic matter is one or more in Organic Alcohol, organic acid, and nitrogenous has
Machine object is one or more in organic amine, organic ammonium salt.
15. according to the method for claim 14, which is characterized in that the organic complexing agent is the organic acid that carbon atom number is 2-7
In it is one or more.
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