CN106607096B - A kind of hydrogenation catalyst and preparation method thereof - Google Patents
A kind of hydrogenation catalyst and preparation method thereof Download PDFInfo
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- CN106607096B CN106607096B CN201510700293.9A CN201510700293A CN106607096B CN 106607096 B CN106607096 B CN 106607096B CN 201510700293 A CN201510700293 A CN 201510700293A CN 106607096 B CN106607096 B CN 106607096B
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Abstract
The present invention relates to a kind of hydrogenation catalysts and preparation method thereof, the preparation method includes: that (1) is loaded to the water soluble salt of hydrogenation metal active component and organic complexing agent on carrier using infusion process, then it is dried, roasts, obtain semi-finished product catalyst, the roasting condition makes on the basis of the total amount of semi-finished product catalyst, and 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 impregnated, is then dried and without roasting；(3) metallic element as auxiliary agent is loaded on carrier；Wherein, step (3) before step (1), neutralization after and any one or more progress before step (2).Not only activity is significantly improved catalyst obtained by this method, but also the service life of catalyst is also obviously improved.
Description
Technical field
The present invention relates to a kind of preparation methods of hydrogenation catalyst and hydrogenation catalyst obtained by this method.
Background technique
It is raw that the environmental consciousness being increasingly enhanced and the environmental regulation being increasingly stringenter force oil refining circle more to focus on clean fuel
Produce technological development.Future market vehicle fuel is intended to " super-low sulfur ", and the fuel for not being able to satisfy discharge standard will be unable to enter city
?.Hydrogen addition technology plays more and more important work as a kind of effective desulfurization means in the production of fuel for cleaning vehicle
With, wherein efficient hydrogenation catalyst is then the core technology of hydrogen addition technology, therefore, develop have more high activity and selectivity it is new
Type hydrogenation catalyst then becomes most urgent one of the demand of petroleum refining industry.
Hydrogenation catalyst generallys use infusion process preparation, i.e., with molten containing required active component (such as Ni, Mo, Co, W)
Liquid impregnates certain carrier, the method for being dried, roasting or not roasting later.
CN103551162A discloses a kind of diesel hydrogenation for removal sulphur denitrification catalyst, the composition of catalyst include carrier, auxiliary agent,
Active metal；Carrier is Al2O3-ZrO2-TiO2-SiO2Multivariant oxide complex carrier；Auxiliary agent is phosphorus；It is with nickel, cobalt, molybdenum and tungsten
Active component；Weight percent content of each component on the basis of catalyst are as follows: in terms of oxide, 1~6wt% of cobalt oxide；Oxygen
Change 1~15wt% of nickel, 2~12wt% of molybdenum oxide, 12~35wt% of tungsten oxide, 1.5~5wt% of auxiliary agent phosphorus pentoxide；Catalysis
Kong Rong ≮ 0.2mL/g of agent, specific surface area are ≮ 140m2/ g, mechanical strength ≮ 15N/mm；Each component is in carrier in complex carrier
In shared specific gravity be respectively as follows: titanium oxide and account for 2~15wt%, silica accounts for 2~20wt%, and zirconium oxide accounts for 5~15wt%；Surplus
For aluminium oxide.The catalyst is made by step impregnation method: co-impregnated solution being divided into isometric two parts, dipping carries in two steps
Body, and all roasted after the completion of each step dipping.
CN103657667A discloses a kind of preparation method of new macroporous structure catalyst for heavy oil hydrogenation demetal, special
Sign is: it specifically comprises the following steps: the preparation of 1) Aluminum sol；2) asphaltic residue powder and Aluminum sol are mixed with macropore knot
Structure catalyst carrier；3) catalyst carrier after molding is used to two step impregnations of isometric branch；It is finally made and urges
Agent.Two step infusion processes of the preparation method specifically: the first step first impregnates Mo, and second step impregnates Ni, also, in maceration extract not
Include organic complexing agent.
By the two step infusion processes that the prior art provides activity of hydrocatalyst is increased, but improves limitation.
CN100469440C, CN102909027A are disclosed by introducing organic dispersing agent into carrier during the preparation process
Or complexing agent (such as ethylene glycol, oxalic acid, citric acid, ethylenediamine tetra-acetic acid, nitrilotriacetic acid) is prepared for Ni-W-Mo ternary metal and adds
Hydrogen catalyst.Compared with the catalyst that existing method provides, resulting catalyst has better hydrofinishing performance.
Compared with traditional infusion process, be complexed dipping technique although the activity of such catalyst can be promoted further,
But have the defects that catalytic activity reduce it is too fast, cause catalyst service life too short.
To sum up, although above-mentioned preparation method can improve the Hydrogenation of catalyst to a certain extent, into
One step research has been found that, there are still catalyst activities lower, the shorter defect of catalyst life of catalyst made from the prior art.
Summary of the invention
For the disadvantage that prior art activity of hydrocatalyst is lower or catalyst service life is short, the present invention provides one
The preparation method of the new hydrogenation catalyst of kind and hydrogenation catalyst obtained by this method, catalyst obtained by this method is not
Only activity is significantly improved, and the service life of catalyst is also obviously improved.
It was found by the inventors of the present invention that above-mentioned complexing dipping technique, by introducing complexing agent in dipping process, and low
The lower drying of temperature can weaken active component and carrier interaction, improve metal dispersity, change metal vulcanization sequence, be formed
The activity phase of more high activities simultaneously improves activated centre number.But due to dry using low temperature in complexing dipping technique
Dry, there is no the process Jing Guo high-temperature roasting, metallic compound is still present in carrier surface in the form of metallic salt, activity
Component and carrier function power are weaker, cause under high temperature and pressure and the hydrogenation conditions of severe raw material, metal was reacting
Constantly assemble in journey, auxiliary agent effect weakens, and activated centre number is reduced, latent active decline, therefore catalyst is active, steady
Qualitative decline.Although and the catalyst stability for using high-temperature roasting method to prepare is preferable, active component and carrier active force
Relatively strong, the latent active in activated centre is lower, and due to the dispersion and barrier action of not no complexing agent, active component platelet is larger,
Activated centre number is less, and activity is very low.
By research it has furthermore been found that by two step preparation catalysts, the first step impregnates the present inventor
It is respectively used to introduce hydrogenation metal active component and organic complexing agent with second step dipping, being added in first step dipping process has
Machine complexing agent is simultaneously run through roasting and is converted into charcoal, can not only improve the activity of catalyst, and can effectively for a long time
The high activity for keeping catalyst, to greatly improve the service life of catalyst.Speculate that its reason may be because the first step is soaked
The organic complexing agent being added during stain, the presence of organic complexing agent hinder the aggregation of active metal in roasting process, make it
That disperses is more uniform；Meanwhile roasting can make metallic compound be converted into metal oxide after first step dipping, make organic network
Mixture is converted into charcoal, to keep the combination between active metal and carrier stronger, improves the activity and stabilization of catalyst
Property.And the organic complexing agent being added in second step dipping process is covered on catalyst surface, can effectively prevent active metal
Aggregation in sulfidation improves metal dispersity, is more advantageous to be formed with higher active II class activity phase and shape
At more activated centres, thus the further very high activity of catalyst.Therefore, which can effectively solve conventional impregnation method
With the technological deficiency of existing complexing infusion process.
As a result, the present invention also provides a kind of preparation method of hydrogenation catalyst, the preparation method the following steps are included:
(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；
(3) metallic element as auxiliary agent is loaded on carrier；
Wherein, step (3) before step (1), neutralization after and before step (2) it is any one or more into
Row.
In addition, method of the invention additionally provides hydrogenation catalyst prepared by the above method.
Higher hydrodesulfurization activity and hydrodenitrogenationactivity activity are had both using hydrogenation catalyst prepared by method of the invention,
It has been obviously prolonged the service life of catalyst.It is provided for example, can be seen that from the data of embodiment 4 and comparative example 3 by the present invention
Method made from the opposite hydrodesulfurization activity that reacts 4 hours of catalyst (S4) be 139%, be with respect to hydrodenitrogenationactivity activity
121%, and the opposite hydrodesulfurization activity that catalyst (D3) reacts 4 hours in comparative example 3 is 112%, opposite hydrodenitrogeneration is living
Property is 106%.Catalyst made from method provided by the present invention (S4) reacts 500 hours opposite hydrodesulfurization activities
130%, opposite hydrodenitrogenationactivity activity is 116%, and catalyst (D3) reacts opposite hydrodesulfurization in 500 hours in comparative example 3
Activity is 75%, and opposite hydrodenitrogenationactivity activity is 86%.It either reacts 4 hours or 500 hours, the opposite hydrodesulfurization of S4
Activity and opposite hydrodenitrogenationactivity activity extend the reaction time obviously higher than D3, and the opposite hydrodesulfurization of catalyst S4 is living
Property and opposite hydrodenitrogenationactivity activity downward trend be significantly less than catalyst D3, the comparing result of other embodiments and comparative example
Same trend is presented.Therefore, method of the invention is adopted with preferable prospects for commercial application.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The preparation method of the hydrogenation catalyst provided according to the present invention, the preparation method the following steps are included:
(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；
(3) metallic element as auxiliary agent is loaded on carrier；
Wherein, step (3) before step (1), neutralization after and before step (2) it is any one or more into
Row.
In accordance with the present invention it is preferred that step (1) described roasting condition makes on the basis of the total amount of semi-finished product catalyst,
Carbon content is 0.04-0.4 weight % in semi-finished product catalyst.
In the present invention, it can be obtained by the intake of maturing temperature and imflammable gas in control roasting condition
Above-mentioned carbon content, the imflammable gas can for various oxygen contents be not less than 20 volume % gas, as air, oxygen with
And one of their mixed gas or a variety of.
The intake of the imflammable gas was not less than for 0.2 liter/gram hour.The imflammable gas is passed through, a side
The condition that face meets burning makes organic complexing agent be converted into charcoal so that the salt of active metal component is converted into oxide；Another party
Face can also emit carbon dioxide that burning is formed and water and other compositions, cause 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 350-450 DEG C, preferably 360-430 DEG C, roast
The time of burning is 0.5-8h, preferably 1-6h.Control maturing temperature can guarantee organic complexing agent energy or more within the above range
It states content range charcoal is formed on carrier, obtains semi-finished product catalyst.
In accordance with the present invention it is preferred that the molar ratio of step (1) organic complexing agent and metal active constituent is 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
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 selected from one of oxygen-containing and/or itrogenous organic substance or a variety of.
The oxygen containing organic matter is preferably selected from one of Organic Alcohol, organic acid or a variety of.
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, such as one of ethylene glycol, glycerine, polyethylene glycol, diethylene glycol, butanediol or a variety of.It is described
The molecular weight of polyethylene glycol is preferably 200-1500.
The organic acid is preferably the compound containing one or more COOH groups of C2-C7, is specifically as follows acetic acid, horse
Come one of sour, oxalic acid, aminotriacetic acid, 1,2- cyclohexanediamine tetraacetic acid, citric acid, tartaric acid, malic acid or a variety of.
The nitrogenous organic matter is preferably selected from one of organic amine, organic ammonium salt or a variety of.
The organic amine is preferably the compound containing one or more NH groups of C2-C7, 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 tetrem
One of acid, citric acid, tartaric acid, malic acid, ethylenediamine and EDTA or a variety of.
Preferably, organic complexing agent described in step (1) is selected from one of organic acid or a variety of, it is highly preferred that step
(1) organic complexing agent is selected from one of fatty acid of C2-C7 or a variety of.Use organic acid as the organic of step (1)
Complexing agent 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) drying temperature is 100-250 DEG C, time 1-12h.
Preferably, step (2) drying temperature is 100-200 DEG C, time 1-12h.
In accordance with the present invention it is preferred that the dosage of the hydrogenation metal active component makes, it is with the total amount of hydrogenation catalyst
Benchmark, in terms of oxide, the content of hydrogenation metal active component is 15-60 weight %, preferably 20-50 weight %, further
The content of preferably 20-40 weight %, metal promoter are no more than 10 weight %, preferably 0.5-6 weight %.
In accordance with the present invention it is preferred that the concentration of the water soluble salt of hydrogenation metal active component is 0.5- with elemental metal
8mol/L, preferably 0.2-5mol/L, further preferably 0.2-2mol/L.Concentration herein is various hydrogenation metal active groups
The respective concentration of water soluble salt divided, rather than total concentration.
The water soluble salt of the hydrogenation metal active component can be various solubility and meet load requirement or in hydrotropy
The water soluble compound for the hydrogenation metal active component that solubility is met the requirements can be formed in the presence of agent in water, such as can
To be one of nitrate, chloride, sulfate, carbonate or a variety of, preferably nitrate.
In accordance with the present invention it is preferred that the hydrogenation metal active component at least one is selected from vib metals element, extremely
It is few a kind of selected from group VIII metallic element.
According to the present invention, the vib metals element is preferably molybdenum and/or tungsten.
According to the present invention, the group VIII metallic element is preferably cobalt and/or nickel.
In accordance with the present invention it is preferred that the compound of the element containing vib metals can selected from ammonium molybdate, ammonium paramolybdate, partially
One of ammonium tungstate, molybdenum oxide and tungsten oxide are a variety of.
The compound of the metallic element containing group VIII can be selected from the nitrate of group VIII metal, group VIII metal
Chloride, the sulfate of group VIII metal, the formates of group VIII metal, the acetate of group VIII metal, Section VIII
The phosphate of race's metal, the citrate of group VIII metal, the oxalates of group VIII metal, group VIII metal carbonic acid
Salt, the subcarbonate of group VIII metal, the hydroxide of group VIII metal, the phosphate of group VIII metal,
The phosphide of group VIII metal, the sulfide of group VIII metal, the aluminate of group VIII metal, group VIII metal molybdenum
One of water-soluble oxide of hydrochlorate, the tungstates of group VIII metal and group VIII metal is a variety of.
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 phosphate of category, the molybdate of group VIII metal, the tungstates of group VIII metal and group VIII metal water-soluble oxygen
One of compound is a variety of.
Further preferably, the compound of the metallic element containing group VIII can be selected from but not limited to nickel nitrate, nickel sulfate, vinegar
One of sour nickel, basic nickel carbonate, cobalt nitrate, cobaltous sulfate, cobalt acetate, basic cobaltous carbonate, cobalt chloride and nickel chloride are a variety of.
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 by infusion process that hydrogenation metal is living
Property component loads on carrier.
According to the present invention, the sequence on carrier is loaded to hydrogenation metal active component there is no particular limitation, Ke Yitong
It crosses containing there are many solution impregnating carrier of water soluble salt, it, can also by all hydrogenation metal active component mutual loads to carrier
To prepare the solution step impregnation carrier containing water soluble salt respectively, hydrogenation metal active component is successively loaded on carrier.
When using step impregnation, preferably it is dried after each dipping and preferably further roasts.It is dry and roasting
Mode and condition are referred to the prior art and are selected.
According to the present invention, the mode of loading of the organic complexing agent is not particularly limited.Organic complexing agent can be with
One of water soluble salt of hydrogenation metal active component or a variety of co-formulations can also individually match at maceration extract impregnated carrier
Maceration extract impregnated carrier is made, preferably the former.
In accordance with the present invention it is preferred that the dosage of metal promoter is 0.05-3mol/L, preferably 0.1- with elemental metal
2mol/L。
According to the present invention, the introducing of metal promoter is not limited specifically, the introducing method of the metal promoter can
It, can also be after carrier preparation by various modes such as example, can be introduced in carrier preparation process with through a variety of ways
The mode of dipping introduces, and can also be and both introduces in carrier preparation process, introduces after preparing further through carrier.
It should be noted that needing to be roasted after introducing metal promoter when introducing by the method for impregnated carrier
The step of, the maturing temperature be 250-600 DEG C, preferably 350-500 DEG C, calcining time 2-8h, preferably 3-6h.
According to the present invention, the introducing of the metal promoter need to carry out before step (2), to ensure what step (2) introduced
Organic complexing agent does not suffer from roasting process.
When using infusion process, preferably metal promoter draws together with metal active constituent and organic complexing agent in step (1)
Enter in carrier.The various soluble-salts of metal promoter can be used in metal promoter, such as in chloride, nitrate, sulfate
It is one or more.
According to the present invention, the infusion process can be incipient impregnation, or supersaturation dipping, to the dipping
Temperature is not particularly limited, and can be the attainable various temperature of maceration extract institute, the time of dipping is not particularly limited, as long as
Upper the desired amount of required component can be loaded, such as: the temperature of dipping can be 15-60 DEG C, and dip time can be 0.5-5
Hour.
According to the present invention, the metal promoter various can improve with hydrogenation catalyst effect to be commonly used in the art
Catalyst performance metallic element, can be selected according to the application of catalyst.
The metal promoter is selected from group iib metallic element, group ia metal element, group iia metallic element and rare earth
One of metallic element is a variety of.
The group iib metallic element for example can be zinc and/or cadmium.
The group ia metal element for example can be one of lithium, sodium, potassium, rubidium, caesium and francium or a variety of.
The group iia metallic element for example can be one of beryllium, magnesium, calcium and strontium or a variety of.
The thulium for example can be one of lanthanum, cerium, praseodymium and neodymium or a variety of.
The metal promoter specifically preferred according to the invention is Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum element
With one of Ce elements or a variety of.
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 of aluminium-magnesia, silica-alumina, zirconia are a variety of, and wherein aluminium oxide is more preferably a kind of hydration oxygen
Change the aluminium oxide obtained after the roasting of aluminium (aluminium hydroxide) glue compound.
The present invention also provides a kind of hydrogenation catalysts as made from preparation method of the invention.
Compared with the catalyst of conventional method preparation, the catalyst as made from method provided by the present invention has higher
Hydrogenation activity.
The catalyst of method preparation provided by the present invention is suitable for hydrodesulfurization, the hydrodenitrogeneration of various hydrocarbon oil crude materials
Etc. subtractive processes.The hydrocarbon oil crude material can be gasoline, diesel oil, lubricating oil, kerosene and naphtha, be also possible to reduced crude,
Decompression residuum, pertroleum wax and Fischer-Tropsch synthesis oil.
By the present invention in that being catalyzed with catalyst prepared by method provided by the present invention to improve in unifining process
Remaining condition of hydrofinishing process is not particularly limited in the activity of agent, can be the conventional selection of this field.Generally
Ground, the condition of the hydrofinishing include: that temperature can be 300-400 DEG C；In terms of gauge pressure, pressure can be 1.0-8.0MPa；
Volume space velocity can be 0.5-3.0 hours when liquid-1, hydrogen to oil volume ratio can be 100-700.
Catalyst provided by the invention is preferably vulcanized using conventional method in that art before the use.Generally, institute
The condition for stating vulcanization may include: in presence of hydrogen, at a temperature of 180-450 DEG C, with sulphur, hydrogen sulfide, carbon disulfide, two
Two sulphur of methyl or other presulfurizations containing one of sulfur feedstock or a variety of progress 2-4 hours.The presulfurization can be in reactor
Outer progress, can also be In-situ sulphiding in reactor.
Below by way of the specific embodiment implementation process that the present invention will be described in detail and generated beneficial effect, it is intended to help
Where reader more clearly understands Spirit Essence of the invention, but any restriction cannot be constituted to practical range of the invention.
Rigaku electric machine industry Co., Ltd. 3271E type Xray fluorescence spectrometer is used in following embodiment, to catalysis
The content of each element carries out analysis measurement in agent.The EMIA-320V analysis of carbon and sulfur that carbon content is produced using HORIBA company, Japan
Instrument carries out analysis measurement.
Embodiment 1
The present embodiment is used to illustrate hydrogenation catalyst according to the present invention and preparation method thereof.
270 grams of magnesium nitrates are weighed, deionized water stirring and dissolving is added, adds deionized water to 850 milliliters, saturation dipping 1000
Grams alumina support 2 hours, then 2 hours dry at 120 DEG C, 400 DEG C roast 4 hours, and obtaining water absorption rate is 0.85 containing magnesium
Aluminium oxide Z1.
Weigh respectively 54 grams of molybdenum trioxides, 21 grams of basic nickel carbonates, 13 grams of phosphoric acid, 30 grams of citric acids be put into 140 grams go from
In sub- water, heating stirring dissolves to obtain clarification dipping solution, impregnates 200 grams using the above-mentioned solution of saturation infusion process and contains magnesia
Aluminium Z1 carrier, dip time are 2 hours, then, 2 hours dry at 120 DEG C, then by it in the state of being passed through air stream into
Row roasting, maturing temperature be 360 DEG C, the time be 6 hours, gas agent ratio be 10.0 liters/(gram hour), obtain semi-finished product catalyst
The carbon content of Z-S1, Z-S1 are shown in Table 1；30 grams of citric acids are added in 150 grams of deionized waters, clear solution is stirred to get, are used
It is saturated the above-mentioned solution of infusion process and impregnates Z-S1, dip time is 2 hours, then, in 200 DEG C of dry 2 hours, is catalyzed
Agent S1.On the basis of the total amount of S1, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Comparative example 1
Hydrogenation catalyst is prepared using method same as Example 1, unlike, by catalyst obtained by embodiment 1
S1 is roasted 3 hours at 400 DEG C, obtains catalyst D1, in catalyst D1, on the basis of the total amount of D1, in terms of oxide, adds hydrogen golden
The content for belonging to active component is shown in Table 2.
Embodiment 2
The present embodiment is used to illustrate hydrogenation catalyst according to the present invention and preparation method thereof.
37 grams of lanthanum nitrates are weighed, deionized water stirring and dissolving is added, adds deionized water to 850 milliliters, saturation dipping 1000
Grams alumina support 2 hours, then 2 hours dry at 100 DEG C, 500 DEG C roast 4 hours, and obtaining water absorption rate is 0.85 containing lanthanum
Aluminium oxide Z2.
It weighs 30 grams of nickel nitrates, 45 grams of ammonium metatungstates, 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 lanthanum containing alumina Z2 carriers are impregnated using the above-mentioned solution of saturation infusion process, dip time is 2 small
When, it is then, 2 hours dry at 120 DEG C, then it is roasted in the state of being passed through air stream, maturing temperature 400
DEG C, the time is 2 hours, gas agent ratio is 1.0 liters/(gram hour), the carbon content for obtaining semi-finished product catalyst Z-S2, Z-S2 is shown in Table
1；10 grams of diethylene glycol (DEG)s are put into 150 grams of deionized waters, clear solution is stirred to get, are soaked using the saturation above-mentioned solution of infusion process
Stain Z-S2, dip time are 2 hours, then, in 150 DEG C of dry 3 hours, obtain catalyst S2.On the basis of the total amount of S2,
In terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Embodiment 3
The present embodiment is used to illustrate hydrogenation catalyst according to the present invention and preparation method thereof.
37 grams of lanthanum nitrates are weighed, deionized water stirring and dissolving is added, adds deionized water to 850 milliliters, saturation dipping 1000
Grams silica support 2 hours, then 2 hours dry at 100 DEG C, 500 DEG C roast 4 hours, and obtaining water absorption rate is 0.85 containing lanthanum
Silica Z3.
83 grams of nickel nitrates, 60 grams of ammonium metatungstates, 10 grams of ammonium molybdates, 20 grams of ammonium dihydrogen phosphates, 20 grams of citric acids are weighed respectively
It is put into 140 grams of deionized waters, stirring and dissolving obtains clear solution, impregnates 200 grams with above-mentioned solution using saturation infusion process and contains
Lanthanum silica Z3 carrier, dip time are 2 hours, then, 2 hours dry at 180 DEG C, then by it in the shape for being passed through air stream
Roasted under state, maturing temperature be 430 DEG C, the time be 3 hours, gas agent ratio be 0.3 liter/(gram hour), obtain semi-finished product
The carbon content of catalyst Z-S3, Z-S3 are shown in Table 1；15 grams of ethylenediamines are put into 150 grams of deionized waters, it is molten to stir to get clarification
Liquid impregnates Z-S3 using the above-mentioned solution of saturation infusion process, and dip time is 1 hour, then, in 120 DEG C of dry 3 hours,
Obtain catalyst S3.On the basis of the total amount of S3, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Embodiment 4
The present embodiment is used to illustrate hydrogenation catalyst according to the present invention and preparation method thereof.
54 grams of molybdenum trioxides, 19 grams of basic cobaltous carbonates, 20 grams of phosphoric acid, 20 grams of citric acids, 20g zinc nitrate is weighed respectively to be put into
In 140 grams of deionized waters, heating stirring dissolves to obtain clarification dipping solution, impregnates 200 using the above-mentioned solution of saturation infusion process
Gram alumina-silica carriers (weight ratio 1:1), dip time are 2 hours, then, 2 hours dry at 120 DEG C, then by it
Roasted in the state of being passed through air stream, maturing temperature be 400 DEG C, calcining time be 2 hours, gas agent ratio be 2.0 liters/
(gram hour), the carbon content for obtaining semi-finished product catalyst Z-S4, Z-S4 are shown in Table 1；5 grams of ethyl alcohol are put into 150 grams of deionized waters
In, clear solution is stirred to get, Z-S4 is impregnated using the above-mentioned solution of saturation infusion process, dip time is 0.5 hour, then,
In 110 DEG C of dry 3 hours, catalyst S4 is obtained.On the basis of the total amount of S4, in terms of oxide, hydrogenation metal active component
Content be shown in Table 1.
Comparative example 2
54 grams of molybdenum trioxides, 19 grams of basic cobaltous carbonates, 20 grams of phosphoric acid, 20 grams of citric acids, 20g zinc nitrate is weighed respectively to be put into
In 140 grams of deionized waters, heating stirring dissolves to obtain clarification dipping solution, impregnates 200 using the above-mentioned solution of saturation infusion process
Gram carrier same as Example 4, dip time are 2 hours, then, 2 hours dry at 120 DEG C, it is then being passed through sky
It being roasted in the state of air-flow, maturing temperature is 400 DEG C, and calcining time is 2 hours, gas agent ratio is 2.0 liters/it is (gram small
When), obtain catalyst D2.On the basis of the total amount of D2, in terms of oxide, the content of hydrogenation metal active component is shown in Table 2.
Comparative example 3
54 grams of molybdenum trioxides, 19 grams of basic cobaltous carbonates, 20 grams of phosphoric acid, 20 grams of citric acids, 20g zinc nitrate and 5 are weighed respectively
Gram ethyl alcohol is put into 140 grams of deionized waters, and heating stirring dissolves to obtain clarification dipping solution, using saturation infusion process with above-mentioned molten
Liquid impregnates 200 grams of carriers same as Example 4, and dip time is 2 hours, then, 2 hours dry at 120 DEG C, is catalyzed
Agent D3.On the basis of the total amount of D3, in terms of oxide, the content of hydrogenation metal active component is shown in Table 2.
Embodiment 5
Hydrogenation catalyst is prepared using method same as Example 2, unlike, metal active constituent is impregnated into carrier
Afterwards, when roasting to it, maturing temperature is 450 DEG C, and the time is 6 hours.Carbon content is shown in Table in obtained catalyst semi-finished product
In 1, obtained catalyst S5, on the basis of the total amount of S5, in terms of oxide, the content of hydrogenation metal active component is shown in Table 1.
Embodiment 6
Hydrogenation catalyst is prepared using method same as Example 1, unlike, gas agent ratio when roasting is 1.0 liters/
(gram hour), in obtained catalyst S6, on the basis of the total amount of S6, in terms of oxide, hydrogenation metal active component contains
Amount is shown in Table 1.
Embodiment 7
Hydrogenation catalyst is prepared using method same as Example 1, unlike, step (1) and step (2) organic network
The amount ratio of mixture is changed to 50 grams: 10 grams by 30 grams: 30 grams, obtains catalyst S7.On the basis of the total amount of S7, with oxide
Meter, the content of hydrogenation metal active component are shown in Table 1.
Table 1
Table 2
| Comparative example 1 | Comparative example 2 | Comparative example 3 | |
| MoO3, weight % | 20.6 | 20.3 | 20.2 |
| CoO, weight % | - | 4.1 | 4.0 |
| NiO, weight % | 4.3 | - | - |
| WO3, weight % | - | - | - |
| ZnO, weight % | - | 2.35 | 2.3 |
| MgO, weight % | 3.1 | - | - |
| La2O3, weight % | - | - | - |
| Carbon content in semi-finished product catalyst, weight % | 0.4 | - | - |
Test example 1
In this test example, add to what the hydrogenation catalyst and comparative example using method provided by the present invention preparation provided
The desulphurizing activated and denitrification activity of hydrogen catalyst is evaluated in accordance with the following methods, and evaluation result is as shown in table 4 below.
Using Middle East straight-run diesel oil as raw material, property is as follows:
Desulfurization, the denitrification activity of catalyst are evaluated on 30 milliliters of diesel hydrotreating units.Need before the reaction to catalyst into
Row presulfurization, Catalyst packing 30mL, presulfurization condition are as follows: 3.2MPa, 320 DEG C, 4h, hydrogen to oil volume ratio 300:1, sulfurized oil
Oil inlet speed is 8mL/h.Reaction condition are as follows: hydrogen partial pressure 3.2MPa, 330 DEG C of reaction temperature, hydrogen to oil volume ratio 300, liquid hourly space velocity (LHSV)
2.0h-1.The sample for negating respectively and answering 4 hours, react 500 hours is reacted with gas Chromatographic Determination hydrodesulfurization, hydrodenitrogeneration
Raw material and sulphur, nitrogen content in the product of acquisition.
Catalysis is evaluated using the opposite hydrodesulfurization activity relative to reference agent D (catalyst prepared in comparative example 2)
The hydrodesulfurization activity of agent is handled hydrodesulfurization reaction as 1.65 order reactions, and the reaction speed of catalyst X is calculated by formula (1)
Rate constant k (X)HDS:
Volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction in formula (1).
The hydrodesulfurization activity of the catalyst D2 prepared with comparative example 2 [is denoted as k (D2)HDS] on the basis of, it is calculated by formula (2)
The opposite hydrodesulfurization activity of catalyst X:
Catalysis is evaluated using the opposite hydrodenitrogenationactivity activity relative to reference agent D (catalyst prepared in comparative example 2)
The hydrodenitrogenationactivity activity of agent is handled hydrodesulfurization reaction as 1 order reaction, and the reaction rate for calculating catalyst X by formula (3) is normal
Number k (X)HDN:
Volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction in formula (1).
The hydrodenitrogenationactivity activity of the catalyst D2 prepared with comparative example 2 [is denoted as k (D2)HDN] on the basis of, it is calculated by formula (4)
The opposite hydrodenitrogenationactivity activity of catalyst X:
The hydrofinishing evaluation result of catalyst obtained by each embodiment and comparative example is as shown in table 3.
Table 3
Note: "-" expression is not detected in table 3.
The result of table 1 to table 3 can illustrate, the hydrogenation catalyst prepared than existing methods, catalyst provided by the invention
With considerably better hydrodesulfurization activity and hydrodenitrogenationactivity activity.In addition, reacting 4 hours and reacting 500 hours in contrast table 3
Opposite hydrodesulfurization activity and the data of opposite hydrodenitrogenationactivity activity can be seen that and react for a long time, it is provided by the invention to urge
Agent activity fall very little, and it is significantly less than comparative example, therefore, the catalyst of method preparation provided by the invention is obvious
Extend the service life of catalyst.The above results sufficiently show that preparation method provided by the present invention has its existing other party
The incomparable superiority of method.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (19)
1. a kind of preparation method of hydrogenation catalyst, the preparation method include:
(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；
(3) metallic element as auxiliary agent is loaded on carrier；
Wherein, step (3) before step (1), step (3) step (1) neutralization procedure (3) after the step (1) and
Any one or more progress before step (2).
2. preparation method according to claim 1, wherein step (1) described roasting condition makes with semi-finished product catalyst
Total amount on the basis of, in semi-finished product catalyst carbon content be 0.04-0.4 weight %.
3. preparation method according to claim 1 or 2, wherein roasting is under conditions of being passed through gas described in step (1)
The temperature for carrying out, and roasting is 350-450 DEG C, and time of roasting is 0.5-8h, the intake of gas be 0.2-20 liter/(gram
Hour).
4. preparation method according to claim 3, wherein described in step (1) roasting under conditions of being passed through gas into
Row, and the temperature roasted is 360-430 DEG C, time of roasting are 1-6h, and the intake of gas is 0.3-10 liter/(gram small
When).
5. preparation method according to claim 1 or 2, wherein in step (1), organic complexing agent and metal active constituent
Molar ratio be 0.03-2:1.
6. preparation method according to claim 5, wherein in step (1), organic complexing agent and metal active constituent rub
You are than being 0.08-1.5:1.
7. preparation method according to claim 1 or 2, wherein the molar ratio of step (1) and step (2) organic complexing agent
For 1:0.25-4.
8. preparation method according to claim 3, wherein step (1) and the molar ratio of step (2) organic complexing agent are 1:
0.25-4。
9. the preparation method according to claim 4, wherein step (1) and the molar ratio of step (2) organic complexing agent are 1:
0.25-4。
10. preparation method according to claim 5, wherein step (1) and the molar ratio of step (2) organic complexing agent are
1:0.25-4.
11. preparation method according to claim 6, wherein step (1) and the molar ratio of step (2) organic complexing agent are
1:0.25-4.
12. preparation method according to claim 1 or 2, wherein step (1) organic complexing agent and step (2) are described
Organic complexing agent is identical or different, and the organic complexing agent is selected from one of oxygen-containing and/or itrogenous organic substance or a variety of.
13. preparation method according to claim 12, wherein the oxygen containing organic matter is in Organic Alcohol, organic acid
It is one or more, nitrogenous organic matter is selected from one of organic amine, organic ammonium salt or a variety of.
14. preparation method according to claim 12, wherein it is 2-7 that step (1) described organic complexing agent, which is carbon atom number,
One of organic acid or a variety of.
15. preparation method according to claim 1 or 2, wherein the dosage of the hydrogenation active component makes, to add hydrogen
On the basis of the total amount of catalyst, in terms of oxide, the content of hydrogenation metal active component is 15-60 weight %；In terms of oxide,
The content of metal promoter is no more than 10 weight %.
16. preparation method according to claim 15, wherein the dosage of the hydrogenation active component makes, to add hydrogen to urge
On the basis of the total amount of agent, in terms of oxide, the content of hydrogenation metal active component is 20-50 weight %, and metal promoter contains
Amount is 0.5-6 weight %.
17. preparation method according to claim 1 or 2, the hydrogenation metal active component at least one is selected from group VIB
Metallic element, at least one are selected from group VIII metallic element；The carrier is selected from gama-alumina, silica, aluminium oxide-oxygen
SiClx, titanium oxide, magnesia, silica-magnesias, silica-zirconia, silica thoria, silica-berylias, oxygen
SiClx-titanium oxide, silica-zirconia, titania-zirconia, silica-alumina thoria, silica-alumina-oxygen
Change one of titanium, silicaalumina-magnesia, silica-alumina, zirconia or a variety of；The auxiliary agent is selected from the
One of Group IIB metal element, group ia metal element, group iia metallic element and thulium are a variety of.
18. preparation method according to claim 17, wherein the vib metals element be molybdenum and/or tungsten, it is described
Group VIII metallic element is cobalt and/or nickel, and the auxiliary agent is selected from Zn-ef ficiency, sodium element, potassium element, magnesium elements, calcium constituent, lanthanum
One of element and Ce elements are a variety of.
19. hydrogenation catalyst made from the preparation method as described in any one of claim 1-18.
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| CN108421554B (en) * | 2017-02-15 | 2020-06-16 | 中国石油化工股份有限公司 | Hydrofining catalyst and preparation method and application thereof |
| CN109701616B (en) * | 2017-10-26 | 2020-10-27 | 中国石油化工股份有限公司 | Hydrogenation catalyst, preparation method thereof and hydrogenation treatment method of aromatic oil |
| CN110064405B (en) * | 2018-01-23 | 2022-03-01 | 中国石油天然气股份有限公司 | Preparation method of hydrotreating catalyst with desulfurization activity |
| CN110964565B (en) * | 2018-09-29 | 2022-01-04 | 中国石油化工股份有限公司 | Hydrogenation production method of jet fuel |
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| CN109364934B (en) * | 2018-10-11 | 2021-06-29 | 江苏华海三联净化材料有限公司 | Nickel series selective hydrogenation catalyst and preparation method thereof |
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