CN104998670B - A kind of hydrogenation catalyst and its application - Google Patents
A kind of hydrogenation catalyst and its application Download PDFInfo
- Publication number
- CN104998670B CN104998670B CN201410168003.6A CN201410168003A CN104998670B CN 104998670 B CN104998670 B CN 104998670B CN 201410168003 A CN201410168003 A CN 201410168003A CN 104998670 B CN104998670 B CN 104998670B
- Authority
- CN
- China
- Prior art keywords
- cobalt
- molybdenum
- concentration
- solution
- catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Abstract
A kind of hydrogenation catalyst,Contain silica alumina carrier and cobalt and molybdenum hydrogenation active metal component,The preparation method of the catalyst includes using dipping solution impregnated carrier,Wherein,The dipping solution contains cobalt compound,Molybdate compound,Phosphorus-containing compound and citric acid,A concentration of 0.01 0.1g/mL of cobalt compound in the solution in terms of cobalt,A concentration of 0.05 0.4g/mL of molybdate compound in terms of molybdenum,A concentration of 0.005 0.10g/mL of phosphorus-containing compound in terms of phosphorus,A concentration of 0.05 0.5g/mL of citric acid,It is analyzed and characterized with ultraviolet-visible diffuse reflectance spectrum,λ≤1 of the dipping solution,λ is the ratio of spectral peak and spectral peak peak height at 772 ± 10nm at 517 ± 10nm in uv-vis spectra.Compared with prior art, catalyst provided by the invention has better Hydrogenation.
Description
Technical field
The present invention relates to a kind of hydrogenation catalysts and its application to use.
Background technology
As environmental requirement is increasingly strict in world wide, various countries are increasingly harsh to the quality requirement of vehicle fuel.In addition,
Since petroleum resources are reduced, oil property change deteriorates again, and refinery has to process crude oil more inferior.Therefore, it is greatly reduced
Bavin well cuts and polycyclic aromatic hydrocarbon content, significantly improve diesel quality, have become oil refining enterprise it is in the urgent need to address one
A problem.Hydrogen addition technology is one of the major technique for reducing oil product impurity content, improving oil quality, and core is hydrogenation catalyst
Agent.Cobalt-molybdenum catalyst is common a kind of hydrogenation catalyst due to having the characteristics that hydrodesulfurization performance is good, hydrogen consumption is low.
Prepared by hydrogenation catalyst generally use infusion process, i.e., with molten containing required active component (such as Ni, Mo, Co, W)
Liquid impregnates certain carrier, dry later, roasting or the method not roasted.But more concern is how to configure height to the prior art
The dipping solution of concentration, high stability, and the components such as organic matter are introduced to realize to catalyst plus hydrogen in maceration extract
The improvement of energy.
CN96109048.0 discloses a kind of high metal concentration, high stability contains Mo, Ni (Co) P solution and its preparation side
The preparation method of method, especially a kind of dipping solution for catalyst preparation.The solution contains MoO3Concentration 45-80g/100mL,
NiO concentration 8-20g/100mL, CoO concentration 0-15g/100mL.P/MoO3Weight ratio is 0.08-0.18.PH value of solution is 0-3.8.
The solution can be stablized 3 years or more at room temperature.
A kind of method that CN201010276669.5 discloses maceration extract and prepares catalyst using the maceration extract, the leaching
Stain liquid contains compound, the acylate containing group VIII metal, inorganic acid and the organic additive of the metal containing group vib, wherein institute
A concentration of 1-150g/L for stating organic additive in maceration extract, in terms of compound, a concentration of 100- of the compound of the metal containing group vib
1100g/L, a concentration of 10-800g/L of the acylate containing group VIII metal, a concentration of 1-100g/L of inorganic acid.Using this
The dipping solution that invention provides prepares hydrogenation catalyst, and performance is improved, and especially lives to the hydrogenation catalyst of heavy arene
Property significantly improves.
CN201210452002.5 discloses a kind of preparation method of reformed pre-hydrogenated catalyst impregnating solution, and feature exists
In；The solution contains Mo, Ni, Co, W, Mg, P and auxiliary agent, contains MoO3Concentration 10-16g/100mL, NiO concentration 5-9g/
100mL, CoO concentration 3-5g/100mL, WO3Concentration 20-28g/100mL, MgO concentration 0.5-2g/100mL, P/MoO3Molar ratio
0.3-0.5, auxiliary agent 5-15g/100mL；Its process for preparation is：Phosphate aqueous solution is heated to 70-80 DEG C, molybdenum trioxide is added and adds
Solution is cooled to 70-80 DEG C, is slowly added to basic nickel carbonate ebuillition of heated stirring and dissolving by heat boiling stirring to dissolving, and is concentrated
To required volume, cobalt nitrate stirring and dissolving is added in concentrate cooling down to room temperature, and ammonium metatungstate stirring and dissolving is added, and is added
Magnesium compound stirring and dissolving, is added auxiliary agent stirring and dissolving, and constant volume obtains maceration extract.
CN200710179765.6 discloses a kind of hydrogenation catalyst steeping fluid composition, and the composition contains hydrogenation activity
Predecessor, impregnation aids and the water of component, wherein the impregnation aids are with the predecessor of hydrogenation active component with similar
Substance containing carbon-carbon double bond and/or carbon-carbon triple bond in pKa value and molecular structure.The present invention also provides a kind of hydrogenation catalysts
Preparation method, this method includes using maceration extract impregnated catalyst support, dry, roasting, wherein the maceration extract is the present invention
The hydrogenation catalyst steeping fluid composition of offer.Prepared using the hydrogenation catalyst steeping fluid composition that the invention provides plus hydrogen
Catalyst under same reaction temperature there is hydrogenation activity more higher than hydrogenation catalyst made from the prior art and cracking to live
Property.
CN201110317245.3 discloses a kind of maceration extract of hydrogenation catalyst and preparation method thereof, and this method includes,
Group VIII metallic compound and the first organic complexing agent are configured to water solution A；Vib metals compound is configured to water
Solution B；The water solution A and aqueous solution B are mixed；Wherein, at least contain in the ligand of first organic complexing agent and match
Position atom N.The invention additionally provides a kind of hydrogenation catalyst and preparation method thereof.The hydrogenation catalyst that the invention provides adds hydrogen de-
Sulphur activity is high.
CN91110935.8 discloses a kind of preparation method of hydrogen refining cobalt molybdenum catalyzer.This method is that cobalt acetate is molten
Ethylenediamine is added after water, forms it into the mixed solution of cobalt ethylenediamine, is eventually adding ammonium molybdate and is made containing cobalt molybdenum
Co-impregnated solution roasts to obtain product after impregnating porous carrier with this solution in anaerobic or micro- oxygen atmosphere.This method device therefor letter
Single, it is short to prepare the time, when roasting not will produce temperature runaway, hereby it is ensured that the high activity of catalyst.It is said that this method preparation is urged
Agent hydrodesulfurization activity is far above the same type catalyst of Uop Inc.'s production.
Invention content
The technical problem to be solved in the present invention is to provide it is a kind of it is new, that performance is further improved, with cobalt, molybdenum be plus
The application of the hydrogenation catalyst of hydrogen activity metal component and the catalyst in hydrogenation reaction.
Inventor has found, to cobalt compound, molybdate compound, phosphorus-containing compound and the lemon using conventional method configuration
Pickling bath liquor further heats, and the property of solution changes.The Hydrogenation of the catalyst prepared by the solution is apparent
It improves, and therefore completes the present invention.
Content of the present invention includes：
1. a kind of hydrogenation catalyst, described containing silicaalumina carrier and cobalt and molybdenum hydrogenation active metal component
The preparation method of catalyst includes using dipping solution impregnated carrier, wherein the dipping solution contains cobalt compound, contains molybdenum
Compound, phosphorus-containing compound and citric acid, a concentration of 0.01-0.1g/mL of the cobalt compound in the solution in terms of cobalt, with
A concentration of 0.05-0.4g/mL of the molybdate compound of molybdenum meter, a concentration of 0.005-0.10g/ of the phosphorus-containing compound in terms of phosphorus
ML, a concentration of 0.05-0.5g/mL of citric acid, is analyzed and characterized with ultraviolet-visible diffuse reflectance spectrum, the λ of the dipping solution
≤ 1, λ are the ratio of spectral peak and spectral peak peak height at 772 ± 10nm at 517 ± 10nm in ultraviolet-visible spectrum.
2. the hydrogenation catalyst according to 1, which is characterized in that the concentration of the cobalt compound in the solution in terms of cobalt
For 0.02-0.09g/mL, a concentration of 0.08-0.35g/mL of the molybdate compound in terms of molybdenum, phosphorus-containing compound in terms of phosphorus
A concentration of 0.007-0.08g/mL, a concentration of 0.1-0.4g/mL of citric acid, is analyzed and characterized with ultraviolet-visible spectrum, the leaching
λ=0-0.95 of stain solution.
3. the hydrogenation catalyst according to 2, which is characterized in that the solution is analyzed and characterized with ultraviolet-visible spectrum, institute
State λ=0-0.80 of dipping solution.
4. the hydrogenation catalyst according to 1, which is characterized in that on the basis of the catalyst, the cobalt content in terms of CoO
For 1-10 weight %, with MoO3The molybdenum content of meter is 5-50 weight %.
5. the hydrogenation catalyst according to 4, which is characterized in that on the basis of the catalyst, the cobalt content in terms of CoO
For 1-7 weight %, with MoO3The molybdenum content of meter is 8-45 weight %.
6. the hydrogenation catalyst according to 5, which is characterized in that on the basis of the catalyst, the cobalt content in terms of CoO
For 3-7 weight %, with MoO3The molybdenum content of meter is 12-30 weight %.
7. according to 1 plus hydrogen urges catalyst, which is characterized in that the silica content in the silica-alumina
Content for 2-45 weight %, aluminium oxide is 55-98 weight %.
8. the hydrogenation catalyst according to 1, which is characterized in that after the use dipping solution impregnated carrier,
Including dry step, the drying condition includes：Drying temperature is 100-300 DEG C, and the time is 1-12 hours.
9. the hydrogenation catalyst according to 8, which is characterized in that the drying condition includes：Drying temperature is 120-
280 DEG C, the time is 2-8 hours.
10. a kind of method of hydrotreating is included in feedstock oil and catalyst haptoreaction under hydrogenation conditions, feature exists
In the catalyst is the catalyst described in aforementioned 1-9 any one.
11. the method according to 10, which is characterized in that the hydrogenation conditions include that temperature is 300-400 DEG C, pressure
Power is 1-10MPa, and volume space velocity is 0.5-3 hours when the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio 100-800.
12. according to the method described in 11, which is characterized in that the hydrogenation conditions include that temperature is 320-380 DEG C, pressure
For 1-8MPa, volume space velocity is 0.5-2.5 hours when the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio 100-700.
In the present invention, the preparation method of the maceration extract includes：(1) by cobalt compound, molybdate compound, phosphorous chemical combination
Object and citric acid are mixed with water, and dissolving reaction is at dipping solution；(2) dipping solution for obtaining step (1) is at 60 DEG C -300 DEG C
At a temperature of react -200 hours 0.5 hour；Wherein, the dosage of each component makes containing in terms of cobalt in the final dipping solution
A concentration of 0.01-0.1g/mL of cobalt compound, a concentration of 0.05-0.4g/mL of the molybdate compound in terms of molybdenum, in terms of phosphorus
A concentration of 0.005-0.1g/mL of phosphorus-containing compound, a concentration of 0.05-0.5g/mL of citric acid, with UV-Vis DRS
Spectrum analysis analysis characterization, λ≤1 of the dipping solution, λ be in ultraviolet-visible spectrum 517 ± 10nm locate spectral peak and 772 ±
The ratio of spectral peak peak height at 10nm.
In a preferred embodiment, the dosage of each component makes to contain cobalt in terms of cobalt in the final dipping solution
Close a concentration of 0.02-0.09g/mL, more preferably 0.03-0.08g/mL of object；Molybdate compound in terms of molybdenum it is a concentration of
0.08-0.35g/mL, more preferably 0.10-0.3g/mL；A concentration of 0.007-0.08g/ of phosphorus-containing compound in terms of phosphorus
ML, more preferably 0.01-0.03g/mL；A concentration of 0.1-0.4g/mL of citric acid, more preferably 0.15-0.3g/mL.
It is analyzed and characterized with ultraviolet-visible spectrum, λ=0-0.95 of the dipping solution；Step (2) reaction temperature is 75 DEG C -180
DEG C, the reaction time is -100 hours 1 hour.
Further, the solution is analyzed and characterized with ultraviolet-visible spectrum, λ=0-0.80 of the dipping solution.It is described
Step (2) handles -50 hours 2 hours the cobalt molybdenum solution routinely prepared at 80 DEG C -150 DEG C.
In the present invention, the cobalt compound is selected from water-soluble cobalt compound, but water solubility refers to that the compound can
Be directly dissolved in water, or under the action of cosolvent it is water-soluble, cosolvent can be ammonium hydroxide, phosphoric acid, ammonium dihydrogen phosphate, phosphoric acid
Hydrogen diammonium, citric acid etc..The example of such compound such as, salt, oxide and the hydroxide of the metal component containing cobalt.They can
With nitrate, chloride, sulfate, formates, acetate, phosphate, citrate, oxalates, carbonate, alkali selected from cobalt
One kind in formula carbonate, hydroxide, phosphate, phosphide, sulfide, aluminate, molybdate, tungstates, oxide or
It is several.Oxalates, carbonate, subcarbonate, hydroxide, phosphate, molybdate, tungstates, oxide preferably wherein
One or more of, it is more highly preferred to subcarbonate and carbonate therein.
The molybdate compound is selected from water-soluble molybdate compound, but water solubility refers to the compound to be directly dissolved in
Water, or under the action of cosolvent it is water-soluble, cosolvent can be ammonium hydroxide, phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate,
Citric acid etc..The example of such compound such as, salt, the oxide of the component containing molybdenum.They can be selected from ammonium molybdate, miscellaneous more
One or more of hydrochlorate, molybdenum oxide.
The phosphorus-containing compound can be selected from phosphoric acid, ammonium dihydrogen phosphate, diammonium hydrogen phosphate, sodium dihydrogen phosphate and phosphoric acid hydrogen two
One or more of sodium, phosphoric acid preferably wherein.
Inventor has found, is analyzed and characterized using ultraviolet-visible diffuse reflectance spectrum, the cobalt-molybdenum-conventionally prepared
Phosphorus-citric acid dipping solution (for example, be separately added into phosphoric acid, citric acid, basic cobaltous carbonate and molybdenum trioxide in deionized water
Afterwards, by the suspension be heated to 80 DEG C it is agitated be easily dissolved, obtain cobalt molybdenum solution) at a temperature of 60 DEG C -300 DEG C further
Heat treatment, the property of solution change.When λ≤1 for controlling the dipping solution, preferably λ=0-0.95, more preferable λ=
When 0-0.80, the Hydrogenation of the catalyst prepared by the record solution significantly improves.Wherein, λ is in ultraviolet-visible spectrum
The ratio of spectral peak and spectral peak peak height at 772 ± 10nm at 517 ± 10nm.Cobalt-molybdenum-phosphorus-the citric acid conventionally prepared
The λ ＞ 1 of solution；Through further heating, spectral peak dies down (peak height reduction) or disappears at 517 ± 10nm of dipping solution.It presses
Definition according to the present invention about λ, when spectral peak disappears at 517 ± 10nm, corresponding λ=0.
It is described at a temperature of 60 DEG C -300 DEG C at heating according to the preparation method of the dipping solution provided by the invention
Reason, preferred temperature are 75 DEG C -200 DEG C, and further preferably 80 DEG C -150 DEG C, the time of heat treatment is at least 0.5 hour.
To meet the present invention claims premised on, the time of heat treatment is preferably -200 hours 0.5 hour, further preferably 1 hour -
100 hours；More preferably -50 hours 2 hours.The heat treatment can in situ carry out in the container for preparing solution,
It can not also carry out in situ.The heat treatment can carry out under static (such as not stirring), can also (example in a dynamic state
Such as stirring) it carries out.
The process of the heat treatment can carry out in closed container (such as autoclave) also can be in open body
It is carried out in system, later, final required volume can be diluted with water into acquired solution.
In this present invention, in the silica-alumina, the content of silica and aluminium oxide can be according to finally preparing
The application scenario of catalyst makes appropriate choice.When being used for the hydrotreating of hydrocarbon ils according to catalyst provided by the invention,
On the basis of the carrier, the content of silica can be 2-45 weight %, preferably 5-40 weight %, further preferably
5-30 weight %；The content of the aluminium oxide can be 55-98 weight %, preferably 60-95 weight %, further preferably
70-95 weight %.
According to catalyst provided by the invention, wherein the carrier optionally can be made into arbitrary molding easy to operation
Object, such as spherical, tabletting and bar shaped.The molding can be carried out by conventional process, such as the methods of tabletting, spin, extrusion.It is adopting
When being molded with customary way, to ensure that molding be smoothed out introduces into the silica-alumina and/or its precursor
Auxiliary agent is allowed, such as when extrusion, appropriate extrusion aid and/or adhesive and water can be added, then extrusion molding.It is described
Extrusion aid, the type of peptizing agent and dosage are that this field is conventional, such as common extrusion aid can be selected from sesbania powder, methyl fibre
Tie up one or more of element, starch, polyvinyl alcohol, polyethanol.The molding obtains of the present invention through drying, roasting
Carrier.Here, the method and operating condition of the drying and roasting are conventional method and operating condition.For example, described is dry
Drying method is heat drying, and drying temperature is 100-300 DEG C, preferably 120-280 DEG C；Drying time is 1-12 hours, preferably
It is 2-8 hours；The condition of the roasting can be the conventional selection of this field.Usually, the condition of the roasting includes：Temperature
It can be 350-650 DEG C, preferably 400-600 DEG C；The time of the roasting can be 2-6 hours, preferably 3-5 hours.
The silica-alumina can be commercially available commodity, such as：The Sira- series oxygen of Condea companies production
SiClx-aluminium oxide；Can also use arbitrary existing method prepare, for example, by using directly by Ludox it is direct with boehmite
It is prepared by mixed method.
It includes hole saturation infusion process, excessive infusion process etc. to prepare the common dipping method of catalyst, and the dipping can be with
It is primary, can also be multiple maceration etc., be dried, roast or do not roast later, these methods can be all adapted to make
Standby catalyst of the present invention.In specific implementation, preferred dip operation condition includes：Solution by volume with weight
The ratio of the carrier of gauge is 0.5-10:1, further preferably 0.7-8：1.When be in the dipping process maceration extract excess
When, preferably include the steps that filtering before being dried in the presence of having free solution in the mixture, it is free to remove
Solution.Drying of the present invention can be the conventional selection of this field.Usually, the condition of the drying includes：Temperature
It can be 100-300 DEG C, preferably 120-280 DEG C；Time can be 1-12 hours, preferably 2-8 hours.When being roasted
When burning, the method and condition of the roasting can be the conventional selection of this field.Usually, the condition of the roasting includes：Temperature
Degree can be 350-550 DEG C, preferably 400-500 DEG C；Time can be 1-8 hours, preferably 2-6 hours.
According to catalyst provided by the invention, any performance or energy for not influencing the present invention and catalyst being provided can also be contained
Improve the substance of catalyst performance provided by the invention.Boron component can such as be contained, based on the element and on the basis of catalyst,
The content of boron is no more than 10 weight %, preferably 0.5-6 weight %.
According to preparation method provided by the invention, the components such as boron are selected from when also containing in the catalyst, further include introducing
The step of selected from components such as boron, the introducing method selected from components such as boron can such as can be through a variety of ways in carrier
It is introduced in preparation process；Can introduce the method that the carrier is impregnated after the compound preparation solution containing auxiliary agent.When helping
Include the steps that being roasted when agent introduces the carrier in the method impregnated, the calcination temperature is 250-600 DEG C, preferably
It it is 350-500 DEG C, roasting time is 2-8 hours, preferably 3-6 hours.
According to hydrofinishing process provided by the invention, this method is to add hydrogen by using the catalyst of the present invention to improve
Catalyst in subtractive process it is active, remaining condition of hydrofinishing process is not particularly limited, can be ability
The conventional selection in domain.Usually, the condition of the hydrofinishing includes：Temperature is 300-400 DEG C；Pressure is 1.0-10.0MPa
(in terms of gauge pressure)；Volume space velocity is 0.5-3.0 hours when the liquid of hydrocarbon ils-1；Hydrogen to oil volume ratio is 100-800.The hydrogen oil volume
Than refer to hydrogen volume flow rate and hydrocarbon ils volume flow rate ratio.
Hydrofinishing process according to the present invention, the catalyst using it is preceding preferably using the conventional method of this field into
Row vulcanization.Usually, the condition of the vulcanization may include：In presence of hydrogen, at a temperature of 360-400 DEG C, with sulphur, sulphur
Change hydrogen, carbon disulfide, dimethyl disulfide or the presulfurization of one or more carry out 2-4 hours in polysulfide.According to this hair
Bright hydrofinishing process, the presulfurization can carry out outside reactor, also can be In-situ sulphiding in reactor.
Hydrodesulfurization, the hydrodenitrogeneration etc. that hydrofinishing process according to the present invention is suitable for various hydrocarbon oil crude materials refined
Journey.The hydrocarbon oil crude material for example can be gasoline, diesel oil, lubricating oil, kerosene and naphtha；Can also be reduced crude, decompression
Residual oil, pertroleum wax and Fischer-Tropsch synthesis oil.
Specific implementation mode
The present invention is described further for the following examples.
Ultraviolet-visible diffuse reflectance spectrum analyzes (UV-Vis), using the Lambda35 types of Perkin-Elmer companies of the U.S.
Multi-functional spectrophotometry instrument in light neon source, measures wavelength 286nm, slit width 1.0nm, sample detection time
4.5min, detection step-length 2.0s experiment condition under measure ultra-violet absorption spectrum of the solution within the scope of 450-900nm.
The content of each element is analyzed in catalyst, using commercially available from Rigaku electric machine industry Co., Ltd.
3271E type Xray fluorescence spectrometers measure.
Comparative example 1-3 illustrates the maceration extract and preparation method thereof for preparing reference catalyst.
Comparative example 1
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively is put into 55mL
It in deionized water, is heated to 80 DEG C and is stirred dissolving 1 hour, obtain clarification dipping solution, add water to 85mL, obtain solution
L1.λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) of dipping solution L1 and rubbing for molybdenum
You are than (nP/nMo), the molar ratio (n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Comparative example 2
28.2 grams of molybdenum trioxides, 9.5 grams of basic cobaltous carbonates, 11.4 grams of phosphoric acid are weighed respectively to be put into 55mL deionized waters,
It is heated to 80 DEG C and is stirred dissolving 1 hour, obtain clarification dipping solution, add water to 85mL, obtain solution L2.Dipping solution L2
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo)、
Molar ratio (the n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Comparative example 3
11.5 grams of molybdenum trioxides, 3.5 grams of basic cobaltous carbonates, 5.8 grams of citric acids are weighed respectively to be put into 55mL deionized waters,
It is heated to 80 DEG C and is stirred dissolving 1 hour, obtain clarification dipping solution, add water to 85mL, obtain solution L3.Dipping solution L3
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo)、
Molar ratio (the n of molybdenum and cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 1-6 illustrates to prepare the maceration extract and preparation method thereof that the present invention provides catalyst.
Embodiment 1
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 7.6 grams of citric acids are weighed respectively is put into 55mL
In deionized water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into burning
In cup, 90 DEG C and under stiring constant temperature 8 hours are heated to, 85mL is added water to, obtains clarification dipping solution S1.Dipping solution S1's
λ value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo), molybdenum
With the molar ratio (n of cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 2
Cobalt molybdenum solution provided by the invention：
20 grams of molybdenum trioxides, 14.5 grams of basic cobaltous carbonates, 8.7 grams of phosphoric acid, 18 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into closed
In container, 100 DEG C of simultaneously constant temperature 1 hours are heated to, 85mL is added water to, obtain clarification dipping solution S2.The λ value of dipping solution S2,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo), molybdenum and cobalt
Molar ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 3
Cobalt molybdenum solution provided by the invention：
38 grams of molybdenum trioxides, 8.6 grams of basic cobaltous carbonates, 4.7 grams of phosphoric acid, 10.7 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into beaker
In, 70 DEG C and under stiring constant temperature 18 hours are heated to, 85mL is added water to, obtain clarification dipping solution S3.The λ of dipping solution S3
Value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo), molybdenum with
Molar ratio (the n of cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 4
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 15 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into closed
In container, 120 DEG C of simultaneously constant temperature 12 hours are heated to, 85mL is added water to, obtain clarification dipping solution S4.The λ value of dipping solution S4,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo), molybdenum and cobalt
Molar ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 5
Cobalt molybdenum solution provided by the invention：
Weigh respectively 24 grams of molybdenum trioxides, 10 grams of basic cobaltous carbonates, 6.5 grams of phosphoric acid, 8.4 grams of citric acids be put into 55mL go from
In sub- water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into closed appearance
In device, 120 DEG C of simultaneously constant temperature 2 hours are heated to, 85mL is added water to, obtain clarification dipping solution S5.The λ value of dipping solution S5, cobalt
(Co), the molar ratio (n of the concentration (g/mL) of molybdenum (Mo), phosphorus (P) and citric acid (CTA) and phosphorus and molybdenumP/nMo), molybdenum and cobalt
Molar ratio (nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 6
Cobalt molybdenum solution provided by the invention：
27.2 grams of molybdenum trioxides, 9.1 grams of basic cobaltous carbonates, 5.5 grams of phosphoric acid, 19 grams of citric acids are weighed respectively to be put into 55mL and go
In ionized water, it is heated to 80 DEG C and is stirred dissolving, become brownish red clear solution after about 1 hour.The solution is put into closed
It in container, is heated to 140 DEG C and constant temperature adds water to 85mL after 10 hours, obtain clarification dipping solution S6.The λ of dipping solution S6
Value, cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/mL) and phosphorus of citric acid (CTA) and the molar ratio (n of molybdenumP/nMo), molybdenum with
Molar ratio (the n of cobaltMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Table 1
Note：It is analyzed and characterized with ultraviolet-visible spectrum, if only occurring spectral peak at 517nm in the spectrogram of solution, but is not occurred
772nm spectral peaks, solution λ=∞ at this time.
Following embodiment and comparative example prepare catalyst used carrier and preparation method thereof：
By 2000 grams of aluminium hydrate powders (dry glue powder of Chang Ling refinery company catalyst plant production, 71 weight % of butt) and
1039 grams of Ludox (Haiyang Chemical Plant, Qingdao's product, dioxide-containing silica are 30 weight %) are uniformly mixed.The mixing that will be obtained
Object is extruded into the butterfly item that circumscribed circle diameter is 1.4 millimeters with banded extruder, and the wet bar of extrusion is 4 hours dry at 120 DEG C, then
It is roasted 3 hours at 600 DEG C, it is 18.0 weight % that silica content in carrier Z1, carrier Z1, which is made, and alumina content is 82.0 weights
Measure %.The water absorption rate of Z1 is 0.85.
Embodiment 7-12 illustrates catalyst provided by the invention and its preparation.
Embodiment 7
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S1 solution 85mL saturation 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 250 DEG C of dryings are 3 small
When, catalyst D1 is obtained, composition is shown in Table 2.
Embodiment 8
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S2 solution 85mL saturation 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings are 3 small
When, catalyst D2 is obtained, composition is shown in Table 2.
Embodiment 9
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S3 solution 85mL saturation 100 grams of dipping Z1 carriers 3 hours, 3 hours of 120 DEG C of dryings, 250 DEG C of dryings are 3 small
When, catalyst D3 is obtained, composition is shown in Table 2.
Embodiment 10
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S4 solution 85mL saturation 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 150 DEG C of dryings are 5 small
When, catalyst D4 is obtained, composition is shown in Table 2.
Embodiment 11
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S5 solution 85mL saturation 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 200 DEG C of dryings are 4 small
When, catalyst D5 is obtained, composition is shown in Table 2.
Embodiment 12
Catalyst prepared by cobalt molybdenum solution provided by the invention：
With S6 solution 85mL saturation 100 grams of leaching stain Z1 carriers 2 hours, 3 hours of 120 DEG C of dryings, 400 DEG C of roastings are 3 small
When, catalyst D6 is obtained, composition is shown in Table 2.
Comparative example 4
With L1 solution 85mL saturation 100 grams of dipping Z1 carriers 2 hours, 2 hours of 120 DEG C of dryings, 180 DEG C of dryings are 3 small
When, catalyst C1 is obtained, composition is shown in Table 2.
Table 2
Embodiment 13-18 is used to prepare application and the hydrofinishing side of hydrogenation catalyst using cobalt molybdenum solution of the present invention
Method.
Embodiment 13-18
This example illustrates that the present invention provides the diesel oil hydrofining performance that cobalt molybdenum dipping prepares hydrogenation catalyst.
Catalyst D1-D6 is evaluated respectively on 30 milliliters of diesel hydrotreating units, is as a result shown in table 3.
Raw materials used is Middle East straight-run diesel oil, and property is as follows：
S contents：9700wppm
N content：97wppm
Density (20 DEG C)：0.8321g/cm3
Refraction index (20 DEG C)：1.4658
Use following process operating condition：
Volume space velocity when liquid：2.0h-1；Hydrogen to oil volume ratio：300；Reaction pressure：3.2MPa；Reaction temperature：330℃
The hydrodesulfurization activity of catalyst is evaluated using opposite hydrodesulfurization activity, computational methods are that hydrodesulfurization is anti-
The processing of 1.65 order reactions is should be used as, the reaction rate constant k (X) of catalyst X is calculated as followsHDS：
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction.
On the basis of the hydrodesulfurization activity (being denoted as k (C1) HDS) of the catalyst C1 prepared by comparative example 4, it is calculated as follows
The opposite hydrodesulfurization activity of catalyst X：
In following embodiment and comparative example, the hydrodenitrogenationactivity activity of catalyst is evaluated using opposite hydrodenitrogenationactivity activity,
Computational methods are to handle hydrodenitrogeneration reaction as 1 order reaction, and the reaction rate constant k of catalyst X is calculated as follows
(X)HDN：
In formula, volume space velocity when LHSV is the liquid of hydrocarbon ils when carrying out hydrofining reaction,
On the basis of the hydrodenitrogenationactivity activity (being denoted as k (C1) HDN) of the catalyst C1 prepared by comparative example 4, it is calculated as follows
The opposite hydrodenitrogenationactivity activity of catalyst X：
Comparative example 5
Using the activity of method identical with embodiment 13-18 evaluation catalyst C1, as a result it is shown in table 3.
Table 3
Table 3 the results show that catalyst prepared according to the methods of the invention has in the hydrofinishing for hydrocarbon ils
Higher catalytic activity.
Claims (12)
1. a kind of hydrogenation catalyst, containing silicaalumina carrier and cobalt and molybdenum hydrogenation active metal component, the catalysis
The preparation method of agent includes using dipping solution impregnated carrier, wherein the dipping solution contains cobalt compound, chemical combination containing molybdenum
Object, phosphorus-containing compound and citric acid, a concentration of 0.01-0.1g/mL of the cobalt compound in the solution in terms of cobalt, in terms of molybdenum
Molybdate compound a concentration of 0.05-0.4 g/mL, a concentration of 0.005-0.10 g/mL of the phosphorus-containing compound in terms of phosphorus,
A concentration of 0.05-0.5 g/mL of citric acid, are analyzed and characterized with ultraviolet-visible diffuse reflectance spectrum, and the λ of the dipping solution≤
1, λ is the ratio of spectral peak and spectral peak peak height at 772 ± 10nm at 517 ± 10nm in ultraviolet-visible spectrum.
2. hydrogenation catalyst according to claim 1, which is characterized in that cobalt compound in the solution in terms of cobalt
A concentration of 0.02-0.09g/mL, a concentration of 0.08-0.35 g/mL of the molybdate compound in terms of molybdenum, the phosphorous chemical combination in terms of phosphorus
A concentration of 0.007-0.08 g/mL of object, a concentration of 0.1-0.4 g/mL of citric acid, are analyzed and characterized with ultraviolet-visible spectrum,
λ=0-0.95 of the dipping solution.
3. hydrogenation catalyst according to claim 2, which is characterized in that the solution is with ultraviolet-visible spectrum analytical table
Sign, λ=0-0.80 of the dipping solution.
4. hydrogenation catalyst according to claim 1, which is characterized in that on the basis of the catalyst, the cobalt in terms of CoO
Content is the carrier of 1-10 weight %, with MoO3The molybdenum content of meter is 5-50 weight %.
5. hydrogenation catalyst according to claim 4, which is characterized in that on the basis of the catalyst, the cobalt in terms of CoO
Content is the carrier of 1-7 weight %, with MoO3The molybdenum content of meter is 8-45 weight %.
6. hydrogenation catalyst according to claim 5, which is characterized in that on the basis of the catalyst, in terms of CoO
Cobalt content is 3-7 weight %, with MoO3The molybdenum content of meter is 12-30 weight %.
7. hydrogenation catalyst according to claim 1, which is characterized in that the silica in the silica-alumina contains
Amount is 2-45 weight %, and the content of aluminium oxide is 55-98 weight %.
8. hydrogenation catalyst according to claim 1, which is characterized in that it is described using dipping solution impregnated carrier it
Afterwards, including dry step, the drying condition include：Drying temperature is 100-300 DEG C, and the time is 1-12 hours.
9. hydrogenation catalyst according to claim 8, which is characterized in that the drying condition includes：Drying temperature is
120-280 DEG C, the time is 2-8 hours.
10. a kind of method of hydrotreating is included in feedstock oil and catalyst haptoreaction under hydrogenation conditions, which is characterized in that
The catalyst is the catalyst described in preceding claims 1-9 any one.
11. according to the method described in claim 10, it is characterized in that, the hydrogenation conditions include
Temperature is 300-400 DEG C, pressure 1-10MPa, and volume space velocity is 0.5-3 hours when the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio is
100-800。
12. according to the method for claim 11, which is characterized in that the hydrogenation conditions include that temperature is 320-380
DEG C, pressure 1-8MPa, volume space velocity is 0.5-2.5 hours when the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio 100-700.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168003.6A CN104998670B (en) | 2014-04-24 | 2014-04-24 | A kind of hydrogenation catalyst and its application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410168003.6A CN104998670B (en) | 2014-04-24 | 2014-04-24 | A kind of hydrogenation catalyst and its application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104998670A CN104998670A (en) | 2015-10-28 |
| CN104998670B true CN104998670B (en) | 2018-07-31 |
Family
ID=54371686
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410168003.6A Active CN104998670B (en) | 2014-04-24 | 2014-04-24 | A kind of hydrogenation catalyst and its application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104998670B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2745607C2 (en) | 2016-09-12 | 2021-03-29 | Чайна Петролеум Энд Кемикал Корпорейшен | Hydration catalyst, its preparation and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853781A (en) * | 2005-04-21 | 2006-11-01 | 中国石油化工股份有限公司 | Phosphor-contained hydrogenation catalyst with silicon oxide-alumin as carrier and its production |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
-
2014
- 2014-04-24 CN CN201410168003.6A patent/CN104998670B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1853781A (en) * | 2005-04-21 | 2006-11-01 | 中国石油化工股份有限公司 | Phosphor-contained hydrogenation catalyst with silicon oxide-alumin as carrier and its production |
| CN101089132A (en) * | 2006-06-16 | 2007-12-19 | 中国石油化工股份有限公司 | Fraction oil hydrodesulfurizing catalyst and its prepn process |
| CN102950003A (en) * | 2011-08-29 | 2013-03-06 | 中国石油化工股份有限公司 | Hydrogenation catalyst with active ingredients distributed non-uniformly and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104998670A (en) | 2015-10-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105435824B (en) | A kind of hydrogenating catalyst composition and its application | |
| CN105498849B (en) | A kind of hydrogenation catalyst and its application | |
| CN101157056B (en) | Hydrogenation catalysts carrier with nickel and cobalt, hydro-catalyst and its preparing method | |
| CN106607039B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN105013499B (en) | A kind of hydrogenation catalyst and its application | |
| CN101530807B (en) | Preparation method of phosphoric hydrogenation catalyst for realizing deep desulfurization and denitrification | |
| RU2402380C1 (en) | Catalyst for hydrofining hydrocarbon material, method of preparing said catalyst and hydrofining process | |
| CN104117362B (en) | A kind of catalyst and preparation method of raising NiMo diesel oil hydrofining catalyst hydrogenation activities | |
| CN105478129B (en) | A kind of hydrotreating catalyst and its application | |
| CN106607096B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN106693982A (en) | Gasoline hydrogenation catalyst and preparation method thereof | |
| CN105498792B (en) | A kind of catalyst combination and its application for hydrotreating | |
| CN106607097B (en) | A kind of hydrogenation catalyst and preparation method thereof | |
| CN105013497B (en) | A kind of hydrogenation catalyst and its application | |
| CN104998670B (en) | A kind of hydrogenation catalyst and its application | |
| CN102423712B (en) | Preparation method of high-activity inferior diesel oil hydrorefining catalyst | |
| CN105542850B (en) | Method for producing ultra low sulfur diesel oil through hydrorefining | |
| CN105498791B (en) | A kind of hydrogenating catalyst composition and its application | |
| RU2649384C1 (en) | Method of hydro-treatment of hydrocracking raw materials | |
| CN106031878B (en) | A kind of hydrogenation catalyst and its application | |
| CN103316687A (en) | Combination catalyst for diesel hydrodesulfurization and diesel hydrodesulfurization method | |
| CN106031877B (en) | A kind of hydrogenation catalyst and its application | |
| CN105623718B (en) | A kind of method of hydrotreating for producing cleaning diesel oil | |
| CN106031881B (en) | A kind of hydrogenation catalyst and its application | |
| CN105498816B (en) | A kind of hydrogenation catalyst and its application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |