CN105498792B - A kind of catalyst combination and its application for hydrotreating - Google Patents
A kind of catalyst combination and its application for hydrotreating Download PDFInfo
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Abstract
A kind of catalyst combination and its application for hydrotreating, the catalyst combination includes Hydrobon catalyst I and Hydrobon catalyst II, the Hydrobon catalyst I contains alumina support, cobalt and molybdenum hydrogenation active metal component, on the basis of the catalyst I, using the cobalt content that CoO is counted as 1 10 weight % in the catalyst I, with MoO3The molybdenum content of meter is 5 50 weight %；The Hydrobon catalyst II contains alumina support, nickel and tungsten hydrogenation active metal component, on the basis of the catalyst II, using the nickel content that NiO is counted as 1 10 weight % in the catalyst II, with WO3The W content of meter is 5 60 weight %；By volume and on the basis of the total amount of the catalyst combination, the content of the catalyst I in the catalyst combination is 5 95%, and the content of catalyst II is 5 95%.Compared with prior art, carbon monoxide-olefin polymeric provided by the invention has better Hydrogenation.
Description
Technical field
The present invention relates to a kind of catalyst combination for hydrotreating and its applications.
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 to reduce one of oil product impurity content, the major technique for improving oil quality, and core is hydrogenation catalyst
Agent.The prior art indicate that the effect that some reactions are carried out with hydrocarbon oil hydrogenation processing using the combination of different hydrogenation catalysts is usual
Better than the effect of single dose.
CN1896191A discloses a kind of combined technical method of converting coal liquefied oil at maximum, the liquefied coal coil after filtering
Enter stable hydrogenation reactor with hydrogen, contacted with hydrogenation protecting agent, Hydrobon catalyst, stable hydrogenation reactor effluent
Gas, naphtha cut, diesel oil distillate and tail oil fraction are isolated to, wherein stable hydrogenation diesel oil distillate, part tail oil evaporates
Hydro-upgrading reactor, hydrocracking reactor are respectively enterd, reactor effluent is isolated to gas, naphtha cut
With diesel oil distillate product, hydrogen rich stream is recycled back to each reactor.Produce to this method energy maximum fine-quality diesel oil, total receipts of diesel oil
For rate more than 92 weight %, Cetane number is more than 45.
In CN96109738, a kind of hydrogenation post-refining process for lubricant oil is disclosed.The technique is included in reaction temperature
200-350 DEG C, hydrogen partial pressure 1.0-10.0MPa, liquid volume air speed 10.5-5.0 hours-1, hydrogen to oil volume ratio 80-500 condition
Under, crude lube stock is contacted successively with catalyst I and II of the volume ratio for 0.05-0.75 layering fillings, catalyst I is by 0.5-
3.0 weight % at least one, VIII race's element, at least one VI B races elements of 3.5-14.5 weights % and aluminium oxide composition；Catalyst II by
VIII race's element of 1.0-5.0 weights % at least one, at least one VI B races elements of 10.0-34.0 weights % and aluminium oxide composition.
In US5068025, disclose a kind of diesel oil distillate two-stage hydrogenation desulfurization, aromatic hydrocarbons saturation Hydrofining Technology.It should
Technology first segment uses a kind of nickeliferous 1-5 weights %, tungsten 10-35 weight %, phosphorus 1-5 weight %, remaining adds hydrogen essence for alumina support
Catalyst processed carries out hydrodesulfurization, denitrogenation, and second segment uses a kind of nickeliferous or cobalt 1-5 weights %, tungsten 8-20 weight %, phosphorus 1-5 weight %,
Remaining carries out aromatic saturated hydrogenation desulfurization for the Hydrobon catalyst of alumina support.
CN102051217A discloses a kind of method of hydrotreating for producing ultra-low sulfur clean diesel.Diesel oil distillate feedstock oil and hydrogen
Enter reactor after gas mixing, successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreactions, react outflow
Object is detached and is fractionated, and obtains diesel product；The Hydrobon catalyst I is activated metal component bearing for cobalt-molybdenum
Load type Hydrobon catalyst, the Hydrobon catalyst II are body phase Hydrobon catalysts.It is provided using the invention
Method handles poor-quality diesel-oil by cut fraction under the conditions of mitigation, can obtain low-sulfur or the cleaning diesel product of super-low sulfur.The invention co-occurrence
There is technology to compare, when reaching identical hydrodesulfurization depth, the chemical hydrogen consumption 5 weight % lower than the prior art of hydrogenation process~
10 weight %.
CN102851070A discloses a kind of method for producing ultra-low-sulphur diesel, and diesel oil distillate feedstock oil is entered from top
In reactor, entered in above-mentioned reactor from bottom after supplementing hydrogen and recycle hydrogen mixing, under the conditions of hydrofining reaction, bavin
Oil distillate feedstock oil successively with Hydrobon catalyst I and Hydrobon catalyst II haptoreactions, reaction effluent carry out
Separation and fractionation, obtain diesel product；The Hydrobon catalyst I is that activated metal component is nickel-molybdenum or nickel-molybdenum-tungsten
Load hydrogenation catalyst for refining, the Hydrobon catalyst II is body phase Hydrobon catalyst.It is soluble to be
When the prior art produces ultra-low sulfur clean diesel, the problems such as operating condition is harsh, and air speed is low.
Invention content
The technical problem to be solved by the present invention is on the basis of existing technology, provide a kind of catalysis for hydrotreating
The application of agent combination and the catalyst combination in hydrotreating reaction.
Content of the present invention includes：
1. a kind of catalyst combination for hydrotreating, including Hydrobon catalyst I and Hydrobon catalyst II,
Wherein,
The Hydrobon catalyst I contains alumina support, cobalt and molybdenum hydrogenation active metal component, with the catalyst
On the basis of I, using the cobalt content that CoO is counted as 1-10 weight % in the catalyst I, with MoO3The molybdenum content of meter is 5-50 weights
Measure %；
The Hydrobon catalyst II contains alumina support, nickel and tungsten hydrogenation active metal component, with the catalysis
On the basis of agent II, using the nickel content that NiO is counted as 1-10 weight % in the catalyst II, with WO3The W content of meter is 5-60 weights
Measure %；
By volume and on the basis of the total amount of the catalyst combination, catalyst I's in the catalyst combination contains
It measures as 5-95%, the content of catalyst II is 5-95%.
2. the catalyst combination according to 1, which is characterized in that on the basis of the catalyst I, in the catalyst I
Using the cobalt content that CoO is counted as 1-7 weight %, further preferably 3-7 weight %, with MoO3The molybdenum content of meter is 8-45 weights
Measure %, further preferably 12-30 weight %.
3. the catalyst combination according to 1, which is characterized in that on the basis of the catalyst II, the catalyst II
In using the nickel content that NiO is counted as 1-8 weight %, further preferably 2-6 weight %, with WO3The W content of meter is 8-50 weights
Measure %, further preferably 20-40 weight %.
4. the catalyst combination according to 1, which is characterized in that by volume and using the total amount of the catalyst combination as
Benchmark, the content of the Hydrobon catalyst I is 10-80%, further preferably 20-70%, and the hydrofinishing is catalyzed
The content of agent II is 20-90%, further preferably 30-80%.
5. the catalyst combination according to 1, which is characterized in that the preparation method of the Hydrobon catalyst I includes
Using dipping solution impregnated carrier, the dipping solution contains cobalt compound, molybdate compound, phosphorus-containing compound and lemon
Acid, a concentration of 0.01-0.1g/mL of the cobalt compound in the dipping solution in terms of cobalt, molybdate compound in terms of molybdenum
A concentration of 0.05-0.4g/mL, a concentration of 0.005-0.10g/mL of the phosphorus-containing compound in terms of phosphorus, citric acid it is a concentration of
0.05-0.5g/mL is characterized with UV-Vis DRS spectrum analysis, and λ≤1 of the dipping solution, λ are ultraviolet-visible light
In spectrum at 517 ± 10nm at spectral peak and 772 ± 10nm spectral peak peak height ratio.
6. the catalyst combination according to 5, which is characterized in that cobalt compound in the dipping solution in terms of cobalt
A concentration of 0.02-0.09g/mL, a concentration of 0.08-0.35g/mL of the molybdate compound in terms of molybdenum, the phosphorous chemical combination in terms of phosphorus
A concentration of 0.007-0.08g/mL of object, a concentration of 0.1-0.4g/mL of citric acid, is analyzed and characterized with ultraviolet-visible spectrum, institute
State λ=0-0.95 of dipping solution.
7. the catalyst combination according to 6, which is characterized in that the dipping solution is with ultraviolet-visible spectrum analytical table
Sign, λ=0-0.80 of the dipping solution.
8. the catalyst combination according to 5, 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 preferably 120-280 DEG C, the time is
1-12 hours, preferably 2-8 hours.
9. a kind of method for hydrotreating hydrocarbon oil, including at hydrotreating reaction conditions, using aforementioned 1-8 any one institute
The catalyst combination stated carries out hydrotreating to hydrocarbon oil crude material oil.
10. the method according to 9, which is characterized in that it is 300-400 DEG C that the hydrogenation conditions, which include temperature, excellent
It is selected as 320-380 DEG C, preferably pressure 1-10MPa, 1-8MPa, volume space velocity is 0.5-3 hours during the liquid of hydrocarbon ils-1, preferably
It is 0.5-2.5 hours-1, hydrogen to oil volume ratio 100-800, preferably 100-700.
In the present invention, the carrier of the Hydrobon catalyst I is selected from the aluminium oxide used frequently as catalyst carrier, example
Such as, selected from γ-, δ-, η-, one or more of θ-aluminium oxide, gama-alumina preferably wherein；The hydrogenation active metals
Component is cobalt and molybdenum.On this basis, the Hydrobon catalyst I can be commercially available commodity or using arbitrary existing skill
It is prepared by art.
Inventor has found, when to cobalt compound, molybdate compound, phosphorus-containing compound and the lemon using conventional method configuration
When lemon pickling bath liquor further heats, the property of solution changes, and is prepared by the changed solution of this property
The Hydrogenation of cobaltmolybdate catalyst is improved.Particularly the catalyst is being combined with the nickel tungsten catalyst that the prior art provides
In use, show good hydrodesulfurization, hydrodenitrogeneration performance.
UV-Vis DRS spectrum analysis characterization can be used in the variation of the maceration extract property, conventionally matches
System cobalt-molybdenum-phosphorus-citric acid dipping solution (for example, be separately added into deionized water phosphoric acid, citric acid, basic cobaltous carbonate and
After molybdenum trioxide, by the suspension be heated to 80 DEG C it is agitated be easily dissolved, obtain the solution containing cobalt and molybdenum component),
The λ ＞ 1 of the solution.Wherein, λ is spectral peak at 517 ± 10nm in ultraviolet-visible spectrum and the ratio of spectral peak peak height at 772 ± 10nm
Value.When the solution is further heated, spectral peak dies down (peak height reduction) or disappears at 517 ± 10nm of dipping solution.According to
Definition of the present invention about λ, when spectral peak disappears at 517 ± 10nm, corresponding λ=0.Control the λ of the dipping solution≤
1, preferably λ=0-0.95, during more preferable λ=0-0.80, the Hydrogenation of the catalyst prepared by the record solution significantly improves.
In the preferred embodiment of the present invention, the Hydrobon catalyst I is changed using aforementioned property
Dipping solution oxide impregnation alumina supporter method prepare.Wherein, the preparation method of the maceration extract includes：(1) cobalt will be contained
Object, molybdate compound, phosphorus-containing compound and citric acid is closed to mix with water, be dissolved into solution；(2) solution for obtaining step (1)
At 60 DEG C -300 DEG C, reacted -200 hours 0.5 hour at preferably 75 DEG C -180 DEG C, further preferably 80 DEG C -150 DEG C, it is excellent
It is selected as -100 hours 1 hour, further preferably -50 hours 2 hours；Wherein, the dosage of each component makes the final leaching
A concentration of 0.01-0.1g/mL of cobalt compound in stain solution in terms of cobalt, molybdate compound in terms of molybdenum it is a concentration of
0.05-0.4g/mL, a concentration of 0.005-0.1g/mL of the phosphorus-containing compound in terms of phosphorus, a concentration of 0.05-0.5g/ of citric acid
mL.With UV-Vis DRS spectrum analysis characterize, λ≤1 of the dipping solution, λ be ultraviolet-visible spectrum in 517 ±
Spectral peak and the ratio of spectral peak peak height at 772 ± 10nm at 10nm.
In further preferred embodiment, the dosage of each component makes in the final dipping solution in terms of cobalt
A concentration of 0.02-0.09g/mL of cobalt compound, more preferably 0.03-0.08g/mL；Molybdate compound in terms of molybdenum
A concentration of 0.08-0.35g/mL, more preferably 0.10-0.3g/mL；A concentration of 0.007- of phosphorus-containing compound in terms of phosphorus
0.08g/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, further preferably λ=0-
0.80。
In the present invention, the cobalt compound in hydrogenation catalyst I preparations is selected from water-soluble chemical combination containing cobalt
Object.For example, salt, oxide and the hydroxide of the metal component containing cobalt.They can be selected from nitrate, chloride, the sulfuric acid of cobalt
Salt, formates, acetate, phosphate, citrate, oxalates, carbonate, subcarbonate, hydroxide, phosphate, phosphorus
One or more of compound, sulfide, aluminate, molybdate, tungstates, oxide.Oxalates, carbonic acid preferably wherein
One or more of salt, subcarbonate, hydroxide, phosphate, molybdate, tungstates, oxide, are more highly preferred to wherein
Subcarbonate and carbonate.
The molybdate compound is selected from water-soluble molybdate compound, for example, salt, the oxide of the component containing molybdenum.It
Can be selected from ammonium molybdate, heteropolyacid salt, one or more of 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.
According to the preparation method of the hydrogenation catalyst I dipping solutions provided by the invention, the heat treatment can be with
It carries out, can not also be carried out in situ in situ in the container for preparing solution.The heat treatment can carry out in the quiescent state,
It can in a dynamic state, such as be carried out under stirring.
When being heated to maceration extract, the evaporation and loss of water can be accompanied by, therefore, the process can be in closed system
It carries out in (such as in closed reaction kettle), when process carries out in open system, carries out at relatively high temperatures, such as temperature
At 90 DEG C or more, process can carry out in the container for being configured with reflux.
According to hydrogenation catalyst I provided by the invention, wherein the carrier optionally can be made into it is arbitrary easy to operation
Molding, such as spherical, tabletting and bar shaped.The molding can be carried out by conventional process, such as the predecessor of aluminium oxide and/or aluminium oxide
The methods of object tabletting, spin, extrusion.When using customary way molding, to ensure molding be smoothed out to treating into
Auxiliary agent is introduced in type material to be allowed, such as when the precursor extrusion of aluminium oxide and/or aluminium oxide, can add in and help in right amount
Squeeze agent and/or adhesive and water, then extrusion molding.The extrusion aid, the type of peptizing agent and dosage are this field routine,
Such as common extrusion aid can be selected from one or more of sesbania powder, methylcellulose, starch, polyvinyl alcohol, polyethanol,
Common peptizing agent can be selected from one kind in nitric acid, citric acid or their mixture.The molding through drying, roast
To carrier of the present invention.Here, the method and operating condition of the drying and roasting are conventional method and operating condition.
For example, the drying means is heat drying, drying temperature is 100-300 DEG C, preferably 120-280 DEG C；Drying time is
1-12 hours, preferably 2-8 hours；The condition of the roasting can be the conventional selection of this field.Usually, the roasting
Condition includes：Temperature can be 350-650 DEG C, preferably 400-600 DEG C；The time of the roasting can be 2-6 hours, preferably
It is 3-5 hours.
The dipping method for preparing the hydrogenation catalyst I is conventional impregnation methods, including hole saturation infusion process, excessive dipping
Method and multiple maceration etc. are dried, roast or do not roast later, these methods can all be adapted to prepare of the present invention
Catalyst.In specific implementation, preferred dip operation condition includes：Solution by volume and carrier by weight
Ratio is 0.5-10:1, further preferably 0.7-8：1.When in the dipping process being maceration extract excess, completed in dipping
It is free to remove at this time preferably include filtering before being dried the step of with the presence of free solution in impregnation product afterwards
Solution.Drying of the present invention can be the conventional selection of this field.Usually, the condition of the drying includes：Temperature can
Think 100-300 DEG C, preferably 120-280 DEG C；Time can be 1-12 hours, preferably 2-8 hours.When being roasted
When, the method and condition of the roasting can be the conventional selection of this field.Usually, the condition of the roasting includes：Temperature
It can be 350-550 DEG C, preferably 400-500 DEG C；Time can be 1-8 hours, preferably 2-6 hours.
According to catalyst I provided by the invention, can also contain it is any do not influence the present invention provide catalyst performance or
The substance of catalyst performance provided by the invention can be improved.Boron component can such as be contained, based on the element and using catalyst as base
Standard, the content of boron are no more than 10 weight %, preferably 0.5-6 weight %.
According to preparation method provided by the invention, when also containing in the catalyst I selected from components such as boron, introducing is further included
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
When agent introduces the carrier in the method that impregnates, the step of including being roasted, 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.
In the present invention, the carrier of the Hydrobon catalyst II is selected from aluminium oxide, gama-alumina preferably wherein；Institute
Hydrogenation active metal component is stated as nickel and tungsten.On this basis, the Hydrobon catalyst II can be commercially available commodity or
Using arbitrary prior art preparation.
For example, Hydrobon catalyst disclosed in CN85104438, it is by γ-Al2O3Support tungsten and nickel oxide and
Auxiliary agent fluorine is formed, and is formed (weight)：Nickel oxide 1~5%, tungsten oxide 12~35%, fluorine are 1~9%.
Catalyst for hydrorefining distillate oil disclosed in CN1169336, consisting of nickel oxide 1-5 weights %, tungsten oxide 12-35
Weight %, fluorine 1-9 weight %, remaining is aluminium oxide, which is by one or more small porous aluminum oxides and one or more macropores
Aluminium oxide is combined according to 75: 25-50: 50 weight ratio, wherein small porous aluminum oxide is less than the hole in 80 angstroms of holes for bore dia
Volume accounts for the aluminium oxide of more than 95% total pore volume, and macroporous aluminium oxide accounts for total pore volume for the pore volume in 60-600 angstroms of hole of bore dia
More than 70% aluminium oxide.The catalyst is especially suitable for inferior distillate oil plus hydrogen essence of the boiling range for 80-550 DEG C of high sulfur content
System.
Hydrocracking catalyst disclosed in CN101733149A, the catalyst contain carrier and load on this carrier
Group vib and VIII group hydrogenation active component and organic additive, on the basis of the total amount of catalyst, carrier in the catalyst
Content is 40-90 weight %, and the content of organic additive is 0.5-30 weight %, and in terms of oxide, the group VIB adds hydrogen to live
Property component content for 5-35 weight %, the content of group VIII hydrogenation active component is 1-15 weight %, and the carrier contains Y
The weight ratio of type molecular sieve, silica binder, silica binder and molecular sieve is 0.01~10.The catalyst by include by
Including Y type molecular sieve and the mixing of silica binder precursor, molding, dry and roast and prepare carrier, the backward carrier
The middle method preparation for introducing hydrogenation active metal component and organic matter.
These catalyst can be used as the catalyst II for the present invention.More detailed preparation about above-mentioned catalyst
Method, it is on the books in above patent document, it is quoted together using them as the part of the content of present invention here.
In the catalyst combination of the present invention, preferably described catalyst I and catalyst II layered arrangement, the layering cloth
It puts in application so that the hydrocarbon oil crude material oil contacts successively with Hydrobon catalyst I and Hydrobon catalyst II；Or
The layered arrangement causes the hydrocarbon oil crude material oil to be contacted successively with Hydrobon catalyst II and Hydrobon catalyst I.
According to hydrofinishing process provided by the invention, this method is improved by using the catalyst combination of the present invention
Other conditions of hydrofinishing process are not particularly limited in catalytic activity in unifining process, can be this field
Conventional selection.Usually, the condition of the hydrofinishing includes：Temperature is 300-400 DEG C；Pressure for 1.0-10.0MPa (with
Gauge pressure meter)；Volume space velocity is 0.5-3.0 hours during the liquid of hydrocarbon ils-1；Hydrogen to oil volume ratio is 100-800.The hydrogen to oil volume ratio is
Refer to the ratio of the volume flow rate of hydrogen and the volume flow rate of hydrocarbon ils.
According to the method provided by the present invention, optionally the catalyst combination can be used in combination with other agent, to reach more preferable
Using effect.For example, it is applied in combination in the catalyst combination and protective agent (Hydrogenation active protective agent).When the catalyst
When combination is used in combination with other agent (such as protective agent), the dosage of other agent is not special to this for the purpose of realizing its function
Limitation.For example, when the catalyst combination and protective agent are used in combination, by volume and on the basis of catalyst total amount, protect
The dosage for protecting agent can be 5-15%.
Hydrofinishing process according to the present invention, the carbon monoxide-olefin polymeric preferably use the routine of this field before use
Method is vulcanized.Usually, the condition of the vulcanization can include：In presence of hydrogen, at a temperature of 360-400 DEG C,
With one or more presulfurizations for carrying out 2-4 hours in sulphur, hydrogen sulfide, carbon disulfide, dimethyl disulfide or polysulfide.Root
According to the hydrofinishing process of the present invention, the presulfurization can carry out outside reactor, also can be In-situ sulphiding in reactor.
Hydrofinishing process according to the present invention is suitable for hydrodesulfurization, hydrodenitrogeneration of various hydrocarbon oil crude materials etc. and 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 embodiment
The present invention is described further for the following examples.
UV-Vis DRS spectrum analysis (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 in the range of 450-900nm.
The content of each element is analyzed in catalyst, using commercially available from Rigaku electric machine industry Co., Ltd.
3271E types Xray fluorescence spectrometer measures.
Embodiment 1-3 illustrates to prepare the maceration extract conventionally prepared that the present invention provides catalyst I.
Embodiment 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 (MTA) 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.
Embodiment 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 (MTA) 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 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 (MTA) 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 4-9 illustrates to prepare the maceration extract prepared according to the preferred process of the present invention that the present invention provides catalyst I.
Embodiment 4
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 in beaker
90 DEG C and under stiring constant temperature 8 hours are heated to, add water to 85mL, obtain clarification dipping solution S1.The λ value of dipping solution S1,
Cobalt (Co), molybdenum (Mo), phosphorus (P) and the concentration (g/ml) and phosphorus of citric acid (MTA) 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：
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 in closed container
In be heated to 100 DEG C and constant temperature 1 hours, add water to 85mL, obtain clarification dipping solution S2.The λ value of dipping solution S2, cobalt
(Co), the concentration (g/ml) of molybdenum (Mo), phosphorus (P) and citric acid (MTA) and the molar ratio (n of 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：
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 adds in beaker
Heat to 70 DEG C and under stiring constant temperature 18 hours, add water to 85mL, obtain clarification dipping solution S3.The λ value of dipping solution S3, cobalt
(Co), the concentration (g/ml) of molybdenum (Mo), phosphorus (P) and citric acid (MTA) and the molar ratio (n of 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 7
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 in closed container
In be heated to 120 DEG C and constant temperature 12 hours, add water to 85mL, obtain clarification dipping solution S4.The λ value of dipping solution S4, cobalt
(Co), the concentration (g/ml) of molybdenum (Mo), phosphorus (P) and citric acid (MTA) and the molar ratio (n of 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 8
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 in closed container
120 DEG C of simultaneously constant temperature 2 hours are heated to, add water to 85mL, obtain clarification dipping solution S5.The λ value of dipping solution S5, cobalt (Co),
The concentration (g/ml) and phosphorus of molybdenum (Mo), phosphorus (P) and citric acid (MTA) and the molar ratio (n of molybdenumP/nMo), the molar ratio of molybdenum and cobalt
(nMo/nCo), the molar ratio (n of citric acid and cobaltCTA/nCo) it is included in table 1.
Embodiment 9
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 in closed container
In be heated to 140 DEG C and constant temperature 10 hours, add water to 85mL, obtain clarification dipping solution S6.The λ value of dipping solution S6, cobalt
(Co), the concentration (g/ml) of molybdenum (Mo), phosphorus (P) and citric acid (MTA) and the molar ratio (n of 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.
Table 1
Note：It is analyzed and characterized with ultraviolet-visible spectrum, occurs spectral peak at 517nm in the spectrogram of solution, but do not occur 772nm
Spectral peak, solution λ=∞ at this time.
Present invention below provides the carrier that catalyst I and reference catalyst I is used and is prepared as follows：Weigh 2000
Gram aluminium hydrate powder (dry glue powder of Chang Ling branch company catalyst plant production, 72 weight % of butt), is extruded into circumscribed circle with banded extruder
A diameter of 1.3 millimeters of butterfly item roasts 3 hours under the conditions of wet bar is 4 hours, 600 DEG C dry in 120 DEG C, carrier Z1 is made.Z1
Water absorption rate be 0.85.
Embodiment 10-16 illustrates catalyst I provided by the invention and its preparation.
Embodiment 10
Catalyst I-1 prepared by cobalt molybdenum solution provided by the invention：
By 1 saturation of 85mL solution Ss, 100 grams of dipping Z1 carriers 2 hours, 3 hours of 250 DEG C of dryings, catalyst I-1 is obtained,
Its composition is shown in Table 2.
Embodiment 11
Catalyst I-2 prepared by cobalt molybdenum solution provided by the invention：
By 2 saturation of 85mL solution Ss, 100 grams of dipping Z1 carriers 2 hours, 3 hours of 200 DEG C of dryings, catalyst I-2 is obtained,
Its composition is shown in Table 2.
Embodiment 12
Catalyst I-3 prepared by cobalt molybdenum solution provided by the invention：
By 3 saturation of 85mL solution Ss, 100 grams of dipping Z1 carriers 3 hours, 3 hours of 250 DEG C of dryings, catalyst I-3 is obtained,
Its composition is shown in Table 2.
Embodiment 13
Catalyst I-4 prepared by cobalt molybdenum solution provided by the invention：
By 4 saturation of 85mL solution Ss, 100 grams of dipping Z1 carriers 2 hours, 5 hours of 150 DEG C of dryings, catalyst I-4 is obtained,
Its composition is shown in Table 2.
Embodiment 14
Catalyst I-5 prepared by cobalt molybdenum solution provided by the invention：
By 5 saturation of 85mL solution Ss, 100 grams of dipping Z1 carriers 2 hours, 4 hours of 200 DEG C of dryings, catalyst I-5 is obtained,
Its composition is shown in Table 2.
Embodiment 15
Catalyst I-6 prepared by cobalt molybdenum solution provided by the invention：
By 6 saturation of 85mL solution Ss, 100 grams of leaching stain Z1 carriers 2 hours, 3 hours of 200 DEG C of dryings, catalyst I-6 is obtained,
Its composition is shown in Table 2.
Embodiment 16
By 85mL solution L1 saturations 100 grams of dipping Z1 carriers 2 hours, 3 hours of 180 DEG C of dryings, catalyst C1 is obtained,
Composition is shown in Table 2.
Table 2
| Embodiment | Catalyst is numbered | MoO3(weight %) | CoO (weight %) | P2O5(weight %) |
| 10 | I-1 | 20.5 | 4.0 | 2.2 |
| 11 | I-2 | 15.2 | 6.4 | 3.9 |
| 12 | I-3 | 25.5 | 3.5 | 1.7 |
| 13 | I-4 | 20.1 | 3.9 | 2.8 |
| 14 | I-5 | 18.2 | 4.5 | 2.8 |
| 15 | I-6 | 20.3 | 4.0 | 2.2 |
| 16 | C1 | 20.1 | 3.9 | 2.1 |
Embodiment 17-19 illustrates the preparation method of catalyst II.
Embodiment 17
Hydrogenation catalyst II -1：Hydrogenation catalyst II -1 is prepared using patent CN85104438 methods, it includes 3 weight %
Nickel oxide, the tungsten oxide of 25 weight %, the fluorine (being calculated with element fluorine) of 2 weight %, remaining is aluminium oxide.
Embodiment 18
Hydrogenation catalyst II -2：Hydrogenation catalyst II -2 is prepared using patent ZL97112397 methods, it includes 3 weight %
Nickel oxide, the tungsten oxide of 25 weight %, the fluorine (being calculated with element fluorine) of 2 weight %, remaining is aluminium oxide.
Embodiment 19
Hydrogenation catalyst II -3：Hydrogenation catalyst II -3 is prepared using patent ZL97112397 methods, it includes 4 weight %
Nickel (in terms of NiO), the tungsten (in terms of tungsten oxide) of 30 weight %, the fluorine (being calculated with element fluorine) of 4 weight %, remaining for oxidation
Aluminium.
Embodiment 20-26
This example illustrates the diesel oil hydrofining performance of hydrogenating catalyst composition provided by the invention.
It evaluates carbon monoxide-olefin polymeric respectively on 30 milliliters of diesel hydrotreating units, is respectively catalyzed in catalyst combination and combination
The content (amount of catalyst II is surplus) of agent is shown in Table 3, 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 during liquid：2.0h-1；Hydrogen to oil volume ratio：300；Hydrogen partial 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 embodiment 16, 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 using hydrodenitrogeneration reaction as the processing of 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 1,2
Using the method evaluation catalyst C1 identical with embodiment 20-26, II -1 activity, as a result it is shown in table 3.
Table 3
Table 3 the results show that carbon monoxide-olefin polymeric prepared according to the methods of the invention in the hydrofinishing for hydrocarbon ils
When, there is higher catalytic activity.
Claims (14)
1. a kind of catalyst combination for hydrotreating, including Hydrobon catalyst I and Hydrobon catalyst II,
In,
The Hydrobon catalyst I contains alumina support, cobalt and molybdenum hydrogenation active metal component, using the catalyst I as
Benchmark, using the cobalt content that CoO is counted as 1-10 weight % in the catalyst I, with MoO3The molybdenum content of meter be 5-50 weight %, institute
The preparation method for stating Hydrobon catalyst I is included using dipping solution impregnated carrier, and the dipping solution contains chemical combination containing cobalt
Object, molybdate compound, phosphorus-containing compound and citric acid, cobalt compound in the dipping solution in terms of cobalt it is a concentration of
0.01-0.1g/mL, a concentration of 0.05-0.4 g/mL of the molybdate compound in terms of molybdenum, the concentration of the phosphorus-containing compound in terms of phosphorus
For 0.005-0.10 g/mL, a concentration of 0.05-0.5 g/mL of citric acid, characterized with UV-Vis DRS spectrum analysis,
λ≤1 of the dipping solution, λ are spectral peak at 517 ± 10nm in ultraviolet-visible spectrum and the ratio of spectral peak peak height at 772 ± 10nm
Value；
The Hydrobon catalyst II contains alumina support, nickel and tungsten hydrogenation active metal component, with the catalyst II
On the basis of, using the nickel content that NiO is counted as 1-10 weight % in the catalyst II, with WO3The W content of meter is 5-60 weight %；
By volume and on the basis of the total amount of the catalyst combination, the content of the catalyst I in the catalyst combination is
5-95%, the content of catalyst II is 5-95%.
2. catalyst combination according to claim 1, which is characterized in that on the basis of the catalyst I, the catalyst
Using the cobalt content that CoO is counted as 1-7 weight % in I, with MoO3The molybdenum content of meter is 8-45 weight %.
3. catalyst combination according to claim 2, which is characterized in that on the basis of the catalyst I, the catalyst
Using the cobalt content that CoO is counted as 3-7 weight % in I, with MoO3The molybdenum content of meter is 12-30 weight %.
4. catalyst combination according to claim 1, which is characterized in that on the basis of the catalyst II, the catalysis
Using the nickel content that NiO is counted as 1-8 weight % in agent II, with WO3The W content of meter is 8-50 weight %.
5. catalyst combination according to claim 4, which is characterized in that on the basis of the catalyst II, the catalysis
Using the nickel content that NiO is counted as 2-6 weight % in agent II, with WO3The W content of meter is 20-40 weight %.
6. catalyst combination according to claim 1, which is characterized in that by volume and with the total of the catalyst combination
On the basis of amount, the content of the Hydrobon catalyst I is 10-80%, and the content of the Hydrobon catalyst II is 20-
90%。
7. catalyst combination according to claim 6, which is characterized in that by volume and with the total of the catalyst combination
On the basis of amount, the content of the Hydrobon catalyst I is 20-70%, and the content of the Hydrobon catalyst II is 30-
80%。
8. catalyst combination according to claim 1, which is characterized in that the chemical combination containing cobalt in the dipping solution in terms of cobalt
A concentration of 0.02-0.09g/mL of object, a concentration of 0.08-0.35 g/mL of the molybdate compound in terms of molybdenum, it is phosphorous in terms of phosphorus
A concentration of 0.007-0.08 g/mL of compound, a concentration of 0.1-0.4 g/mL of citric acid, with ultraviolet-visible light spectrum analysis
Characterization, λ=0-0.95 of the dipping solution.
9. catalyst combination according to claim 8, which is characterized in that the dipping solution is with ultraviolet-visible spectrum point
Analysis characterization, λ=0-0.80 of the dipping solution.
10. catalyst combination according to claim 9, which is characterized in that use dipping solution impregnated carrier in described
Later, including dry step, the drying condition includes：Drying temperature is 100-300 DEG C, and the time is 1-12 hours.
11. catalyst combination according to claim 10, which is characterized in that use dipping solution impregnated carrier in described
Later, including dry step, the drying condition includes：Drying temperature is 120-280 DEG C, and the time is 2-8 hours.
It is arbitrary using preceding claims 1-11 including at hydrotreating reaction conditions 12. a kind of method for hydrotreating hydrocarbon oil
Catalyst combination described in one carries out hydrotreating to hydrocarbon oil crude material oil.
13. according to the method for claim 12, which is characterized in that it is 300- that the hydrotreating reaction condition, which includes temperature,
400 DEG C, pressure 1-10MPa, volume space velocity is 0.5-3 hours during the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio 100-800.
14. according to the method for claim 13, which is characterized in that it is 320- that the hydrotreating reaction condition, which includes temperature,
380 DEG C, pressure 1-8MPa, volume space velocity is 0.5-2.5 hours during the liquid of hydrocarbon ils-1, hydrogen to oil volume ratio 100-700.
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| RU2732944C1 (en) * | 2020-03-19 | 2020-09-24 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of producing low-sulphur diesel fuel |
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| CN107446621B (en) * | 2016-06-01 | 2019-11-15 | 中国石油化工股份有限公司 | A kind of method of long-cycle production ultra-low-sulphur diesel |
| CN111437823A (en) * | 2020-04-01 | 2020-07-24 | 深圳泰利能源有限公司 | Animal and vegetable oil hydrogenation catalyst composition and application thereof |
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| CN1176290A (en) * | 1996-09-11 | 1998-03-18 | 中国石油化工总公司 | Hydrogenation post-refining process for lubricant oil |
| CN1463204A (en) * | 2001-06-20 | 2003-12-24 | 克斯莫石油株式会社 | Catalyst for hydrogenation treatmet of gas oil and method for prepn. thereof and process for hydrogenation treatment of gas oil |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
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| CN1176290A (en) * | 1996-09-11 | 1998-03-18 | 中国石油化工总公司 | Hydrogenation post-refining process for lubricant oil |
| CN1463204A (en) * | 2001-06-20 | 2003-12-24 | 克斯莫石油株式会社 | Catalyst for hydrogenation treatmet of gas oil and method for prepn. thereof and process for hydrogenation treatment of gas oil |
| CN101092573A (en) * | 2006-06-22 | 2007-12-26 | 中国石油化工股份有限公司 | A hydrogenation method for producing diesel oil in low sulphur |
| CN102051217A (en) * | 2009-10-30 | 2011-05-11 | 中国石油化工股份有限公司 | Hydrogenation method for producing ultra-low sulfur clean diesel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| RU2732944C1 (en) * | 2020-03-19 | 2020-09-24 | Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») | Method of producing low-sulphur diesel fuel |
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