CN109092347A - Hydrogenation catalyst and its preparation method and application - Google Patents
Hydrogenation catalyst and its preparation method and application Download PDFInfo
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- CN109092347A CN109092347A CN201710474322.3A CN201710474322A CN109092347A CN 109092347 A CN109092347 A CN 109092347A CN 201710474322 A CN201710474322 A CN 201710474322A CN 109092347 A CN109092347 A CN 109092347A
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- hydrogenation catalyst
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- hydrogen
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- 239000003054 catalyst Substances 0.000 title claims abstract description 109
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 83
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000011280 coal tar Substances 0.000 claims abstract description 20
- 238000005121 nitriding Methods 0.000 claims abstract description 17
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 41
- 239000001257 hydrogen Substances 0.000 claims description 41
- 229910052739 hydrogen Inorganic materials 0.000 claims description 41
- 229910052751 metal Inorganic materials 0.000 claims description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 19
- 239000008246 gaseous mixture Substances 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 9
- 150000002739 metals Chemical class 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 2
- 241000416536 Euproctis pseudoconspersa Species 0.000 claims 1
- 239000012018 catalyst precursor Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 17
- 238000004517 catalytic hydrocracking Methods 0.000 description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 16
- 239000003921 oil Substances 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000012298 atmosphere Substances 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 150000004767 nitrides Chemical class 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 5
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910052593 corundum Inorganic materials 0.000 description 4
- 238000005336 cracking Methods 0.000 description 4
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 description 4
- 229910017318 Mo—Ni Inorganic materials 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 239000010426 asphalt Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002283 diesel fuel Substances 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000004073 vulcanization Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- -1 metals sulfide Chemical class 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 150000002429 hydrazines Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/166—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/888—Tungsten
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
- C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
- C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to coal tar hydrogenating process fields, and in particular, to a kind of hydrogenation catalyst and its preparation method and application.The preparation method of the hydrogenation catalyst includes: that hydrogenation catalyst precursor is carried out Nitrizing Treatment containing in nitrogen atmosphere, wherein the condition of the Nitrizing Treatment makes the content of nitrogen in resulting hydrogenation catalyst be 0.1-3 weight %.The hydrogenation catalyst of nitriding can be simply and rapidly made in method of the invention, and resulting hydrogenation catalyst can significantly improve associated catalytic activity.
Description
Technical field
The present invention relates to coal tar hydrogenating process fields, and in particular, to a kind of hydrogenation catalyst and preparation method thereof and
Using.
Background technique
Coal tar is thick liquid obtained in dry distillation of coal process.For the processing and utilization of coal tar, current conventional side
Method is divided into two classes: one is a physically separate extraction chemicals, second is that hydrotreating produced fluid fuel.It is increasingly deficient with petroleum resources
It is weary, coal tar is subjected to hydrotreating and is increasingly taken seriously with producing liquid fuel (such as diesel oil).
CN103785442A discloses a kind of metal nitride hydrocracking catalyst, in terms of catalyst carrier weight, point
The content of son sieve is 2%~45%；With catalyst weight, vib metals component (W and/or Mo) containing in terms of nitride
Amount is 10%-40%；The content of group VIII metal component (Ni and/or Co) in terms of nitride is 1%-10%.And
The preparation method of the above-mentioned hydrocracking catalyst of CN103785442A, comprising: (1) preparation contains molecular sieve and inorganic refractory oxygen
The catalyst carrier of compound；(2) dipping solution containing group vib metallic compound and group VIII metal compound is prepared；(3) step
Suddenly hydrazine derivative is added in the dipping solution that (2) are prepared, carries out ultrasonic wave dispersion, then the catalyst of impregnation steps (1) carries
Then body is dried；(4) material that step (3) obtains carries out Hydrogen activation, and for hydrocracking reaction plus hydrogen is obtained after activation
Cracking catalyst.It can be seen that this method using organic nitrogen as nitrogen source by above-mentioned preparation method disclosed in CN103785442A
Presoma is as nitrogen source, higher cost, although and nitride catalyst activity preferably, long-time stability and the de- drip of de- carbon residue
Green mass-energy power will be lower than conventional metals sulfide catalyst.And hydrocracking catalyst disclosed in this application mainly for the treatment of
Heavy hydrocarbon material so as to maximum produces intermediate oil.For coal tar hydrogenating processing for, there are raw material carbon residue,
Asphalt content is high and contains a large amount of condensed-nuclei aromatics, it more difficult to add hydrogen to be saturated, the defect of catalyst long-time stability difference.Similar goes back
There is CN 103785440A.
CN101099933A discloses a kind of diesel oil aromatic saturated hydrogenation catalyst, it is by powder or molding γ-Al2O3
It is Ni for carrier loaded chemical formula2Mo3The molybdenum nickel bimetal nitride of N is constituted, wherein Ni2Mo3The weight percentage of N is 7%
~50%.The catalyst is using the ammonium hydroxide that carrier impregnation is contained nickel nitrate and ammonium molybdate, then obtained by temperature programmed nitridation.
Although the catalyst has higher plus hydrogen saturated activity to aromatic rings, applied to can make wherein in FCC diesel oil aromatic saturated hydrogenation
Most aromatic hydrocarbons saturation.But for coal tar hydrogenating processing, there is also raw material carbon residue, asphalt content is high and contains
A large amount of condensed-nuclei aromatics, it more difficult to the defect for adding hydrogen to be saturated.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods simply, preparation fast speed and catalyst performance preferably add
The preparation method of hydrogen catalyst and its hydrogenation catalyst obtained and application.
To achieve the goals above, the present invention provides a kind of preparation method of hydrogenation catalyst, this method comprises: nitrogenous
In gas atmosphere, hydrogenation catalyst precursor is subjected to Nitrizing Treatment, wherein the condition of the Nitrizing Treatment urges resulting plus hydrogen
The content of nitrogen is 0.1-3 weight % in agent.
The present invention also provides hydrogenation catalysts prepared by the above method.
The present invention provides application of the above-mentioned hydrogenation catalyst in coal tar hydrogenating upgrading.
The present invention provides a kind of methods of coal tar hydrogenating upgrading, wherein the catalyst that this method uses adds to be above-mentioned
Hydrogen catalyst.
The hydrogenation catalyst of nitriding can be made in method of the invention simple, quickly, on a large scale, and resulting plus hydrogen is urged
Agent can significantly improve associated catalytic activity and de- carbon residue depitching ability, while using having both after catalyst vulcanization
The advantages of metal nitride and sulfide catalyst.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
The present invention provides a kind of preparation method of hydrogenation catalyst, this method comprises: hydrogen will be added to urge containing in nitrogen atmosphere
Agent precursor carries out Nitrizing Treatment, wherein the condition of the Nitrizing Treatment makes containing for nitrogen in resulting hydrogenation catalyst
Amount is 0.1-3 weight %.
According to the present invention, the present invention will be impregnated with nitrogen in hydrogenation catalyst precursor, to obtain by way of Nitrizing Treatment
Nitrogenous hydrogenation catalyst.Preferably, the condition of the Nitrizing Treatment makes the content of nitrogen in resulting hydrogenation catalyst
For 0.5-2 weight %, preferably 1-2 weight %, such as 1.4-2 weight %.
According to the present invention, in order to realize that above-mentioned nitrogenizing effect, the Nitrizing Treatment preferably meet the following conditions, i.e. temperature is
450-700 DEG C, time 0.1-4h, electric current 30-200A, by controlling such nitriding condition, it can not only to add hydrogen
Catalyst is infiltrated with nitrogen, and to improve the nitrogen resistance of the hydrogenation catalyst, and resulting hydrogenation catalyst can be with
Higher catalytic activity is obtained, for example, just there is better desulfurization, nitrogen and carbon residue performance for for Hydrobon catalyst；
And for for hydrocracking catalyst, just there is better cracking performance.It is highly preferred that the condition packet of the Nitrizing Treatment
Include: temperature is 500-600 DEG C, time 0.5-2h, electric current 80-150A.Wherein, the temperature of Nitrizing Treatment, which can be, directly exists
Nitrizing Treatment is carried out at this temperature, is also possible to carry out Nitrizing Treatment again after being warming up at this temperature with certain heating rate,
Such as it can be the temperature that the Nitrizing Treatment is warming up to the heating rate of 5-10 DEG C/min.
According to the present invention, the nitrogen containing atmosphere can be any gas for being suitable for the invention preparation method containing nitrogen
Atmosphere, it is preferable that described is the gaseous mixture of nitrogen and hydrogen and/or ammonia, the i.e. gaseous mixture of nitrogen and hydrogen containing nitrogen atmosphere, or
The gaseous mixture of the gaseous mixture or nitrogen of person's nitrogen and ammonia, hydrogen and ammonia.By using nitrogen and hydrogen and/or ammonia
Gaseous mixture as under nitrogen containing atmosphere, hydrogen and/or ammonia can be ionized generation Nitrogen ion, thus obtain more nitriding
Effect.Preferably, the volume ratio of nitrogen and hydrogen and/or ammonia is 1:0.5-2.The preferred mixing for using nitrogen and hydrogen
Gas is as the nitrogen containing atmosphere.
Wherein, the intake of the gaseous mixture can carry out suitably according to the content and required nitrogen content of reactant
Adjustment, such as the intake of the gaseous mixture is 50-200mL/min.
According to the present invention, the Nitrizing Treatment can be carried out by the way of the Nitrizing Treatment of this field routine, such as should
Nitrizing Treatment carries out in nitriding furnace.Preferably, the mode of the Nitrizing Treatment includes: that hydrogenation catalyst precursor is configured at yin
At pole, using the inner wall of nitriding furnace as anode, glow discharge occurs by applying high pressure, so that free nitrogen infiltration has
The hydrogenation catalyst of active surface.
According to the present invention, it is generally the case that the hydrogenation catalyst also contains active metallic element and carrier.Wherein, institute
The active metallic element for hydrogenation catalyst that active metallic element can be this field routine is stated, especially conventional is used for
The active metallic element of Hydrobon catalyst and hydrocracking catalyst, it is preferable that the active metallic element is group VIB
Metallic element and group VIII metallic element.Wherein, the vib metals element is preferably W and/or Mo, the Section VIII
Race's metallic element is preferably Ni and/or Co.
According to the present invention, the content of the active metallic element can change in a wider range, in order to obtain performance more
For excellent hydrogenation catalyst, it is preferable that on the basis of the total weight of hydrogenation catalyst resulting after the Nitrizing Treatment, with gold
The content for belonging to oxide meter vib metals element is preferably 10-35 weight %, more preferably 14-30 weight %, further
Preferably 15-28 weight %, for example, 15-18 weight %；The content of group VIII metallic element is preferred in terms of metal oxide
For 1-10 weight %, more preferably 2-6 weight %, more preferably 3-5.5 weight %.
According to the present invention, as described above, the hydrogenation catalyst can urge for Hydrobon catalyst or be hydrocracked
Agent.It should be understood that usual resulting hydrogenation catalyst is hydrocracking catalyst when vib metals element is W
Agent, when vib metals element is Mo, usual resulting hydrogenation catalyst is Hydrobon catalyst.
According to the present invention, the carrier contained by the hydrogenation catalyst is each as hydrogenation catalyst of this field routine
Plant carrier, for example, one of aluminium oxide, silicon-containing alumina, molecular sieve (specific such as HY), silica and active carbon or more
Kind.
Wherein, above-mentioned hydrogenation catalyst precursor can be outlined above with corresponding active constituent and carrier plus hydrogen
Catalyst can be and is made by the conventional method of this field, be also possible to commercially available, such as can be purchased from Chinese stone
The hydrogenation catalyst of oily Fushun Petrochemical Research Institute of chemical inc (calling Fu Yan institute in the following text), such as FH series or FC system
Column.
The present invention also provides hydrogenation catalysts made from the above method.
The present invention also provides application of the above-mentioned hydrogenation catalyst in coal tar hydrogenating upgrading.
The present invention also provides a kind of methods of coal tar hydrogenating upgrading, wherein the catalyst that this method uses is described
Hydrogenation catalyst.
Under normal conditions, for coal tar hydrogenating upgrading, shape that coal tar and hydrogen are passed through into fixed bed reactors
Formula carries out that hydrogen upgrading namely hydrogenation catalyst is added to be set in fixed bed reactors.Wherein, for hydrofinishing, should add
The reaction condition of hydrogen purification includes: that temperature is 230-410 DEG C, and Hydrogen Vapor Pressure (gauge pressure) is 8-20MPa, hydrogen to oil volume ratio 500-
2000:1, volume space velocity is 0.2-2h when liquid-1.And in the feedstock oil for passing through hydrofinishing fixed bed reactors, nitrogen content is usual
For 5000-10000ppm, sulfur content is usually 1500-8000ppm, and carbon residue content is usually 6.2-8.6 weight %, and asphalitine contains
Amount is usually 12-22 weight %.
For being hydrocracked, which includes: that temperature is 320-410 DEG C, Hydrogen Vapor Pressure (table
Pressure) it is 8-20MPa, hydrogen to oil volume ratio 500-2000:1, volume space velocity is 0.2-2h when liquid-1.And by being hydrocracked fixation
In the feedstock oil of bed reactor, nitrogen content is usually 200-2000ppm, and sulfur content is usually 20-200ppm, and carbon residue content is usual
For 0.5-2%, asphalt content is usually 1-10 weight %.
According to the present invention it is possible to understand, by by the feedstock oil after Hydrobon catalyst bed again by adding hydrogen
Cracking catalyst bed.It is possible thereby to which hydrogen upgrading is preferably added to handle to coal tar.
The present invention will be described in detail by way of examples below.
Embodiment 1
The present embodiment is for illustrating hydrogenation catalyst and preparation method thereof of the invention.
By 20g Hydrobon catalyst Mo-Ni/Al2O3(it is purchased from Fu Yan institute, trade mark FH-30, with MoO3The content of the Mo of meter
For 16.5 weight %, the content of the Ni in terms of NiO is 3.2 weight %) it is put on the cathode in nitriding furnace, and be sun with nitriding furnace
Pole, in gaseous mixture (the volume ratio N of nitrogen and hydrogen2: H2=2:1, intake 100mL/min) in atmosphere, electric current be 50A and temperature
After degree is electrolysed 0.5h under conditions of being 550 DEG C, nitrogenous Hydrobon catalyst A1 is obtained, with MoO3The content of the Mo of meter is 15
The content of weight %, the Ni in terms of NiO are 3.2 weight %, and nitrogen content is 0.7 weight %.
Embodiment 2
The present embodiment is for illustrating hydrogenation catalyst and preparation method thereof of the invention.
By 20g Hydrobon catalyst Mo-Ni/Al2O3(with embodiment 1) is put on the cathode in nitriding furnace, and with nitriding
Furnace is anode, in gaseous mixture (the volume ratio N of nitrogen and hydrogen2: H2=2:1, intake 100mL/min) in atmosphere and electric current is
Under conditions of 100A, after being warming up to 600 DEG C from room temperature (about 25 DEG C) with 5 DEG C/min, then it is electrolysed 1h, obtains nitrogenous hydrofinishing
Catalyst A2, with MoO3The content of the Mo of meter is 15 weight %, and the content of the Ni in terms of NiO is 3.2 weight %, nitrogen content 1
Weight %.
Comparative example 1
Directly by 20g Hydrobon catalyst Mo-Ni/Al2O3(with embodiment 1) is used as Hydrobon catalyst DA1.
Embodiment 3
The present embodiment is for illustrating hydrogenation catalyst and preparation method thereof of the invention.
By 20g hydrocracking catalyst W-Ni/Al2O3(it is purchased from Fu Yan institute, trade mark FC-28, with WO3The content of the W of meter is
The content of 15 weight %, the Ni in terms of NiO are 4.8 weight %) it is put on the cathode in nitriding furnace, and using nitriding furnace as anode,
In gaseous mixture (the volume ratio N of nitrogen and hydrogen2: H2=1:1, intake 100mL/min) in atmosphere and electric current is the condition of 100A
Under, after being warming up to 550 DEG C from room temperature (about 25 DEG C) with 5 DEG C/min, then it is electrolysed 1h, obtains nitrogenous hydrocracking catalyst A3,
With WO3The content of the W of meter is 14 weight %, and the content of the Ni in terms of NiO is 4.8 weight %, and nitrogen content is 0.9 weight %.
Embodiment 4
The present embodiment is for illustrating hydrogenation catalyst and preparation method thereof of the invention.
20g hydrocracking catalyst W-Ni/HY (is purchased from Fu Yan institute, the content of trade mark FC-34, the W in terms of WO3 are 16
The content of weight %, the Ni in terms of NiO are 5.2 weight %) it is put on the cathode in nitriding furnace, and using nitriding furnace as anode,
Gaseous mixture (the volume ratio N of nitrogen and hydrogen2: H2=1:2, intake 100mL/min) in atmosphere and electric current is the condition of 100A
Under, after being warming up to 650 DEG C from room temperature (about 25 DEG C) with 5 DEG C/min, then it is electrolysed 1h, obtains nitrogenous hydrocracking catalyst A4,
With WO3The content of the W of meter is 15 weight %, and the content of the Ni in terms of NiO is 5.2 weight %, and nitrogen content is 1.4 weight %.
Embodiment 5
The present embodiment is for illustrating hydrogenation catalyst and preparation method thereof of the invention.
20g hydrocracking catalyst W-Ni/HY (with embodiment 4) is put on the cathode in nitriding furnace, and with nitriding furnace
For anode, in gaseous mixture (the volume ratio N of nitrogen and ammonia2: ammonia=1:1, intake 100mL/min) in atmosphere and electric current is
Under conditions of 100A, after being warming up to 650 DEG C from room temperature (about 25 DEG C) with 5 DEG C/min, then it is electrolysed 1.5h, obtains nitrogenous plus hydrogen and split
Change catalyst A5, with WO3The content of the W of meter is 15 weight %, and the content of the Ni in terms of NiO is 5.2 weight %, and nitrogen content is
1.8 weight %.
Comparative example 2
Directly it regard 20g hydrocracking catalyst W-Ni/-HY (with embodiment 4) as hydrocracking catalyst DA2.
Comparative example 3
According to method described in embodiment 1, the difference is that, nitrogen is replaced using pure nitrogen (intake 100mL/min)
With the gaseous mixture of hydrogen, and under conditions of electric current is 40A and temperature is 500 DEG C be electrolysed 20min after；It is nitrogenous to obtain
Hydrobon catalyst DA3, with MoO3The content of the Mo of meter is 15 weight %, and the content of the Ni in terms of NiO is 3.2 weight %,
Nitrogen content is 0.05 weight %.
Test case
Using Shenmu County's coal tar as feedstock oil, (nitrogen content 6800ppm, sulfur content 1800ppm, carbon residue content are usually
8.6 weight %) and hydrogen pass through being urged equipped with above-mentioned nitrogenous Hydrobon catalyst A1-A2 and DA1, DA3-DA4 respectively
Agent bed uses after catalyst vulcanization, wherein the reaction temperature of hydrofinishing is 380 DEG C, hydrogen pressure (gauge pressure) be 12MPa,
Hydrogen to oil volume ratio is 1500:1, Mean fluid air speed is 1.00h-1；Resulting catalyst activity analysis and production after reaction 500 hours
Product distributed architecture is shown in Table 1；
By the feedstock oil obtained by Shenmu County's coal tar, (nitrogen content 560ppm, sulfur content 30ppm, carbon residue content are usual
Pass through the catalyst bed equipped with above-mentioned nitrogenous hydrocracking catalyst A3-A5 and DA2 respectively for 2.3 weight %) and hydrogen
Layer, it is used after catalyst vulcanization, wherein the reaction temperature being hydrocracked is 380 DEG C, hydrogen pressure (gauge pressure) is 12MPa, hydrogen oil body
Product ratio is 1500:1, Mean fluid air speed is 1.00h-1；Resulting catalyst activity analysis and product distribution after reaction 500 hours
Structure is shown in Table 1；
Table 1
Can be seen that the resulting nitrogenous Hydrobon catalyst of the present invention by the result of table 1, have more preferable desulfurization,
Nitrogen and carbon residue performance are conducive to improve fuel oil is made in coal tar hydrogenating product quality and catalyst service life, extend coal
The operation cycle of hydrogenation of tar equipment.Similarly, the resulting nitrogenous hydrocracking catalyst of the present invention has better cracking
With anti-nitrogen performance, be conducive to improve fuel oil is made in coal tar hydrogenating liquid yield, product quality and catalyst service life.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, can be combined in any appropriate way, in order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should also be regarded as the disclosure of the present invention.
Claims (10)
1. a kind of preparation method of hydrogenation catalyst, which is characterized in that this method comprises: hydrogen will be added to urge containing in nitrogen atmosphere
Agent precursor carries out Nitrizing Treatment, wherein the condition of the Nitrizing Treatment makes containing for nitrogen in resulting hydrogenation catalyst
Amount is 0.1-3 weight %.
2. according to the method described in claim 1, wherein, the condition of the Nitrizing Treatment makes nitrogen in resulting hydrogenation catalyst
The content of element is 0.5-2 weight %.
3. method according to claim 1 or 2, wherein the condition of the Nitrizing Treatment includes: that temperature is 450-700 DEG C,
Time is 0.1-4h, electric current 30-200A；
Preferably, it is 500-600 DEG C, time 0.5-2h, electric current 80-150A that the condition of the Nitrizing Treatment, which includes: temperature,.
4. method according to claim 1 or 2, wherein described containing nitrogen atmosphere is the mixed of nitrogen and hydrogen and/or ammonia
Close gas, it is preferable that the volume ratio of nitrogen and hydrogen and/or ammonia is 1:0.5-2；
Preferably, the intake of the gaseous mixture is 50-200mL/min.
5. according to the method described in claim 1, wherein, resulting hydrogenation catalyst also contains active gold after the Nitrizing Treatment
Belong to element and carrier, the active metallic element is vib metals element and group VIII metallic element, with metal oxide
The content for counting vib metals element is 10-35 weight %, preferably 14-30 weight %, more preferably 15-28 weight %；With
The content of metal oxide meter group VIII metallic element is 1-10 weight %；
Preferably, the vib metals element is W and/or Mo；
Preferably, the group VIII metallic element is Ni and/or Co.
6. method according to claim 1 or 5, wherein the hydrogenation catalyst is Hydrobon catalyst or hydrogen is added to split
Change catalyst.
7. method described in any one of -6 according to claim 1, wherein the mode of the Nitrizing Treatment includes: that will add hydrogen
Catalyst precarsor is configured at cathode, using the inner wall of nitriding furnace as anode.
8. hydrogenation catalyst made from the method as described in any one of claim 1-7.
9. application of the hydrogenation catalyst according to any one of claims 8 in coal tar hydrogenating upgrading.
10. a kind of method of coal tar hydrogenating upgrading, wherein the catalyst that this method uses is according to any one of claims 8 plus hydrogen
Catalyst.
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