CN107297215A - Hydrotreating catalyst and preparation method thereof - Google Patents
Hydrotreating catalyst and preparation method thereof Download PDFInfo
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- CN107297215A CN107297215A CN201610235219.9A CN201610235219A CN107297215A CN 107297215 A CN107297215 A CN 107297215A CN 201610235219 A CN201610235219 A CN 201610235219A CN 107297215 A CN107297215 A CN 107297215A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 148
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 22
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 19
- 238000009826 distribution Methods 0.000 claims abstract description 16
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 11
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 5
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 239000007864 aqueous solution Substances 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 17
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- 239000011148 porous material Substances 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 12
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 11
- 239000000243 solution Substances 0.000 claims description 11
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 239000011574 phosphorus Substances 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- -1 molybdate compound Chemical class 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000007524 organic acids Chemical class 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 5
- 235000015165 citric acid Nutrition 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 5
- 239000007791 liquid phase Substances 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- 230000002198 cosolvency Effects 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 4
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 4
- 150000002816 nickel compounds Chemical class 0.000 claims description 4
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 4
- 238000010521 absorption reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 235000011090 malic acid Nutrition 0.000 claims description 2
- 239000001630 malic acid Substances 0.000 claims description 2
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 2
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 31
- 238000011156 evaluation Methods 0.000 description 12
- 229910018104 Ni-P Inorganic materials 0.000 description 10
- 229910018536 Ni—P Inorganic materials 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 229910021417 amorphous silicon Inorganic materials 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000010792 warming Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000012512 characterization method Methods 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000008246 gaseous mixture Substances 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000007493 shaping process Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- CKQGJVKHBSPKST-UHFFFAOYSA-N [Ni].P#[Mo] Chemical compound [Ni].P#[Mo] CKQGJVKHBSPKST-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000000748 compression moulding Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000320 mechanical mixture Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004073 vulcanization Methods 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
- B01J27/19—Molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of hydrotreating catalyst and preparation method thereof, and the hydrotreating catalyst is using Mo and Ni as active metal component, and P is auxiliary agent, and carrier is amorphous silica-alumina；On the basis of the weight of catalyst, MoO3The content that content is 10%~25%, NiO is 2%~6%, and P content is 0.5%~2.5%, and surplus is carrier.A kind of preparation method of above-mentioned hydrotreating catalyst is also provided.Catalyst activity metal component distribution prepared by this method is more reasonable, and utilization rate is high, had both reduced the metal consumption of catalyst, the activity of catalyst is improved again.
Description
Technical field
The present invention relates to a kind of hydrotreating catalyst and preparation method thereof, catalyst and preparation method thereof is handled more particularly, to a kind of load hydrogenation.
Background technology
As sulfur content declines year by year in fuel oil for vehicles specification, hydrodesulfurization has become the main path that processing inferior raw material produces clean fuel oil.The activity of Hydrobon catalyst determines the economic benefit of whole hydrodesulfurization.The Hydrobon catalyst of high activity can produce the product of low-sulfur under conditions of mitigation, so as to extend service cycle and save operating cost.
Hydrobon catalyst generally uses vib and group VIII metal for active component, it is possible to add a variety of auxiliary agents to improve catalyst activity.At present, the method for preparing catalyst that countries in the world are generally used is exactly to use solution dipping method, i.e., active metal component is supported on carrier, then obtains corresponding catalyst by steps such as drying, roastings.Catalyst activity component prepared by this preparation method is distributed on the surfaces externally and internally of catalyst carrier, including on the inner surface in deep inside space.
CN1872962A discloses a kind of hydrotreating catalyst containing molecular sieve, the catalyst is using aluminum oxide and Y type molecular sieve as carrier, supported active metals component nickel, molybdenum and tungsten, i.e. first by boehmite and molecular sieve mechanical mixture, in step load active metal component, active component can be made dispersed on carrier, make catalyst that there is higher hydrodesulfurization activity.
CN1339563A discloses a kind of catalyst for hydrodesulfurizationfraction fraction oil, catalyst is with aluminum oxide, or silicon-containing alumina is carrier, using molybdenum nickel as active component, total immersion carrier is segmented using alkaline impregnation, making on catalyst Metal Distribution, evenly, the fraction oil hydrodesulfurizing activity of catalyst is significantly improved.
CN1289828A discloses a kind of catalyst for hydrorefining distillate oil, and catalyst is using aluminum oxide or silicon-containing alumina as carrier, using W, Mo, Ni as active component, adds phosphate builder.By using segmentation total immersion technology so that the Metal Distribution on catalyst is more uniform, and the activity of catalyst, particularly hydrodenitrogenationactivity activity are greatly improved.
These existing preparation methods, can make active component dispersed on carrier.But catalyst still has problems with：One is that active component utilization rate is not high, and the active component of catalyst granules deep inside is difficult to play due effect, and most of catalyst use metal as active component, wherein many active metal component prices are expensive.Two be that catalyst granules deep inside duct mass transfer is difficult, deposit substantial amounts of reactant or reaction product, and unmanageable side reaction occurs at high temperature, causes catalyst choice to reduce.
The content of the invention
In order to overcome weak point of the prior art, the invention provides load hydrogenation processing catalyst that a kind of Active components distribution is more reasonable, cost is low, catalyst activity is high and preparation method thereof.
The present invention provides a kind of hydrotreating catalyst, and the hydrotreating catalyst is using Mo and Ni as active metal component, and P is auxiliary agent, and carrier is amorphous silica-alumina；On the basis of the weight of catalyst, MoO3The content that content is 10%~25%, NiO is 2%~6%, and P content is 0.5%~2.5%, and surplus is carrier；The hydrotreating catalyst Active components distribution is as follows：The content that molybdenum oxide is distributed in the radius of catalyst 3/4 to catalyst external surface is 96.0wt%~99.0wt% of total content, and nickel oxide is in 96.0wt%~99.0wt% that the content of the radius of catalyst 3/4 to catalyst external surface is total content.
Hydrotreating catalyst of the present invention, specific nature is as follows：Specific surface area is 160~310m2/ g, preferably 180~290m2/g；Pore volume is 0.30~0.80mL/g, preferably 0.40~0.70mL/g；Average pore diameter is 5.0~11.0nm, preferably 6.0~10.0nm.
The present invention provides a kind of preparation method of hydrotreating catalyst, and the preparation method of the hydrotreating catalyst comprises the following steps：
（1）The cosolvency aqueous solution of nickeliferous, molybdenum, phosphorus simultaneously is prepared with molybdate compound, nickel compound containing, phosphorus-containing compound and water；
（2）Carrier and long chain alkane are added in autoclave, 1.0~6.0h is reacted at 300~450 DEG C；
（3）By step（2）In reacted catalyst carrier filter out, be dried at 30 DEG C~40 DEG C, until sample surfaces are without liquid phase, obtain catalyst precarsor A；
（4）By step（3）Obtained catalyst precarsor A is added in aqueous solutions of organic acids, is stood 3~20min, is then filtered, obtain catalyst precarsor B；
（5）By step（4）Obtained catalyst precarsor B adsorbs ammonia at 20 DEG C ~ 40 DEG C, obtains catalyst precarsor C；
（6）Catalyst precarsor C is added to step（1）In the nickeliferous of preparation, molybdenum, the cosolvency aqueous solution of phosphorus, stir to solution and be evaporated at 60 DEG C~90 DEG C；
（7）By step（6）Obtained solid sample after drying, calcination process, obtains catalyst again.
In preparation method of the present invention, step（1）Described in molybdate compound can be molybdenum oxide；The nickel compound containing can be basic nickel carbonate, and phosphorus-containing compound can be phosphoric acid.
In preparation method of the present invention, step（1）In, preparing for the aqueous solution containing Mo, Ni and P can be prepared by method commonly used in the art, wherein Mo（With MoO3Meter）Concentration be 0.05~0.52 g/mL, Ni（In terms of NiO）Concentration be 0.005~0.12 g/mL, P concentration is 0.005~0.05 g/mL.
In preparation method of the present invention, step（2）Described in amorphous silicon aluminium carrier can use commercially available product, can also be prepared by method well known in the art.Carrier can be molded using existing conventional molding techniques, such as extruded moulding, roller forming, compression molding etc., and shape can be bar shaped, spherical, sheet etc..In forming process, binding agent and shaping assistant can be added as needed, and binding agent typically uses small porous aluminum oxide.Shaping assistant such as peptizing agent, extrusion aid etc..
In preparation method of the present invention, step（2）Described in amorphous silica-alumina in silica weight content be 10%~40%.
In preparation method of the present invention, step（2）Described in long chain alkane be one or more in C10~C16 long chain alkanes, preferably one or more in n-decane, dodecane, hexadecane；The addition of long chain alkane and the mass ratio of carrier are 5~15.
In preparation method of the present invention, step（4）In, the organic acid is the one or more in citric acid, tartaric acid, malic acid.Described organic acid and the mass ratio of carrier are 0.5 ~ 5.0.
In preparation method of the present invention, step（5）In, by step（4）Obtained catalyst precarsor B absorption ammonias, adsorption time is generally the min of 5 min ~ 30.
In preparation method of the present invention, step（5）In, described ammonia can use pure ammonia, it would however also be possible to employ in the gaseous mixture containing ammonia, mixed gas in addition to ammonia, and other is the one or more in inert gas and nitrogen.
In preparation method of the present invention, step（7）Described in drying condition be 90~120 DEG C of dry 3.0~12.0h；Roasting condition is 400~600 DEG C of 2.0~6.0h of roasting.
In preparation method of the present invention, the one or more that can also be added in described carrier in molecular sieve, such as SBA-15, SBA-3, MCM-41, Y type, ZSM-5 etc., the weight content of molecular sieve in the carrier is below 20%, and generally 5%~15%.Molecular sieve kneading can be introduced in carrier forming process.
Compared with prior art, the load hydrogenation processing catalyst that a kind of active metal outer layer is distributed can be obtained by preparation method of the present invention.In the present invention, by carrying out the cracking reaction of long chain alkane to acid carrier, two aspect effects can be played：On the one hand the liquid alkane of generation is adsorbed on a catalyst support, the duct of carrier can effectively be blocked, carrier surface is by adsorbing ammonia simultaneously, carry out basic treatment, it can be interacted with the acid molybdenum nickel phosphorus aqueous solution, diffusion of the inhibitory activity metal into carrier, makes the active metal subsequently loaded be distributed on carrier surface；During another aspect cracking reaction, carrier surface produces a large amount of carbon distributions, can effectively prevent the strong interaction between metal component and carrier, it is to avoid active component formation Spinel, is conducive to the vulcanization of active component.Catalyst activity metal component distribution prepared by this method is more reasonable, and utilization rate is high, had both reduced the metal consumption of catalyst, the activity of catalyst is improved again.
Embodiment
Below by embodiment, the present invention is described further, and in the present invention, wt% is mass fraction.
Specific surface area, pore volume are measured using low temperature liquid nitrogen physisorphtion in the present invention, and the specific nitrogen absorption under low temperature instrument using Merck ＆ Co., Inc of U.S. ASAP2420 models is measured；Detailed process：A small amount of sample 3 ~ 4h of application of vacuum at 300 DEG C is taken, product is finally placed in liquid nitrogen cryogenics（-200℃）Under the conditions of carry out nitrogen suction-desorption test.Wherein surface area is obtained according to BET equations, and pore-size distribution is obtained according to BJH models.SEM（SEM）The SEM of the specific JSM-7500F types using the production of JEOL companies of Japan（SEM）, it is equipped with EDAX-EDS, accelerating potential：20Kv, operating distance：8mm, resolution ratio：1nm.
Embodiment 1
（1）
The preparation of the Mo-Ni-P aqueous solution：
By 7.0g phosphoric acid H3PO4（The wt% of concentration 85）It is dissolved in 80mL water, then adds 23.8g molybdenum trioxides and 8.8g basic nickel carbonates, it is 100mL to be warming up to 100 DEG C and be stirred at reflux constant volume after 2.0h, filtering, produces the Mo-Ni-P aqueous solution.Wherein MoO3Concentration be 0.23g/mL, NiO concentration is 0.046g/mL, and P concentration is 0.019g/mL.
（2）The preparation of catalyst：
By 79.3g amorphous silicon alumina supporters（Silica content 20wt%, pore volume is 0.78mL/g, and specific surface area is 320m2/ g, cylindrical bars, diameter 0.8mm）It is added to 550g n-decane solutions in autoclave, is warming up to 400 DEG C, is reacted 3h, after reaction terminates, catalyst filtration is come out, dried at 30 DEG C to carrier surface without liquid phase, obtain catalyst precarsor A；It is then added in the aqueous solution containing 100.0g citric acids, stands 5min, then filter, obtain catalyst precarsor B, 10v% NH is adsorbed at 30 DEG C3/ Ar gaseous mixture 10min, obtain catalyst precarsor C, measure the 64mL Mo-Ni-P aqueous solution and are added in catalyst precarsor C, stir to solution and be evaporated at 70 DEG C, and then gained solid sample is calcined 3.0h in 110 DEG C of dry 8.0h at 450 DEG C, and catalyst is made.Wherein MoO3Content is 15wt%, and NiO contents are 3.0 wt%, and P content is 1.2 wt%.The physico-chemical property of catalyst is shown in Table 1.
（3）Catalyst characterization：
Elementary analysis is carried out to catalyst by SEM, the distribution situation of activity over catalysts metal is listed in table 2.
（4）The evaluation of catalyst：
Evaluating catalyst is carried out on micro-reactor, and presulfurization is carried out to catalyst before activity rating.Evaluating catalyst condition is Hydrogen Vapor Pressure 6.0
MPa, volume space velocity 1.8h during liquid-1, hydrogen-oil ratio 500:1,360 DEG C of reaction temperature.Activity rating raw material oil nature is shown in Table 3.Activity evaluation is shown in Table 4.
Embodiment 2
（1）
The preparation of the Mo-Ni-P aqueous solution：
By 8.7g phosphoric acid H3PO4（The wt% of concentration 85）It is dissolved in 80mL water, then adds 30.3g molybdenum trioxides and 11.2g basic nickel carbonates, it is 100mL to be warming up to 100 DEG C and be stirred at reflux constant volume after 2.0h, filtering, produces the Mo-Ni-P aqueous solution.Wherein MoO3Concentration be 0.30g/mL, NiO concentration is 0.06g/mL, and P concentration is 0.023 g/mL.
（2）The preparation of catalyst：
By 75.2g amorphous silicon alumina supporters（Silica content 20wt%, pore volume is 0.78mL/g, and specific surface area is 320m2/ g, cylindrical bars, diameter 0.8mm）It is added to 550g n-decane solutions in autoclave, is warming up to 400 DEG C, is reacted 3h, after reaction terminates, catalyst filtration is come out, dried at 30 DEG C to carrier surface without liquid phase, obtain catalyst precarsor A；It is then added in the aqueous solution containing 100.0g citric acids, stands 5min, then filter, obtain catalyst precarsor B, 10v% NH is adsorbed at 30 DEG C3/ Ar gaseous mixture 10min, obtain catalyst precarsor C, measure the 60mL Mo-Ni-P aqueous solution and are added in catalyst precarsor C, stir to solution and be evaporated at 70 DEG C, and then gained solid sample is calcined 3.0h in 110 DEG C of dry 8.0h at 450 DEG C, and catalyst is made.Wherein MoO3Content is 18wt%, and NiO contents are 3.6 wt%, and P content is 1.4 wt%.The physico-chemical property of catalyst is shown in Table 1.
（3）Catalyst characterization：
Elementary analysis is carried out to catalyst by SEM, the distribution situation of activity over catalysts metal is listed in table 2.
（4）The evaluation of catalyst：
Evaluating catalyst be the same as Example 1, Activity evaluation is shown in Table 4.
Embodiment 3
（1）
The preparation of the Mo-Ni-P aqueous solution：
By 10.2g phosphoric acid H3PO4（The wt% of concentration 85）It is dissolved in 80mL water, then adds 34.8g molybdenum trioxides and 12.8g basic nickel carbonates, it is 100mL to be warming up to 100 DEG C and be stirred at reflux constant volume after 2.0h, filtering, produces the Mo-Ni-P aqueous solution.Wherein MoO3Concentration be 0.34
G/mL, NiO concentration are 0.069
G/mL, P concentration are 0.03
g/mL。
（2）The preparation of catalyst：
By 72.3g amorphous silicon alumina supporters（Silica content 20wt%, pore volume is 0.78mL/g, and specific surface area is 320m2/ g, cylindrical bars, diameter 0.8mm）It is added to 550g n-decane solutions in autoclave, is warming up to 400 DEG C, is reacted 3h, after reaction terminates, catalyst filtration is come out, dried at 30 DEG C to carrier surface without liquid phase, obtain catalyst precarsor A；It is then added in the aqueous solution containing 100.0g citric acids, stands 5min, then filter, obtain catalyst precarsor B, 10v% NH is adsorbed at 30 DEG C3/ Ar gaseous mixture 10min, obtain catalyst precarsor C, measure the 58mL Mo-Ni-P aqueous solution and are added in catalyst precarsor C, stir to solution and be evaporated at 70 DEG C, and then gained solid sample is calcined 3.0h in 110 DEG C of dry 8.0h at 450 DEG C, and catalyst is made.Wherein MoO3Content is 20wt%, and NiO contents are 4.0 wt%, and P content is 1.6 wt%.The physico-chemical property of catalyst is shown in Table 1.
（3）Catalyst characterization：
Elementary analysis is carried out to catalyst by SEM, the distribution situation of activity over catalysts metal is listed in table 2.
（4）The evaluation of catalyst：
Evaluating catalyst be the same as Example 1, Activity evaluation is shown in Table 4.
Embodiment 4
（1）The preparation of catalyst：
In embodiment 3, by amorphous silicon alumina supporter（Silica content 20wt%, pore volume is 0.78mL/g, and specific surface area is 320m2/ g, cylindrical bars, diameter 0.8mm）It is changed to silica content 30wt% amorphous silicon alumina supporter（Pore volume is 0.79mL/g, and specific surface area is 315m2/ g, cylindrical bars, diameter 0.8mm）, remaining be the same as Example 3, obtained catalyst, wherein MoO3Content is 20wt%, and NiO contents are 4.0 wt%, and P content is 1.6 wt%.The physico-chemical property of catalyst is shown in Table 1.
（2）Catalyst characterization：
Elementary analysis is carried out to catalyst by SEM, the distribution situation of activity over catalysts metal is listed in table 2.
（3）The evaluation of catalyst：
Evaluating catalyst be the same as Example 1, Activity evaluation is shown in Table 4.
Embodiment 5
（1）The preparation of catalyst：
In embodiment 3, n-decane solution is changed to hexadecane solution, catalyst, wherein MoO is made in remaining be the same as Example 33Content is 20wt%, and NiO contents are 4.0 wt%, and P content is 1.6 wt%.The physico-chemical property of catalyst is shown in Table 1.
（2）Catalyst characterization：
Elementary analysis is carried out to catalyst by SEM, the distribution situation of activity over catalysts metal is listed in table 2.
（3）The evaluation of catalyst：
Evaluating catalyst be the same as Example 1, Activity evaluation is shown in Table 4.
Comparative example 1
In embodiment 3, by 58mL
The Mo-Ni-P aqueous solution is diluted to 100mL, is then added to 72.3
G amorphous silicon alumina supporters（Silica content 20wt%, pore volume is 0.78mL/g, and specific surface area is 320m2/ g, cylindrical bars, diameter 0.8mm）In, stir to solution and be evaporated at 70 DEG C, by obtained solid in 110 DEG C of dry 8.0h, be then calcined 3.0h at 450 DEG C, catalyst is made.Wherein MoO3Content is 20wt%, and NiO contents are 4.0 wt%, and P content is 1.6 wt%.The physico-chemical property of catalyst is shown in Table 1.The distribution situation of activity over catalysts metal is listed in table 2.Evaluating catalyst be the same as Example 1, Activity evaluation is shown in Table 4.
The property of 1 each catalyst of table
The activity over catalysts metal MoO of table 23With NiO distribution situation
The raw material oil nature of table 3
The Activity evaluation of 4 each catalyst of table
Claims (15)
1. a kind of hydrotreating catalyst, the hydrotreating catalyst is using Mo and Ni as active metal component, and P is auxiliary agent, and carrier is amorphous silica-alumina；On the basis of the weight of catalyst, MoO3The content that content is 10%~25%, NiO is 2%~6%, and P content is 0.5%~2.5%, and surplus is carrier；The hydrotreating catalyst Active components distribution is as follows：The content that molybdenum oxide is distributed in the radius of catalyst 3/4 to catalyst external surface is 96.0wt%~99.0wt% of total content, and nickel oxide is in 96.0wt%~99.0wt% that the content of the radius of catalyst 3/4 to catalyst external surface is total content.
2. according to the hydrotreating catalyst described in claim 1, it is characterised in that：The hydrotreating catalyst property is as follows：Specific surface area is 160~310m2/ g, pore volume is 0.30~0.80mL/g, and average pore diameter is 5.0~11.0nm.
3. according to the hydrotreating catalyst described in claim 1, it is characterised in that：The hydrotreating catalyst property is as follows：Specific surface area is 180~290m2/ g, pore volume is 0.40~0.70mL/g, and average pore diameter is 6.0~10.0nm.
4. the preparation method of the hydrotreating catalyst in claim 1-3 described in any claim, the preparation method comprises the following steps：
（1）The cosolvency aqueous solution of nickeliferous, molybdenum, phosphorus simultaneously is prepared with molybdate compound, nickel compound containing, phosphorus-containing compound and water；
（2）Carrier and long chain alkane are added in autoclave, 1.0~6.0h is reacted at 300~450 DEG C；
（3）By step（2）In reacted catalyst carrier filter out, be dried at 30 DEG C~40 DEG C, until sample surfaces are without liquid phase, obtain catalyst precarsor A；
（4）By step（3）Obtained catalyst precarsor A is added in aqueous solutions of organic acids, is stood 3~20min, is then filtered, obtain catalyst precarsor B；
（5）By step（4）Obtained catalyst precarsor B adsorbs ammonia at 20 DEG C ~ 40 DEG C, obtains catalyst precarsor C；
（6）Catalyst precarsor C is added to step（1）In the nickeliferous of preparation, molybdenum, the cosolvency aqueous solution of phosphorus, stir to solution and be evaporated at 60 DEG C~90 DEG C；
（7）By step（6）Obtained solid sample after drying, calcination process, obtains catalyst again.
5. in accordance with the method for claim 4, it is characterised in that：Step（1）In Mo in the aqueous solution containing Mo, Ni and P（With MoO3Meter）Concentration be 0.05~0.52g/mL, Ni（In terms of NiO）Concentration be 0.005~0.12g/mL, P concentration is 0.005~0.05g/mL.
6. in accordance with the method for claim 4, it is characterised in that：Step（1）Described in molybdate compound be molybdenum oxide；The nickel compound containing is basic nickel carbonate, and phosphorus-containing compound is phosphoric acid.
7. in accordance with the method for claim 4, it is characterised in that：Step（2）Described in amorphous silica-alumina in silica weight content be 10%~40%.
8. in accordance with the method for claim 4, it is characterised in that：Step（2）Described in long chain alkane be C10~C16 long chain alkanes in one or more.
9. in accordance with the method for claim 8, it is characterised in that：Step（2）Described in long chain alkane be n-decane, dodecane, hexadecane in one or more.
10. in accordance with the method for claim 4, it is characterised in that：Step（2）The mass ratio of middle long chain alkane and carrier is 5~15.
11. in accordance with the method for claim 4, it is characterised in that：Step（4）Described in organic acid be citric acid, tartaric acid, malic acid in one or more.
12. in accordance with the method for claim 4, it is characterised in that：Step（4）Described in organic acid and carrier mass ratio be 0.5 ~ 5.0.
13. in accordance with the method for claim 4, it is characterised in that：Step（5）The adsorption time of middle catalyst precarsor B absorption ammonia is 5~30 min.
14. in accordance with the method for claim 4, it is characterised in that：Step（5）In, described ammonia uses pure ammonia, or uses in the mixed gas containing ammonia, mixed gas in addition to ammonia, other one or more in inert gas or nitrogen.
15. in accordance with the method for claim 4, it is characterised in that：Step（7）Described in drying condition be 90~120 DEG C of dry 3.0~12.0h；Roasting condition is 400~600 DEG C of 2.0~6.0h of roasting.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926074A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738889A (en) * | 2003-01-16 | 2006-02-22 | 道达尔菲纳埃尔弗法国公司 | Hydrorefining catalyst, production and use thereof in a hydrocarbon refining method |
| CN101407731A (en) * | 2007-10-10 | 2009-04-15 | 中国石油天然气股份有限公司 | Hydrotreating process for producing low-sulfur oil |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
| CN103071526A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof, and hydroisomerizing method |
| CN103285940A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN103801313A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Distillate hydrotreating catalyst and preparation method thereof |
| CN104293381A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Method for improving property of heavy oil hydrogenation product |
| CN103191753B (en) * | 2012-01-06 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst |
-
2016
- 2016-04-16 CN CN201610235219.9A patent/CN107297215B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1738889A (en) * | 2003-01-16 | 2006-02-22 | 道达尔菲纳埃尔弗法国公司 | Hydrorefining catalyst, production and use thereof in a hydrocarbon refining method |
| CN101407731A (en) * | 2007-10-10 | 2009-04-15 | 中国石油天然气股份有限公司 | Hydrotreating process for producing low-sulfur oil |
| CN101927176A (en) * | 2009-06-26 | 2010-12-29 | 中国石油天然气股份有限公司 | Hydrogenation catalyst showing gradient increase and distribution of concentration of active metal and acid additive and preparation method thereof |
| CN103071526A (en) * | 2011-10-25 | 2013-05-01 | 中国石油化工股份有限公司 | Catalyst and preparation method and application thereof, and hydroisomerizing method |
| CN103191753B (en) * | 2012-01-06 | 2015-06-17 | 中国石油化工股份有限公司 | Preparation method of hydrotreatment catalyst |
| CN103285940A (en) * | 2012-03-02 | 2013-09-11 | 中国石油化工股份有限公司 | Catalyst for catalyzing hydrogenation, preparation method and application thereof, and hydrofining method |
| CN103801313A (en) * | 2012-11-08 | 2014-05-21 | 中国石油化工股份有限公司 | Distillate hydrotreating catalyst and preparation method thereof |
| CN104293381A (en) * | 2013-07-18 | 2015-01-21 | 中国石油化工股份有限公司 | Method for improving property of heavy oil hydrogenation product |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109926074A (en) * | 2017-12-15 | 2019-06-25 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
| CN109926074B (en) * | 2017-12-15 | 2021-08-06 | 中国石油化工股份有限公司 | Hydrocracking catalyst and preparation method thereof |
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