CN105435831A - Microspherical catalyst as well as preparation method and application thereof - Google Patents
Microspherical catalyst as well as preparation method and application thereof Download PDFInfo
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- CN105435831A CN105435831A CN201510770123.8A CN201510770123A CN105435831A CN 105435831 A CN105435831 A CN 105435831A CN 201510770123 A CN201510770123 A CN 201510770123A CN 105435831 A CN105435831 A CN 105435831A
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- preparation
- catalyst
- zeolite
- microspherical
- microspherical catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 86
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 32
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000002184 metal Substances 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 18
- 238000005470 impregnation Methods 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000002002 slurry Substances 0.000 claims abstract description 13
- 239000000295 fuel oil Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 238000005245 sintering Methods 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 238000007598 dipping method Methods 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 12
- 238000004513 sizing Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 8
- 238000007667 floating Methods 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 238000005507 spraying Methods 0.000 claims description 5
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 3
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims 4
- 235000010344 sodium nitrate Nutrition 0.000 claims 2
- 239000004317 sodium nitrate Substances 0.000 claims 2
- 239000004005 microsphere Substances 0.000 abstract description 16
- 239000000571 coke Substances 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000004517 catalytic hydrocracking Methods 0.000 abstract 1
- 238000006392 deoxygenation reaction Methods 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000000725 suspension Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 150000001723 carbon free-radicals Chemical class 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000004939 coking Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000013467 fragmentation Methods 0.000 description 2
- 238000006062 fragmentation reaction Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000005987 sulfurization reaction Methods 0.000 description 2
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002605 large molecules Chemical class 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 125000001741 organic sulfur group Chemical group 0.000 description 1
- 238000005325 percolation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 150000004032 porphyrins Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- -1 silicon (aluminium) oxygen Chemical compound 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 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
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- B01J35/51—
-
- 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
- C10G45/12—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 crystalline alumino-silicates, e.g. molecular sieves
-
- 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
- C10G45/14—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 with moving solid particles
- C10G45/16—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 with moving solid particles suspended in the oil, e.g. slurries
-
- 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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
-
- 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
- C10G2300/205—Metal content
-
- 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
- C10G2300/70—Catalyst aspects
Abstract
The invention discloses a microspherical catalyst as well as a preparation method and an application thereof. The preparation method comprises the following steps: 1) mixing and stirring zeolite powder and ethyl alcohol so as to obtain slurry; 2) sequentially drying, forming, setting and sintering the slurry obtained in the step 1), thereby obtaining zeolite catalyst microspheres; and 3) impregnating the zeolite catalyst microspheres obtained in the step 2) into a metal impregnation liquid, and then drying the impregnated zeolite catalyst microspheres so as to obtain the microspherical catalyst. The preparation method is simple and convenient to operate; the prepared microspherical catalyst has high cracking performance, high desulfuration, denitrification and deoxygenation performance, high hydrogenation performance, high demetalization performance and high coke adsorption performance, and can be widely applied to heavy oil slurry bed hydrocracking process.
Description
Technical field
The invention belongs to field of catalyst preparation in heavy oil floating bed hydrogenation process, be specifically related to a kind of microspherical catalyst and preparation method thereof and application, particularly a kind of microspherical catalyst for heavy oil floating bed hydrogenation process and preparation method thereof and application.
Background technology
Along with the fast development of China's economy, petroleum consumption increases rapidly.The general layout of China's energy is oil starvation, weak breath, rich coal, needs oil product and combustion gas from national energy strategy.Therefore, light materialization of heavy oil more and more receives the concern of people, and wherein the suspension bed technique of heavy oil is one of the most effective technique of heavy oil lighting, and requisite in the process of heavy oil lighting is the use of various hydrogenation catalyst.
Common residual oil hydrocatalyst take aluminium oxide as carrier, with Mo/W and Ni/Co for main active component.It take aluminium oxide as the residual oil hydrocatalyst of carrier that patent CN102240555A discloses a kind of, the content of described catalyst n i/Co is 0.1-4wt%, the content of Mo/W is 1-5wt%, described alumina support is obtained through shaping, roasting by the boehmite comprising at least one 1.1≤n≤2.5, this catalyst functional, demetallization per is higher.But, this catalyst carrier due to pore size less than normal, distribute wide, open not enough, cause that pore passage structure is not good, specific area is less, not only bad for absorption carbon residue, and oxygen content is higher in unstripped gas, if the piece-rate system after refining can not be discharged in time have dysgenic water to hydrogenation catalyst, hydrone can cause the activity decrease of catalyst with the temporary absorption of catalytic center, in addition, exist and interact between the active metal component of load and aluminium, have impact on the sulfuration of metal component, limit the raising of catalyst activity.
Patent CN102049252A discloses the preparation method that a kind of active carbon is the suspension bed residual oil hydrogenation catalyst of carrier.Porous active carbon is as the carrier of this catalyst, improve the specific area of carrier, improve the load capacity of active component to a certain extent, this catalyst activity increases, but be enriched vanadium in residual oil, the metallic elements such as nickel, these metallic elements exist with the form of macromolecular porphyrin, the large molecule organic ligand containing metallic element when making residual oil carry out catalytic cracking is again easy to the microcellular structure blocked on carrier and causes the poisoning of catalyst, in addition, in the catalytic hydrogenation of residual oil, required hydrogen is added by outside, and form H under the effect of hydrogenation sites on a catalyst, residual oil flows through in the process of catalyst, cracking center on catalyst is first by short hydrocarbon that generate longer-chain hydrocarbons cracking is containing carbon radicals, under the environment of HTHP, the short hydrocarbon containing carbon radicals being in catalyst duct inside configuration cannot be reacted with the H of outside in a short period of time, the direct coking of carbon radicals is made to form collection charcoal on a catalyst, catalyst activity is caused to reduce.
Summary of the invention
The object of the invention is to the defect easily blocked for catalyst aperture in suspension bed hydrogenation process in solution prior art, specific area is less, absorption coke ability is weak, and then provide a kind of microspherical catalyst and preparation method thereof.
For this reason, the technical solution used in the present invention is,
A preparation method for microspherical catalyst, comprises the steps:
1) zeolite and ethanol mixing are carried out stir process, obtain slurry;
2) to step 1) in the slurry that obtains carry out drying, shaping and sizing successively, obtain zeolite catalyst microballoon;
3) by step 2) in zeolite catalyst microballoon impregnated in metal impregnation liquid, then to dipping after catalyst microspheres dry, obtain described microspherical catalyst.
In above-mentioned preparation method, step 1) in, the mass ratio of described zeolite and described ethanol is 1:(1 ~ 3).
The temperature of described stir process is 20 ~ 50 DEG C, and the time is 5 ~ 10h.
Described zeolite is the manosil AS mineral of a kind of moisture alkali metal or alkaline-earth metal.10 ~ 30nm is preferentially chosen in the aperture of selected zeolite, and pore volume preferentially chooses 0.2 ~ 1.0cm
3/ g.Zeolite race mineral are common in effusive rock, particularly in basaltic hole, also see in sedimentary rock, metamorphic rock and hydrothermal deposit and some hot spring deposition in modern age.Jinyun county of Zhejiang Province is the area that zeolite reserves that current China has found within the border are the highest.The general chemical formula of zeolite is: AmBpO
2pnH
2o, structural formula is A (x/q) [(AlO
2) x (SiO2) y] and n (H2O) wherein, A is the cations such as Ca, Na, K, Ba, Sr; B is Al and Si; P is cationic compound valency; M is cation number; N is water molecule number; X is Al atomicity; Y is Si atomicity; (y/x) usually between 1 ~ 5; (x+y) be tetrahedral number in unit cell.Zeolite is mainly formed at the low temperature hot liquid stage, is common in effusive rock pore, also see hydrothermal deposit and modern age hot spring deposition in.Zeolite can borrow the percolation of water, and to carry out cationic exchange, the cobalt in its composition, calcium ion can exchange with the potassium in the aqueous solution, magnesium plasma, industrial in order to softening of water.The crystal structure of zeolite is linked to be three-dimensional screen work by silicon (aluminium) oxygen tetrahedron, has hole of all sizes and passage, have very large opening in screen work.Alkali metal or alkaline-earth metal ions and hydrone are distributed in hole and passage, more weak with contacting of screen work.Different ion-exchange is very little on zeolite structured impact, but the character of zeolite is changed.The cavity that varies in size existed in lattice, can draw or filter the molecule of other materials varied in size.Natural zeolite is carried out fragmentation (conventional crumbling method can be selected to carry out repeatedly formula fragmentation alone or in combination), make the particle diameter of described zeolite powder be less than 1 μm.
In above-mentioned preparation method, step 2) in, described drying is specially spraying dry; Described spray-dired condition is as follows: temperature is 50 ~ 75 DEG C, and the time is 5 ~ 10h.
The condition of described sizing is as follows: pressurize 3 ~ 5min under 150 ~ 300MPa.
Described shaping and described sizing specifically can adopt ball press to operate.
After described sizing, before described dipping, also comprise the step that the product after to described sizing carries out degumming process; Described degumming process specifically can come unstuck 6 ~ 10h at 1000 ~ 1200 DEG C; Described degumming process specifically can carry out in vacuum degumming stove.
In above-mentioned preparation method, step 3) in, described metal impregnation liquid is the mixed aqueous solution of ferric nitrate, nickel nitrate and cobalt nitrate.
In described metal impregnation liquid, the gross mass mark of ferric nitrate, nickel nitrate and cobalt nitrate is (20-60) %.
Further, in described metal impregnation liquid, the mass ratio of Fe, Ni, Na is (2-5): 1:(1-5).
Described dipping specifically can adopt equi-volume impregnating, and the time of described dipping is 1-3h.
The temperature of described oven dry is (80-150) DEG C (being specially 110 DEG C), and the time is 2-4h.
The preparation-obtained microspherical catalyst of the present invention also belongs to protection scope of the present invention.
The size of described microspherical catalyst specifically can be 1 ~ 1000 μm.
In addition, the application of the preparation-obtained microspherical catalyst of the present invention in floating bed hydrogenation process also belongs to protection scope of the present invention.
The preparation-obtained microspherical catalyst of the present invention can be used in heavy oil floating bed hydrogenation process, as the carrier of catalytic carrier, absorption coke, has excellent hydrogenation activity, cracking activity, wear resistance and coke adsorption capacity.
Compared with prior art, tool of the present invention has the following advantages:
1) preparation method of microspherical catalyst provided by the present invention, have employed cheap zeolite, prepared microspherical catalyst is made to have a large amount of acid centres, and these acid centres have very strong cracking function to oil product, can by macromolecular oil product (such as wax oil, colloid, asphalitine component) optionally cracking become micromolecular oil product (such as diesel oil and naphtha component), when making final microspherical catalyst carry out hydrocrack to heavy oil, improve tar light oil yield;
Moreover, by selecting zeolite, preparation-obtained microspherical catalyst is had, and pore size is large, quantity is many, size uniformity and the large advantage of coke adsorbance, is applicable to very much the coke generated in the reaction of absorption floating bed hydrogenation, avoids, in wall of reactor and pipeline, coking phenomenon occurs; Solve the defect that catalyst aperture in suspension bed hydrogenation process easily blocks, specific area is less and absorption coke ability is weak;
By flooding in metal impregnation liquid, make load iron on preparation-obtained microspherical catalyst, nickel, these active metals of cobalt.Iron, nickel and cobalt can provide activated centre for oil product generation hydrogenation reaction, the organic nitrogen in heavy oil, organic sulfur, organic oxygen can be converted into NH
3, H
2s, H
2o, also contributes to the carrying out carrying out the reaction such as olefin saturated, aromatic saturation simultaneously;
Meanwhile, prepared microspherical catalyst has very high extrusion rate for metal component entrained in raw material heavy oil, can reduce the probability of the inactivation of catalyst coking in follow-up fixed bed hydrogenation operation.
2) by the size controlling of zeolite powder when being less than 1 μm, be conducive to the carrying out of follow-up work.Because raw material is more tiny, be more conducive to forming evenly good institutional framework and hole dimension.
3) the preparation-obtained microspherical catalyst of the present invention is few relative to the adding proportion of feedstock oil, is only the 0.5%-3% of the mass fraction of feedstock oil, but the specific area of catalyst is equivalent to more than 100,000,000 times of floating bed hydrogenation reactor internal surface area;
Meanwhile, preparation-obtained microspherical catalyst granularity can adjust according to the size of suspended-bed reactor, can as the regulating measure of the operating parameter of the keys such as the gas holdup in suspended-bed reactor, catalyst inventory.
4) the simple convenient operation of preparation method of the present invention, is convenient to extensive preparation.
Detailed description of the invention
Embodiment 1, prepare microspherical catalyst:
1) zeolite powder of 1000g being crushed to particle diameter is 0.4 μm, then adds the ethanol of 1000g wherein respectively, fully mixes, and stir 10h at 30 DEG C, obtain slurry;
2) to step 1) in slurry carry out spraying dry, spray-dired temperature is 50 DEG C, and the time is 5h; Then utilize ball press to be shaped to catalyst microspheres, under 200MPa, suppress 5min afterwards and shape; Again the catalyst microspheres of sizing is placed in vacuum degumming stove to come unstuck, the temperature of coming unstuck is 1200 DEG C, and the time is 10h;
3) by Fe (NO
3)
39H
2o, Ni (NO
3)
26H
2o and Co (NO
3)
2obtained metal impregnation liquid soluble in water, gross mass mark is 30%, makes the mass ratio of Fe, Ni and Na in described metal impregnation liquid be 8:2:3; Adopt equi-volume impregnating again by step 2) in catalyst microspheres impregnated in 1h in described metal impregnation liquid, by dipping after catalyst microspheres in 110 DEG C dry 2h, obtain microspherical catalyst.
Embodiment 2, prepare microspherical catalyst:
1) zeolite powder of 1000g being crushed to particle diameter is 0.4 μm, then adds the ethanol of 1500g wherein respectively, fully mixes, and stir 8h at 40 DEG C, obtain slurry;
2) to step 1) in slurry carry out spraying dry, spray-dired temperature is 60 DEG C, and the time is 8h; Then utilize ball press to be shaped to catalyst microspheres, under 300MPa, suppress 5min afterwards and shape; Again the catalyst microspheres of sizing is placed in vacuum degumming stove to come unstuck, the temperature of coming unstuck is 1000 DEG C, and the time is 6h;
3) by Fe (NO
3)
39H
2o, Ni (NO
3)
26H
2o and Co (NO
3)
2obtained metal impregnation liquid soluble in water, gross mass mark is 20%, makes the mass ratio of Fe, Ni and Na in described metal impregnation liquid be 2:1:1; Adopt equi-volume impregnating again by step 2) in catalyst microspheres impregnated in 2h in described metal impregnation liquid, by dipping after catalyst microspheres in 90 DEG C dry 4h, obtain microspherical catalyst.
Embodiment 3, prepare microspherical catalyst:
1) zeolite powder of 1000g being crushed to particle diameter is 0.4 μm, then adds the ethanol of 3000g wherein respectively, fully mixes, and stir 5h at 50 DEG C, obtain slurry;
2) to step 1) in slurry carry out spraying dry, spray-dired temperature is 75 DEG C, and the time is 10h; Then utilize ball press to be shaped to catalyst microspheres, under 150MPa, suppress 5min afterwards and shape; Again the catalyst microspheres of sizing is placed in vacuum degumming stove to come unstuck, the temperature of coming unstuck is 1100 DEG C, and the time is 8h;
3) by Fe (NO
3)
39H
2o, Ni (NO
3)
26H
2o and Co (NO
3)
2obtained metal impregnation liquid soluble in water, gross mass mark is 60%, makes the mass ratio of Fe, Ni and Na in described metal impregnation liquid be 5:1:5; Adopt equi-volume impregnating again by step 2) in catalyst microspheres impregnated in 3h in described metal impregnation liquid, by dipping after catalyst microspheres in 130 DEG C dry 3h, obtain microspherical catalyst.
Comparative example 1, catalyst prepared by Commercial active carbon:
Taking 100g granularity is 280 orders, and BET specific surface area is 985m
2the merchandise active carbon of/g, as catalyst carrier, adopts equi-volume impregnating dipping 66.4gCoSO
47H
2o and 14.5g (NH
4)
6mo
7o
244H
2o is on 100g Commercial active carbon, and after dipping, dry 6h at 120 DEG C, then through ball milling 12h, obtaining particle diameter is 1-7 μm of catalyst.
The performance evaluation of evaluation Example 1, microspherical catalyst:
The specific surface of microspherical catalyst and pore structure are tested on the ASAP2020 instrument of Micrometrics company of the U.S.; Specific surface calculates according to Berrett-Emmett-Teller (BET) method; Pore volume and pore-size distribution prop up according to desorption and calculate according to Berret-Joyner-Halenda (BJH) model.
The performance data of table 1, microspherical catalyst
| Numbering | Specific area | Average pore size | Pore volume (cm 3/g) | Mesopore and macropore |
| (m 2/g) | (nm) | Rate (%) | ||
| Embodiment 1 | 400 | 28 | 0.40 | 50 |
| Embodiment 2 | 520 | 31 | 0.51 | 55 |
| Embodiment 3 | 600 | 45 | 0.85 | 62 |
| Blue carbon raw material | 128 | 13 | 0.33 | 28 |
| Merchandise active carbon | 985 | 8 | 0.28 | 26 |
The applicating evaluating of application examples 1, microspherical catalyst:
Respectively by the finished catalyst that embodiment 1-3 (numbering F1-F3) and comparative example 1 (numbering F4) prepare, test in suspension bed residual oil hydrogenation system.Technical process is as follows: in autoclave reaction system, and residual oil raw material, appropriate microspherical catalyst join in still together with vulcanizing agent.Pass into hydrogen, carry out sulfuration and reaction at a certain temperature, finally isolate gaseous product and product liquid, carry out analysis and calculation respectively, draw experimental result.
According to following formulae discovery bottoms conversion and distillate yield, the evaluation index as reaction effect:
Constituent mass (containing gas)/feedstock oil quality × 100% below bottoms conversion=520 DEG C
Liquid component quality/feedstock oil quality × 100% below distillate yield=520 DEG C
Metal removal rate=(1-generates the tenor in the tenor/raw material in oil) × 100%
Detailed step is as follows: take decompression residuum as reaction raw materials, be in 500ml autoclave still, add 150.0g feedstock oil and 800 μ g/g microspherical catalysts to volume, vulcanizing agent is Sublimated Sulphur powder, addition is 0.08g, first with hydrogen, air in still is fully replaced under room temperature, then 5.0MPa is pressurized to, curing temperature is 320 DEG C, cure time 60min, reaction temperature is 420 DEG C, when reaching reaction temperature, reaction time continues 60min, after reaction terminates, treat that temperature is down to room temperature, collect gas with airbag to analyze, solid residue is separated with product liquid and weighs, calculate the conversion ratio of boiling point cut below 520 DEG C.Concrete reaction result is in table 1.
Table 2, residual oil hydrocatalyst performance data
Obviously, above-described embodiment is only for clearly example being described, and the restriction not to embodiment.For those of ordinary skill in the field, can also make other changes in different forms on the basis of the above description.Here exhaustive without the need to also giving all embodiments.And thus the apparent change of extending out or variation be still among the protection domain of the invention.
Claims (10)
1. a preparation method for microspherical catalyst, comprises the steps:
1) zeolite powder and ethanol mixing are carried out stir process, obtain slurry;
2) to step 2) in the slurry that obtains carry out drying, shaping and sizing successively, obtain zeolite catalyst microballoon;
3) by step 2) in zeolite catalyst microballoon impregnated in metal impregnation liquid, then to dipping after zeolite catalyst microballoon dry, obtain described microspherical catalyst.
2. preparation method as claimed in claim 1, is characterized in that: step 1) in, the mass ratio of described zeolite powder and described ethanol is 1:(1 ~ 3);
The temperature of described stir process is 20 ~ 50 DEG C, and the time is 5 ~ 10h.
3. preparation method as claimed in claim 1 or 2, is characterized in that: step 1) in, the particle diameter < of described zeolite powder 1 μm.
4. the preparation method according to any one of claim 1-3, is characterized in that: step 2) in, described drying is spraying dry;
Described spray-dired condition is specific as follows: temperature is 50 ~ 75 DEG C, and the time is 5 ~ 10h.
5. the preparation method according to any one of claim 1-4, is characterized in that: step 2) in, the condition of described sizing is as follows: pressurize 3 ~ 5min under 150 ~ 300MPa;
After described sizing, before described sintering, also comprise the step that the product after to described sizing carries out degumming process;
Described degumming process specifically comes unstuck 6 ~ 10h at 1000 ~ 1200 DEG C;
Described degumming process specifically carries out in vacuum degumming stove.
6. the preparation method according to any one of claim 1-5, it is characterized in that: step 3) in, described metal impregnation liquid is the mixed aqueous solution of ferric nitrate, nickel nitrate and sodium nitrate, and wherein the gross mass mark of ferric nitrate, nickel nitrate and sodium nitrate is (20-60) %.
7. the preparation method as described in claim 6, is characterized in that: step 3) in, in described metal impregnation liquid, the mass ratio of Fe, Ni, Na is (2-5): 1:(1-5).
8. the preparation method according to any one of claim 1-7, is characterized in that: step 3) in, described dipping specifically can adopt equi-volume impregnating;
The time of described dipping is 1-3h;
The temperature of described oven dry is 80-150 DEG C, and the time is 2-4h.
9. the microspherical catalyst that the preparation method according to any one of claim 1-8 obtains.
10. the application of microspherical catalyst according to claim 9 in heavy oil floating bed hydrogenation process.
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| CN110624548A (en) * | 2019-09-26 | 2019-12-31 | 中国矿业大学(北京) | Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil |
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