CN105435831B - A kind of microspherical catalyst and preparation method and application - Google Patents
A kind of microspherical catalyst and preparation method and application Download PDFInfo
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- CN105435831B CN105435831B CN201510770123.8A CN201510770123A CN105435831B CN 105435831 B CN105435831 B CN 105435831B CN 201510770123 A CN201510770123 A CN 201510770123A CN 105435831 B CN105435831 B CN 105435831B
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- zeolite
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- 239000003054 catalyst Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 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 27
- 239000002184 metal Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 19
- 238000005470 impregnation Methods 0.000 claims abstract description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000007598 dipping method Methods 0.000 claims abstract description 13
- 239000000295 fuel oil Substances 0.000 claims abstract description 12
- 239000002002 slurry Substances 0.000 claims abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 10
- 238000007667 floating Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 230000008569 process Effects 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004513 sizing Methods 0.000 claims description 8
- 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 7
- 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 6
- 239000002245 particle Substances 0.000 claims description 6
- 238000001694 spray drying Methods 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000002386 leaching Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000004005 microsphere Substances 0.000 abstract description 14
- 239000000571 coke Substances 0.000 abstract description 7
- 238000005336 cracking Methods 0.000 abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 26
- 238000006243 chemical reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000011148 porous material Substances 0.000 description 8
- 239000002994 raw material Substances 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000011435 rock Substances 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001723 carbon free-radicals Chemical class 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000008859 change Effects 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
- 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
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 2
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 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
- 239000003610 charcoal Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 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
- 238000009826 distribution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 235000019580 granularity Nutrition 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011707 mineral Substances 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
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-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
- -1 Silicon (aluminium) oxygen Chemical compound 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 210000004556 brain Anatomy 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
- 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
- 239000003245 coal Substances 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 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
- 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
- 230000007423 decrease Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000002283 diesel fuel Substances 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 125000001477 organic nitrogen 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
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 150000003384 small molecules Chemical class 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
-
- 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
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of microspherical catalyst and preparation method and application.The preparation method includes the following steps：1) zeolite powder and ethanol are mixed and are stirred, obtain slurry；2) slurry obtained in step 2) is dried, be molded, shaped and sintered successively, obtain zeolite catalyst microballoon；3) the zeolite catalyst microballoon in step 2) is impregnated in metal impregnation liquid, then the zeolite catalyst microballoon after dipping is dried, obtain the microspherical catalyst.The preparation method is simply easy to operation, and preparation-obtained catalyst microspheres have high cracking performance, desulfurization, denitrogenation, deoxy performance, and high Hydrogenation, demetalization performance, adsorbs coke property, can be widely used in during heavy oil floating bed hydrogenation.
Description
Technical field
The invention belongs to field of catalyst preparation during heavy oil floating bed hydrogenation, and in particular to a kind of microspherical catalyst and
Its preparation method with application, more particularly to a kind of microspherical catalyst for heavy oil floating bed hydrogenation process and preparation method thereof with
Using.
Background technology
With the fast development of China's economy, petroleum consumption increases rapidly.The general layout of China's energy is oil starvation, few gas,
Rich coal, needs oil product and combustion gas from national energy strategy.Therefore, light materialization of heavy oil has been to be concerned by more and more people, its
The suspension bed process of middle heavy oil is one of most effective technique of heavy oil lighting, essential during heavy oil lighting
It is the use of various hydrogenation catalysts.
Common residual oil hydrocatalyst is using aluminium oxide as carrier, using Mo/W and Ni/Co as main active component.Patent
CN102240555A discloses a kind of residual oil hydrocatalyst using aluminium oxide as carrier, and the content of the catalyst n i/Co is
The content of 0.1-4wt%, Mo/W are 1-5wt%, and the alumina support is by including the thin water of plan of at least one 1.1≤n≤2.5
Aluminium stone is obtained through being molded, roasting, the catalyst it is functional, demetallization per is higher.However, the catalyst carrier is due to duct
Size is less than normal, and distribution is wide, open deficiency, causes that pore passage structure is bad, specific surface area is smaller, residual not only bad for adsorbing
Charcoal, and oxygen content is higher in unstripped gas, if the piece-rate system after refined cannot discharge in time has hydrogenation catalyst bad shadow
Loud water, hydrone can with catalytic center it is temporary absorption and cause catalyst activity decline, in addition, load active metal
There is interaction between component and aluminium, have impact on the vulcanization of metal component, limit the raising of catalyst activity.
Patent CN102049252A discloses a kind of preparation side for the suspension bed residual oil hydrogenation catalyst that activated carbon is carrier
Method.Carrier of the porous activated carbon as the catalyst, improves the specific surface area of carrier, improves work to a certain extent
The load capacity of property component, which increases, but the metallic elements such as vanadium, nickel are enriched in residual oil, these metals
Element exists in the form of the porphyrin of macromolecular so that the macromolecular that residual oil carries out containing metallic element during catalytic cracking again is organic
The microcellular structure that ligand is easy to block on carrier causes the poisoning of catalyst, in addition, in the catalytic hydrogenation of residual oil, institute
The hydrogen needed is added by outside, and forms H under the action of hydrogenation sites on a catalyst, and residual oil flows through the mistake of catalyst
Cheng Zhong, cracking center on catalyst is the short hydrocarbon containing carbon radicals first by long-chain cracking hydrocarbon, in high temperature and pressure
Under environment, the short hydrocarbon containing carbon radicals in catalyst duct inside configuration in a short period of time can not be with outside
H reacts so that the direct coking of carbon radicals forms collection charcoal on a catalyst, causes catalyst activity to reduce.
The content of the invention
It is an object of the invention to solve easily to block for catalyst aperture in suspension bed hydrogenation process in the prior art, compare
The defects of surface area is smaller, absorption coke ability is weak, and then provide a kind of microspherical catalyst and preparation method thereof.
For this reason, the technical solution adopted by the present invention is,
A kind of preparation method of microspherical catalyst, includes the following steps：
1) zeolite and ethanol are mixed and are stirred, obtain slurry；
2) slurry obtained in step 1) is dried, be molded and shaped successively, obtain zeolite catalyst microballoon；
3) the zeolite catalyst microballoon in step 2) is impregnated in metal impregnation liquid, then to the catalyst microspheres after dipping
Dried, obtain the microspherical catalyst.
In above-mentioned preparation method, in step 1), the mass ratio of the zeolite and the ethanol is 1：(1~3).
The temperature of the stir process is 20~50 DEG C, and the time is 5~10h.
The zeolite is a kind of manosil AS mineral of aqueous alkali or alkaline earth metal.Preferentially select in the aperture of selected zeolite
10~30nm is taken, pore volume preferentially chooses 0.2~1.0cm3/g.Zeolite race mineral are common in effusive rock, particularly basaltic hole
In gap, also see in sedimentary rock, metamorphic rock and hydrothermal deposit and some modern age hot springs deposition.Jinyun county of Zhejiang Province is current China
The highest area of zeolite reserves having found within the border.The general chemical formula of zeolite is：AmBpO2p·nH2O, structural formula are A (x/q)
[(AlO2) x (SiO2) y] and n (H2O) wherein, the cation such as A Ca, Na, K, Ba, Sr；B is Al and Si；P is cationic compound
Valency；M is cation number；N is moisture subnumber；X is Al atomicities；Y is Si atomicities；(y/x) usually between 1~5；(x+y)
It is tetrahedral number in unit cell.Zeolite is mainly formed in the low temperature hot liquid stage, is common in effusive rock stomata, also sees
In hydrothermal deposit and modern age hot spring deposition.Zeolite can borrow the percolation of water, to carry out the exchange of cation, in its component
Cobalt, calcium ion can be exchanged with the potassium in aqueous solution, magnesium plasma, industrially to softening of water.The crystal structure of zeolite be by
Silicon (aluminium) oxygen tetrahedron is linked to be the screen work of three-dimensional, has hole of all sizes and passage in screen work, has very big opening
Property.Alkali or alkaline earth metal ion and hydrone are distributed in hole and passage, weaker with contacting for screen work.It is different from
Son is exchanged on zeolite structured influence very little, but the property of zeolite is changed.Cavity of different sizes present in lattice, can be with
Draw or filter the molecule of other materials of different sizes.Natural zeolite is crushed (can be selected conventional crumbling method into
Repeatedly formula crushes row alone or in combination), the particle diameter of the zeolite powder is less than 1 μm.
In above-mentioned preparation method, in step 2), the drying is specially to be spray-dried；The condition of the spray drying is such as
Under：Temperature is 50~75 DEG C, and the time is 5~10h.
The condition of the sizing is as follows：3~5min of pressurize under 150~300MPa.
The shaping and the sizing can specifically use ball press to operate.
After the sizing, before the dipping, the step of degumming process is carried out to the product after the sizing is further included；
The degumming process specifically can at 1000~1200 DEG C 6~10h of degumming；The degumming process specifically can be in vacuum degumming stove
Carry out.
In above-mentioned preparation method, in step 3), the metal impregnation liquid is the mixing water of ferric nitrate, nickel nitrate and cobalt nitrate
Solution.
The total mass fraction of ferric nitrate, nickel nitrate and cobalt nitrate is (20-60) % in the metal impregnation liquid.
Further, in the metal impregnation liquid, the mass ratio of Fe, Ni, Na are (2-5):1:(1-5).
The dipping can specifically use equi-volume impregnating, and the time of the dipping is 1-3h.
The temperature of the drying is (80-150) DEG C (being specially 110 DEG C), time 2-4h.
The preparation-obtained microspherical catalyst of the present invention falls within protection scope of the present invention.
Concretely 1~1000 μm of the size of the microspherical catalyst.
In addition, application of the preparation-obtained microspherical catalyst of the present invention during floating bed hydrogenation also belongs to the present invention
Protection domain.
The preparation-obtained microspherical catalyst of the present invention can be used for during heavy oil floating bed hydrogenation, as catalytic carrier,
The carrier of coke is adsorbed, there is excellent hydrogenation activity, cracking activity, wear resistance and coke adsorption capacity.
Compared with prior art, the invention has the advantages that：
1) preparation method of microspherical catalyst provided by the present invention, employs cheap zeolite, makes prepared microballoon
Catalyst has substantial amounts of acid centre, and these acid centres have the function of oil product very strong cracking, will can divide greatly
Optionally cracking becomes oil product (such as diesel oil and the stone brain of small molecule to the oil product (such as wax oil, colloid, asphalitine component) of son
Oil ingredient), when making final microspherical catalyst to heavy oil progress hydrogenation cracking, improve tar light oil yield；
Furthermore by selecting zeolite, having preparation-obtained microspherical catalyst, pore size is big, quantity is more, size
The advantages of homogeneous and coke large amount of adsorption, the coke being very suitable for generated in absorption floating bed hydrogenation reaction, avoids reacting
Coking phenomenon occurs on device wall and pipeline；Solve catalyst aperture in suspension bed hydrogenation process easily block, specific surface area compared with
The defects of small and absorption coke ability is weak；
By being impregnated in metal impregnation liquid, make these activity of load iron, nickel, cobalt on preparation-obtained microspherical catalyst
Metal.Iron, nickel and cobalt are hydrogenation reaction can to occur for oil product provide activated centre, can be by the organic nitrogen in heavy oil, organic
Sulphur, organic oxygen are converted into NH3、H2S、H2O, while additionally aid the progress for carrying out the reactions such as alkene saturation, aromatic hydrocarbons saturation；
Meanwhile prepared microspherical catalyst has very high extrusion rate for metal component entrained in raw material heavy oil,
The probability of the inactivation of catalyst coking in subsequent fixed bed hydroprocessing process can be reduced.
2) by the size controlling of zeolite powder when less than 1 μm, the progress of follow-up work is conducive to.Because raw material is more tiny,
More advantageously form uniformly good institutional framework and pore size.
3) the preparation-obtained microspherical catalyst of the present invention is few relative to the adding proportion of feedstock oil, is only the matter of feedstock oil
Measure the 0.5%-3% of fraction, but the specific surface area of catalyst equivalent to 100,000,000 times of floating bed hydrogenation reactor internal surface area with
On；
Meanwhile preparation-obtained microspherical catalyst granularity can be adjusted according to the size of suspended-bed reactor,
Can be as the regulating measure of the operating parameter of the key such as the gas holdup in suspended-bed reactor, catalyst inventory.
4) preparation method of the present invention is simply easy to operation, easy to prepare on a large scale.
Embodiment
Embodiment 1, prepare microspherical catalyst：
1) zeolite powder of 1000g is crushed to particle diameter as 0.4 μm, then is separately added into the ethanol of 1000g thereto, it is fully mixed
Close uniformly, and 10h is stirred at 30 DEG C, obtain slurry；
2) slurry in step 1) is spray-dried, the temperature of spray drying is 50 DEG C, time 5h；Followed by
Ball press is shaped to catalyst microspheres, after under 200MPa suppress 5min shape；The catalyst microspheres of sizing are put again
Degumming is carried out in vacuum degumming stove, the temperature of degumming is 1200 DEG C, time 10h；
3) by Fe (NO3)3·9H2O、Ni(NO3)2·6H2O and Co (NO3)2Obtained metal impregnation liquid soluble in water, gross mass
Fraction is 30%, and the mass ratio for making Fe, Ni and Na in the metal impregnation liquid is 8：2：3；It will be walked using equi-volume impregnating again
It is rapid 2) in catalyst microspheres be impregnated in 1h in the metal impregnation liquid, by the catalyst microspheres after dipping in 110 DEG C dry 2h,
Obtain microspherical catalyst.
Embodiment 2, prepare microspherical catalyst：
1) zeolite powder of 1000g is crushed to particle diameter as 0.4 μm, then is separately added into the ethanol of 1500g thereto, it is fully mixed
Close uniformly, and 8h is stirred at 40 DEG C, obtain slurry；
2) slurry in step 1) is spray-dried, the temperature of spray drying is 60 DEG C, time 8h；Followed by
Ball press is shaped to catalyst microspheres, after under 300MPa suppress 5min shape；The catalyst microspheres of sizing are put again
Degumming is carried out in vacuum degumming stove, the temperature of degumming is 1000 DEG C, time 6h；
3) by Fe (NO3)3·9H2O、Ni(NO3)2·6H2O and Co (NO3)2Obtained metal impregnation liquid soluble in water, gross mass
Fraction is 20%, and the mass ratio for making Fe, Ni and Na in the metal impregnation liquid is 2：1：1；It will be walked using equi-volume impregnating again
It is rapid 2) in catalyst microspheres be impregnated in 2h in the metal impregnation liquid, by the catalyst microspheres after dipping in 90 DEG C dry 4h,
Obtain microspherical catalyst.
Embodiment 3, prepare microspherical catalyst：
1) zeolite powder of 1000g is crushed to particle diameter as 0.4 μm, then is separately added into the ethanol of 3000g thereto, it is fully mixed
Close uniformly, and 5h is stirred at 50 DEG C, obtain slurry；
2) slurry in step 1) is spray-dried, the temperature of spray drying is 75 DEG C, time 10h；Then it is sharp
Be shaped to catalyst microspheres with ball press, after under 150MPa suppress 5min shape；Again by the catalyst microspheres of sizing
It is placed in vacuum degumming stove and carries out degumming, the temperature of degumming is 1100 DEG C, time 8h；
3) by Fe (NO3)3·9H2O、Ni(NO3)2·6H2O and Co (NO3)2Obtained metal impregnation liquid soluble in water, gross mass
Fraction is 60%, and the mass ratio for making Fe, Ni and Na in the metal impregnation liquid is 5：1：5；It will be walked using equi-volume impregnating again
It is rapid 2) in catalyst microspheres be impregnated in 3h in the metal impregnation liquid, by the catalyst microspheres after dipping in 130 DEG C dry 3h,
Obtain microspherical catalyst.
Catalyst prepared by comparative example 1, Commercial active carbon：
It is 280 mesh to weigh 100g granularities, BET specific surface area 985m2The merchandise active carbon of/g is adopted as catalyst carrier
With equi-volume impregnating dipping 66.4g CoSO4·7H2O and 14.5g (NH4)6Mo7O24·4H2O on 100g Commercial active carbon,
After dipping, the dry 6h at 120 DEG C, then through ball milling 12h, it is 1-7 μm of catalyst to obtain particle diameter.
Evaluate example 1, the performance evaluation of microspherical catalyst：
The ratio surface of microspherical catalyst and pore structure carry out on the ASAP2020 instruments of Micrometrics companies of the U.S.
Test；Calculated than surface according to Berrett-Emmett-Teller (BET) method；Pore volume and pore-size distribution are according to desorption branch
Calculated according to Berret-Joyner-Halenda (BJH) model.
The performance data of table 1, microspherical catalyst
| Numbering | Specific surface area | Average pore size | Pore volume (cm3/g) | Mesoporous and macropore |
| (m2/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：
The finished catalyst that embodiment 1-3 (numbering F1-F3) and comparative example 1 (numbering F4) are prepared respectively, outstanding
Tested in floating bed residual hydrogenation system.Technical process is as follows：It is residual oil raw material, appropriate in autoclave reaction system
Microspherical catalyst and vulcanizing agent be added to together in kettle.Hydrogen is passed through, is vulcanized at a certain temperature and is reacted, is finally divided
Gaseous product and product liquid are separated out, is analyzed and is calculated respectively, draws experimental result.
Bottoms conversion and cut oil yield, the evaluation index as reaction effect are calculated according to the following formula：
Bottoms conversion=520 DEG C following components quality (containing gas)/raw material oil quality × 100%
Liquid component quality below cut oil yield=520 DEG C/raw material oil quality × 100%
Metal removal rate=(tenor in tenor/raw material in 1- generation oil) × 100%
Detailed step is as follows：It is former to add 150.0g in 500ml autoclave kettles to volume using decompression residuum as reaction raw materials
Material oil and 800 μ g/g microspherical catalysts, vulcanizing agent are Sublimated Sulphur powder, addition 0.08g, at room temperature first with hydrogen by kettle
Interior air is sufficiently displaced from, and is then pressurized to 5.0MPa, and curing temperature is 320 DEG C, vulcanization time 60min, reaction temperature 420
DEG C, when reaching reaction temperature, the reaction time continues 60min, after reaction, treats that temperature is down to room temperature, and gas is collected with airbag
Analyzed, solid residue is separated and weighed with product liquid, calculate the conversion ratio of boiling point cut below 520 DEG C.Specifically
Reaction result is shown in Table 1.
Table 2, residual oil hydrocatalyst performance data
Obviously, the above embodiments are merely examples for clarifying the description, and the restriction not to embodiment.It is right
For those of ordinary skill in the art, can also make on the basis of the above description it is other it is various forms of change or
Change.There is no necessity and possibility to exhaust all the enbodiments.And the obvious change thus extended out or
Among changing still in the protection domain of the invention.
Claims (9)
1. a kind of preparation method of microspherical catalyst, is made of following steps：
1) zeolite powder and ethanol are mixed and are stirred, obtain slurry；
2) slurry obtained in step 1) be dried successively, be molded, shaped and degumming process, it is micro- to obtain zeolite catalyst
Ball, the drying are spray drying, and the condition of the spray drying is as follows：Temperature is 50~75 DEG C, and the time is 5~10h, described
The condition of sizing is as follows：3~5min of pressurize under 150~300MPa；
3) the zeolite catalyst microballoon in step 2) is impregnated in metal impregnation liquid, then to the zeolite catalyst microballoon after dipping
Dried, obtain the microspherical catalyst, wherein, the metal impregnation liquid is the mixing of ferric nitrate, nickel nitrate and cobalt nitrate
Aqueous solution.
2. preparation method as claimed in claim 1, it is characterised in that：In step 1), the matter of the zeolite powder and the ethanol
Amount is than being 1：(1~3)；
The temperature of the stir process is 20~50 DEG C, and the time is 5~10h.
3. preparation method as claimed in claim 1 or 2, it is characterised in that：In step 1), 1 μm of the particle diameter ＜ of the zeolite powder.
4. preparation method as claimed in claim 1 or 2, it is characterised in that：The degumming process is specifically in 1000~1200 DEG C
6~10h of lower degumming；
The degumming process specifically carries out in vacuum degumming stove.
5. preparation method as claimed in claim 1 or 2, it is characterised in that：In step 3), nitric acid in the metal impregnation liquid
The total mass fraction of iron, nickel nitrate and cobalt nitrate is (20-60) %.
6. preparation method as claimed in claim 5, it is characterised in that：In step 3), in the metal impregnation liquid, Fe, Ni, Co
Mass ratio be (2-5):1:(1-5).
7. preparation method as claimed in claim 6, it is characterised in that：In step 3), the dipping is specifically using isometric leaching
Stain method；
The time of the dipping is 1-3h；
The temperature of the drying is 80-150 DEG C, time 2-4h.
8. the microspherical catalyst that the preparation method any one of claim 1-7 obtains.
9. application of the microspherical catalyst described in claim 8 during heavy oil floating bed hydrogenation.
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