CN105964294B - A kind of hydrogenating catalyst composition and preparation method thereof - Google Patents
A kind of hydrogenating catalyst composition and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 39
- 239000000203 mixture Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 40
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 40
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002253 acid Substances 0.000 claims abstract description 24
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims abstract description 14
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000011959 amorphous silica alumina Substances 0.000 claims abstract description 13
- 239000011787 zinc oxide Substances 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 8
- 239000000395 magnesium oxide Substances 0.000 claims abstract description 7
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims abstract description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000292 calcium oxide Substances 0.000 claims abstract description 5
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910021536 Zeolite Inorganic materials 0.000 claims description 8
- 239000010457 zeolite Substances 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- 229910000765 intermetallic Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims description 3
- 238000005470 impregnation Methods 0.000 claims description 3
- 238000004898 kneading Methods 0.000 claims description 3
- 238000000465 moulding Methods 0.000 claims description 3
- 238000001935 peptisation Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- -1 β-carboxyethyl Chemical group 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 238000000034 method Methods 0.000 abstract description 12
- 238000004517 catalytic hydrocracking Methods 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 6
- 238000007670 refining Methods 0.000 abstract description 6
- 239000000295 fuel oil Substances 0.000 abstract description 5
- 239000004115 Sodium Silicate Substances 0.000 description 12
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 12
- 229910052911 sodium silicate Inorganic materials 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- 229910001388 sodium aluminate Inorganic materials 0.000 description 6
- 239000002994 raw material Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 3
- 230000008025 crystallization Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 229910052809 inorganic oxide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 235000019795 sodium metasilicate Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- WEUCTTBUEWINIJ-UHFFFAOYSA-N acetic acid;zinc;dihydrate Chemical compound O.O.[Zn].CC(O)=O WEUCTTBUEWINIJ-UHFFFAOYSA-N 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- QMMOXUPEWRXHJS-UHFFFAOYSA-N pent-2-ene Chemical group CCC=CC QMMOXUPEWRXHJS-UHFFFAOYSA-N 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 238000005360 mashing Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000009423 ventilation 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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/005—Mixtures of molecular sieves comprising at least one molecular sieve which is not an aluminosilicate zeolite, e.g. from groups B01J29/03 - B01J29/049 or B01J29/82 - B01J29/89
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/106—Y-type faujasite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- 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
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrogenating catalyst compositions and preparation method thereof, by the material composition of following parts by weight, 30 parts of amorphous silica-alumina, 40 parts of molecular sieve, 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, 8 parts of calcium oxide.The present invention uses the hydrogenating catalyst composition of above-mentioned technical proposal, hydrogenating function and acid function can effectively be adjusted, feed stock conversion is high, and stability is good, and activity is high, growing up for the active component crystal grain of catalyst during the reaction can also be effectively prevented, service life is long, has large hole appearance and specific surface area, the ability for handling macromolecular in heavy oil strong, it can be used for the single-stage hydrocracking technique of no refining stage, it can also be used to have the one-stage serial hydrocracking technique of refining stage.
Description
Technical field
The invention belongs to oil product processing technique field, a kind of hydrogenating catalyst composition and its preparation are concretely related to
Method.
Background technology
Hydrocracking technology is one of the important means of crude oil secondary operation, heavy oil lighting.Since it is suitable with raw material
Ying Xingqiang, production operation and products scheme have become the high-quality lightweight cleaning of production flexibly and the features such as good product quality
Oil product and the important channel for solving industrial chemicals source.
Hydrocracking catalyst is usually bifunctional catalyst, and lytic activity and hydrogenation activity are by the acid in catalyst
What property component and hydrogenation active component provided respectively.Acidic components in catalyst are usually the molecule contained in catalyst
The refractory inorganic oxides of carrier are sieved and/or constitute to provide.Refractory inorganic oxides generally comprise amorphous silica-alumina, nothing
It is one or more in the aluminium oxide that shapes.
The conjugation between molecular sieve and refractory inorganic oxides in carrier and dispersion degree have between reacting with it performance
Inseparable relationship, the activity of catalyst and the selectivity to various purpose products are largely influenced.It is right
For hydrocracking catalyst, matched difference can generate different reaction effects between cracking function and hydrogenating function,
That is, it is directed to different purpose products, need the cracking function and hydrogenating function that adjust catalyst.Existing hydrogenation catalyst is deposited
Poor in stability, service life is short, and hole holds and surface area is small, in processing heavy oil the shortcomings of macromolecular energy force difference.
Invention content
The technical problem to be solved by the present invention is to provide one kind in view of the deficiencies of the prior art and can effectively adjust to add hydrogen
Function and acid function, feed stock conversion is high, and stability is good, and activity is high, can also be effectively prevented catalyst in reaction process
In active component crystal grain grow up, service life is long, and there is large hole to hold and specific surface area, handle the energy of macromolecular in heavy oil
Power is strong, can be used for the single-stage hydrocracking technique of no refining stage, it can also be used to have the one-stage serial hydrocracking technique of refining stage
Hydrogenating catalyst composition.
The present invention also provides a kind of preparation methods of above-mentioned catalyst, and easily operated, the prices of raw materials are cheap, prepare
Journey is discharged without NOx, can be met cleaning and be prepared catalyst requirement, reaction is continuous, and the reaction time is short, at low cost, suitable for industry
Using.
The present invention uses following technical scheme to solve above-mentioned technical problem：A kind of hydrogenating catalyst composition, by following
The material composition of parts by weight, 30 parts of amorphous silica-alumina, 40 parts of molecular sieve, 12 parts of magnesia, 15 parts of diboron trioxide, three oxidations two
20 parts of iron, 25 parts of nano granular of zinc oxide, 8 parts of calcium oxide.
It is further improvement of the present invention below：
The molecular sieve is the mixture of SAPO-11 molecular sieves, beta-zeolite molecular sieve and Y type molecular sieve, the SAPO-
The mass ratio of 11 molecular sieves, beta-zeolite molecular sieve and Y type molecular sieve is 3:2：1.
It is further improved：
The relative crystallinity of the SAPO-11 molecular sieves is 98%, and crystal particle diameter is 2.5 μm.
It is further improved：
The relative crystallinity 95%~110% of the Y type molecular sieve, crystal particle diameter are 1.8 μm.
It is further improved：
The grain size of the nano granular of zinc oxide is 100-20nm, length 80-30nm.
It is further improved：
The amorphous silica-alumina silicon oxide-containing 8wt%-50wt%, specific surface area 700-800m2/ g, Kong Rongwei
1.6-1.8ml/g, bore dia 8-15nm, shared Kong Rong account for the 95%- 98% of total pore volume, and infrared total acid content is 0.30
- 0.45mmol/g, middle strong acid amount/infrared total acid content are that 0.56-0.81, L acid amount/B acid amounts are 1.40-2.30.
A kind of preparation method of hydrogenating catalyst composition, includes the following steps：
1）, the amorphous silica-alumina of above-mentioned parts by weight, molecular sieve be sufficiently mixed in kneading machine, acetic acid and β-carboxylic is added
Ethyl propylene acid esters mixed acid solution carries out peptization, is extruded into a diameter of 0.5mm cylindrical types, and then drying 2 is small at 300 DEG C
When, it is roasted 2 hours at 800 DEG C, prepares molding catalyst carrier；
2）, by 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, oxidation
8 parts of calcium is uniformly mixed, and is sent into calcining furnace, is roasted 4-6 hours at 1500-2000 DEG C and obtain particle；
3）, above-mentioned particle incorporated in the zinc nitrate solution of a concentration of 0.5mol/L, metallic compound mixed solution is made；
4）, said catalyst carrier carries out to dip operation in above-mentioned metallic compound mixed solution, time 50min,
Then it is dried；
5）, material carries out impregnation using the ammonium hydroxide of a concentration of 8mol/L after drying, ammonia volume be it is dry after object
Expect the 90% of water absorption rate, is then dried and roasts again, obtain final catalyst.
It is further improved：
Step 4）Middle drying temperature is 150 DEG C, 6 hours drying times.
It is further improved：
Step 5）Middle calcination temperature is 450 DEG C, and roasting time is 3 hours.
It is further improved：
Step 1）Described in acetic acid concentration be 6mol/L.
The present invention uses the hydrogenating catalyst composition of above-mentioned technical proposal, can effectively adjust hydrogenating function and acidity
Function, feed stock conversion is high, and stability is good, and activity is high, can also be effectively prevented the activearm of catalyst during the reaction
Divide growing up for crystal grain, service life is long, has large hole appearance and specific surface area, the ability for handling macromolecular in heavy oil is strong, can use
In the single-stage hydrocracking technique of no refining stage, it can also be used to there is the one-stage serial hydrocracking technique of refining stage.The present invention adopts
Easily operated with above-mentioned preparation method, the prices of raw materials are cheap, and preparation process is discharged without NOx, can meet cleaning preparation and urge
Agent requirement, reaction is continuous, and the reaction time is short, at low cost, suitable for commercial Application.
Specific implementation mode
Embodiment, a kind of hydrogenating catalyst composition, by the material composition of following parts by weight, 30 parts of amorphous silica-alumina divides
40 parts of son sieve, 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, calcium oxide 8
Part.
The molecular sieve is the mixture of SAPO-11 molecular sieves, beta-zeolite molecular sieve and Y type molecular sieve, the SAPO-
The mass ratio of 11 molecular sieves, beta-zeolite molecular sieve and Y type molecular sieve is 3:2：1.
The relative crystallinity of the SAPO-11 molecular sieves is 98%, and crystal particle diameter is 2.5 μm.
The relative crystallinity 95%~110% of the Y type molecular sieve, crystal particle diameter are 1.8 μm.
The grain size of the nano granular of zinc oxide is 100-20nm, length 80-30nm.
The amorphous silica-alumina silicon oxide-containing 8wt%-50wt%, specific surface area 700-800m2/ g, Kong Rongwei
1.6-1.8ml/g, bore dia 8-15nm, shared Kong Rong account for the 95%- 98% of total pore volume, and infrared total acid content is 0.30
- 0.45mmol/g, middle strong acid amount/infrared total acid content are that 0.56-0.81, L acid amount/B acid amounts are 1.40-2.30.
The preparation method of amorphous silica-alumina described above is as follows：
A, sodium aluminate solution and sodium silicate solution are prepared respectively；
B, part or all of sodium silicate solution will be added in sodium aluminate solution, then passes to CO2Gas, control reaction temperature
Degree is 40 DEG C of 10-, and the pH values for controlling cemented into bundles are 8- 11；Wherein as the CO being passed through2 Gas flow accounts for total intake
40%~100%, remaining sodium silicate solution is added；
C, at the control temperature and pH values of step b, the mixture ventilation obtained by step b is stablized 40-60 minutes
；
D, the solidliquid mixture obtained by step c is filtered, Washing of Filter Cake；
E, the filter cake obtained by step d is beaten, then carries out hydro-thermal process, through filtering, drying, obtains amorphous silica-alumina
；The hydrothermal conditions are as follows：Under 120~150 DEG C, 0.5~4.0MPa water vapor pressures processing 2~
5 hours.
In step b, as the CO being passed through2When gas flow accounts for the 50%-80% of total intake, it is added remaining
Sodium silicate solution.
In the step a, a concentration of 15-55g Al of sodium aluminate solution2O3/ l, sodium silicate solution it is dense
Degree is 50-200g SiO2/l。
All or part of sodium silicate solution is added in step b, the whole sodium silicate solutions being as added
5wt%- 100wt%.
The CO2A concentration of 30v%-60v% of gas.
The detailed process of step b is using one of following methods：(1) it after whole sodium metasilicate are added into sodium aluminate, is passed through
CO2Gas；(2) after part sodium metasilicate being added into sodium aluminate, whole CO are passed through2Then gas is added into mixture
Remaining sodium silicate solution；(3) after part sodium metasilicate being added into sodium aluminate, it is passed through part CO2Gas, then lead to CO on one side2
Remaining sodium silicate solution is added in gas on one side.
Washing described in step d is that filter cake is washed till neutrality with 50-90 DEG C of deionized water.
It is 8 that mashing described in step e, which is by solid-liquid volume ratio,：1 - 10：1, into filter cake plus water is beaten.
Drying condition described in step e is as follows：It is 6-8 hours dry at 110-130 DEG C.
The preparation method of above-mentioned Y types molecular sieve includes following processes：Fresh NaY Crystallization of Zeolite slurries are filtering
When separation molecular sieve filter cake, concentration of lye 0.001-0.5mol/L, alkali are rinsed with the lye of 4-6 times of molecular sieve butt quality
Liquid temperature is 30-90 DEG C；Then above-mentioned NaY molecular sieves filter cake is beaten, the compound solution of the ion containing H+ is added,
So that the pH values of NaY molecular sieve pulps are maintained at 2.5-7.0, reaction temperature is 5-100 DEG C, exchange reaction 0.2-6
Hour, it is swapped with H+ and the sodium in zeolite, H+ has filtering, washing, roasting process after exchanging.
The preparation method of above-mentioned nano granular of zinc oxide is as follows：
1, methanol is added in round-bottomed flask first, sequentially adds potassium hydroxide and acetic acid dihydrate zinc, electromagnetic agitation
1-5 minutes, obtain the solution of water white transparency；
It 2 and then is stirred 40 hours in 80 DEG C of heating temperature, being heated at reflux in device for 15 DEG C of circulating water temperature, obtains breast
The solution of white；
3, supernatant liquor is outwelled after obtained milky white solution being stood 4-8 hours, is cleaned with methanol, centrifuge separation
It is 3-5 times, finally that particle is dry in vacuum drying chamber, obtain nano granular of zinc oxide.
The mass concentration of the potassium hydroxide is not less than 85%.
The mass concentration of the acetic acid dihydrate zinc is not less than 99%.
The volumetric concentration of the methanol solution is not less than 99.5%.
The drying temperature is 20-30 DEG C, and the time is 24-96 hours.
The preparation method of the SAPO-11 molecular sieves is as follows, and the raw material phosphoric acid of 90% aqueous solution is mixed with deionized water
After stir evenly, boehmite is added under stiring, is added containing SiO after stirring evenly2For 25% Ludox, stir
After mixing reaction plastic, finally diethylamine solution and hydrofluoric acid solution are slowly added into above-mentioned gel again, continues stirring and is made
Gel reaction mixture；Above-mentioned reaction mixture is fitted into the crystallizing kettle with polytetrafluoroethylene bushing, it is spontaneous in 160 DEG C
Crystallization product, is finally washed with deionized, filters by crystallization 48 hours under pressure, is dried in 100 DEG C of air, is made
SAPO-11 molecular sieves, relative crystallinity 98%.
A kind of preparation method of hydrogenating catalyst composition, includes the following steps：
1）, the amorphous silica-alumina of above-mentioned parts by weight, molecular sieve be sufficiently mixed in kneading machine, acetic acid and β-carboxylic is added
Ethyl propylene acid esters mixed acid solution carries out peptization, is extruded into a diameter of 0.5mm cylindrical types, and then drying 2 is small at 300 DEG C
When, it is roasted 2 hours at 800 DEG C, prepares molding catalyst carrier.
2）, by 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, oxidation
8 parts of calcium is uniformly mixed, and is sent into calcining furnace, is roasted 4-6 hours at 1500-2000 DEG C and obtain particle；
3）, above-mentioned particle incorporated in the zinc nitrate solution of a concentration of 0.5mol/L, metallic compound mixed solution is made.
4）, said catalyst carrier carries out to dip operation in above-mentioned metallic compound mixed solution, time 50min,
Then it is dried.
5）, material carries out impregnation using the ammonium hydroxide of a concentration of 8mol/L after drying, ammonia volume be it is dry after object
Expect the 90% of water absorption rate, is then dried and roasts again, obtain final catalyst.
Step 4）Middle drying temperature is 150 DEG C, 6 hours drying times.
Step 5）Roasting roasts 3 hours at 450 DEG C.
Step 1）Described in acetic acid concentration be 6mol/L.
Claims (5)
1. a kind of hydrogenating catalyst composition, it is characterised in that：By the material composition of following parts by weight, 30 parts of amorphous silica-alumina,
40 parts of molecular sieve, 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, calcium oxide
8 parts；
The molecular sieve is the mixture of SAPO-11 molecular sieves, beta-zeolite molecular sieve and Y type molecular sieve, and the SAPO-11 divides
The mass ratio of son sieve, beta-zeolite molecular sieve and Y type molecular sieve is 3:2：1；
The relative crystallinity of the SAPO-11 molecular sieves is 98%, and crystal particle diameter is 2.5 μm；
The relative crystallinity 95%~110% of the Y type molecular sieve, crystal particle diameter are 1.8 μm；
The grain size of the nano granular of zinc oxide is 100-20nm, length 80-30nm；
The amorphous silica-alumina silicon oxide-containing 8wt%-50wt%, specific surface area are 700-800m 2/g, Kong Rongwei 1.6-
1.8ml/g, bore dia 8-15nm, shared Kong Rong account for the 95%- 98% of total pore volume, and infrared total acid content is 0.30-
0.45mmol/g, middle strong acid amount/infrared total acid content are that 0.56-0.81, L acid amount/B acid amounts are 1.40-2.30.
2. the preparation method of hydrogenating catalyst composition according to claim 1, it is characterised in that：Include the following steps：
1）, the amorphous silica-alumina of above-mentioned parts by weight, molecular sieve be sufficiently mixed in kneading machine, acetic acid and β-carboxyethyl is added
Crylic acid ester mixture acid solution carries out peptization, is extruded into a diameter of 0.5mm cylindrical types, then 2 hours dry at 300 DEG C,
It is roasted 2 hours at 800 DEG C, prepares molding catalyst carrier；
2）, by 12 parts of magnesia, 15 parts of diboron trioxide, 20 parts of di-iron trioxide, 25 parts of nano granular of zinc oxide, calcium oxide 8
Part is uniformly mixed, and is sent into calcining furnace, is roasted 4-6 hours at 1500-2000 DEG C and obtain particle；
3）, above-mentioned particle incorporated in the zinc nitrate solution of a concentration of 0.5mol/L, metallic compound mixed solution is made；
4）, said catalyst carrier carries out to dip operation in above-mentioned metallic compound mixed solution, time 50min, then
It is dried；
5）, material carries out impregnation using the ammonium hydroxide of a concentration of 8mol/L after drying, ammonia volume be it is dry after material inhale
Then the 90% of water rate is dried and roasts again, obtain final catalyst.
3. the preparation method of hydrogenating catalyst composition according to claim 2, it is characterised in that：Step 4）In, it is dry
Temperature is 150 DEG C, 6 hours drying times.
4. the preparation method of hydrogenating catalyst composition according to claim 2, it is characterised in that：Step 5）In, roasting
Temperature is 450 DEG C, and roasting time is 3 hours.
5. the preparation method of hydrogenating catalyst composition according to claim 2, it is characterised in that：Step 1）In, it is described
Acetic acid concentration is 6mol/L.
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| CN107841336B (en) * | 2017-11-24 | 2019-08-09 | 福州大学 | A kind of heavy oil suspended bed hydrocracking method |
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