CN1054153C - Hydrocracking catalyst for producing intermediate fraction oil - Google Patents
Hydrocracking catalyst for producing intermediate fraction oil Download PDFInfo
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- CN1054153C CN1054153C CN97116403A CN97116403A CN1054153C CN 1054153 C CN1054153 C CN 1054153C CN 97116403 A CN97116403 A CN 97116403A CN 97116403 A CN97116403 A CN 97116403A CN 1054153 C CN1054153 C CN 1054153C
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- catalyzer
- zeolite
- oil
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- hydrocracking
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- 238000004517 catalytic hydrocracking Methods 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 32
- 239000010457 zeolite Substances 0.000 claims abstract description 72
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 70
- 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 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 10
- 238000004519 manufacturing process Methods 0.000 claims abstract description 8
- 150000004706 metal oxides Chemical class 0.000 claims abstract 6
- LKTZODAHLMBGLG-UHFFFAOYSA-N alumanylidynesilicon;$l^{2}-alumanylidenesilylidenealuminum Chemical compound [Si]#[Al].[Si]#[Al].[Al]=[Si]=[Al] LKTZODAHLMBGLG-UHFFFAOYSA-N 0.000 claims description 15
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 239000011148 porous material Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 10
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 60
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002283 diesel fuel Substances 0.000 abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000377 silicon dioxide Substances 0.000 abstract description 9
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 8
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract description 2
- 229910052782 aluminium Inorganic materials 0.000 abstract description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 2
- 238000005520 cutting process Methods 0.000 abstract description 2
- 229910021417 amorphous silicon Inorganic materials 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 15
- 238000000034 method Methods 0.000 description 11
- 239000003795 chemical substances by application Substances 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910017604 nitric acid Inorganic materials 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 230000004913 activation Effects 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000000465 moulding Methods 0.000 description 6
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- -1 X type and Y type Chemical compound 0.000 description 5
- 238000005336 cracking Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000002209 hydrophobic effect Effects 0.000 description 5
- 238000010306 acid treatment Methods 0.000 description 4
- 239000003245 coal Substances 0.000 description 4
- 238000007598 dipping method Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000001935 peptisation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 230000009466 transformation Effects 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 3
- 230000008033 biological extinction Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000007710 freezing Methods 0.000 description 3
- 230000008014 freezing Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 230000009257 reactivity Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000010742 number 1 fuel oil Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000011973 solid acid Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000219793 Trifolium Species 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000011280 coal tar Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003350 kerosene Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000003079 shale oil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 235000012976 tarts Nutrition 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7815—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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Combustion Methods Of Internal-Combustion Engines (AREA)
- Catalysts (AREA)
- Liquid Carbonaceous Fuels (AREA)
Abstract
The present invention relates to a hydrocracking catalyst for producing intermediate distillate oil, which is composed of 5 to 40w% of beta zeolite, 10 to 50w% of amorphous silicon aluminium, 15 to 30w% of alumina, 10 to 40 of w% of metal oxides in a VIB group and 1 to 10w% of metal oxides in a VIII group, wherein the SiO2 /Al2O3 ratio of the beta zeolite is from 30 to 90; the infrared acidity is from 0.1 to 0.5 mmol/g; the water absorption amount is smaller than 10w% at 25 DEG C when the vapor pressure is <=12 mmhg. The catalyst of the present invention has good hydrocracking performance and hydrogenation dewaxing performance, which makes the obtained hydrocracking product have excellent characteristic. The present invention particularly can be used for producing diesel oil having a low solidifying point and wide temperature range of distillate cutting, and is suitable for increase production of diesel oil.
Description
The present invention relates to a kind of hydrocracking catalyst, especially for production middle distillate oil.
It is more and more heavier that each refinery of the present world all is faced with raw material, quality problem worse and worse, and hydrocracking process has become one of important means of light materialization of heavy oil.Simultaneously, world wide constantly increases middle fraction oil demand, thereby the exploitation of middle oil type hydrocracking catalyst is active day by day, particularly has the exploitation that flexibility of operation and energy maximum are produced the middle distillate oil type hydrocracking catalyst of boat coal and/or diesel oil.
Hydrocracking catalyst is a kind of dual-function catalyst, has hydrogenation performance and cracking performance, and base metal power hydrocracking catalyst generally selects for use VIB and VIII family metal to make the hydrogenation component, optional platelet-shaped zeolite of acidic components and/or amorphous aluminum silicide.Use amorphous aluminum silicide merely, though selectivity is higher, active low, operational handiness is restricted, and along with the appearance of new zeolite material, comprehensively uses this two kinds of materials, to obtain the novel hydrogenation cracking catalyst of the high middle distillates oil selectivity of high reactivity.
Current, the crystal formation zeolite that hydrocracking catalyst is commonly used has large pore zeolite such as X type and Y type, especially y-type zeolite, the higher hydrocabon of stock oil can enter in the zeolite pore and transform, for cerul stock oil, when＞343 ℃ of fractions are cracked into 165-343 ℃ of fraction, the diesel oil zero pour height that is obtained, and then also have influence on intermediate oil (middle oil) yield.An other class is to use pore zeolite or selects the shape zeolite such as ZSM-5 is the catalyzer of cracking component, have only the alkane of chain type, short-side chain can enter zeolite structured in, promptly have only straight chain hydrocarbon to be transformed, can dewax and make diesel oil and tail oil in the product depression of the freezing point, but because the duct is little, reactant can not in time shift out, and causes excessive fragmentation, and middle distillates oil selectivity is descended; The macromole hydrocarbon is difficult for entering on the other hand, and especially when treatment of heavy hydrocarbon material, activity is lower.
" Chinese oil Refining Technologies " (Sinopec press, the Hou Xianglin chief editor, the 511st page) delivered and a kind ofly can handle heavier feeds, carry out hydrocracking and Hydrodewaxing simultaneously, 3812 catalyzer of production high-quality middle distillate oil and low freezing point diesel fuel and lubricant base, the characteristics of this catalyzer are to contain a kind of β zeolite, though it is good by the hydrocracking product property that uses this catalyzer to obtain, but this catalyzer when treatment of heavy hydrocarbon material temperature of reaction generally more than 390 ℃, and light-end productss such as petroleum naphtha are more, as handle grand celebration VGO, one way is by transformation efficiency 70w%, 393 ℃ of temperature of reaction, gas and gasoline yield reach 27.9w%, and middle distillates oil selectivity is low.
US4820402 discloses a kind of hydrocracking catalyst, inventive point is to have used the high silica alumina ratio zeolite, wherein also relate to high silica alumina ratio β zeolite, this patent is thought, in order to improve middle distillates oil selectivity and to reduce the hydrogen consumption, the silica molecular ratio at least 50: 1 of the zeolite component in the catalyzer, general 100: 1, even 200: 1.This patent catalyzer is used to handle Arabic VGO, under the situation that control 60v% transforms, and middle distillates oil selectivity 45-65v%, different high silica alumina ratio zeolite (SiO
2: Al
2O
3=200: 1) middle distillates oil selectivity that is used for this catalyzer is in proper order: ZSM-20＞β＞Y type.Wherein effect is best contains the ZSM-20 catalyzer, air speed 0.54, and 413 ℃ of temperature of reaction, middle distillates oil selectivity 72v% is the β zeolite as acidic components, during transformation efficiency 60v%, this patent catalyzer middle distillates oil selectivity is no more than 70v%.
EP0028938 discloses a kind of hydrocracking catalyst, characteristics have been to use a kind of y-type zeolite UHP-Y, handle Arabic VGO, though middle distillates oil selectivity 86v%, transformation efficiency has only 60v%, temperature of reaction is but up to 407 ℃, handle easily cracked Kuwait VGO, reach the 70v% transformation efficiency, although temperature of reaction reduces, be 397 ℃, but middle distillates oil selectivity 74v% only.
The objective of the invention is to a kind of middle distillate oil type hydrocracking catalyst, be used for treatment of heavy hydrocarbon material, with production middle distillate oil.The present invention also aims to the middle distillate oil type hydrocracking catalyst of a kind of β of containing zeolite as the main acidic components of catalyzer, has the high middle distillates oil selectivity of high reactivity, operation scheme can maximum be produced high smoke point boat coal and low condensation point full range gas oil flexibly.
Catalyzer of the present invention has used a kind of modified beta zeolite as the main acid constituents of catalyzer and amorphous aluminum silicide auxiliary acid component and the carrier component as catalyzer, and supports and be selected from least a group vib and a kind of VIII family metal is made the hydrogenation component.Catalyst specific surface 200-300m of the present invention
2/ g, pore volume 0.3-0.4ml/g, infrared acidity 0.3-0.5mmol/g.The infrared acidity 0.1-0.5mmol/g of modified beta zeolite that catalyzer of the present invention uses, SiO
2/ Al
2O
3Than (chemical method) 30-90, Na
2O content＜0.2w%.
Catalyzer of the present invention consists of β zeolite 5-40w%, amorphous aluminum silicide 10-50w%, tackiness agent (butt aluminum oxide meter) 15-30w%, the group vib metal is selected from Mo or W, contain 10-40w% (by the metal oxide compound) in the catalyzer, VIII family metal is selected from Co or Ni, contains 1-10w% (by the metal oxide compound) in the catalyzer.
For the common modification technology of β zeolite, generally be the silica alumina ratio that improves the β zeolite, these class methods mainly comprise following two steps:
1. amine is taken off in high-temperature roasting, at 500-600 ℃ of following roasting some hrs to remove β zeolite organic amine template.
2. acid treatment dealuminzation is sloughed aluminium on the zeolite framework with the effect of raw material β zeolite at a certain temperature with certain density mineral acid, improves its silica alumina ratio.
After amine is taken off in high-temperature roasting, can be reduced to 0.8-1.0mmol/g to the infrared acidity of raw material β zeolite, again behind the acid treatment dealuminzation, the infrared acidity of β zeolite can be reduced to 0.5-0.6mmol/g, though above-mentioned modified beta zeolite solid acid amount is reduced to a certain extent, is not enough to significantly improve middle distillates oil selectivity.
β zeolite involved in the present invention is raw material β zeolite to be carried out pressurized thermal water again handle after amine and acid treatment dealuminzation step are taken off in roasting, its modified beta zeolite not only sial molecular ratio improves, the solid acid amount further reduces, make β zeolite involved in the present invention be used for catalyzer of the present invention, can make catalyzer have good middle distillates oil selectivity.
The β zeolite that catalyzer of the present invention uses is the β zeolite of handling through modification, and it has very high absorption property to non-polar hydrocarbon, and poor to the polar water molecules adsorptivity, is commonly referred to hydrophobic type β zeolite.β zeolite pore＞5 * 10 that catalyzer of the present invention is related
-10M, the characteristics of its preparation method are after amine and dealuminzation step are taken off in roasting, again through hydrothermal treatment consists, promptly 50-500KPa water vapour pressure and 400-900 ℃ of following the processing 0.5-5 hour.
The purpose of the hydrothermal treatment consists of β zeolite involved in the present invention is to change zeolite structured, be used to improve the hydrocracking catalyst middle distillates oil selectivity, and being different from high-temperature roasting or the hydrothermal treatment consists before the acid treatment dealuminzation in the prior art, the latter's purpose mainly is to slough the organic amine template in the zeolite.
β zeolite involved in the present invention is after deep sealumination modified, the acid site number reduces, infrared acidity is reduced to 0.1-0.5mmol/g, general 0.2-0.3mmol/g, can satisfy and produce the intermediate oil hydrocracking catalyst to the active needs of cracking, the chance of the generation of second pyrolysis has been reduced in less acid site simultaneously.On the other hand, the degree of β zeolite dealuminzation involved in the present invention is through strict control, and the modified beta zeolite silica alumina ratio that is obtained is at 30-90.
The super-hydrophobic β zeolite of modification involved in the present invention characteristics are a kind of low acidity modified zeolites, find out from subordinate list one, compare with a kind of Y zeolite, β zeolite of the present invention has the characteristics of low acidity, but have enough cracking performances, be used for hydrocracking catalyst of the present invention, and with have certain tart amorphous aluminum silicide and match, not only show higher activity, shown the middle distillates oil selectivity of higher level simultaneously.In addition, its structure deteriorate temperature height illustrates to have good thermostability.Therefore β zeolite involved in the present invention is used for the hydrocracking catalyst component, shows activity and middle distillates oil selectivity preferably, has good thermostability, anti-nitrogen and anti-carbon deposition ability simultaneously.
β zeolite character before and after subordinate list one modification
Zeolite numbering USY H β zeolite β zeolite of the present invention
Silica alumina ratio, mol/mol 6.55 49.16 62.16
Infrared acidity, mmol/g
B acid 0.634 0.245 0.115
L acid 0.301 0.184 0.097
B+L acid 0.935 0.429 0.212
The structure deteriorate temperature, ℃ 1,080 1,340 1420
Catalyzer of the present invention also uses auxiliary acid component and the carrier component of amorphous aluminum silicide as catalyzer, the SiO of this amorphous aluminum silicide
2Content 10-60w%, specific surface 300-500m
2/ g, pore volume 0.7-1.2ml/g, infrared acidity 0.3-0.5mmol/g is a kind of active carrier component, cooperates the zeolite component to provide lytic activity for catalyzer, supports the hydrogenation metal component simultaneously.
The moulding of catalyzer of the present invention can be adopted various known routine techniquess, and as balling-up or extrusion, supporting of metal can be adopted coprecipitation method, kneading method, pickling process etc.The first extruded moulding of general employing, the mode of impregnating metal component again, with β zeolite involved in the present invention by 5-40w% (by catalyzer) and amorphous aluminum silicide 30-80w% (by catalyzer) dry powder blend evenly after, the tackiness agent that adding 15-30w% (by catalyzer) aperture aluminum oxide makes through the nitric acid peptization mixes pinches or is rolled into paste, extruded moulding, be generally garden post bar, diameter 1.3-1.8mm also can adopt special-shaped bar such as trifolium or Herba Galii Bungei type.Behind carrier strip drying, the calcination activation, adopt the saturated or excess solution dipping hydrogenation metal in hole, the hydrogenation metal dipping solution comprises at least a group vib and a kind of VIII family metal, after the carrier strip drying behind the carrying metal, the activation finished catalyst.
Catalyzer of the present invention preferably contains β zeolite 10-30w% (by catalyzer), amorphous aluminum silicide 20-40w% (by catalyzer), tackiness agent (butt aluminum oxide meter) 15-30w% (by catalyzer), the group vib metal is selected from Mo and/or W, contain 20-30w% (by the metal oxide compound) in the catalyzer, VIII family metal is selected from Co and/or Ni, contains 4-8w% (by the metal oxide compound) in the catalyzer.
Catalyzer of the present invention is used for hydrocracking process, be particularly suitable for treatment of heavy hydrocarbon material, the boiling range scope of heavy hydrocarbon material is at 250-600 ℃, generally at 300-550 ℃, have These characteristics stock oil such as gas oil, decompression fraction oil, take off pitch prill oil, catalytic cracking turning oil, shale oil, coal tar wet goods.Reaction conditions generally under the hydrogen existence condition, reaction pressure 5-20MPa, hydrogen-oil ratio 100-5000, air speed 0.1-5.0hr
-1, temperature of reaction 350-450 ℃.Hydrocracking process generally comprises the hydrofining of leading portion, is used for removing the most S of stock oil, N, and polycyclic aromatic hydrocarbons is saturated, can reduce the severity of hydrocracking section operation like this.Catalyzer of the present invention has higher anti-nitrogen ability, thereby has higher flexibility on technology, can use this catalyzer separately, promptly adopts single hop list agent art breading heavy hydrocarbon material, all shows higher catalytic performance on active and middle distillates oil selectivity.
Catalyzer of the present invention is when handling common VGO, and generally under the hydrogen existence condition, reaction pressure is preferably in 10-20MPa to reaction conditions, hydrogen-oil ratio 500-2000, air speed 0.5-2.0hr
-1, temperature of reaction 370-420 ℃.Catalyzer of the present invention is used for the production of hydrocracking process middle distillate oil, has the characteristics of the high middle distillates oil selectivity of high reactivity.Compare with 3812 hydrocracking catalysts, adopt catalyzer of the present invention to handle grand celebration VGO equally, 389 ℃ of temperature of reaction, middle distillates oil selectivity 75w%.Catalyzer of the present invention has operational handiness, can take recycle to extinction or once-through operation mode according to product demand, and by adjusting operational condition, coal or diesel oil but the production of maximum ground is navigated.Catalyzer of the present invention has good hydrocracking performance and Hydrodewaxing performance, makes the hydrocracking product property excellence that is obtained, and particularly can produce low freezing point diesel fuel, and fraction of diesel oil cutting temperature wide ranges, helps high-yield diesel oil.
Example 1
H type β zeolite (SiO
2/ Al
2O
3=25.1) handled 2 hours with 0.5NHCl, make SiO
2/ Al
2O
3=48,25 ℃ of water vapor pressure 12 mmhg, water regain 16.9w%.Again through 750 ℃ of hydrothermal treatment consists after 2 hours, 25 ℃ of water vapor pressure 12 mmhg, water regain 2.6w%, after the drying treatment β zeolite FA of the present invention.Get FA20.7g, macropore amorphous aluminum silicide 86.3g (SiO
2Content 45w%, specific surface 365m
2/ g, pore volume 0.956ml/g, infrared acidity 0.40mol/g), ammonium metawolframate 47g, nickelous nitrate 42.1g, the back that is mixed is dissolved in 5.7ml40% nitric acid that tackiness agent that rare nitric acid peptization 28g aperture pseudo-boehmite of 85ml distilled water makes is mixed pinches into paste, behind the post orifice plate extruded moulding of φ 1.7mm garden, 110 ℃ of dryings, got catalyzer CA of the present invention in 3 hours through 500 ℃ of activation again.Catalyzer consists of WO
323.8w%, NiO 7.4w%, hydrophobic β zeolite 10w%.Catalyst specific surface 264m
2/ g, pore volume 0.322ml/g.
Example 2
H type β zeolite (SiO
2/ Al
2O
3=25.1) handled 2 hours with 0.5NHCl, make SiO
2/ Al
2O
3=48,25 ℃ of water vapor pressure 12 mmhg, water regain 16.9w%.Again through 550 ℃ of hydrothermal treatment consists after 2 hours, 25 ℃ of water vapor pressure 12 mmhg, water regain 7.3w%, after the drying treatment β zeolite FB of the present invention.Get FB41.6g, macropore amorphous aluminum silicide 116.4g (SiO
2Content 25w%, specific surface 332m
2/ g, pore volume 0.922ml/g, infrared acidity 0.34mmol/g), the back that is mixed is dissolved in tackiness agent that rare nitric acid peptization 28g aperture pseudo-boehmite of 85ml distilled water makes with 5.7ml40% nitric acid and mixes and pinch into paste, excessively behind the post orifice plate extruded moulding of φ 1.7mm garden, 110 ℃ of dryings, got carrier in 3 hours through 500 ℃ of activation again, use by molybdenum oxide 39g nickelous nitrate 41g, 85%H
3PO
4The steeping fluid dipping of preparation got CB of the present invention in 3 hours through 500 ℃ of activation again.Catalyzer consists of MoO
323.4w%, NiO 6.7w%, hydrophobic β zeolite 15w%.Catalyst specific surface 268m2/g, pore volume 0.329ml/g.
Example 3
Get FA62.4g in the example 1, macropore amorphous aluminum silicide 106.3g (SiO
2Content 35w%, specific surface 396m
2/ g, pore volume 0.996ml/g, infrared acidity 0.34mmol/g), the back that is mixed is dissolved in the mixed paste of pinching into of tackiness agent that rare nitric acid peptization 28g aperture pseudo-boehmite of 85ml distilled water is made with 5.7ml40% nitric acid, after crossing φ 1.7mm garden post orifice plate extruded moulding,, use ammonium metawolframate 47g at 110 ℃ of dry carriers that get, the steeping fluid dipping of nickelous nitrate 42.1g preparation got catalyzer CC of the present invention in 3 hours through 500 ℃ of activation again.Catalyzer consists of WO
324.5w%, NiO 6.8w%, hydrophobic β zeolite 30w%.Catalyst specific surface 278m
2/ g, pore volume 0.318ml/g.
Comparative example 1
Preparation of Catalyst is identical with example 1, except hydrophobic type β zeolite being changed into super-hydrophobic Y type zeolite (infrared acidity 1.1mmol/g), i.e. and the USY that mentions of preamble.Catalyzer consists of MoO
318.7w%, NiO5.7w%, Y zeolite 15w%.Catalyst specific surface 301m
2/ g, pore volume 0.386ml/g, numbering YC.
Example 5
Example 1-example 4 evaluating catalysts adopt the 200ml fixed-bed reactor, estimate and see Table 1 with stock oil character, and catalyzer goes into operation needs sulfuration.To one-stage serial technology, hydrocracking catalyst is contained in second reactor, first reactor dress Hydrobon catalyst, make the treated oil nitrogen content＜10 μ g/g that enter second reactor, the one-stage serial technology assessment the results are shown in Table 2, one-stage serial extinction recycle operation process results sees Table 3, and the hydrocracking product property sees Table 4.Catalyzer of the present invention is owing to the acid sites characteristics that had, and nitrogen resistance is strong, can adopt the agent of single hop list to handle stock oil, uses grand celebration VGO equally, and single hop list agent technology assessment result reaches with 3812 comparing results and sees Table 5.
Table 1. stock oil character
Stock oil triumph VGO grand celebration VGO Saudi Arabia VGO
Density, g/cm
30.8861 0.8571 0.9133
Boiling range, ℃
IBP 294 284 319
50％ 443 453 432
95％ 529 531 504
Carbon residue, w% 0.15 0.04 0.08
S，w％ 0.53 0.07 2.20
N，w％ 1.72 0.54 0.79
Table 2 one-stage serial is once by the technology assessment result
Number 1,001 1,002 1003
Catalyzer CA CB CC
Stock oil Saudi Arabia VGO Saudi Arabia VGO Saudi Arabia VGO
Temperature of reaction (℃) 390 378 375
The product distribution (to raw material, v%):
Light naphthar 4.6 5.0 5.6
Heavy naphtha 10.1 10.1 11.0
Boat coal 36.1 37.5 38.2
Diesel oil 27.4 26.4 23.5
Tail oil 30.2 29.2 29.1
Liquid receives 108.4 108.2 108.0
Middle distillates oil selectivity, % 81.2 80.9 78.2
Table 3. one-stage serial extinction recycle operation process results number 1,004 1005 catalyzer CB YC stock oils triumpies VGO triumph VGO temperature of reaction (℃) 380 384 products distribute (to raw material, v%):
Light naphthar 12.8 23.2
Heavy naphtha 14.9 16.1
Boat coal 47.1 44.6
Diesel oil 33.2 24.0
C
5+Liquid is received 108.0 107.9 middle distillates oil selectivities, and % 80.3 68.6
Table 4 hydrocracking product property is numbered 1,001 1,002 1,003 1,004 1005 boat coal smoke points, mm 26 27 28 30 28 condensation point of diesel oil, ℃-11-14-17-12 0
Table 5. single hop list agent technology assessment is catalyzer 3812 as a result
☆CB stock oil grand celebration VGO grand celebration VGO volume space velocity, hr
-11.0 1.0 temperature of reaction (℃) distribution of 393 389 products (to raw material, w%):
Gasoline 24.7 17.2
Kerosene 31.1 32.7
Diesel oil 11.2 17.7
Tail oil 29.8 30.9
Liquid is received 96.8 98.5 middle distillates oil selectivities, and the data of % 58.4 74.6 ☆ 3812 catalyzer are selected from " Chinese oil Refining Technologies " the 511st page
Claims (8)
1, a kind of hydrocracking catalyst that is used for production middle distillate oil, it consists of β zeolite 5-40w%, amorphous aluminum silicide 10-50w%, aluminum oxide 15-30w%, group vib metal oxide 10-40w%, VIII metal oxide 1-10w% is characterized in that said β zeolite SiO
2/ Al
2O
3Than 30-90, water regain＜10% under the infrared acidity 0.1-0.5mmol/g, 25 ℃, water vapor pressure≤12mmHg.
2, catalyzer as claimed in claim 1 is characterized in that the specific surface 200-300m of catalyzer
2/ g, pore volume 0.3-0.4ml/g, infrared acidity 0.3-0.5mmol/g.
3, catalyzer as claimed in claim 1 is characterized in that described β zeolite is that H type β zeolite obtains after hydrothermal treatment consists.
4, catalyzer as claimed in claim 3 is characterized in that described H type β zeolite is to obtain with mineral acid extracting dealuminzation.
5, catalyzer as claimed in claim 1 is characterized in that said group vib metal is selected from Mo or W, accounts for the 10-40w% that catalyzer is formed by oxide compound.
6, catalyzer as claimed in claim 1 is characterized in that said VIII family metal selects white Co or Ni, accounts for the 1-10w% that catalyzer is formed by oxide compound.
7, catalyzer as claimed in claim 1 is characterized in that consisting of β zeolite 10-30w%, amorphous aluminum silicide 20-40w%, aluminum oxide 15-30w%, group vib metal oxide 20-30w%, VIII metal oxide 4-8w%.
8, catalyzer as claimed in claim 1 is characterized in that said amorphous aluminum silicide specific surface 300-500m
2/ g, pore volume 0.7-1.1ml/g, infrared acidity 0.3-0.5mmol/g.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116403A CN1054153C (en) | 1997-09-10 | 1997-09-10 | Hydrocracking catalyst for producing intermediate fraction oil |
| KR10-1998-0037230A KR100376563B1 (en) | 1997-09-10 | 1998-09-09 | Hydrocracking Catalysts for Intermediate Fraction Oil Production |
| JP25664798A JP3688476B2 (en) | 1997-09-10 | 1998-09-10 | Hydrocracking catalyst for medium distillate oil production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN97116403A CN1054153C (en) | 1997-09-10 | 1997-09-10 | Hydrocracking catalyst for producing intermediate fraction oil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1210881A CN1210881A (en) | 1999-03-17 |
| CN1054153C true CN1054153C (en) | 2000-07-05 |
Family
ID=5173824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN97116403A Expired - Lifetime CN1054153C (en) | 1997-09-10 | 1997-09-10 | Hydrocracking catalyst for producing intermediate fraction oil |
Country Status (3)
| Country | Link |
|---|---|
| JP (1) | JP3688476B2 (en) |
| KR (1) | KR100376563B1 (en) |
| CN (1) | CN1054153C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986747B (en) * | 2005-12-23 | 2011-06-15 | 中国石油化工股份有限公司 | Diesel oil fraction hydrogenating modification process |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002519281A (en) * | 1998-06-29 | 2002-07-02 | カリフォルニア インスティチュート オブ テクノロジー | Molecular sieve CIT-6 |
| EP1147811A1 (en) * | 2000-04-20 | 2001-10-24 | Engelhard Corporation | Catalyst, catalyst support and process for hydrogenation, hydroisomerization, hydrocracking and/or hydrodesulfurization. |
| CN1108356C (en) * | 2000-10-26 | 2003-05-14 | 中国石油化工股份有限公司 | High-activity high-or medium-oilness hydrocracking catalyst and its preparing process |
| KR100419288B1 (en) * | 2001-06-22 | 2004-02-19 | 인천정유 주식회사 | Method for preparing catalysts for dearomatization in distillate |
| US7048845B2 (en) * | 2001-11-07 | 2006-05-23 | Uop Llc | Middle distillate selective hydrocracking process |
| US7169291B1 (en) | 2003-12-31 | 2007-01-30 | Uop Llc | Selective hydrocracking process using beta zeolite |
| CN1331604C (en) * | 2004-06-21 | 2007-08-15 | 中国石油化工股份有限公司 | Hydrogenation catalyst carrier and production thereof |
| CN1313206C (en) * | 2004-06-21 | 2007-05-02 | 中国石油化工股份有限公司 | Hydrogenation catalyst of diesel production at most amount and production thereof |
| CN100340639C (en) * | 2004-10-29 | 2007-10-03 | 中国石油化工股份有限公司 | Hydrocracking catalyst containing IIB metal oxide and uses |
| CN100413944C (en) * | 2005-10-08 | 2008-08-27 | 中国石油化工股份有限公司 | Method for producing lubricating oil base oil by hydrogenating tail oil |
| CN100422295C (en) * | 2005-10-08 | 2008-10-01 | 中国石油化工股份有限公司 | Method for producing food grade white oil by hydrogenating tail oil |
| KR100968385B1 (en) * | 2008-10-01 | 2010-07-09 | 한국화학연구원 | Method for Preparing Ni-Mo/Silica-Alumina Catalyst and Method for Producing Middle Distillate Using Said Catalyst |
| US8394255B2 (en) * | 2008-12-31 | 2013-03-12 | Exxonmobil Research And Engineering Company | Integrated hydrocracking and dewaxing of hydrocarbons |
| JP5492431B2 (en) * | 2009-03-13 | 2014-05-14 | 出光興産株式会社 | Hydrocracking catalyst, method for hydrocracking, and method for producing hydrocracking catalyst |
| JP5508744B2 (en) * | 2009-03-13 | 2014-06-04 | 出光興産株式会社 | Method for producing beta zeolite and method for producing hydrocracking catalyst |
| CN102773117A (en) * | 2012-08-21 | 2012-11-14 | 中国海洋石油总公司 | Medium-oil-type hydrocracking catalyst and preparation method thereof |
| KR101840773B1 (en) * | 2013-11-26 | 2018-03-21 | 차이나 페트로리움 앤드 케미컬 코포레이션 | Beta molecular sieve, preparation method therefor and hydrogenation catalyst containing same |
| CN108499600B (en) * | 2018-04-19 | 2021-03-30 | 润和催化剂股份有限公司 | Catalytic cracking catalyst for increasing diesel oil yield and preparation method thereof |
| JP2021080132A (en) * | 2019-11-19 | 2021-05-27 | 東ソー株式会社 | Hydrophobic zeolite and method for producing the same |
| CN112844465A (en) * | 2021-01-25 | 2021-05-28 | 中国石油天然气股份有限公司 | Hydrocracking catalyst and application thereof |
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-
1997
- 1997-09-10 CN CN97116403A patent/CN1054153C/en not_active Expired - Lifetime
-
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- 1998-09-10 JP JP25664798A patent/JP3688476B2/en not_active Expired - Lifetime
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| EP0028938A1 (en) * | 1979-11-13 | 1981-05-20 | Union Carbide Corporation | Catalytic conversion of hydrocarbons |
| US4820402A (en) * | 1982-05-18 | 1989-04-11 | Mobil Oil Corporation | Hydrocracking process with improved distillate selectivity with high silica large pore zeolites |
| CN1006873B (en) * | 1985-07-19 | 1990-02-21 | 厄尔特公司 | Text and graphics image setting apparatus |
| CN1037168A (en) * | 1987-12-08 | 1989-11-15 | 环球油品公司 | The new improved catalyst and the using method thereof that are used for the middle runnings hydrocracking |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1986747B (en) * | 2005-12-23 | 2011-06-15 | 中国石油化工股份有限公司 | Diesel oil fraction hydrogenating modification process |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH11156198A (en) | 1999-06-15 |
| KR19990029665A (en) | 1999-04-26 |
| KR100376563B1 (en) | 2003-05-17 |
| CN1210881A (en) | 1999-03-17 |
| JP3688476B2 (en) | 2005-08-31 |
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