CN1024135C - Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst - Google Patents
Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst Download PDFInfo
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- CN1024135C CN1024135C CN 89108358 CN89108358A CN1024135C CN 1024135 C CN1024135 C CN 1024135C CN 89108358 CN89108358 CN 89108358 CN 89108358 A CN89108358 A CN 89108358A CN 1024135 C CN1024135 C CN 1024135C
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- catalyzer
- macropore
- pore space
- catalyst
- diameter
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- 239000003054 catalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims description 36
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title 1
- 229910052760 oxygen Inorganic materials 0.000 title 1
- 239000001301 oxygen Substances 0.000 title 1
- 239000011148 porous material Substances 0.000 claims abstract description 83
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 30
- 239000000463 material Substances 0.000 claims abstract description 19
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims description 45
- 239000002184 metal Substances 0.000 claims description 44
- 229910052720 vanadium Inorganic materials 0.000 claims description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- 238000006477 desulfuration reaction Methods 0.000 claims description 17
- 230000023556 desulfurization Effects 0.000 claims description 17
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 12
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000003921 oil Substances 0.000 claims description 9
- 239000002994 raw material Substances 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 239000011733 molybdenum Substances 0.000 claims description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical group O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 102000040350 B family Human genes 0.000 claims 1
- 108091072128 B family Proteins 0.000 claims 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims 1
- 229910052814 silicon oxide Inorganic materials 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 17
- 239000004215 Carbon black (E152) Substances 0.000 abstract description 5
- 229930195733 hydrocarbon Natural products 0.000 abstract description 5
- 238000002459 porosimetry Methods 0.000 abstract 1
- 229910052782 aluminium Inorganic materials 0.000 description 27
- 239000004411 aluminium Substances 0.000 description 26
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 26
- 238000009826 distribution Methods 0.000 description 15
- 239000002245 particle Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 8
- 239000012153 distilled water Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000000126 substance Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000295 fuel oil Substances 0.000 description 4
- 231100000614 poison Toxicity 0.000 description 4
- 230000007096 poisonous effect Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000010779 crude oil Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 125000002524 organometallic group Chemical group 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 238000004438 BET method Methods 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000002826 coolant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004453 electron probe microanalysis Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003189 isokinetic effect Effects 0.000 description 1
- JCCNYMKQOSZNPW-UHFFFAOYSA-N loratadine Chemical compound C1CN(C(=O)OCC)CCC1=C1C2=NC=CC=C2CCC2=CC(Cl)=CC=C21 JCCNYMKQOSZNPW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 230000036651 mood Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Abstract
For heavy hydrocarbon materials, the catalyst used has 5-11% of its pore volume in its macropores and a surface area greater than 75m2In terms of/g, particularly good hydrodemetallization and hydrodesulfurization effects can be achieved. It is preferred that the catalyst have a maximum mesopore diameter of greater than 165A as measured by mercury porosimetry and an average mesopore diameter of greater than 160A.
Description
Carry out the method for hydrodemetallation (HDM) and hydrogenating desulfurization.
The present invention relates to hydrodemetallation (HDM) and hydrogenating desulfurization, and relate to and be used for taking place simultaneously the hydrodemetallation (HDM) of heavy oil feedstock and the catalyzer of hydrogenating desulfurization effect.Catalyzer involved in the present invention has certain hole, and is particularly macroporous.Have now found that the macrovoid catalyzer for heavy oil hydrodemetallation (HDM) takes place simultaneously and the hydrogenating desulfurization effect has beyond thought effect.
United States Patent (USP) 3898155 discloses a kind of heavy oil that contains the 50ppm metal at least, at hydrogenation with use under the condition of catalyzer, thereby the method for demetalization and desulfurization takes place simultaneously.Used catalyzer contains the metal of V1 family and contains the metal of a V111 family at least, and is mixed with the oxide compound of indissoluble.The pore space of catalyzer macropore is 10-40%, and the pore space of micropore is 60-90%, wherein has at least the aperture of 80% micropore to be at least 100
In addition, total pore space of said catalyzer is at least 0.5ml/g, and its average aperture is greater than 100
, surface-area is at least 100m
2/ g.
The Taiwan patent NI23976 that announces on April 16th, 1986 discloses a kind of be used to contain the bituminous demetalization of hydrocarbon polymer and the method for desulfurization, promptly under the condition of hydrogenation, the catalyzer that uses contains molybdenum, at least also contain a V111 family metal and aluminium, said its total pore space capacity of catalyzer with water silver penetration test is at least 0.4cc/g, macropore accounts for the 5-50% of catalyst pores capacity, and in every milliliter of catalyst pores capacity, the pore space of mesopore is at least 0.12 milliliter.
United States Patent (USP) 4008149 discloses a kind of catalyzer that is used for hydrogenating desulfurization, hydrodemetallation (HDM) and hydrodenitrification.The surface-area that this catalyzer has is 250～300m
2/ g is at 0-150
In the scope; At least 80% pore space is by 60-150
The hole form; And less than the pore space of 0.01cc/g is to be formed by 150 to 2000A hole; Face is at 0-600
Pore space in the scope is approximately between 0.45～0.60 milliliter of every gram catalyzer.
United States Patent (USP) 4301037 discloses a kind of bimodal Al catalysts carrier, and its most surfaces is amassed in the micropore district, and the hole is less than 500A, and has big porose area, and the aperture is 1000
To 10000
United States Patent (USP) 4225421 discloses a kind of hydrodemetallation (HDM) of the hydrocarbon polymer that is used to contain pitch and metal and the double-peak catalyst of hydrogenating desulfurization.This catalyzer contains active, as to play a hydrogenization metal, and it is selected from the B of V1 family, and attached on a kind of carrier that comprises aluminium.The surface-area of this catalyzer is about 140-300m
2In/g the scope.Total pore space capacity with the mercury penetration test is in about 0.4-1.0cc/g scope.Its micropore pore space is approximately its micropore size of 60-95% in about 50A to 200A scope; Its micropore pore space is 0% to about 15%, and its micropore size is at about 200A to 600
In the scope; 3-30% with the said total pore space of mercury penetration test capacity is a macropore, and its aperture is 600
Or it is bigger.
United States Patent (USP) 4454026 discloses a kind of hydrotreating catalyst, it comprises hydrogenant component and carrier, this carrier comprises the inorganic oxide of a kind of porous, indissoluble at least, and the catalyst surface area of measuring with cloth Shandong Nao E-Ai Meite-taylor rule (BET) of this catalyzer is 150 to about 190m
2/ g, tap density is approximately 0.2g/cc at least, measure total pore space with the mercury osmose process and be approximately 0.9cc/g at least, and its aperture of macropore that pore space is at least about 0.1cc/g is 600 to 25000
Above-mentioned surface-area, size distribution and total pore space can obtain being at least 230 effectively
Mean pore size, calculate by the ratio of four times pore spaces and surface-area.
The invention provides a kind of hydrodemetallation (HDM) and hydrodesulfurizationprocess process that is used for the higher boiling point hydrocarbon raw materials of compound.This method is included in temperature between 600 °F and 1000 °F, and pressure is at 100 and 10000 pounds/inch
2Under the condition between the gauge pressure, and under the situation that has hydrogen to exist, material is contacted with catalyzer, what this catalyzer comprised the metal that is selected from V1 family and V111 family has a hydrogenization component, and contains and tie up molten inorganic oxide carrier, and wherein this catalyzer has:
The pore space of the macropore of a, catalyzer is 5-11%, and
The surface-area of b, catalyzer is greater than 75m
2/ g.
Be preferably, the average mesopore diameter of catalyzer is greater than 160
, being more preferably when measuring with the mercury porosimeter, the maximum median pore diameter that catalyzer has is greater than 165
In other factors, the present invention is based on to find with a kind of catalyzer and makes heavy oil feedstock can obtain beyond thought hydrodemetallation (HDM) (HDM) and hydrogenating desulfurization (HDS) effect.Wherein the pore space of the macropore of catalyzer is the 5-11% of the total pore space capacity of catalyzer in scope relatively, is preferably the 6.5-10% of the pore space of catalyzer, and catalyzer has sizable surface-area, promptly greater than 75m
2/ g is preferably greater than 100m
2/ g, best is greater than 115m
2/ g.Equally, we find, if the maximum diameter of hole of catalyzer is greater than 165
, can obtain good especially HDM and HDS effect.More preferably, when measuring with the mercury porosimeter maximum diameter of hole greater than 185
, and the average mesopore aperture is greater than 160
, more preferably greater than 180
After extensive studies, we find to have the catalyzer of lower macrovoid capacity, can have attractive hydrodesulfurization activity, and still, its hydrodemetallation (HDM) is active and the metal percent of pass is lower.In addition, we also find, if macrovoid is higher than the macrovoid scope of the used catalyzer of the present invention, high hydrodemetallation (HDM) activity and metal percent of pass can keep, and still, its desulphurizing activated reduction is rapider.Equally, if macrovoid greater than the used range of catalysts of the present invention, the damping capacity of the carbon residue of catalyzer [measure unit of the variation tendency of coke can be expressed as trace carbon residue (MCR)] promptly descends in time.
Though, the present invention is not limited by any production theory, and in view of our discovery, a kind of proper explanations is as follows: (for example be lower than 6.5% in the low situation of macrovoid, particularly be lower than 5%), the organo-metallic molecule can not easily infiltrate the catalyst particle neutralization and react.Therefore, the catalyzer that macrovoid is low, its activity and metal percent of pass are low.In the high situation of macrovoid, the organo-metallic molecular energy more easily penetrates in the catalyst particle.Yet " poisonous substance " in the raw material also is seeped in the catalyst particle, and the active zone that reduces desulfurization and remove MCR.We have found that macrovoid is between 5% to 11%, particularly in 6.5% to 10% scope, hydrodemetallation (HDM) activity, hydrodesulfurization activity and removal MCR activity obtain desirable balance.The organo-metallic molecule can penetrate in the particle with comparalive ease, and still " poisonous substance " but can easily not penetrate in the catalyzer.Therefore, catalyzer has high hydrodemetallation (HDM) active and metal percent of pass and high sulphur and MCR removal activity.Here said " poisonous substance " do not make good explanation, but thinks may contain many metals by the high-molecular weight molecule.
Use patent NI23976 described catalyzer in Taiwan to have the high hydrogenating desulfurization and the activity of hydrodemetallation (HDM).Yet, have been found that and use catalyzer of the present invention, can obtain the activity that high-grade hydrogenating desulfurization and hydrodemetallation (HDM) combine usually.The above-mentioned described catalyzer of Taiwan patent has bigger macropore pore space to obtain the active and metal percent of pass of high hydrodemetallation (HDM).The macropore pore space that this catalyzer has is 25%.In order to obtain very high hydrodesulfurization activity, perhaps need from the inner poisonous substance of getting rid of of catalyst particle, the described catalyzer of Taiwan patent, its mesopore is less, promptly about 110A.Now obtained such reasoning, compared with the hydrodemetallation (HDM) activity that catalyzer reached that the present invention is used, less mesopore is the active major cause of its lower hydrodemetallation (HDM).This point hereinafter will be done further explanation by embodiment 8.
Can use prepared in various methods to be used for the catalyzer of the inventive method, make the catalyzer that makes have above-mentioned various characteristics.
Preparing a kind of method preferably of catalyzer of the present invention is, makes needed metal and suitable carriers material such as silicon, aluminium etc. altogether not with fixed attention when the catalyzer of preparation.
Another kind method preferably is to prepare support of the catalyst or solid support material individually, then impregnating metal.Can use acid or carrier dispersive the whole bag of tricks.
Utilize the whole bag of tricks of the prior art can regulate macropore per-cent in the catalyzer.The per-cent of macropore pore space mainly depends on two factors; The characteristic of mixedness and used raw material (as aluminium).
Mixedness depends on the energy of used specific equipment, mixing time and mixing machine input.Usually, mixedness improves the per-cent that can reduce macropore.Otherwise the mixedness reduction can cause the raising of macropore per-cent.When shaping of catalyst (as extruding), the energy of input also can influence the per-cent of macropore pore space.
The type of raw material also influences the per-cent of the macropore of formation.This can be changed by the dispersing characteristic of aluminium (common catalyzer raw material) and illustrates that aluminium has various dispersed indexes (DI), and the DI testing sequence can be recognized from the communique NO22 of Kaiser chemical preparations engineering department is interim.The per-cent of DI test determination aluminium, promptly under the test conditions of standard acid, aluminium is dispersed into less than 1 micron.Crystalline aluminium such as pseudobochmite have very wide DI value scope (10-100).These DI values are usually above V-aluminium or Calcined polishing aluminum oxide (DI＜10).In order to improve the macropore per-cent of catalyzer or support of the catalyst, can add the lower aluminium of DI value; In order to reduce the macropore per-cent of catalyzer or support of the catalyst, can add the higher aluminium of DI value.
The pore space of macropore that special recommendation is used for the catalyzer of the inventive method is in the scope of the 7.5-10% of catalyzer total pore space capacity.Best macropore pore space is about 8-9% of total pore space capacity.The indissoluble inorganic oxide carrier that recommendation is used for catalyzer of the present invention comprises: aluminium, silicon-inscription and silicon.Special recommendation be alumina supporter.
The catalyzer that is used for the inventive method requires to contain the component of hydrogenization, preferably V1 family metal or V111 family metal.The molybdenum and the tungsten of the V1 family metal of special recommendation, and molybdenum is the most desirable.The V1 family of recommending and the content range of V111 family metal are summarized as follows:
V111 family of V1 family
0～30 heavy % 0～15 heavy % that recommends
1～20 heavy % 0.5～10 weighs % preferably
2～20 best heavy % 1～4 heavy %
The metal of the V111 family of special recommendation is nickel and cobalt, and nickel is the most desirable.
Can be in various manners with melts combine in catalyzer, a kind of mode preferably is that metal is impregnated in the carrier.
Catalyzer can be used for the reactor of different structure, but preferably is used for fixing catalytic bed reactor.
The shape of selecting catalyst and size are minimum for diffusional limitation and reactor pressure are fallen.Though the shape of catalyzer can be a different shape, comprise cylindrical particle or spheroid or other shape, preferably, the diameter of catalyzer is the 1/8-1/100 inch, more preferably diameter is the 1/18-1/40 inch.The preferably non-cylinder of catalyzer, tetragonal body, described as United States Patent (USP) 4394303.
The material of method of the present invention, higher boiling point hydrocarbon compound preferably, normal boiling point almost all is higher than 600 °F.
Therefore, method of the present invention is mainly used in the Residual oil material, and it is different with the gasoline material.Usually the metal content of Residual oil material is greater than 10ppm, and the metal content of gasoline is almost always less than 10ppm, and for example, metal content only is 1-4PPm usually, even for the gasoline of high vacuum.Therefore, the material that the present invention uses always is crude oil atmospheric distillation tower bottom distillate Residual oil or atmospheric tower Residual oil, vacuum distilling tower bottom distillate (vacuum resid) and solvent desulfurization Residual oil.Very the metal content of Chong gasoline is can be greater than 10PPm, and in the case, method of the present invention just can be used for the material of oily thing.Yet method of the present invention is applied to have the material of metal content greater than 20PPm, can obtain bigger benefit.Therefore, have been found that method of the present invention is applied to contain very high molecular weight and also contains material greater than the 20PPm metal, benefit is best.Here related metal is meant to be pure metal etc., i.e. metallic element by weight.And said metal is considered to exist with the form of organometallic compound, and the concentration of metal that relates to is here calculated with the pure metal of ppm.
At the impurities in raw materials metal, generally include nickel, vanadium and iron.
For the present invention, the material of recommendation preferably contains greater than 0.1% sulphur (by weight), and sulphur is that the form with organosulfur compound exists, and the heavy % that calculates sulphur is based on elementary sulfur.
Implementing method of the present invention is at 600～1000 °F, more preferably 680～800 °F; The pressure of recommending is 100～10000 pounds/square inch gauge, more preferably 1000～3000 pounds/square inch gauge.The ratio of hydrogen and hydrocarbon polymer material is recommended as 500～20000, more desirable amount 2000～8000.Fluid adds the catalyst fixed bed fluid hourly space velocity of recommending (LHSV) and is preferably at 0.01～10/ o'clock, at more preferably 0.1～2/ o'clock.
According to other embodiments of the invention, catalyzer that provides and support of the catalyst meet requirement recited above and have the macrovoid of prescribed value, the largest hole diameter of regulation and the middle pore property of regulation.The carrier of catalyzer has the macrovoid substantially the same with above-mentioned catalyzer, maximum diameter of hole and mesoporosity.But the metal that does not have V1 family or V111 family hydrogenization.
Express the distribution and the pore space of hole size in an embodiment.Embodiment 6 provides the explanation of mercury porosimeter and by the data of its acquisition.
Here used " macropore " term is meant that (ASTMD4284) aperture of measuring with mercury porosimeter is greater than 1000
The hole.
Here used " mesopore " term is meant that the aperture of measuring with mercury porosimeter is 35～1000
The hole of scope, the mesopore pore space is also measured with mercury porosimeter.
The present invention is calculated as follows average mesopore diameter.
Average mesopore diameter=(mesopore pore space (cc/g))/(surface-area (m
2/ g)) * 40000
Maximum median pore diameter=maximum dV/dD is at 35～1000A diameter range.
Maximum median pore diameter depends on the mercury contact angle of supposition when calculating with the mercury porosimeter.In all calculating, be that support of the catalyst or the catalyzer that processes (having filled metal) are all used 140 ° of contact angles.
Support of the catalyst component such as aluminium, silicon and silicon/aluminium, its contact angle are similar to 140 °.Can change contact angle after in support of the catalyst, adding various metals.Yet,, in calculating, suppose that contact angle is 140 ° for the catalyzer that processes.Therefore, we find, the support of the catalyst that the present invention recommends, and the diameter of maximum mesopore is greater than 145
; We find, the catalyzer that the present invention recommends, and maximum median pore diameter simultaneously, even may median pore diameter can diminish greater than 165A.Therefore, greater than 165
Diameter is calculated and is " apparent " diameter.
Terminology used here " surface-area " is meant the surface-area of measuring by absorption nitrogen with the BET method, promptly uses known BET method, uses the data information of the micrometer ASAP2800 of instrument company, and uses nitrogen can measure surface-area.
Here used MCR, its meaning is exactly little carbon residue, with ASTMD4530～85 determination of test method.According to ASTMD4530-85, MCR equals carbon residue exactly.
Here used vanadium dispersion index is meant at the ratio of the average metal concentration of the boundary of catalyst particle with peak concentration, because the catalyst sample that after experiment is finished, is taken out with electron microprobe analysis, can record dispersion index, so it represents the average Metal Distribution of this batch catalyzer.Equal the average efficiency index of this batch catalyzer owing to simple first isokinetic reason distribution coefficient.Owing to the dynamic (dynamical) reason of other grade, if peak concentration occurs in the border of catalyst particle, the proportional relation of average efficiency index of distribution coefficient and this batch catalyzer.
For most practical application, the border that maximum concentration occurred in or approached particle.Therefore, high dispersion index (being similar to 1) means that contained metal more in depth is penetrated into catalyzer and is sedimentary more even in each hole.Low distribution coefficient (near 0) means the boundary vicinity of metal preferential deposition at granules of catalyst.
Embodiment 1
Disperse aluminium to make the support of the catalyst of macropore with acid
With 865gkaiser versal 250 aluminium of sour dispersity (DI value) between the 20-28 Baker-perkins agitator of packing into, and be heated to 130～140 °F, stir uniformly simultaneously.After 5 minutes, 873ml distilled water was slowly joined in the agitator with the time more than 15 minutes.Add the dense HNO of 13.9g then
3(70%) and 42ml distilled water.After 8 minutes, add the dense NH of 9.9g with the time more than 3 minutes
4OH(58%) and 30ml distilled water, make temperature remain on 140 °F.After 25 minutes, in agitator, add 859gkaiser versal 150 aluminium of PI value between 10-20.Then, add 704ml distilled water.After about 20 minutes, mixture is cooled to about room temp.After storing an evening, with 2 inches Bonnott forcing machines, its die head is 0.039 inch, and water coolant is arranged in the cylindrical shell, extrusioning catalyst, and immediately 250 °F dry 2 hours down, and 400 °F dry more than 2 hour down.Last support of the catalyst use 1 cubic feet/time (CFH) dry air 1700 following roastings 1 hour.
Final resulting support of the catalyst has following characteristic:
Particle density 0.94g/cc
Bulk density 3.4g/cc
BET surface-area 146.8m
2/ g
Mercury porosimeter is measured:
Total pore space 0.802cc/g
Macropore pore space 0.0612cc/g
Macropore 7.6%
Maximum median pore diameter 192
The average mesopore diameter of calculating 202
Embodiment 2
The support of the catalyst of dipping macropore
Be placed in the air evening of rehydration by the support of the catalyst of embodiment 1 preparation.The total pore space capacity of 150g rehydration carrier is 129cc.Stirring contains the 88.9g phosphorus molybdenum acid solution of 15.6% molybdenum and 2.0% phosphorus, and it is heated to 40 ℃, with the preparation dipping solution.Then, add 30% hydrogen peroxide, one once clear up to solution becomes, and be straw yellow.Add distilled water, the total pore space capacity is brought up to 97cc.The Nico that adds 7.44g
3(the science engineering manual 48.4%Ni) stirs down at 40 ℃ simultaneously.Behind the lather collapse, solution is cooled to 30 ℃, and arrives 129cc with distilled water diluting.Support of the catalyst is sprayed filling perforation with above-mentioned solution.Wet catalyzer keeps an evening, and the catalyzer that obtains is following dry 1 hour at 250 °F.The exsiccant catalyzer uses the 20CFH dry air 200 following roastings 6 hours in retort furnace, 450 following roastings 4 hours, and 750 following roastings 4 hours, and 950 following roastings 5 hours.
Resulting catalyzer has following characteristic:
Particle density 1.11g/cc
Bulk density 3.6g/cc
BET surface-area 130.7m
2/ g
Mercury total porosity 0.6167
Mercury macropore porosity 0.0479
Mercury porosimeter is measured:
Total pore space capacity 0.802cc/g
Macropore pore space 0.0612cc/g
Macropore 7.8%
Maximum median pore diameter 219
Calculate average mesopore diameter 174
This catalyzer sees Table the NO.3 catalyzer of II.
Embodiment 3
Use NH
4OH disperses aluminium to make macropore carrier.
The Davison sra aluminium of 785g is packed in the large-scale Baker-Perkins mixing tank.1800ml distilled water and 146ccNH
4OH(58%) mix, the pH value of resulting solution is 10.5.This solution of 1500g with in 200ml/ minute adding agitator, is stirred simultaneously.All solution stirred the mixture more than 10 minute after adding.Then, join the kaiser versal250 aluminium of 785g in the mixture and restir 50 minutes.With 2 inches Bonnott forcing machines, its die head is 0.039 inch and has cooling, extrudes a semifused.Extrudate is dry and be broken into the particle that L/D is 2-3, put into the Freas stove then and temperature was brought up to 400 °F again in 2 hours, and kept 2 hours 250 ° of following preheatings.Last support of the catalyst uses the 1CFH dry air 1700 following roastings 1 hour.The characteristic of resulting support of the catalyst is as follows:
Particle density 0.87g/cc
Bulk density 3.4g/cc
BET surface-area 142m
2/ g
Mercury porosimeter is measured:
Total pore space capacity 0.855cc/g
Macropore pore capacities 0.077cc/g
Macropore 9%
Maximum median pore diameter 184
Calculate average mesopore diameter 219
Embodiment 4
The support of the catalyst of dipping macropore
Flood the prepared support of the catalyst of embodiment 3 in the mode of similar embodiment 2.Resulting catalyzer is as follows:
Particle density 1.053g/cc
Bulk density 3.706g/cc
BET surface-area 130m
2/ g
Mercury porosimeter is measured:
Total pore space 0.680cc/g
Macropore pore space 0.0621cc/g
Macropore 9.1%
Maximum median pore diameter 215
Calculate average mesopore diameter 190
This catalyzer sees Table the catalyzer of the No.4 of II.
Embodiment 5
The preparation of support of the catalyst
With the aluminium particulate of the small roasting of 865 pounds versal250 aluminium (DI=24) and 96 pounds, in the L:ttleford agitator, stirred about more than 20 minutes with the solution of 650 pounds of water and 17.5 pounds of nitric acid.Added the back continuously stirring 15 minutes at all liquid.Add 6 pounds of aqueous ammonia and 174 pounds of water then and stirred 5 minutes.Extrude said mixture with 6 inches Bonnott forcing machines, extruding needs about 1 hour.Extrudate is dry in Procfor-Schwari travelling belt drying machine, 200 ℃ dry about 15 minutes down, then in the immobilized air 900 ℃ of following roastings 1 hour.
Resulting support of the catalyst has following characteristic:
Particle density 0.89g/cc
Bulk density 3.44g/cc
BET surface-area 137m
2/ g
Mercury porosimeter is measured:
Total pore space capacity 0.788cc/g
Macropore pore space 0.0544cc/g
Macropore 6.9%
Maximum median pore diameter 184
The average mesopore diameter of calculating 214
Embodiment 6
Measure pore size distribution with mercury porosimeter.
With the pore size distribution of mercury porosimeter mensuration catalyzer, the catalyst pores size all can record in the scope of 35A-20000A.
Method is summarized as follows.This method relates to ASTM D4284 and " measures the distribution of catalyst pores capacity with mercury intrusive mood porosity meter ".Under vacuum condition, catalyzer was heated 30 minutes down at 450 ℃, so that remove water vapor and other volatile component.The sample of certainweight (0.3-0.5g decides according to predetermined total pore space capacity) is placed in volume-correction stopple coupon, fills in the pipe with mercury, and will manage in the pressure chamber that inserts quantitative chromium autoscan (Quatachvome Auto-Scan) porosity meter.Room pressure is brought up to 60000 pounds/square inch gauge from 0.Along with pressure improves, the mercury volume in the stopple coupon reduces, because mercury is pressed in the hole of sample.Apparent mercury volume becomes along with applied pressure, apparent mercury volume with exert pressure relevant with pore space (V) respectively with bore dia (D).Test-results shows, pore space (CC) and cumulative pore space (CC) and diameter (
) exist curved line relation.Equally, the pore size distribution situation has also been write down in test.Comprise from analyzing the data that obtain:
The total pore space capacity
Mesopore pore space (aperture 35～1000
Pore space);
(aperture is greater than 1000 for the macropore pore space
Pore space);
Macropore pore space %=(macropore pore space)/(total pore space capacity) * 100%
The dv/dD(aperture of maximum median pore diameter=maximum is at 35-1000
Scope); The pore space of differential is the function (dv/dD is the function of D) of diameter
For all calculating, suppose that contact angle is 140 °.If sample and mercury have other contact angle, the X coordinate figure (diameter) of curve will depart from real value so.For aluminium, silicon or silicon/aluminum, contact angle is suitable for 140 °.Yet if be added into metal (as with osmose process and roasting), apparent mesopore maximum diameter improves about 20
, because higher 140 ° of actual contact angle.
Embodiment 7
The catalyst screening test.
During test, be to carry out in 1 inch upper reaches packed bed reactor at the internal diameter of hydrotreatment testing apparatus with the 120cc catalyzer.
Test conditions is:
Total pressure 2000(pound/square inch gauge)
Liquid hourly space velocity (LHSV) 0.75
One-pass 713 of gaseous hydrogen 5000 standard cubic feet per barrel catalyst temperatures (in 0-250 hour)
755 °F (in 250-700 hour)
Material is a Residual oil, is the mixture of 23% Arabic heavy crude oil and 77% Mayan crude oil.(650 of the character of material
+Residual oil) as follows:
American Petroleum Institute (API) (API) proportion 9.8
Sulphur, (weight) % 4.4
Nitrogen, (weight) % 0.5
Nickel, ppm 66
Vanadium, ppm 350
MCR, (weight) % 16.8
Viscosity cst 280 in the time of 100 ℃
D1160 650F-， 22
650-850°F 23.9
850-1000°F 19.4
1000°F
+54.4
D1160 50LV% 1035°F
1000 of VTGA
+, (weight) % 58.5
Tested 700 hours, and analyzed the product of demetalization and desulfurization, determine the conversion of vanadium, sulphur, MCR percentage ratio.Analysis of catalyst is to determine the vanadium distribution coefficient.
Catalyzer of the present invention under above-mentioned test conditions, obtains following result:
Vanadium distribution coefficient＞0.45
Vanadium conversion＞75%
Sulphur conversion＞65%
MCR conversion＞38%
Embodiment 8
Catalyzer relatively
Present embodiment is used according to the catalyzer of Taiwan patent NI-23976 and is compared according to catalyzer of the present invention, and catalyzer is used for hydrodemetallation (HDM) and hydrogenating desulfurization.Through after 700 hours working process, the main characteristic of catalyzer and desulfurization, go the results are shown in Table of MCR and vanadium removal.(table is seen the literary composition back)
Catalyzer according to the present invention's preparation is compared with other catalyzer, has high vanadium removal per-cent and high vanadium distribution coefficient.This demetalization performance that shows this catalyzer is improved.
This catalyzer is the No.10 catalyzer of table II.
Embodiment 9
No, the 1.2.5.6.7.8.9 Preparation of catalysts.
Other Preparation of catalysts is similar to the mode of embodiment 1 and 2 or 3 and 4.By changing the type of aluminium, the DI value of aluminium and reaction conditions can be regulated the percentage ratio of macropore, as top said.The catalyzer that can prepare No.2 of the present invention and 5 by this way, same, can prepare comparative catalyst NO.1.6.7.8 and 9 by this way.
The table II has been summarized the characteristic and the test-results of catalyzer.As the catalyzer of the present invention that can see in the table, promptly catalyzer 2-5 has high vanadium conversion (after 700 hours＞74%) and high vanadium distributes, and this is that catalyzer also has the conversion of high sulphur, after 700 hours greater than 65%.
Usually, conversion of the macropore amount of being few (catalyzer) vanadium and vanadium distribution coefficient are just low, and have the catalyzer of the macropore percentage ratio bigger than the present invention catalyzer (catalyzer 6-10), have the low sulphur conversion that has.
The table II
Specificity of catalyst and experimental result (1)
The maximum mesopore average mesopore of pore space BET sulphur conversion MCR conversion vanadium conversion vanadium distributes
Catalyzer % diameter diameter surface is amassed % % % coefficient
71000A
m
2/ g 700 hours 700 hours 700 hours
- - - - - - - - -
1, macropore few 3.6 221 209 118 72.1 41.0 69.3 0.36
Catalyzer
2, catalyzer of the present invention, 6.9 215 198 127 65.3 39.1 79.1 (2)
Use HNO
3Disperse
3, catalyzer of the present invention, 7.8 219 174 130 69.3 41.0 75.6 0.47
Use HNO
3Disperse, embodiment 2
4, catalyzer of the present invention, 9.1 215 190 130 68.4 39.6 76.3 0.55
Use HNO
3H disperses, and embodiment 4
5, catalyzer of the present invention, 10.6 208 209 124 65.7 39.1 79.8 (2)
Use HNO
2Disperse
6, have 13% big by 12.7 189 170 135 61.6 36.7 78.3 0.52
The catalyzer in hole
7, have 14% big by 13.7 165 170 135 64.6 38.3 73.8 0.39
The catalyzer in hole
8, have 14% big by 13.8 185 189 119 60.5 36.7 76.7 0.52
The catalyzer in hole
9, macropore many 25.4 161 148 158 55.2 32.9 76.6 0.53
Catalyzer
10, Taiwan patent 25.3 107 110 186 73.7 41.3 66.9 0.39
NT23-977 embodiment 8
(1) catalyzer 2～5 is a catalyzer of the present invention.
(2) non-cylindrical catalyzer, its vanadium distribution coefficient is not measurable, the conversion of very high vanadium shows that family's catalyzer has high vanadium and distributes.
Claims (11)
1, a kind of method that is used for higher boiling point hydrocarbon compound material hydrodemetallation (HDM) and hydrogenating desulfurization, it comprises:
Temperature between 600 ℃ of F and 100 ℃ of F and pressure at 100 and 10000 pounds/inch
2Under the condition between the gauge pressure, under the situation that has hydrogen to exist, material is contacted with catalyzer, this catalyzer comprises group vib and the component that hydrogenization is arranged of VIII family metal and the inorganic oxide support of indissoluble, and this catalyzer has
A. macropore accounts for the 5-11% of catalyst pores capacity,
B. the surface-area of catalyzer is greater than 75m
2/ g,
C. the average mesopore diameter of catalyzer is greater than 160
2, according to the said method of claim 1, wherein the maximum median pore diameter of the catalyzer of measuring with mercury porosimeter is greater than 165
3, according to the said method of claim 1, wherein the macropore pore space is in the scope of 6.5-10%.
4, according to the said method of claim 3, wherein the largest hole diameter of measuring with mercury porosimeter is greater than 185A, and average mesopore is greater than 180
5, according to the said method of claim 1, wherein the macropore pore space is between 7.5-10%.
6, according to the said method of claim 1, wherein the macropore pore space is about 8-9%.
7, according to the said method of claim 1, wherein said carrier is aluminum oxide, silica-alumina or silicon oxide.
8, according to the said method of claim 1, wherein said carrier is an aluminum oxide.
9, according to the said method of claim 1, wherein said VI B family metal is molybdenum or tungsten, VIII family metallic nickel or cobalt.
10, according to the said method of claim 1, wherein said material is a vanadium Residual oil or from the vanadium Residual oil.
11, according to the said method of claim 1, wherein said material contains organic vanadium metal, nickel and/or iron, and it is measured greater than 10ppm, and contains the sulphur that exists with the organic sulfide form, and its amount is the 0.1(weight of raw material) %.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89108358 CN1024135C (en) | 1988-10-04 | 1989-10-04 | Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/253,010 US4976848A (en) | 1988-10-04 | 1988-10-04 | Hydrodemetalation and hydrodesulfurization using a catalyst of specified macroporosity |
| CN 89108358 CN1024135C (en) | 1988-10-04 | 1989-10-04 | Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1050736A CN1050736A (en) | 1991-04-17 |
| CN1024135C true CN1024135C (en) | 1994-04-06 |
Family
ID=25742590
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89108358 Expired - Lifetime CN1024135C (en) | 1988-10-04 | 1989-10-04 | Process for oxygen demetallization and hydrodesulfurization using a macroporous catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1024135C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1055952C (en) * | 1997-11-24 | 2000-08-30 | 中国石油化工总公司 | Method for heavy oil hydrogenation for removal of metals and sulphur |
| CN1091136C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Hydrogenating catalyst for demetalation and its preparing process and application method |
| CN103380197A (en) * | 2011-02-09 | 2013-10-30 | Sk新技术株式会社 | Method of simultaneously removing sulfur and mercury from hydrocarbon material using catalyst by means of hydrotreating reaction |
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1989
- 1989-10-04 CN CN 89108358 patent/CN1024135C/en not_active Expired - Lifetime
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1055952C (en) * | 1997-11-24 | 2000-08-30 | 中国石油化工总公司 | Method for heavy oil hydrogenation for removal of metals and sulphur |
| CN1091136C (en) * | 1999-09-29 | 2002-09-18 | 中国石油化工集团公司 | Hydrogenating catalyst for demetalation and its preparing process and application method |
| CN103380197A (en) * | 2011-02-09 | 2013-10-30 | Sk新技术株式会社 | Method of simultaneously removing sulfur and mercury from hydrocarbon material using catalyst by means of hydrotreating reaction |
| CN103380197B (en) * | 2011-02-09 | 2015-04-01 | Sk新技术株式会社 | Method of simultaneously removing sulfur and mercury from hydrocarbon material using catalyst by means of hydrotreating reaction |
| CN104053500A (en) * | 2011-09-01 | 2014-09-17 | 先进炼制技术有限公司 | Catalyst Support And Catalysts Prepared Therefrom |
| CN104053500B (en) * | 2011-09-01 | 2018-01-12 | 先进炼制技术有限公司 | Catalyst carrier and catalyst prepared therefrom |
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| Publication number | Publication date |
|---|---|
| CN1050736A (en) | 1991-04-17 |
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