CN101094720B - Hydrocracking catalysts for vacuum gas oil & de-metalized blend - Google Patents
Hydrocracking catalysts for vacuum gas oil & de-metalized blend Download PDFInfo
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- CN101094720B CN101094720B CN2005800455824A CN200580045582A CN101094720B CN 101094720 B CN101094720 B CN 101094720B CN 2005800455824 A CN2005800455824 A CN 2005800455824A CN 200580045582 A CN200580045582 A CN 200580045582A CN 101094720 B CN101094720 B CN 101094720B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 62
- 239000000203 mixture Substances 0.000 title claims abstract description 17
- 238000004517 catalytic hydrocracking Methods 0.000 title description 13
- 230000003197 catalytic effect Effects 0.000 claims abstract description 82
- 229910052751 metal Inorganic materials 0.000 claims abstract description 73
- 239000002184 metal Substances 0.000 claims abstract description 73
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 38
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 36
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 33
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000012876 carrier material Substances 0.000 claims description 38
- 239000003921 oil Substances 0.000 claims description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 19
- 229910021536 Zeolite Inorganic materials 0.000 claims description 12
- 239000010457 zeolite Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052750 molybdenum Inorganic materials 0.000 claims description 7
- 239000011733 molybdenum Substances 0.000 claims description 7
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 5
- 239000011959 amorphous silica alumina Substances 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000000428 dust Substances 0.000 claims description 4
- 239000011148 porous material Substances 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 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
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 238000002360 preparation method Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 6
- -1 middle distillate Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 235000021050 feed intake Nutrition 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 150000002605 large molecules Chemical class 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 101100224937 Paramecium tetraurelia DHC-8 gene Proteins 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000013401 experimental design Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 230000001050 lubricating effect Effects 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 150000002898 organic sulfur compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000001932 seasonal effect Effects 0.000 description 1
- PTISTKLWEJDJID-UHFFFAOYSA-N sulfanylidenemolybdenum Chemical group [Mo]=S PTISTKLWEJDJID-UHFFFAOYSA-N 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
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Abstract
This invention relates to a catalyst and a process for treating heavy hydrocarbons using the catalyst. The catalyst is useful for treating heavy hydrocarbons, de-metallize oil (DMO) and is particularly useful in VGO/DMO hydrocarbon blend. It is also useful for DAO. The catalyst acts to catalytically convert the VGO/DMO blend to shorter-chain valuable hydrocarbon products. The catalyst includes a catalytic support material, a catalytic metal impregnated upon the catalytic support material, and a promoter metal on the catalytic support material to enhance catalytic conversion. The combination of the catalytic support material with catalytic metal and promoter metal is operable to catalytically convert VGO/DMO into hydrocarbon products having shorter carbon chains.
Description
Background of invention
Related application
Present patent application requires by reference it to be incorporated in full this in the priority of the U.S. Provisional Patent Application series number 60/639,909 of submission on December 29th, 2004.
The invention technical field
The present invention relates generally to the heavy hydrocarbon catalytic treatment to obtain the hydrocarbon products field of expectation, particularly a kind of raw catelyst that operates catalytic treatment metal removal oil (DMO).
Description of the Prior Art
As the technique that is used for refining petroleum, hydrocracking has caused its in the past phenomenal growth between 15 years with its flexibility.By catalytic treatment, feeding intake to be converted to more low boiling or the more product of expectation.The hydrocarbon that is suitable for this processing feeds intake from the residual oil to the naphtha.Product comprises the different material of wide region, for example gasoline, kerosene, middle distillate, lubricating oil, fuel oil and various chemicals.
Commercial hydrocracking is typically carried out in single-stage reactor or in the second reactor of series connection.After deliberation many hydrocracking catalysts process different hydrocarbon, accessory substance and/or the extending catalyst life-span do not expected to reduce catalytic treatment.Developed the catalyst that has obtained to be suitable for the critical operation condition.Carry out cost-efficient effort.The selection of catalyst and special process figure will depend on such as material performance, expectation product property, the size of hydrocracking element and many factors of various other economic considerations.
When investing in hydrocracking when the purpose of past medium or heavy vacuum gas oil (VGO) for hydrocracking, the needs of processing such as the heavier with different hydrocarbon of deasphalted oil (DAO) or metal removal oil (DMO) are arranged, convert it into suitable product for gasoline line, aviation kerosine and diesel oil with the needs according to geography and seasonal variations.LPG and lubricating base oil also can be the expectation products.The catalyst that can process a large amount of hydrocarbon molecules and heavy polyaromatic molecule, particularly DMO will be favourable.Can process VGO/DMO feed intake the catalyst of mixture will be advantageous particularly.Because world market is significantly trending towards heavier hydrocarbon, the catalyst that is suitable for this heavy hydrocarbon will be favourable.
Brief summary of the invention
The present invention includes a kind of catalyst and with the technique of this catalyst treatment heavy hydrocarbon.This catalyst is particularly suitable for processing metal removal oil (DMO) and is particularly suitable for the VGO/DMO hydrocarbon mixture.Catalyst changes into the more valuable hydrocarbon products of short chain to the VGO/DMO mixture.Catalyst comprises the catalytic carrier material, impregnated in the promoter metal that is used for strengthening catalytic conversion on catalytic metal in the catalytic carrier material and the catalytic carrier material.The combination of catalytic carrier material and catalytic metal (being also referred to as reactive metal) and promoter metal is exercisable VGO/DMO is catalytically converted into the hydrocarbon products that has than short carbon chain.
In a preferred embodiment, the catalytic metal component comprises that molybdenum and promoter metal comprise nickel.
As for the catalytic carrier material, a preferred embodiment comprises that super steady Y (USY) zeolite is as the catalytic carrier material.Gama-alumina is used as the adhesive of all catalyst of preparation in this research.The amount of the gama-alumina that uses is approximately for 70% of all catalytic carriers of test run.At one particularly preferably in the embodiment, the USY zeolite does not contain γ-zeolite.
Particularly preferred catalytic carrier material comprises the MCM-41 mesopore material.
In another preferred embodiment, the catalytic carrier material is beta-zeolite.In another preferred embodiment, the catalytic carrier material is amorphous silica alumina, is also referred to as ASA.ASA has the non-homogeneous structural with low acidity and high surface.Non-homogeneous structural trends towards creating can not be by the acid sites of large molecule utilization, and when comparing with the combination of ASA with MCM-41 or MCM-41, this produces the inferior effect of using separately ASA.Similarly, USY and beta-zeolite carrier suffer and the performance-relevant defective of carrier micropore, because diffusion restriction, this is so that catalyst is effective not to large molecule.These carriers that use separately trend towards rapid obstruction, like this passivation catalyst.MCM-41, independent or with the combination of USY or beta-zeolite carrier, overcome these defectives.In a preferred embodiment, the catalytic carrier material is independent overstable gamma zeolite, MCM-41 mesopore material, beta-zeolite, amorphous silica alumina or their combination.One particularly preferably embodiment comprise that a kind of all is the single catalytic carrier material of MCM-41 basically.This material is mesopore, that is to say, it is trap formula structure and has form with the homogeneous of high surface.Compare with the USY carrier material with β, it also has low acid.The present invention includes suitable carrier material use and in the situation that in the whole carrier material metal balance between suitable distribution acidity and metal function is arranged.Specific trap formula structural form feature by the MCM-41 carrier material realizes above-mentioned purpose, and this material comprises can approach acidity and the metal position that is found in the large hydrocarbon molecule among VGO and the DMO.For this reason, obtained high conversion.Advantageously, compare the low acidity of MCM-41 with other carrier material and order about optionally turning to middle distillate, limited the generation of not expecting lighter-than-air gas.
In a preferred embodiment of the invention, catalytic metal is in sulphided form.For example, the molybdenum of preferred molybdenum sulfide form.Similarly, when using tungsten as catalytic metal, tungsten sulfide is preferred embodiment.
In a preferred embodiment, promoter metal comprises independent nickel, cobalt or their combination.
Catalyst of the present invention is particularly suitable for comprising the VGO/DMO hydrocarbon mixture of at least 10 volume %DMO.The VGO/DMO hydrocarbon mixture that comprises at least 15 volume %DMO has been carried out test run.
Catalytic metal and the promoter metal dipping on catalytic carrier realizes by methods known in the art, for example by total immersion stain or dipping successively.
The technique that catalyzed conversion comprises the heavy hydrocarbon of metal removal oil comprises step: the heavy hydrocarbon that comprises metal removal oil is introduced the reactor stage and catalyst is introduced the reactor stage.The catalyst of introducing the reactor stage comprises the catalytic carrier material, be immersed in the promoter metal that is used for strengthening catalytic conversion on catalytic metal in the catalytic carrier material and the catalytic carrier material.With the operation of the catalytic carrier material of catalytic metal and promoter metal at least a portion metal removal oil is catalytically converted into and has the more hydrocarbon products of short carbon chain.
Technique reaches and keeps in the reactor exercisable predefined temperature to finish conversion.In a preferred embodiment, predefined temperature is at least 390 ℃.At one more particularly preferably in the embodiment, predefined temperature is at least 400 ℃.
In a preferred embodiment, most of hole of catalytic carrier be positioned at the 20-50 dust (
) scope and when measuring by pore size distribution catalytic carrier have large surface area.Table 1 has shown the example of preferred embodiment.
The catalysagen eigen of table 1 preparation
Sample | BET surface area (meters squared per gram) | Pore volume (cubic centimetre/gram) | Average pore size (dust) |
NiMo-ASA | 186 | 0.33 | 36 |
NiMo-MCM-41 | 324 | 0.40 | 25 |
NiMo-β | 313 | 0.41 | 26 |
NiMo-USY | 300 | 0.35 | 23 |
Brief description of drawings
Can understand in more detail like this mode of the apparent thing of inventive features, advantage and purpose and other change, by can the invention of sketching above more specifically being illustrated with reference to the embodiment of in the accompanying drawing of book part as an illustration, annotating.Yet, should be noted in the discussion above that accompanying drawing only annotated the preferred embodiment of invention, because it approves that other is equal to effective embodiment, therefore should not be understood to limit invention scope.
Fig. 1 has described the schematic diagram that adopts the preferred embodiment of catalyst process of the present invention.
Detailed description of the invention
Adopt nickel (Ni)/molybdenum (Mo) metal to prepare several catalyst with top definite four kinds of different carriers materials load.Adopt gas absorption analyzer, temperature programmed reduction (TPR) and temperature programming desorb (TPD) to characterize by this way four kinds of catalytic preparations of preparation.In addition, testing catalytic agent formulation and with itself and commercial catalysts relatively in batch reactor.This working result show comprise MCM-41 catalyst carrier result be the preparation of NiMo-MCM-41 for heavy hydrocarbon, especially the VGO/DMO mixture has than the better effect of commercial catalysts.Other three kinds of catalytic preparations of the present invention also provide outstanding effect.NiMo-MCM-41 has shown higher hydro-desulfurization (HDS) and hydrogenation activity.In addition, it has higher conversion ratio and the diesel yield of Geng Gao than commercial catalysts.
Most of commercial interested hydrocracking catalyst is dual-use function in nature, is comprised of hydrogenation-dehydrogenation component and acid carrier.Reaction by independent component catalyst is very different.In special catalyst, the relative intensity of two kinds of components can be various.Reaction occurs and product forms the balance influence that is subjected between these two kinds of components.
The acidity of the catalyst that table 2 ownership is standby
Catalyst | Acid (mmol/g) | The peak temperature (℃) |
NiMo-MCM-41 | 0.33 | 264 |
NiMo-ASA | 0.50 | 252 |
NiMo-β | 0.56 | 233 |
NiMo-USY | 0.59 | 238 |
Table 4-2 has shown the TPD of ammoniacal liquor to the standby hydrocracking catalyst of the ownership.The acid range of the catalyst of preparation is that 0.33mmol/g (NiMo-MCM-41) is to 0.59mmol/g (NiMo-USY).Because MCM-41 is based on the material of silica and contains a small amount of aluminium oxide, so the low acidity of NiMo-MCM-41 catalyst is expected.Therefore, the NiMo-MCM-41 catalyst contains still less gama-alumina than the catalyst of other preparation.
Catalytic metal and promoter metal such as molybdenum provide hydrogenation and dehydrogenation functionality.As mentioned, this is preferably with the form of sulfide.Other VIA family and VIIIA family metal are suitable for as promoter metal and catalytic metal.The hydrogenation that these metal catalytics feed intake makes it to cracking and removes the hetero atom activity that more responds, and reduces the coking ratio.By forming the alkene intermediate through dehydrogenation, they are initiation cracking also.
Because the hydrocracking of the raw material of industry is in the situation that exist hydrogen sulfide and organosulfur compound to carry out, so the preferable alloy position is the form of the VIA family metal sulfide that promotes by nickel or cobalt sulfide.
Three kinds of main routes are taked in the reaction that occurs in the hydrocracking process.The first, through the on-catalytic thermofission of hydrocarbon free radical C-C key, be accompanied by hydrogenation (hydropyrolysis).The second, by the hydrogenation component that is comprised of metal, simple function C-C key is accompanied by hydrogenation division, oxidation or sulfuration (hydrogenolysis).The 3rd, by the bifunctional catalyst that is comprised of the hydrogenation component that is dispersed in porous, the acid carrier, difunctionality C-C key is accompanied by the hydrogenation division.Except above-mentioned reaction, in hydrocracking process, also have other reaction to occur.These may comprise hydro-desulfurization, hydrodenitrogeneration, hydrogenation deoxidation, olefin hydrogenation and the hydrogenation of part aromatic ring hydrocarbon.
Table 3 experimental design
DHC-8 from oil universal product (UOP) company with the commercial catalysts of making comparisons.The adhesive of all catalyst that prepare in the test that gama-alumina is used as showing above.The use amount of gama-alumina is 70% of all catalyst carriers.
The table 3-2 explanation that feeds intake
Performance feeds intake | VGO | DMO | VGO/DMO85%/15% |
Proportion | 0.92-0.93 | 0.96-0.97 | 0.93-0.94 |
Nitrogen pool, wt ppm | 700-900 | 1300-2100 | 1100-1200 |
Total sulfur content, wt% | 2-3 | 3-3.5 | 2.6-2.8 |
The ASTM distillation, D2887 | ? | ? | ? |
5%,℃ | 279 | 402 | ? |
50%, maximum ℃ | 472 | 596 | 495 |
90%, maximum ℃ | 543 | 678 | 615 |
Ni+V?wt.ppm | <1 | 8.0-13.5 | 2-3 |
Table 800-900 °F of section of 4-7 and the 900-1050 °F of Catalyst Conversion that section is measured
That describes in the above is contained in four kinds of catalytic preparations of the present invention, and the NiMo-MCM-41 catalyst has minimum acidity and highest face temperature is long-pending.This gives the credit to the fact that MCM-41 is based on the material of silica and contains a small amount of aluminium oxide.Mesopore and have an advantage that low acidity is MCM-41.The mesoporosity of MCM-41 catalyst and low acidity have promoted the highest conversion and have generated minimum gas.
Although only show with its some forms or described the present invention, yet should it is evident that for a person skilled in the art the present invention is defined in this, but allow various variations in the situation that do not break away from spirit of the present invention.
Claims (25)
1. catalyst, for the treatment of vacuum gas oil/metal removal oil hydrocarbon mixture vacuum gas oil/metal removal oil hydrocarbon mixture is catalytically converted into the more valuable hydrocarbon products of short chain, described vacuum gas oil/metal removal oil hydrocarbon mixture comprises the metal removal oil of at least 10 volume %, and this catalyst comprises:
The catalytic carrier material that comprises the MCM-41 mesopore material, the most of hole in the wherein said catalytic carrier material has the diameter of 20-50 dust,
Be immersed in the catalytic metal on the catalytic carrier material, and,
On the catalytic carrier material in order to strengthening the promoter metal of catalytic conversion,
Can be catalytically converted into vacuum gas oil/metal removal oil with the catalytic carrier material of catalytic metal and promoter metal and to have the more hydrocarbon products of short carbon chain;
Wherein said catalytic metal is molybdenum, and described promoter metal is nickel, and wherein said catalyst has the average pore diameter of 25 dusts.
2. the catalyst of claim 1, wherein the catalytic carrier material comprises overstable gamma zeolite.
3. the catalyst of claim 1, wherein the catalytic carrier material is independent MCM-41 mesopore material.
4. the catalyst of claim 1, wherein the catalytic carrier material comprises beta-zeolite.
5. the catalyst of claim 1, wherein the catalytic carrier material comprises amorphous silica alumina.
6. the catalyst of claim 1, wherein at least a portion nickel is the form of nickel sulfide.
7. the catalyst of claim 1, wherein at least a portion cobalt is the form of cobalt sulfide.
8. the catalyst of claim 1, wherein vacuum gas oil/metal removal oil hydrocarbon mixture comprises the metal removal oil of at least 15 volume %.
9. the catalyst of claim 1, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by the total immersion stain.
10. the catalyst of claim 1, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by flooding successively.
11. catalyzed conversion comprises the technique of the heavy hydrocarbon of metal removal oil, described heavy hydrocarbon is the vacuum gas oil that comprises at least 10 volume % metal removal oils/metal removal oil hydrocarbon mixture, comprises following steps:
The heavy hydrocarbon that comprises metal removal oil is introduced the reactor stage,
Catalyst is introduced the reactor stage, and catalyst comprises:
The catalytic carrier material that comprises the MCM-41 mesopore material, the most of hole in the wherein said catalytic carrier material has the diameter of 20-50 dust,
Be immersed in the catalytic metal on the catalytic carrier material, and,
On the catalytic carrier material in order to strengthening the promoter metal of catalytic conversion,
Can be catalytically converted at least a portion metal removal oil with the catalytic carrier material of catalytic metal and promoter metal and to have the more hydrocarbon products of short carbon chain.
12. the technique of claim 11, wherein said catalytic metal is molybdenum, and promoter metal is nickel.
13. the technique of claim 11 or 12, wherein the catalytic carrier material comprises overstable gamma zeolite.
14. the technique of claim 11 or 12, wherein the catalytic carrier material is independent MCM-41 mesopore material.
15. the technique of claim 11 or 12, wherein the catalytic carrier material comprises beta-zeolite.
16. the technique of claim 11 or 12, wherein the catalytic carrier material comprises amorphous silica alumina.
17. the technique of claim 11 or 12, wherein catalytic metal is selected from by molybdenum, tungsten and their group that constitutes, and wherein promoter metal is selected from by nickel, cobalt and their group that constitutes.
18. the technique of claim 11 or 12, wherein vacuum gas oil/metal removal oil hydrocarbon mixture comprises the metal removal oil of at least 15 volume %.
19. the technique of claim 12, wherein at least a portion nickel is the form of nickel sulfide.
20. the technique of claim 17, wherein at least a portion cobalt is the form of cobalt sulfide.
21. the technique of claim 11 or 12, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by the total immersion stain.
22. the technique of claim 11 or 12, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by flooding successively.
23. the technique of claim 11 or 12 further is included in the step of keeping predefined temperature in the reactor.
24. the technique of claim 23, wherein predefined temperature is at least 390 ℃.
25. the technique of claim 23, wherein predefined temperature is at least 400 ℃.
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US63990904P | 2004-12-29 | 2004-12-29 | |
US60/639,909 | 2004-12-29 | ||
PCT/US2005/047341 WO2006071963A1 (en) | 2004-12-29 | 2005-12-29 | Hydrocracking catalysts for vacuum gas oil & de-metalized blend |
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CN101094720B true CN101094720B (en) | 2013-04-24 |
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US (1) | US20060157386A1 (en) |
EP (1) | EP1835993A1 (en) |
JP (1) | JP5260059B2 (en) |
CN (1) | CN101094720B (en) |
BR (1) | BRPI0519581A2 (en) |
RU (1) | RU2416462C2 (en) |
WO (1) | WO2006071963A1 (en) |
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US7455762B2 (en) * | 2004-08-31 | 2008-11-25 | Exxonmobil Research And Engineering Company | Selective hydrodesulfurization process |
US7910761B2 (en) * | 2007-10-31 | 2011-03-22 | Chevron U.S.A. Inc. | Hydroconversion processes employing multi-metallic catalysts and method for making thereof |
WO2009134941A2 (en) * | 2008-04-29 | 2009-11-05 | Iovation Inc. | System and method for facilitating secure payment in digital transactions |
US8173009B2 (en) * | 2009-02-06 | 2012-05-08 | Uop Llc | Process for improving a hydrotreated stream |
US8058203B2 (en) * | 2009-04-29 | 2011-11-15 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7931799B2 (en) * | 2009-04-29 | 2011-04-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8080492B2 (en) * | 2009-04-29 | 2011-12-20 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964524B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964526B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US8383543B2 (en) * | 2009-04-29 | 2013-02-26 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US7964525B2 (en) * | 2009-04-29 | 2011-06-21 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalyst and method for making thereof |
US9266098B2 (en) | 2012-09-05 | 2016-02-23 | Chevron U.S.A. Inc. | Hydroconversion multi-metallic catalysts and method for making thereof |
RU2672269C1 (en) * | 2017-08-08 | 2018-11-13 | Публичное акционерное общество "Нефтяная компания "Роснефть" (ПАО "НК "Роснефть") | Catalyst for hydrogenation of olefins at producing synthetic oil and method for synthesis thereof (options) |
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Also Published As
Publication number | Publication date |
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JP2008525194A (en) | 2008-07-17 |
US20060157386A1 (en) | 2006-07-20 |
BRPI0519581A2 (en) | 2009-02-17 |
RU2416462C2 (en) | 2011-04-20 |
EP1835993A1 (en) | 2007-09-26 |
WO2006071963A1 (en) | 2006-07-06 |
CN101094720A (en) | 2007-12-26 |
JP5260059B2 (en) | 2013-08-14 |
RU2007128968A (en) | 2009-02-10 |
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