CN101094720A - 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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- CN101094720A CN101094720A CNA2005800455824A CN200580045582A CN101094720A CN 101094720 A CN101094720 A CN 101094720A CN A2005800455824 A CNA2005800455824 A CN A2005800455824A CN 200580045582 A CN200580045582 A CN 200580045582A CN 101094720 A CN101094720 A CN 101094720A
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- catalytic
- catalyst
- metal
- carrier material
- dmo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 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 81
- 229910052751 metal Inorganic materials 0.000 claims abstract description 64
- 239000002184 metal Substances 0.000 claims abstract description 64
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 36
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 34
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 26
- 239000000463 material Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 22
- 238000005516 engineering process Methods 0.000 claims description 20
- 229910021536 Zeolite Inorganic materials 0.000 claims description 16
- 239000010457 zeolite Substances 0.000 claims description 16
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- -1 DMO hydrocarbon Chemical class 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical group [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 8
- 239000011733 molybdenum Substances 0.000 claims description 8
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 7
- 239000011959 amorphous silica alumina Substances 0.000 claims description 6
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 238000007598 dipping method 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
- 238000005728 strengthening Methods 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims 3
- 230000002708 enhancing effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 description 12
- 238000005984 hydrogenation reaction Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000000969 carrier Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 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
- 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
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000012545 processing Methods 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
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 125000004429 atom Chemical group 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
- 238000012512 characterization method 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
- 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
- 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
- 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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- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
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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 into this in full 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 of operating catalytic treatment metal removal oil (DMO).
Description of the Prior Art
As the technology that is used for refining petroleum, hydrocracking has caused its phenomenal growth in the period of 15 in the past 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 handle different hydrocarbon, to reduce the accessory substance that catalytic treatment do not expect and/or to prolong catalyst life.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 that heavier with the different hydrocarbon of processing such as deasphalted oil (DAO) or metal removal oil (DMO) is arranged convert it into the suitable product that is used for gasoline line, aviation kerosine and diesel oil with the needs according to geographical and seasonal variations.LPG and lubricating base oil also can be the expectation products.The catalyst that can handle a large amount of hydrocarbon molecules and heavy polyaromatic molecule, particularly DMO will be favourable.Can handle VGO/DMO feed intake the catalyst of mixture will 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 technology of this catalyst treatment heavy hydrocarbon.This catalyst is particularly suitable for handling 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 catalytic carrier material is exercisable VGO/DMO is catalytically converted into the hydrocarbon products that has than short carbon chain with combining of catalytic metal (being also referred to as reactive metal) and promoter metal.
In a preferred implementation, the catalytic metal component comprises that molybdenum and promoter metal comprise nickel.
As for the catalytic carrier material, a preferred implementation 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 70% of all catalytic carriers of being used for test run.In a special preferred implementation, the USY zeolite does not contain γ-zeolite.
Particularly preferred catalytic carrier material comprises the MCM-41 mesopore material.
In another preferred implementation, the catalytic carrier material is a beta-zeolite.In another preferred implementation, the catalytic carrier material is an amorphous silica alumina, is also referred to as ASA.ASA has the non-homogeneous structural that has low acidity and high surface.Non-homogeneous structural trends towards creating can not be by the acid sites of big molecule utilization, and when comparing with the combination of ASA with MCM-41 or MCM-41, this produces the inferior effect of using ASA separately.Similarly, USY and beta-zeolite carrier suffer and the performance-relevant defective of carrier micropore, because diffusion-restricted, this makes catalyst effective inadequately to big molecule.These carriers that use separately trend towards rapid obstruction, like this passivation catalyst.MCM-41, independent or with the combining of USY or beta-zeolite carrier, overcome these defectives.In a preferred implementation, the catalytic carrier material is independent overstable gamma zeolite, MCM-41 mesopore material, beta-zeolite, amorphous silica alumina or their combination.A special preferred implementation comprises that a kind of all is the single catalytic carrier material of MCM-41 basically.This material is a mesopore, that is to say, it is trap formula structure and has the form of the homogeneous that has high surface.Compare with the USY carrier material with β, it also has low acid.The present invention includes the use of suitable carrier material and in whole carrier material metal the balance between acidity and metal function under the situation of suitable distribution is arranged.Specific trap formula structural form feature by the MCM-42 carrier material realizes above-mentioned purpose, and this material comprises can be near the acidity and the metal position that are found in the big 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, limited the generation of not expecting lighter-than-air gas optionally turning to middle distillate.
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 implementation, promoter metal comprises independent nickel, cobalt or their combination.
Catalyst of the present invention is suitable for comprising the VGO/DMO hydrocarbon mixture of at least 10 volume %DMO especially.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 is realized by methods known in the art, for example by dipping or dipping altogether successively.
The technology 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.The catalytic carrier material operation that has catalytic metal and promoter metal is catalytically converted at least a portion metal removal oil has the more hydrocarbon products of short carbon chain.
Technology reaches and keeps in the reactor exercisable predefined temperature to finish conversion.In a preferred implementation, predefined temperature is at least 390 ℃.In a more special preferred implementation, predefined temperature is at least 400 ℃.
In a preferred implementation, most of hole of catalytic carrier be positioned at the scope of 20-50 dust (° A) and when measuring by pore size distribution catalytic carrier have big surface area.Table 1 has shown the example of preferred implementation.
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 the mode of the conspicuous thing of inventive features, advantage and purpose and other change so in more detail, 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 implementation of invention, because it approves that other is equal to effective embodiment, therefore should not be understood that to limit invention scope.
Fig. 1 has described the schematic diagram that adopts the preferred implementation 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 four kinds of catalytic preparations of preparation by this way.In addition, testing catalytic agent formulation and relatively in batch reactor with itself and commercial catalysts.This working result show comprise MCM-41 catalyst carrier result for 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 made up 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 takes place and product forms the balance influence that is subjected between these two kinds of components.
The acidity of the catalyst of all preparations of table 2
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 hydrocracking catalyst of all preparations.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 small amounts aluminium, 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 with remove the hetero atom activity that more responds, and reduces the coking ratio.By forming the alkene intermediate through dehydrogenation, they also cause cracking.
Because the hydrocracking of the raw material of industry is to carry out under the situation that has hydrogen sulfide and organosulfur compound, so the preferable alloy position is the form by the VIA family metal sulfide of nickel or the promotion of cobalt sulfide.
Three kinds of main routes are taked in the reaction that takes place 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 of being made up of metal, simple function C-C key is accompanied by hydrogenation division, oxidation or sulfuration (hydrogenolysis).The 3rd, by the bifunctional catalyst of being made up 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 take place.These may comprise hydro-desulfurization, hydrodenitrogeneration, hydrogenation deoxidation, olefin hydrogenation and the hydrogenation of part aromatic ring hydrocarbon.
Table 3 experimental design
Antigravity system | ||||||
Preparation of CatalystThe gama-alumina adhesive, the wt% carrier, wt% NiO, wt% MoO3, wt% Ni, wt% Mo, the wt% atom ratio Catalyst characterizationSurface area, m 2/ g pore volume, cm 2/ g hole size, dust acidity, mmol/gm The catalyst assessment Batch reactorThe transit number temperature, ℃ pressure, kg/cm 2The weight that feeds intake, g catalyst weight, g | - - | Commercial | NiMo- MCM-41 | NiMo- USY | NiMo- β | NiMo- ASA |
- 5 410 150 100 3 | 70 30 2.5 12 2 8 0.2 32 4 0.4 25 0.33 1 410 150 100 3 | 70 30 2.5 12 2 8 0.2 300 0.35 23 0.59 1 410 150 100 3 | 70 30 2.5 12 2 8 0.2 313 0.41 26 0.56 1 410 150 100 3 | 70 30 2.5 12 2 8 0.2 186 0.33 36 0.5 1 410 150 100 3 |
With the commercial catalysts of making comparisons is DHC-8 from general oily product (UOP) company.Gama-alumina is used as the adhesive of all catalyst that prepare in the test that shows above.Gamma oxidation companion's use amount is 70% of all catalyst carriers.
The table 3-2 explanation that feeds intake
Performance feeds intake | VGO | DMO | VGO/DMO 85%/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 |
The catalyst conversion ratio that table 4-7 800-900 section and 900-1050 section are measured
1Conversion ratio % | |||||
Segment limit, | Commercial | NiMo- MCM-41 | NiMo- β | NiMo- ASA | NiMo- USY |
800-900 | 13.37 | 19.23 | 17.57 | 15.78 | 15.04 |
900-1050 | 35.29 | 36.33 | 32.74 | 34.56 | 35.69 |
All | 27.01 | 29.97 | 27.01 | 27.47 | 27.89 |
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 spot 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 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 under the situation that does not break away from spirit of the present invention, allow various variations with its some forms.
Claims (32)
1, a kind of catalyst is used to handle the VGO/DMO hydrocarbon mixture the VGO/DMO mixture through catalytic is changed into the more valuable hydrocarbon products of short chain, and this catalyst comprises:
The stretching carrier material that comprises the MCM-41 mesopore material,
Be immersed in the catalytic metal in the catalytic carrier material, and,
On the catalytic carrier material in order to strengthening the promoter metal of catalytic conversion,
The catalytic carrier material that has catalytic metal and promoter metal can be catalytically converted into VGO/DMO has the more hydrocarbon products of short carbon chain.
2, the catalyst of claim 1, wherein the catalytic metal component is a molybdenum, promoter metal is a nickel.
3, the catalyst of any aforementioned claim, wherein the catalytic carrier material comprises overstable gamma zeolite.
4, claim 1 or 2 catalyst, wherein the catalytic carrier material is independent MCM-41 mesopore material.
5, claim 1 or 2 catalyst, wherein the catalytic carrier material comprises beta-zeolite.
6, claim 1 or 2 catalyst, wherein the catalytic carrier material comprises amorphous silica alumina.
7, claim 1 or 2 catalyst, wherein the catalytic carrier material is selected from by overstable gamma zeolite, MCM-41 mesopore material, beta-zeolite, amorphous silica alumina and their group that constitutes.
8, the catalyst of claim 2, wherein at least a portion nickel is the form of nickel sulfide.
9, the catalyst of any aforementioned claim, wherein the catalytic metal component 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.
10, the catalyst of claim 9, wherein at least a portion nickel is the form of nickel sulfide.
11, the catalyst of claim 9, wherein at least a portion cobalt is the form of cobalt sulfide.
12, the catalyst of any aforementioned claim, wherein the VGO/DMO hydrocarbon mixture comprises the DMO of at least 10 volume %.
13, the catalyst of any aforementioned claim, wherein the VGO/DMO hydrocarbon mixture comprises the DMO of at least 15 volume %.
14, the catalyst of any aforementioned claim, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by flooding altogether.
15, claim 1,2,3,4,5,6,7,8,9,10,11,12 or 13 catalyst, wherein catalytic metal and promoter metal are by being immersed on the catalytic carrier successively.
16, catalyzed conversion comprises the technology of the heavy hydrocarbon of metal removal oil, 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,
Be immersed in the stretching metal in the catalytic carrier material, and,
On the catalytic carrier material in order to the promoter metal of stretching of enhancing conversion ratio,
The catalytic carrier material that has catalytic metal and promoter metal can be catalytically converted at least a portion metal removal oil has the more hydrocarbon products of short carbon chain
17, the technology of claim 16, wherein the catalytic metal component is a molybdenum, promoter metal is a nickel.
18, claim 16 or 17 catalyst, wherein the catalytic carrier material comprises overstable gamma zeolite.
19, claim 16 or 17 technology, wherein the catalytic carrier material is independent MCM-41 mesopore material.
20, claim 16,17 or 18 technology, wherein the catalytic carrier material comprises beta-zeolite.
21, claim 16,17 or 18 technology, wherein the catalytic carrier material comprises amorphous silica alumina.
22, claim 16 or 17 technology, wherein the catalytic carrier material is selected from by overstable gamma zeolite, MCM-41 mesopore material, beta-zeolite, amorphous silica alumina and their group that constitutes.
23, the technology of any aforementioned claim, wherein the catalytic metal component is selected from by nickel, cobalt and their group that constitutes, and wherein promoter metal is selected from by molybdenum, tungsten and their group that constitutes.
24, the technology of any aforementioned claim, wherein the VGO/DMO hydrocarbon mixture comprises the DMO of at least 10 volume %.
25, the technology of any aforementioned claim, wherein the VGO/DMO hydrocarbon mixture comprises the DMO of at least 15 volume %.
26, claim 17 or 23 technology, wherein at least a portion nickel is the form of nickel sulfide.
27, the technology of claim 23, wherein at least a portion cobalt is the form of cobalt sulfide.
28, claim 16,17,18,19,20,21,22,23,24,25,26 or 27 technology, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by dipping altogether.
29, claim 16,17,18,19,20,21,22,23,24,25,26 or 27 technology, wherein catalytic metal and promoter metal are submerged on the catalytic carrier by flooding successively.
30, claim 16,17,18,19,20,21,22,23,24,25,26,27,28 or 29 technology further are included in the step of keeping predefined temperature in the reactor.
31, the technology of claim 30, wherein predefined temperature is at least 390 ℃.
32, the technology of claim 30, wherein predefined temperature is at least 400 ℃.
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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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- 2005-12-29 CN CN2005800455824A patent/CN101094720B/en not_active Expired - Fee Related
- 2005-12-29 US US11/320,928 patent/US20060157386A1/en not_active Abandoned
- 2005-12-29 WO PCT/US2005/047341 patent/WO2006071963A1/en active Application Filing
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JP2008525194A (en) | 2008-07-17 |
US20060157386A1 (en) | 2006-07-20 |
CN101094720B (en) | 2013-04-24 |
WO2006071963A1 (en) | 2006-07-06 |
RU2416462C2 (en) | 2011-04-20 |
BRPI0519581A2 (en) | 2009-02-17 |
JP5260059B2 (en) | 2013-08-14 |
RU2007128968A (en) | 2009-02-10 |
EP1835993A1 (en) | 2007-09-26 |
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