CN101370912A - Non-sulfided Ni-based hydrocracking catalysts - Google Patents
Non-sulfided Ni-based hydrocracking catalysts Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
- C10G47/12—Inorganic carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/301—Boiling range
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Abstract
The invention provides a method for reducing methane formation when hydrocracking hydrocarbons, and a process for the hydrocracking of hydrocarbons, said method and process utilizing a non-sulfided hydrocracking catalyst, which has Ni and Sn, wherein the Ni content is at least 1 mass% and the silica content is at least 20 mass%, present in the form of silica-alumina.
Description
Technical field
The present invention relates to hydrocracking catalyst.
Background technology
Low temperature Fischer-Toro Pu Xifa (LTFT) is included in the heavy hydrocarbon of the remarkable volume in its primary product, totally is called wax.Usually, these waxes (its substantially not sulfur-bearing) are hydroconverted into overhead product by hydrocarbon hydrocracking reaction.
As J Scherzer and AJ Gruia at " Hydrocracking Science andTechnology " (Marcel Dekker, 1996) pointed in, normally used industrial hydrocracking catalyst is the catalyzer based on the NiW that fastens at soft silica-alumina body, NiMo and CoMo.All these catalyzer need successive to add the sulfur-bearing sample to keep their performance.
With the result who on highly acid Zeolite support, finds (people such as Calemma, Studies in SurfaceScience and Catalyst, 136 (2001) 302) opposite, use soft silica-aluminum oxide can produce higher selectivity to overhead product as matrix, this is the result of its lower acid intensity.
By using such hydrocracking process, begin and will lose with sweet stock with the advantage that no sulphur product finishes, and simultaneously, H
2S will appear in the tail gas.But, most important ground, it will be favourable to heavens aspect the process economics of the non-precious metal catalyst of developing unvulcanised.
Ciapetta and Hunter be at Industrial Engineering and Chemistry, reported the Ni/SiO about the unvulcanised of the hydrocracking that is used for normal hexane and octane in 45 (1953) 147
2-Al
2O
3The use of catalyzer.But, in technical literature (for example referring to people such as Lugstein, AppliedCatalysis A:Geneal, 152 (1997) 93) as everyone knows, the Ni catalyzer of load demonstrates high hydrogenolytic cleavage activity, causes producing methane (low value products of not expecting as a rule).This observation be applicable to load on all common carrier such as silicon-dioxide, aluminum oxide, silica-alumina, zeolite and even basic supports (for example, magnesium oxide) on Ni.And the formation of methane has to be minimized, because the hydrogen dividing potential drop in the hydrocracker that its influence moves under the gas circulation pattern.
Because business reason, in the conversion of valuable carbon containing kind, also wish in the production of product (namely for methane) consumption of hydrogen is minimized in less value.
Can sum up from above, have a kind of needs of base metal F-T wax hydrocracking catalyst of the unvulcanised to low hydrogenolysis action activity.
Summary of the invention
Surprisingly, the contriver has found to be used for activity and the catalyst based available prescription of selectivity unvulcanised Ni of active and long lifetime (avoiding because the loss of dehydrogenation/hydrogenation activity that metal sintering etc. cause) of low hydrogenolysis, and the precious metal of the main unvulcanised with on zeolite or nonzeolite acid carrier of prior art document or sulfurized NiW, CoMo or NiMo are relevant.
According to an aspect of the present invention, provide a kind of hydrocracking catalyst, this catalyzer be unvulcanised and have the Ni content of at least 1 quality % and the dioxide-containing silica of at least 20 quality %.
Described catalyzer can have the Ni content of at least 3 quality %.
Described catalyzer can have the Ni content of at least 4.5 quality %.
Described catalyzer can have the Ni content up to 50 quality %.
In some embodiments, described Ni content is 5 quality %～12 quality %, typically is 6 quality %～10 quality %.
Described catalyzer can have the silicon-dioxide of at least 40 quality %.
Described catalyzer can comprise the silicon-dioxide that surpasses 60 quality % and even the silicon-dioxide of about 80 quality %, perhaps even up to the silicon-dioxide of 99 quality %.
Described silicon-dioxide can the silica-alumina form exist.
Described catalyzer can comprise Sn.
Described catalyzer can comprise the more Ni than Sn.
Typically, described catalyzer can comprise Ni and Sn, and wherein said Ni:Sn mol ratio surpasses 1:1.
Described Ni:Sn mol ratio can surpass 2:1,3:1 or even higher.
In one embodiment, described Ni:Sn mol ratio is 6:1.
According to another aspect of the present invention, provide a kind of method that methane forms when reduce the hydrocracking hydrocarbon in the presence of the Ni catalyzer containing of unvulcanised that is used for.
Described catalyzer can contain Sn.
Described silicon-dioxide can the silica-alumina form exist.
Described method can be decreased to the selectivity to methane and be lower than 0.13 quality %, typically is decreased to 0.011 quality % or still less and even be decreased to 0.008 quality % or still less.
Described method can comprise that containing a certain amount of Sn makes described Ni:Sn mol ratio surpass 1:1.
Described method can comprise that containing a certain amount of Sn makes described Ni:Sn mol ratio surpass 5:1.
Described method can comprise using to have the Ni that surpasses 3 quality %, typically surpasses the Ni of 4.5 quality %, preferably surpasses the catalyzer of the Ni of 5 quality %.
Described method can comprise uses the carrier of silica-alumina as described catalyzer.
According to further aspect of the present invention, a kind of technology that is used for the hydrocracking of hydrocarbon is provided, described technology is included in the reactor of operation under the hydrocracking temperature and pressure, described hydrocarbon (ebullient paraffinic hydrocarbon in 370 ℃+scope for example is also referred to as wax or derives from the elementary wax of F-T) is exposed to above-mentioned catalyzer.
Described technology also can be used for the hydrocracking of low boiling hydrocarbon (as petroleum naphtha or the middle runnings that obtains) from the F-T process.
Described technology can be in 200-450 ℃ temperature range, the pressure of 5-250 crust and 0.1-10 hour
-1Weight hourly space velocity (WHSV) scope under carry out.
Described nickel-Xi (NiSn) catalyzer also can be used on the technology of the hydrocracking that is used for crude oil fractions, biomass and common any available hydrocarbon material source.
The formation of methane can be reduced to by the Ni base hydrocracking catalyst that uses unvulcanised and be lower than 1 quality %, typically be lower than 0.1 quality %.
When using Sn in catalyzer, the formation of described methane can be reduced to and be lower than 0.03 quality %, preferably is lower than 0.01 quality %.
Described silicon-dioxide can the silica-alumina form exist.
Multiply by the conversion mark by selection rate and calculate described methane formation or methane production.
Embodiment
Use has the aluminum oxide (silicatedalumina) of industrial silication of the dioxide-containing silica of 40 quality %, and it is catalyst based to have synthesized a series of Ni.
3 and the alumina sample of 4.5%Ni/ silication prepare by wet impregnation, described wet impregnation uses the metal load of the aqueous solution to obtain expecting of the nickelous nitrate of suitable concn.These samples are tested as the catalyzer of the hydrocracking that is used for n-hexadecane, and wherein n-hexadecane is as model compound.The products distribution that obtains by these catalyzer (it is a unvulcanised) seems symmetrical, and approach JWeitkamp and S Ernst at " Guidelines for Mastering the Properties of MolecularSieves ", Plenum Press, the ideal hydrocracking of definition in 1990, the 343 pages.In the hydrocracking than the hydrocarbon (as F-T wax) of heavy, the ideal hydrocracking means that the overhead product selectivity of expectation will be at its theoretical maximum place.Therefore, the result of acquisition is positive indication, and promptly the Ni of unvulcanised is the metal that is fit to that plays dehydrogenation/hydride functional in hydrocracking catalyst.But the amount of also observing the methane of generation is tangible.
During 1968-1970, many patents that relate to the sulfurized nickel-Xi hydrocracking catalyst of load are authorized to the (United States Patent (USP) 3,399 to Chevron Research Compony, 132 (1968), 3,542,696 (1970) and 3,598,724 (1971)).As pointed in these patents, the purpose that adds tin in nickel catalyzator is to increase activity of such catalysts.But tin was never noted the influence of hydrogenolytic cleavage, because hydrogenolytic cleavage has been eliminated in sulfuration fully.
It is catalyst based that the contriver has prepared a series of Ni that contain Sn that are used for hydrocracking.The alumina sample of NiSn/ silication prepares by using Ni:Sn mol ratio=3:1 to flood the Sn compound altogether.The NiSn catalyzer of this load is tested for the hydrocracking of n-tetradecane subsequently.
There is not the catalyzer (that is the aluminum oxide of 7%Ni/ silication) of Sn to produce highly symmetric hydrocracking products distribution and the obvious methane of measuring (about 20 moles of %).But, find that surprisingly the Ni base hydrocracking catalyst that Sn is added to the alumina load of silication has caused that the hydrogenolytic cleavage of catalyzer is active almost all to be eliminated (these the results are shown among Fig. 2 among the embodiment 2).Before in about the patent of the nickel base hydrogenation catalyst for cracking of unvulcanised or open source literature, do not do such observation.
Therefore, demonstrate from above-mentioned experiment, by add tin in Ni base hydrocracking catalyst, we can overcome the problem of hydrogenolytic cleavage.But the discovery problem relevant with the aluminium oxide catalyst of Ni or NiSn/ silication is the stability along with the catalyzer of working time (TOS), that is, and and the loss of metal function and to the skew of lighter products.When initial operation, obtain almost ideal hydrocracking, move a couple of days continuously after, observe skew to lighter products.These observations are proved to be in embodiment 3.
From being carried on the contrast temperature programmed reduction(TPR) research of the nickel oxide on reference supports such as silicon-dioxide, aluminum oxide and the silica-alumina, reach a conclusion: in the nickel catalyzator precursor of the alumina load of silication, nickel oxide preferably combines mutually with aluminum oxide.Because the loss of metal function can be this bonded result, we will concentrate on commercial silica-alumina sample, and this commercial silica-alumina sample can only have the aluminum oxide (usually as binding agent) of low levels, high dioxide-containing silica and high tetrahedral aluminium content in mutually to have high proton acidity at silica-alumina.Because the character of these catalyzer can not obtain from manufacturer, catalysis test reaction (dehydrogenation of 1-hexanol) is used to determine the acid activity of silica-alumina extrudate.For this reason, temperature of reaction kept lower (200 ℃) so that the aluminum oxide that is present in the silica-alumina extrudate minimizes with respect to the contribution of dehydration activity, and therefore main catalytic activity of observing silica-alumina (with its tetrahedral aluminium content).For understanding foregoing better, the table 1 in should reference example 4, it has provided the dehydration results that adopts different Industrial products to obtain.
Follow above-mentioned research, it is catalyst based to use commercial silica-aluminum oxide also to prepare the Ni that contains Sn that is used for hydrocracking of another series, this commercial silica-aluminum oxide contains the silicon-dioxide (being designated as SA2 in table 1) of 50 quality % and demonstrates high acid catalysis activity (for example, dehydration of alcohols is a hexene).Ni content from 6 to 10 quality % change and use the Ni:Sn molar ratio of 6:1.These catalyzer are tested up to 600 hours in the reactor of bench scale, reuse n-tetradecane as model compound.From the result who obtains, can determine easily that the interpolation of Sn almost completely eliminated the degree of hydrogenolytic cleavage (to the selectivity of 0.008 quality % of methane).Be used for being suppressed at the beneficial effect also clearly obvious from these embodiment (referring to the result of the table 3 among the embodiment 5 and 4) of the adding of the Sn that the methane of hydrocarbon hydrocracking reaction forms.
But owing to comprise Sn, the molar distribution of split product is to the lighter products skew and have to add more Ni to obtain better balance and therefore obtain the ideal hydrocracking between acid function and metal function.And, can only be for the optimization of each catalyst system decision at the hydrocracking catalyst aspect the ratio of Ni% and Ni:Sn.
And, use the catalyzer of the aluminum oxide of silication although used as preparing carriers, but skew has been clear significant after 300 hours working time, and NiSn/ silica-alumina catalyzer is stable and along with TOS produces similar transformation efficiency and products distribution under identical operational conditions.
Also find to use these to have the catalyzer of the metal load of increase, the also slight shift of oriented higher carbon number in products distribution.These results clearly illustrate for this special silica-alumina needs higher metal load to obtain the suitable balance between metal function and the acid function.
Find surprisingly once more that also the methane by the Ni/ silica-alumina forms and is less than the methane that the aluminum oxide by the Ni/ silication obtains significantly and forms.Therefore, can obtain conclusion, the dioxide-containing silica of support/acidic component is high more, and is low more to the selectivity of methane.These comparing results and exceed to the results are shown in unexpectedly in the table 5 of embodiment 5.
Embodiment 1
The aluminum oxide of 3 and 4.5% Ni/ silication is prepared as follows: (99% purity, aqueous solution Aldrich) is to obtain described metal load percentage ratio (considering the loss=13.8 quality % of calcination) for the Nickelous nitrate hexahydrate of use suitable concn.Using rotatory evaporator to remove down at 50 millibars and 55 ℃ desolvates.Calcined 2 hours down 120 ℃ of following dried overnight with at 300 ℃ subsequently.In reactor, pack into behind the sample, under atmospheric pressure use hydrogen under 400 ℃, to carry out in-situ reducing 16 hours.Subsequently, with sample as being used for n-hexadecane (n-C
16) hydrocracking catalyzer and test, wherein, n-hexadecane is used as model compound.For the aluminum oxide of 3%Ni/ silication, reaction conditions is 350 ℃, 55 crust, WHSV=2.3 hour
-1And H
2/ n-C
16Mol ratio is about 10, and for the aluminum oxide of 4.5%Ni/ silication, and reaction conditions is 345 ℃, 55 crust, WHSV=2.5 hour
-1And H
2/ n-C
16Mol ratio is about 9.By these catalyzer (non-sulphur), the products distribution that when about 41% transformation efficiency, the is obtained symmetry that seems, and therefore near the ideal hydrocracking.
The alumina sample of NiSn/ silication prepares by the common dipping of the tin compound of use Ni:Sn mol ratio=3:1.This sample is by the Ni (NO with 13.5g
3)
26H
2The SnCl of O and 3.5g
22H
2O (Aldrich) is dissolved in 95% ethanol of 150ml and prepares.In this solution, add 40g silication alumina supporter and this mixture was at room temperature left standstill 1 hour.Solvent is removed and drying step carrying out as described in example 1 above, calcines 3 hours down at 600 ℃ subsequently.450 ℃ of down reduction after 16 hours, the NiSn catalyzer of this load is tested subsequently and is used at 340 ℃, 50 crust, WHSV=1.5 hour
-1And H
2/ n-C
14Mol ratio is about the n-tetradecane (n-C when 31 quality % transformation efficiencys under 10 the reaction conditions
14) hydrocracking.The products distribution that aluminum oxide by Ni and NiSn/ silication obtains is shown among Fig. 2, and it has clearly illustrated that and has added tin for the beneficial effect that suppresses hydrogenolysis in the nickel base hydrogenation catalyst for cracking.
The same process that use is described in embodiment 2 has also prepared the NiSn catalyzer of the alumina load of silication, and it contains the Ni of 5 quality % and the Sn of 1.7 quality %.350 ℃ of down calcinings 2 hours, 350 ℃ of reduction 4 hours, catalyzed reaction was at 343 ℃, 50 crust, WHSV=1.8 hour with catalyst precursor
-1And H
2/ n-C
14Mol ratio is about 10 times and carries out.Under 16 and 514 hours run duration and the products distribution that obtains is shown among Fig. 3.Because the loss of metal function, be clear obvious to the skew of lighter products along with the increase of TOS.
Embodiment 4
Table 1. uses the dehydration of 1-hexanol to be used for the proton tart evaluation of commercial silica-aluminum oxide
Reaction conditions: 200 ℃, WHSV=3.0 hour
-1With TOS=1.0 hour
1Use the pure silica-alumina of literature method (J Heveling, Cp NiColaides and MS Scurrel, AppliedCatalysis A:General, 173 (1998) 1) preparation
2Commercial silica-alumina sample.
Embodiment 5 (a)
The NiSn catalyzer of second series uses peracidity SA2 silica-alumina to prepare as carrier, and it has the dioxide-containing silica of 50 quality %.Ni content from 6 to 10 quality % change and use the Ni:Sn of 6:1 mol ratio.All samples is calcined down at 350 ℃, and 10ml is added in the reactor with 10ml silicon carbide diluted catalyst precursor.Reduction reaction uses 201
NThe hydrogen flow rate of/h under atmospheric pressure carried out 16 hours under 350 ℃.Table 2 shows the fundamental characteristics of catalyzer.
The characteristic of table 2.NiSn/ silica-alumina catalyzer
| Catalyzer | Ni (quality %) | Sn (quality %) |
| A | 6.0 | 2.0 |
| B | 8.0 | 2.7 |
| C | 10.0 | 3.4 |
| D | 10.0 | There is not tin |
Embodiment 5 (b)
Be described in the hydrocracking that catalyzer among the embodiment 5 (a) is used to the n-tetradecane under the reaction conditions listed in table 3.The selectivity percentage ratio of resulting transformation efficiency percentage ratio and methane also provides in same table.
The about 0.13 quality % of methane selectively during from 7%Ni/ silica-alumina sample drops to the 0.008 quality % (seeing Table 3 and 4) when containing the Sn catalyzer.The beneficial effect of adding that is used for being suppressed at the tin that the methane of hydrocarbon hydrocracking reaction forms is also clearly obvious in these embodiments.
The hydrocracking of the n-tetradecane of table 3. on catalyzer with different Ni% and Sn load
1
| Catalyzer | A | B | C | | |
| Pressure | Crust | ||||
| 50 | 50 | 50 | 50 | ||
| WHSV | h -1 | 1.7 | 1.6 | 1.7 | 1.9 |
| Temperature | ℃ | 325 | 328 | 329 | 315 |
| Transformation efficiency | Quality % | 69.0 | 72.8 | 72.5 | 71.8 |
| CH 4Selectivity | Quality % | 0.008 | 0.008 | 0.008 | 0.13 |
1Be reflected in the reactor of bench scale, use the catalyzer of 10ml to carry out with the dilution of 10ml silicon carbide.
Embodiment 5 (c)
For 10%Ni, 3.4%Sn/ silica-alumina catalyzer, list in the table 4 as the transformation efficiency percentage ratio of the function of TOS with to the selectivity percentage ratio of methane.Reaction conditions is 323 ℃, 50 crust and H
2/ n-C
14Mol ratio is about 10.The result has shown that catalyzer forms with stability and the extremely low-level methane that TOS changes.
Table 4. for 10%Ni, 3.4%Sn/ silica-alumina catalyzer as the transformation efficiency percentage ratio of the function of working time and the selectivity percentage ratio of methane
| Working time (hour) | Transformation efficiency (quality %) | Methane selectively (quality %) |
| 40 | 45.9 | 0.009 |
| 136 | 44.0 | 0.007 |
| 184 | 34.2 | 0.010 |
| 232 | 38.3 | 0.011 |
| 352 | 37.8 | 0.009 |
| 400 | 38.9 | 0.008 |
| 496 | 34.5 | 0.009 |
Embodiment 5 (d)
By being described in the catalyzer among the embodiment 5 (c), the products distribution that obtains under different working times is shown among Fig. 4.Reaction conditions provides at table 3.The result shows, with this catalyzer similar products distribution of acquisition and do not have significantly skew to lighter products under different working times.
Embodiment 5 (e)
Fig. 5 shows the products distribution that obtains by the catalyzer with different metal load (being described in the table 3).Can see, along with the increase of metal load, to higher carbon number (C
6-C
11) skew increase.
In this embodiment, observed selectivity percentage ratio in the experiment of relatively carrying out to methane at the catalyzer that uses only nickeliferous and two kinds of different carriers.Even the result clearly illustrates the higher nickel load of use in Ni/ silica-alumina catalyzer, also obtain much lower selectivity to methane.Thereby proved and be used for making the high silicon dioxide content of the minimized hydrocracking catalyst of methane formation degree and the beneficial effect of al suboxide content.
Table 5. alumina content is to the influence of methane selectively
| Catalyzer | Aluminum oxide (quality %) | Methane (quality %) |
| The aluminum oxide of 7%Ni/ silication | 60 | 4.3 |
| The 10%Ni/ silica- |
20 | 0.1 |
Claims (32)
1. one kind is used for the method that methane forms when reduce the hydrocracking hydrocarbon in the presence of the Ni catalyzer containing of unvulcanised, this catalyzer has the Ni content of at least 1 quality % and the dioxide-containing silica of at least 20 quality %, and described silicon-dioxide exists with the form of silica-alumina.
2. the process of claim 1 wherein described methane formed to be reduced to and be lower than 1 quality %.
3. the method for claim 2 wherein forms described methane to be reduced to and is lower than 0.1 quality %.
4. each method in the aforementioned claim, it has the Ni content of at least 3 quality %.
5. the method for claim 4, it has the Ni content of at least 4.5 quality %.
6. each method in the aforementioned claim, it has the silicon-dioxide of at least 40 quality %.
7. each method in the aforementioned claim, wherein said catalyzer contains Sn.
8. the method for claim 7 wherein forms described methane to be reduced to and is lower than 0.01 quality %.
9. the method for claim 7, wherein the Ni:Sn mol ratio surpasses 1:1.
10. each method in the aforementioned claim, this method comprise uses the carrier of silica-alumina as described catalyzer.
11. technology that is used for the hydrocracking of hydrocarbon, described technology is included in the reactor of operation under the hydrocracking temperature and pressure, contain the Ni catalyzer with what described hydrocarbon was exposed to unvulcanised, this catalyzer has the Ni content of at least 1 quality % and the dioxide-containing silica of at least 20 quality %, and described silicon-dioxide exists with the silica-alumina form.
12. the technology of claim 11, wherein said hydrocarbon are ebullient paraffinic hydrocarbon in 370 ℃+scope.
13. the technology of claim 11, wherein said hydrocarbon is more lower boiling paraffinic hydrocarbon.
14. each technology in the claim 11 to 13, this technology was the pressure of 200～450 ℃ temperature, 5～250 crust and WHSV=0.1-10 hour
-1Following operation.
15. each technology in the claim 11 to 14, it has the Ni content of at least 3 quality %.
16. the technology of claim 15, it has the Ni content of at least 4.5 quality %.
17. each technology in the claim 11 to 16, it has the silicon-dioxide of at least 40 quality %.
18. each technology in the claim 11 to 17, wherein said silicon-dioxide exists with the silica-alumina form.
19. each technology in the claim 11 to 18, wherein said catalyzer contains Sn.
20. the technology of claim 19, wherein the Ni:Sn mol ratio surpasses 1:1.
21. comprising, each technology in the claim 11 to 20, this technology uses the carrier of silica-alumina as described catalyzer.
22. catalyzer that is used in the method that when the hydrocracking hydrocarbon, reduces methane formation, described catalyzer be unvulcanised and contain Ni and silicon-dioxide, wherein said Ni content is at least 1 quality %, described dioxide-containing silica is at least 20 quality %, and described silicon-dioxide exists with the silica-alumina form.
23. the catalyzer of claim 22, it has the Ni content of at least 3 quality %.
24. the catalyzer of claim 23, it has the Ni content of at least 4.5 quality %.
25. each catalyzer in the claim 22 to 24, it has the silicon-dioxide of at least 40 quality %.
26. each catalyzer in the claim 22 to 25, this catalyzer contains Sn.
27. the catalyzer of claim 26, wherein the Ni:Sn mol ratio surpasses 1:1.
28. comprising, each catalyzer in the claim 22 to 27, this method use the carrier of silica-alumina as described catalyzer.
29. one kind as claimed in claim 1 is used for the method that methane forms when reduce the hydrocracking hydrocarbon in the presence of the Ni catalyzer containing of unvulcanised, substantially as in this description and explanation.
30. a technology that is used for the hydrocarbon hydrocracking as claimed in claim 11 is substantially as in this description and explanation.
31. one kind is used in the catalyzer that reduces in the method that methane forms as claimed in claim 22 when the hydrocracking hydrocarbon, substantially as in this description and explanation.
32. a novel method, a kind of novel process or a kind of raw catalyst are basic as described here.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/299,836 US20070131586A1 (en) | 2005-12-12 | 2005-12-12 | Non-sulfided Ni-based hydrocracking catalysts |
| US11/299,836 | 2005-12-12 | ||
| PCT/ZA2006/000140 WO2007070894A2 (en) | 2005-12-12 | 2006-12-01 | Non-sulfided ni-based hydrocracking catalysts |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101370912A true CN101370912A (en) | 2009-02-18 |
| CN101370912B CN101370912B (en) | 2012-07-18 |
Family
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Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200680052694.7A Expired - Fee Related CN101370912B (en) | 2005-12-12 | 2006-12-01 | Non-sulfided Ni-based hydrocracking catalysts |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US20070131586A1 (en) |
| CN (1) | CN101370912B (en) |
| AU (1) | AU2006325738A1 (en) |
| WO (1) | WO2007070894A2 (en) |
| ZA (1) | ZA200804999B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102099113A (en) * | 2008-07-23 | 2011-06-15 | 三井化学株式会社 | Catalyst for ethylene oligomerization and use thereof |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2911356A (en) * | 1957-02-18 | 1959-11-03 | Union Oil Co | Hydrocracking of hydrocarbons with reaction conditions dependent on nitrogen contentof feed |
| US3206391A (en) * | 1962-04-13 | 1965-09-14 | Standard Oil Co | Catalytic conversion of hydrocarbons |
| GB1059692A (en) * | 1964-09-01 | 1967-02-22 | Shell Int Research | Process for the preparation of a catalyst suitable for the hydrogenerative cracking of a hydrocarbon oil |
| US3232864A (en) * | 1964-03-23 | 1966-02-01 | Universal Oil Prod Co | Preparation of a hydrocarbon hydrocracking catalyst for use in the conversion of hydrocarbons |
| US3401125A (en) * | 1964-05-22 | 1968-09-10 | Chevron Res | Coprecipitation method for making multi-component catalysts |
| US3399132A (en) * | 1966-07-28 | 1968-08-27 | Chevron Res | Hydrocaracking of hydrocarbons with a catalyst composite comprising nickel and tin associated with a porous acidic inorganic oxide carrier |
| US3542696A (en) * | 1968-10-14 | 1970-11-24 | Chevron Res | Hydrocracking catalyst |
| US3598724A (en) * | 1969-09-15 | 1971-08-10 | Chevron Res | Production of propane and butanes |
| US4062809A (en) * | 1976-03-18 | 1977-12-13 | Union Oil Company Of California | Catalyst for production of middle distillate oils |
| EP0587245A1 (en) * | 1992-09-08 | 1994-03-16 | Shell Internationale Researchmaatschappij B.V. | Hydroconversion catalyst |
| US6245709B1 (en) * | 1995-07-14 | 2001-06-12 | Exxon Research And Engineering Company | Supported Ni-Cu hydroconversion catalyst |
| FR2780311B1 (en) * | 1998-06-25 | 2000-08-11 | Inst Francais Du Petrole | HYDROCRACKING CATALYST COMPRISING A NON-GLOBALLY DESALUMINATED Y ZEOLITE, A VB GROUP ELEMENT, AND A PROMOTING ELEMENT SELECTED IN THE GROUP FORMED BY BORON, PHOSPHORUS AND SILICON |
-
2005
- 2005-12-12 US US11/299,836 patent/US20070131586A1/en not_active Abandoned
-
2006
- 2006-12-01 CN CN200680052694.7A patent/CN101370912B/en not_active Expired - Fee Related
- 2006-12-01 AU AU2006325738A patent/AU2006325738A1/en not_active Abandoned
- 2006-12-01 WO PCT/ZA2006/000140 patent/WO2007070894A2/en active Search and Examination
-
2008
- 2008-06-09 ZA ZA200804999A patent/ZA200804999B/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| WO2007070894A3 (en) | 2007-08-02 |
| AU2006325738A1 (en) | 2007-06-21 |
| CN101370912B (en) | 2012-07-18 |
| US20070131586A1 (en) | 2007-06-14 |
| ZA200804999B (en) | 2009-11-25 |
| WO2007070894A2 (en) | 2007-06-21 |
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