CN101395253B - Method of wax hydrocracking - Google Patents

Method of wax hydrocracking Download PDF

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Publication number
CN101395253B
CN101395253B CN200780008028.8A CN200780008028A CN101395253B CN 101395253 B CN101395253 B CN 101395253B CN 200780008028 A CN200780008028 A CN 200780008028A CN 101395253 B CN101395253 B CN 101395253B
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hydrocracking catalyst
catalyst layer
hydrogen
hydrocracking
wax
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CN101395253A (en
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关浩幸
绀野博文
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Eneos Corp
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Nippon Oil Corp
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • 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
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products

Abstract

A method of wax hydrocracking, characterized by disposing in a fixed-bed reactor a first hydrocracking catalyst layer and a second hydrocracking catalyst layer respectively on the upstream side and downstream side in the reactor so as to satisfy the requirement represented by the following relationship (1), passing hydrogen and a wax through the first hydrocracking catalyst layer, additionally adding hydrogen to a decomposition product from the first hydrocracking catalyst layer upstream from the upstream end of the second hydrocracking catalyst layer, and passing a mixture comprising the decomposition product and the hydrogen additionally added through the second hydrocracking catalyst layer. d1/(d1+d2)=1/3 (1) [In the relationship (1), d1 indicates the distance between the upstream end and downstream end of the first hydrocracking catalyst layer; and d2 indicates the distance between the upstream end and downstream end of the second hydrocracking catalyst layer].

Description

The process for hydrocracking of hydrocarbonaceous of wax
Technical field
The present invention relates to a kind of process for hydrocracking of hydrocarbonaceous of wax.
Background technology
In recent years, from the position of environment protection, to rapid the change strictly of regulation of the sulphur content in the liquid fuels such as gasoline or light oil.Therefore, sulphur content or the expectation that contains the low clean fuel liquid of aromatic hydrocarbons amount are grown to even greater heights.
As one of method of making such clean fuel, the carbon monoxide that obtains take the reformation by Sweet natural gas and hydrogen as fischer-tropsch (FT) synthesis method of raw material or further so-called natural gas liquefaction (GTL) synthesis methods such as method of the wax (FT wax) that generated by the FT synthesis method of hydrocracking get most of the attention.Because the fuel base that is obtained by the FT synthesis method take normal paraffin as main component, therefore directly is restricted as gasoline or light oil, but has the feature that is rich in isoparaffin by the fuel base that the hydrocracking of FT wax obtains.GTL is usually to make middle runnings (fuel bases such as kerosene or light oil) as purpose.
Up to the present, still make the technology of fuel base at research hydrocracking wax, for example record the process for hydrocracking of hydrocarbonaceous that uses specific hydrocracking catalyst in the following patent documentation 1～3.
Patent documentation 1: the international brochure that discloses No. 2004/028688
Patent documentation 2: TOHKEMY 2004-255241 communique
Patent documentation 3: TOHKEMY 2004-255242 communique
Summary of the invention
The problem that invention will solve
But in the process for hydrocracking of hydrocarbonaceous of present wax, as described in above-mentioned patent documentation 1～3, the exploitation of high performance hydrocracking catalyst is the center, and relating to the report that improvement by technique improves the fuel base yield does not almost have.In addition, from the viewpoint of the economy of technique, the consumption that reduces the hydrogen that uses in the hydrocracking is important, also goes out to send fully from such viewpoint hardly and studies.
The present invention is the invention of carrying out in view of such practical situation, and its purpose is to provide a kind of process for hydrocracking of hydrocarbonaceous of wax, and described method can fully improve the yield of middle runnings, and can fully reduce the consumption of hydrogen.
Solve the method for problem
In order to solve above-mentioned problem, the process for hydrocracking of hydrocarbonaceous of wax of the present invention is characterised in that, at the upstream side of fixed-bed reactor the 1st hydrocracking catalyst layer is set respectively, the 2nd hydrocracking catalyst layer is set in the downstream side with the condition that satisfies following formula (1) expression, make hydrogen and wax by the 1st hydrocracking catalyst layer, upstream side at the upstream extremity of the 2nd hydrocracking catalyst layer appends hydrogen to the split product from the 1st hydrocracking catalyst layer, makes the mixture of the hydrogen that contains split product and append by the 2nd hydrocracking catalyst layer.
d 1/(d 1+d 2)≥1/3 (1)
[in the formula (1), d 1Represent that the upstream extremity of above-mentioned the 1st hydrocracking catalyst layer is to the distance of downstream end, d 2Represent that the upstream extremity of above-mentioned the 2nd hydrocracking catalyst layer is to the distance of downstream end.]
According to the process for hydrocracking of hydrocarbonaceous of wax of the present invention, so that the upstream extremity of the 1st and the 2nd hydrocracking catalyst layer is to the distance of the downstream end thickness of circulating direction (namely along) d 1, d 2The condition that satisfies above-mentioned formula (1) expression arranges the 1st and the 2nd hydrocracking catalyst layer, simultaneously, except supplying with the hydrogen to the 1st hydrocracking catalyst layer, append hydrogen at above-mentioned specific position to the split product from the 1st hydrocracking catalyst layer, can fully improve thus the yield of middle runnings contained in the split product from the 2nd hydrocracking catalyst layer.In addition, compare with situation from hydrogen to the 1st hydrocracking catalyst layer that only supply with, can fully reduce the hydrogen consumption of the 1st and the 2nd hydrocracking catalyst layer.
Be explained, from can containing unreacted hydrogen in the split product of the 1st hydrocracking catalyst layer, the hydrogen and the above-mentioned unreacted hydrogen that are appended to split product at the upstream side of the upstream extremity of the 2nd hydrocracking catalyst layer distinguish.
In the present invention, with respect to the hydrogen amount of supplying with the 1st hydrocracking catalyst layer, the hydrogen amount of appending to the split product from the 1st hydrocracking catalyst layer at the upstream side of the upstream extremity of the 2nd hydrocracking catalyst layer is preferably more than the 5 capacity %.
In addition, in the present invention, the wax that uses as raw material preferably synthesizes the wax that obtains by Fischer-Tropsch process.
In addition, in the present invention, the preferred the 1st and the 2nd hydrocracking catalyst layer contains respectively hyperstabilized y-type zeolite (USY zeolite).
The invention effect
As mentioned above, according to the process for hydrocracking of hydrocarbonaceous of wax of the present invention, can fully improve the yield of middle runnings, and can fully reduce the consumption of hydrogen.
Description of drawings
Fig. 1 is the explanatory view of an example of the fixed-bed reactor that uses among the present invention of expression.
Fig. 2 is another routine explanatory view of the fixed-bed reactor that uses among the present invention of expression.
Nomenclature
1a, 1b, 1c... reaction tower, 2a, 2b... hydrocracking catalyst layer.
Embodiment
Below, preferred implementation of the present invention is at length described.
Fig. 1 is the explanatory view of a routine preference of the fixed-bed reactor that uses of expression the 1st embodiment of the present invention.In fixed-bed reactor shown in Figure 1,2 reaction tower 1a, 1b are connected in series by transport pipe L3.And, the condition setting hydrocracking catalyst layer 2a, the 2b that represent to satisfy following formula (1) in reaction tower 1a, 1b inside separately.Be explained, when reaction tower 1a, 1b have mutually identical shape, can adjust d by the loading level of adjusting each hydrocracking catalyst that consists of hydrocracking catalyst layer 2a, 2b 1, d 2
d 1/(d 1+d 2)≥1/3 (1)
[in the formula (1), d 1The upstream extremity of expression hydrocracking catalyst layer 2a is to the distance of downstream end, d 2The upstream extremity of expression hydrocracking catalyst layer 2b is to the distance of downstream end.]
In addition, from the viewpoint that can realize with higher standard improving the middle runnings yield and reduce the consumption of hydrogen, the d in the above-mentioned formula (1) 1/ (d 1+ d 2) be preferably 1/3～5/6, more preferably 7/12～9/12.
The hydrocracking catalyst that consists of hydrocracking catalyst layer 2a each other can be identical with the catalyzer that consists of hydrocracking catalyst layer 2b, also can be different.
As the hydrocracking catalyst that consists of hydrocracking catalyst layer 2a, 2b, as long as have the hydrocracking performance, just be not particularly limited, as its carrier, preferably contain the amorphous solid acid such as silica-alumina, silicon-dioxide-zirconium white, aluminum oxide-boron oxide, silica-magnesia, perhaps the crystalline solid acid such as USY zeolite, mordenite, β zeolite, ZSM-22, SAPO-11 wherein particularly preferably contain the USY zeolite.
When the formation of the carrier of hydrocracking catalyst contains the USY zeolite, the shared ratio of USY zeolite is not particularly limited in the carrier, from suppressing the viewpoint of fuel base lighting, take the carrier total amount as benchmark, the ratio of USY zeolite is preferably below the 15 quality %, more preferably below the 5 quality %.
In addition, the mol ratio of the silica/alumina in the USY zeolite is not particularly limited, and is preferably 30～200, and more preferably 30～100, most preferably be 30～60.And the median size of USY zeolite is preferably below the 1.0 μ m, more preferably below the 0.5 μ m.Be explained, if the median size of USY zeolite is larger than above-mentioned higher limit, then might make the fuel base lighting that obtains.
In addition, hydrocracking catalyst can also contain the tackiness agent that is useful on the carrier moulding.Tackiness agent is not particularly limited, and as preferred tackiness agent, can exemplify aluminum oxide or silicon-dioxide.The shape of carrier is not particularly limited, and can be shapes such as granular, cylindric (particulate state).
In addition, as hydrocracking catalyst, preferably load has the catalyzer of periodic table of elements group VIII metal on above-mentioned carrier.As the group VIII metal, specifically can exemplify: cobalt, nickel, rhodium, palladium, iridium, platinum etc.Wherein, be preferably selected from palladium and the platinum more than a kind, particularly take the slack wax that contains oil content during as raw material, preferably on carrier supported palladium and platinum both.The amount of metal that is carried on carrier is not particularly limited, and is 0.01～2 quality % with respect to carrier preferably.
The top of reaction tower 1a is connecting the pipeline L1 that is used for supplying with hydrogen in reaction tower 1a, and pipeline L1 is being connected the pipeline L2 that is used for supplying with wax with the upstream side of the connection section of reaction tower.Thus, wax and hydrogen can be delivered in the reaction tower 1a together, make it carry out hydrocracking by hydrocracking catalyst layer 2.
As the wax that is used for hydrocracking, can enumerate and for example contain that the above carbon number of 30 quality % is 16 or more, preferably carbon number is petroleum-type wax or the synthetic class wax of the normal paraffin more than 20.As petroleum-type wax, can enumerate: slack wax, microcrystalline wax etc.; As synthetic class wax, can enumerate: by the synthetic so-called FT wax of making of FT.
Be explained, Fig. 1 represents is the example of the reaction unit that converges of hydrogen service L1 and wax service L2, and hydrogen service L1 is also with wax service L2 and can be connected with reaction tower 1a respectively separately.In addition, the preferred top side by reaction tower 1a as shown in Figure 1 of the circulating direction of wax flows to the direction of bottom side.
Condition when carrying out the hydrocracking of wax in reaction tower 1a is not particularly limited, preferred 250～370 ℃ of temperature of reaction.When surpassing 370 ℃, temperature of reaction generates easily aromatics, and not preferred from the viewpoint that obtains the clean fuel base material.In addition, the preferred 1～12MPa of reaction pressure (hydrogen dividing potential drop), more preferably 2～6MPa.If reaction pressure is lower than above-mentioned lower value, then the easy inactivation of hydrocracking catalyst in addition, if surpass above-mentioned higher limit, then might rise for the temperature of reaction that obtains same cleavage rate, and is therefore all not preferred.In addition, liquid hourly space velocity is not particularly limited, preferred 0.1～3.0h -1In addition, the ratio (hydrogen/oil ratio) of whole hydrogen amounts of supplying with and oil is not particularly limited, and is preferably 100～850NL/L, more preferably 200～650NL/L.
The split product that is obtained by hydrocracking in reaction tower 1a is transported to reaction tower 1b by transport pipe L3.At this moment, append hydrogen from the hydrogen service L4 that is connected in transport pipe L3 to split product.
From can further improving the viewpoint of the yield of the middle runnings that among reaction tower 1b, obtains after the hydrocracking, with respect to the amount by the hydrogen of hydrogen service L1 supply response tower 1a, the amount of the hydrogen that is appended to split product by hydrogen service L4 is preferably more than the 5 capacity %.
Be explained, what Fig. 1 represented is the example that hydrogen service L4 is connected in the device of transport pipe L3, the link position of hydrogen service L4 needs only between the upstream extremity of the downstream end of hydrocracking catalyst layer 2a and hydrocracking catalyst layer 2b, for example can connect at the top of reaction tower 1b hydrogen service L4 and append hydrogen.
To having appended thus the split product of hydrogen, pass through the hydrocracking catalyst layer 2b of reaction tower 1b by making it, further carry out hydrocracking.Hydrocracking condition among the reaction tower 1b is identical with hydrocracking condition among the reaction tower 1a, therefore omits repeat specification at this.Be explained, the hydroconversion condition among reaction tower 1a and the reaction tower 1b can be identical or different.
According to above-mentioned the 1st embodiment, so that the upstream extremity of hydrocracking catalyst layer 2a, 2b is to the distance of the downstream end thickness of circulating direction (namely along) d 1, d 2The condition that satisfies above-mentioned formula (1) expression arranges hydrocracking catalyst layer 2a, 2b, simultaneously, except being supplied with the hydrogen to hydrocracking catalyst layer 2a by hydrogen service L1, append hydrogen to the split product from the 1st hydrocracking catalyst layer by hydrogen service L4, can fully improve thus the yield of middle runnings contained in the split product from hydrocracking catalyst layer 2b.In addition, and only compared to the situation that hydrocracking catalyst layer 2a supplies with hydrogen by hydrogen service L1, can fully reduce the hydrogen total amount consumed among hydrocracking catalyst layer 2a, the 2b.Be explained, in the split product that obtains, generally, except middle runnings, also contain petroleum naphtha (boiling point is lower than 145 ℃ cut) and wax (boiling point surpasses 360 ℃ cut), but by split product is taken out, distills etc. from the pipeline L5 that is connected in reaction tower 1b bottom, can separate the base material that above-mentioned cut obtains being applicable to various uses.
Fig. 2 is the explanatory view of a preference of the fixed-bed reactor of expression the 2nd embodiment of the present invention.In fixed-bed reactor shown in Figure 2, in reaction tower 1c, to satisfy condition setting hydrocracking catalyst layer 2a, the 2b of above-mentioned formula (1) expression.
The top of reaction tower 1c is connecting the pipeline L1 that is used for supplying with hydrogen in reaction tower 1c, and pipeline L1 is connected the upstream side of connection section and is being connected the pipeline L2 that is used for supplying with wax with reaction tower.Thus, wax and hydrogen can be delivered in the reaction tower 1c together, make it to carry out the hydrocracking of wax by hydrocracking catalyst layer 2a, 2b successively.
In addition, between the upstream extremity of the downstream end of hydrocracking catalyst layer 2a and hydrocracking catalyst layer 2b, be provided with the space, connecting hydrogen service L4 in the position in the corresponding above-mentioned space of sidepiece of reaction tower 1c.Thus, can append hydrogen to the split product from hydrocracking catalyst layer 2a, and the mixture that makes split product and the hydrogen that appends carries out hydrocracking by hydrocracking catalyst layer 2b.
Be explained, in the present embodiment, the hydrocracking catalyst of formation hydrocracking catalyst layer 2a, 2b is identical with the hydrocracking catalyst in the 1st embodiment, therefore omits repeat specification at this.In addition, for reaction tower 1c, the catalyzer filled band is being used sectional area when cutting off perpendicular to the plane of flow direction irrelevant and have in the definite shape situation of (as cylindric etc.) with off-position, the loading level of each hydrocracking catalyst that can be by regulating formation hydrocracking catalyst layer 2a, 2b be regulated d 1, d 2
In addition, the hydrocracking condition that can be set as among reaction tower 1a, the 1b with the 1st embodiment of the hydrocracking condition among the reaction tower 1c is identical.
According to above-mentioned the 2nd embodiment, so that the upstream extremity of hydrocracking catalyst layer 2a, 2b is to the distance of the downstream end thickness of circulating direction (namely along) d 1, d 2The condition that satisfies above-mentioned formula (1) expression arranges hydrocracking catalyst layer 2a, 2b, simultaneously, except being supplied with the hydrogen to hydrocracking catalyst layer 2a by hydrogen service L1, append hydrogen to the split product from the 1st hydrocracking catalyst layer by hydrogen service L4, can fully improve thus the yield of the middle runnings that comprises in the split product from hydrocracking catalyst layer 2b.In addition, and only compared to the situation that hydrocracking catalyst layer 2a supplies with hydrogen by hydrogen service L1, can fully reduce the hydrogen total amount consumed among hydrocracking catalyst layer 2a, the 2b.Be explained, in the split product that obtains, generally, except middle runnings, also contain petroleum naphtha (boiling point is lower than 145 ℃ cut) and wax (boiling point surpasses 360 ℃ cut), but by split product is taken out, distills etc. from the pipeline L5 that is connected in reaction tower 1c bottom, can separate above-mentioned cut, obtain being applicable to the base material of various uses.
Embodiment
Below, according to embodiment and comparative example the present invention is described more specifically, but the present invention is not subjected to any restriction of the following examples.
(embodiment 1)
Utilize silica-alumina (mol ratio of silica/alumina: 6.2) and alumina adhesive form the cylindric carrier (silica-alumina/alumina adhesive=80:20 (mass ratio)) of the about 1.5mm of φ, long 3mm.Make this carrier impregnation chloroplatinic acid aqueous solution, with respect to the platinum of carrier loaded 0.8 quality %.By be dried, sintering, obtain hydrocracking catalyst.
Then, the hydrocracking catalyst that obtains is filled in respectively among reaction tower 1a, the 1b of the fixed-bed reactor with structure shown in Figure 1, forms hydrocracking catalyst layer 2a, 2b.In the present embodiment, as reaction tower 1a, 1b, using the catalyzer filled band is the reaction tower of same shape cylindraceous, is 60ml in reaction tower 1a, is 90ml in reaction tower 1b, with the d in the above-mentioned formula (1) by the loading level that makes hydrocracking catalyst 1/ (d 1+ d 2) be set as 1/3.For each hydrocracking catalyst of the hydrocracking catalyst layer 2a, the 2b that consist of reaction tower 1a, 1b, before hydrocracking begins, under hydrogen stream, process deactivated catalyst in 345 ℃ of reduction of carrying out 4 hours.
Then use above-mentioned fixed-bed reactor to carry out the hydrocracking of wax.As paraffin, use FT wax (carbon number: 21～80, the content of normal paraffin: 95 quality %).When carrying out the hydrocracking of wax, the flow velocity from the hydrogen of hydrogen service L4 that to make flow velocity by the hydrogen of hydrogen service L1 supply response tower 1a be 200NL/h, make that the split product of autoreaction tower 1a always appends is 50NL/h.In addition, in reaction tower 1a, 1b, the liquid hourly space velocity that makes raw material is 2.0h -1(counting 300ml/h take flow rate of liquid), hydrogen dividing potential drop are 3.5MPa, reconcile temperature of reaction ( reaction tower 1a, 1b are same temperature), so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin.Temperature of reaction in the present embodiment is 355 ℃.
The split product that is obtained by hydrocracking is carried out gas chromatographic analysis, obtain the yield of middle runnings (145～360 ℃ cuts).In addition, the hydrogen consumption is by the hydrogen in the quantitative tail gas (working off one's feeling vent one's spleen), calculate according to the difference of itself and feed rate.Acquired results is shown in table 1.
(embodiment 2)
Be that all the other operate similarly to Example 1 the 20NL/h except making the flow velocity by the hydrogen of hydrogen service L1 supply response tower 1a, carry out the hydrocracking of wax, obtain yield and the hydrogen consumption of middle runnings.Acquired results is shown in table 1.Be explained, in the present embodiment, similarly to Example 1, conditioned reaction temperature ( reaction tower 1a, 1b are same temperature) is so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin, and the bearing reaction temperature is 358 ℃.
(comparative example 1)
Except not always the split product of autoreaction tower 1a append the hydrogen from hydrogen service L4, all the other operate similarly to Example 1, carry out the hydrocracking of wax, obtain yield and the hydrogen consumption of middle runnings.Acquired results is shown in table 1.Be explained, in this comparative example, similarly to Example 1, conditioned reaction temperature ( reaction tower 1a, 1b are same temperature) is so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin, and the bearing reaction temperature is 360 ℃.
(comparative example 2)
Except make the catalyzer loading level in reaction tower 1a for 30ml, in reaction tower 1b for the 120ml, all the other operate similarly to Example 1, carry out the hydrocracking of wax, obtain yield and the hydrogen consumption of middle runnings.Acquired results is shown in table 1.Be explained, in this comparative example, similarly to Example 1, conditioned reaction temperature ( reaction tower 1a, 1b are same temperature) is so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin, and the bearing reaction temperature is 356 ℃.
(embodiment 3)
Utilize USY zeolite (SiO 2/ Al 2O 3=40mol/mol) and silicon-dioxide-zirconium white (silicon-dioxide/zirconium white=1.5mol/mol) and alumina adhesive form the cylindric carrier (USY zeolite/silicon-dioxide-zirconium white/alumina adhesive=3:7:90 (mass ratio)) of the about 1.5mm of φ, long 3mm.Make this carrier impregnation chloroplatinic acid aqueous solution, with respect to the platinum of carrier loaded 0.8 quality %.By be dried, sintering, obtain hydrocracking catalyst.
Except using the hydrocracking catalyst that obtains thus, all the other operate similarly to Example 1, carry out the hydrocracking of wax, obtain yield and the hydrogen consumption of middle runnings.Acquired results is shown in table 1.Be explained, in the present embodiment, similarly to Example 1, conditioned reaction temperature ( reaction tower 1a, 1b are same temperature) is so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin, and the bearing reaction temperature is 311 ℃.
(comparative example 3)
Except not from the supplying opening 3b supply hydrogen of reaction tower 1a, all the other operate similarly to Example 3, carry out the hydrocracking of wax, obtain yield and the hydrogen consumption of middle runnings.Acquired results is shown in table 1.Be explained, in this comparative example, similarly to Example 1, conditioned reaction temperature ( reaction tower 1a, 1b are same temperature) is so that the quality of the light ends of boiling point below 360 ℃ is 80 quality % with respect to the quality of paraffin, and the bearing reaction temperature is 313 ℃.
[table 1]
d 1/(d 1+d 2) Have or not and append hydrogen The yield of middle runnings (quality %) Hydrogen consumption (SCF/B)
Embodiment 1 1/3 Have 57.4 520
Embodiment 2 1/3 Have 56.1 530
Comparative example 1 1/3 Nothing 54.6 570
Comparative example 2 1/5 Have 55.2 570
Embodiment 3 1/3 Have 60.4 510
Comparative example 3 1/3 Nothing 55.6 580
As shown in table 1, in embodiment 1～3 so that the upstream extremity of hydrocracking catalyst layer 2a, 2b to downstream end apart from d 1, d 2The condition that satisfies formula (1) expression arranges hydrocracking catalyst layer 2a, 2b, simultaneously, except supplying with the hydrogen to hydrocracking catalyst layer 2a, between hydrocracking catalyst layer 2a and hydrocracking catalyst layer 2b, append hydrogen to the split product from hydrocracking catalyst layer 2a, the yield of middle runnings can be fully improved thus, in addition, the hydrogen consumption can be fully reduced.
Industrial applicibility
According to the process for hydrocracking of hydrocarbonaceous of wax of the present invention, can fully improve the yield of middle runnings, and can fully reduce the consumption of hydrogen.

Claims (2)

1. the process for hydrocracking of hydrocarbonaceous of wax, it is characterized in that, with the condition that meets following formula (1) expression, at the upstream side of fixed-bed reactor, the 1st hydrocracking catalyst layer is set respectively, the 2nd hydrocracking catalyst layer is set in downstream, make hydrogen and pass through described the 1st hydrocracking catalyst layer by the wax that Fischer-Tropsch synthesis obtains, upstream side at the upstream extremity of described the 2nd hydrocracking catalyst layer appends hydrogen to the pyrolysis product from described the 1st hydrocracking catalyst layer, the mixture of the described hydrogen that makes to contain described pyrolysis product and append is by described the 2nd hydrocracking catalyst layer, in reaction temperature, it is 250～370 ℃, reaction pressure is 1～12MPa, liquid hourly space velocity (LHSV) is 0.1～3.0h -1the ratio of whole hydrogen amounts of supplying with and oil is to carry out hydrocracking under the condition of 100～850NL/L, described the 1st hydrocracking catalyst layer comprises and contains carrier and the hydrocracking catalyst of the periodic table of elements group VIII metal of load on above-mentioned carrier, described carrier contains hyperstabilized y-type zeolite or silica-alumina, described the 2nd hydrocracking catalyst layer comprises and contains carrier and the hydrocracking catalyst of the periodic table of elements group VIII metal of load on above-mentioned carrier, described carrier contains hyperstabilized y-type zeolite or silica-alumina
d 1/(d 1+d 2)≥1/3(1)
In the formula (1), d 1Represent that the upstream extremity of described the 1st hydrocracking catalyst layer is to the distance of downstream end, d 2Represent that the upstream extremity of described the 2nd hydrocracking catalyst layer is to the distance of downstream end.
2. the process for hydrocracking of hydrocarbonaceous of wax claimed in claim 1, it is characterized in that, with respect to the hydrogen amount of supplying with described the 1st hydrocracking catalyst layer, the hydrogen amount of appending to the split product from described the 1st hydrocracking catalyst layer at the upstream side of the upstream extremity of described the 2nd hydrocracking catalyst layer is more than the 5 capacity %.
CN200780008028.8A 2006-03-06 2007-03-01 Method of wax hydrocracking Expired - Fee Related CN101395253B (en)

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RU2428457C2 (en) 2011-09-10
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