CN105038844A - Processes for production of liquid fuel - Google Patents
Processes for production of liquid fuel Download PDFInfo
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- CN105038844A CN105038844A CN201510314020.0A CN201510314020A CN105038844A CN 105038844 A CN105038844 A CN 105038844A CN 201510314020 A CN201510314020 A CN 201510314020A CN 105038844 A CN105038844 A CN 105038844A
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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
- C10G47/16—Crystalline alumino-silicate carriers
- C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
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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
- C10G65/14—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
- C10G65/16—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only including only refining steps
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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
Abstract
The present invention relates to processes for production of liquid fuel. A first process which comprises fractionating a stock oil which contains normal paraffins, oxygen-containing compounds and olefins and exhibits distillation properties involving a final point of 360 DEG C or below into a first fraction and a second fraction with the boundary point falling within the range of 130 to 160 DEG C and hydrorefining the first and second fractions respectively with a first catalyst and a second catalyst which each comprise both a carrier containing a solid acid and a Group VIII metal of the periodic table supported on the carrier. A second process which comprises bringing a stock oil containing paraffin-base hydrocarbons into contact with a supported platinum catalyst prepared from a carrier containing both crystalline aluminosilicate and an amorphous solid acid and a platinum compound free from constituent chlorine element to conduct hydrocracking of the oil and thus obtain a cracked oil.
Description
The application is the divisional application of Chinese patent application 200880001359.3, and the applying date of original application 200880001359.3 is on January 11st, 2008, and its name is called " manufacture method of liquid fuel ".
Technical field
The present invention relates to by hydrofinishing process or hydrogenolysis process, manufacture the method for liquid fuel from paraffins.
Background technology
In recent years, the sulphur content rate restriction in the liquid fuel such as oil, light oil is promptly strictly got up.Therefore, for sulphur content rate and the requirement of the green liquid fuel that aromatic hydrocarbons content is low, environment is excellent increase rapidly.Corresponding, even if also studied the manufacture method of various green fuel in oil fuel production.Green fuel such as can manufacture as follows: such as utilizing gasification reaction or upgrading reaction to manufacture synthesis gas (carbon monoxide and hydrogen) using pitch, biomass (biomass), coal, Sweet natural gas etc. as starting raw material, is that prepared using fischer-tropsch (FT) synthesis method manufactures afterwards with synthesis gas.And then, by the wax hydrogenolysis using the heavy ends as FT synthetic product, the fuel base being rich in isoparaffin can be manufactured, expectation is full of to the technique of in the presence of a catalyst paraffinss such as wax being carried out hydrogenolysis.
In general, the fuel base utilizing FT synthesis method to obtain is owing to taking normal paraffin as main component, containing oxygenatedchemicals or alkene, being therefore unsuitable for directly using as gasoline or light oil, being necessary to carry out hydrofinishing.This hydrofinishing turns to main purpose (such as with reference to patent documentation 1,2) to remove oxygenatedchemicals, the hydrogenation (to alkane conversion) of alkene and the isomery of normal paraffin, particularly for light oil in order to ensure good low-temperature fluidity, importantly normal paraffin is transformed into isoparaffin.
On the other hand, when setting forth for hydrogenolysis technique, the hydrogenolysis technique being raw material with the light oil that reduces pressure is the technology of the establishment with many decades history, commercialization.But, in this hydrogenolysis technique, when replacing decompression light oil to take paraffins as raw material, because the reactivity of the hydrogenolysis of paraffins is different greatly with decompression light oil, be therefore difficult to catalyzer during direct conversion decompression light oil.Thus, with the high performance catalyst of paraffins be developed as object do one's utmost to research and develop time, propose such as at the catalyzer (such as with reference to patent documentation 3) of the supported on carriers platinum containing silica-alumina.
Patent documentation 1: United States Patent (USP) No. 5378348 specification sheets
Patent documentation 2: International Publication No. 01/057160 brochure
Patent documentation 3: Japanese Unexamined Patent Publication 6-41549 publication
Summary of the invention
the problem that invention will solve
In order to improve the economy of the technique manufacturing green fuel, the most important thing is the yield increasing each fuel base of target.That is, in hydrofinishing, how to suppress decomposition reaction to be hold the key improving process economy.In addition, when using as fuel, for gasoline, contribute to the raising of octane value from normal paraffin to the conversion of isoparaffin, for light oil, contribute to the raising of low-temperature fluidity, therefore very important from the viewpoint of fuel quality.
But, during for hydrofinishing method disclosed in above-mentioned patent documentation 1,2, when using containing the fuel base of normal paraffin, oxygenatedchemicals and alkene as raw material, be difficult to reach the isomerization from normal paraffin to isoparaffin, removing oxygenatedchemicals, the hydrogenation of alkene and the high yield of desired fuel base material simultaneously.Particularly be very difficult to take into account the high yield of abundant isomerization from from normal paraffin to isoparaffin and desired fuel base material.
In addition, the existing hydrogenolysis technique employing the catalyzer disclosed in above-mentioned patent documentation 3 is to be improved in the following areas.That is, in the hydrogenolysis technique of paraffins, from the view point of economy, the degrading activity of (1) catalyzer is high, the yield of (2) middle runnings is high is very important in raising process economics.But when the degrading activity height of catalyzer, because the middle runnings temporarily generated is easy to decompose, the yield of therefore middle runnings reduces, and the economy of its result technique reduces.That is, because (1) and (2) is in trade-off relation, be therefore very difficult to take into account (1) and (2), the huge obstacle that this economy becoming the hydrogenolysis technique of paraffins improves.
The present invention completes in view of this fact, and its 1st object is to provide yield to manufacture the manufacture method of the liquid fuel of the fuel base being rich in isoparaffin well.In addition, when the 2nd object of the present invention is that being provided in hydrogenolysis contains the stock oil of paraffins, the alternative manufacture method improving the liquid fuel of middle runnings yield while fully highland maintains the degrading activity of catalyzer.
for the scheme of dealing with problems
The present invention provides a kind of manufacture method (being simply called below " the first manufacture method ") of liquid fuel in order to solve above-mentioned problem, it is characterized in that, possesses following operation: to be in frontier point within the scope of 130 ~ 160 DEG C for boundary, by containing normal paraffin, oxygenatedchemicals and alkene and the terminal that the stock oil that the terminal of distillation proterties is less than 360 DEG C is separated into distillation proterties is the 1st cut of below above-mentioned frontier point and the initial boiling point that distills proterties is the step of the 2nd cut of more than above-mentioned frontier point; The carrier containing solid acid and the 1st catalyzer being carried on the periodictable group VIII metal on this carrier is used above-mentioned 1st cut to be carried out to the step of hydrofinishing; The carrier containing solid acid and the 2nd catalyzer being carried on the periodictable group VIII metal on this carrier is used above-mentioned 2nd cut to be carried out to the step of hydrofinishing.
In above-mentioned 1st manufacture method, above-mentioned 1st catalyzer and the 2nd catalyzer are preferably respectively containing as the palladium of the group VIII element of periodictable and/or platinum.
In addition, in above-mentioned 1st manufacture method, above-mentioned 1st catalyzer and the 2nd catalyzer are preferably respectively containing boron or phosphorus.
In addition, the stock oil used as raw material in above-mentioned 1st manufacture method preferably utilizes the reduction reaction manufacture of carbon monoxide.
In addition, the invention provides a kind of manufacture method (being simply called below " the 2nd manufacture method ") of liquid fuel, it is characterized in that, catalyzer containing carrier and platinum is contacted with the stock oil containing paraffins and carries out hydrogenolysis process, thus obtain cracking generation oil, wherein, described carrier contains crystallinity aluminosilicate and amorphous solid acid, and described platinum is used as the not chloride platinic compound of constitution element to be carried on carrier.
Be explained, so-called in the present invention " middle runnings " refers to that boiling spread is the cut of 145 ~ 360 DEG C.In addition, so-called in the present invention " hydrogenolysis ", except the decomposition reaction of paraffins, also can comprise the isomerization reaction from normal paraffin to isoparaffin.
The normal paraffin of preferred above-mentioned raw materials oil containing more than 70 quality % in above-mentioned 2nd manufacture method.By by this stock oil hydrogenolysis, while fully highland maintains the degrading activity of catalyzer, the yield of middle runnings optionally can be improved further.
In addition, in above-mentioned 2nd manufacture method, preferred crystallinity aluminosilicate is hyperstabilized y-type zeolite.Thus, the yield of middle runnings can optionally be improved further.
In addition, in above-mentioned 2nd manufacture method, the charge capacity being carried on the platinum of carrier is preferably 0.1 ~ 2.0 quality % relative to the quality of carrier.Thus, while fully highland maintains the degrading activity of catalyzer, the yield of middle runnings can optionally be improved further.
In addition, in above-mentioned 2nd manufacture method, stock oil is preferably containing the paraffins utilizing the reduction reaction of carbon monoxide to produce.Thus, while the degrading activity maintaining catalyzer at a high level and middle runnings yield, efficiently normal paraffin can be transformed into isoparaffin.
In addition, in above-mentioned 2nd manufacture method, it is more than 70 quality % relative to the ratio of stock oil mid-boiling point more than 360 DEG C paraffinss that preferred cracking generates the paraffins that oily mid-boiling point is less than 360 DEG C.
In addition, in above-mentioned 2nd manufacture method, preferred platinic compound is for being selected from the compound of more than a kind of four ammino platinum nitrates (II) and dinitrobenzene two ammino platinum (II).
the effect of invention
By the manufacture method of liquid fuel of the present invention, the fuel base being rich in isoparaffin can be manufactured efficiently.In addition, the manufacture method of liquid fuel of the present invention is particularly when utilizing above-mentioned 2nd manufacture method, when utilizing hydrogenolysis process to manufacture liquid fuel from the stock oil containing paraffins, while fully highland maintains the degrading activity of catalyzer, can optionally improve the yield of middle runnings.
Embodiment
Below, the preferred embodiment of the present invention is explained.
[the 1st embodiment]
1st embodiment shown below is the preferred implementation of above-mentioned 1st manufacture method.In 1st embodiment, the raw material as hydrofinishing uses containing normal paraffin, oxygenatedchemicals and alkene and the terminal of distillation proterties is the stock oil of less than 360 DEG C.Here when " terminal of distillation proterties is the stock oil of less than 360 DEG C " refers to and utilizes distillation to obtain the stock oil used in the present invention, " be 360 DEG C below and carry out the stock oil of distillation acquisition to distill the terminal of proterties for target ".Namely when using common business distillation plant to carry out the operation of acquisition less than 360 DEG C cuts, during sometimes on a small quantity containing the cut of boiling point more than 360 DEG C in gained cut, this cut is included in " terminal of distillation proterties is the stock oil of less than 360 DEG C ".Wherein, stock oil mid-boiling point more than the content of the cut of 360 DEG C with stock oil total amount for benchmark, be preferably below 10 quality %, be more preferably below 5 quality %.
Any one of this stock oil can be petroleum base material or synthesis be base material in addition, can also be petroleum base material be the mixture of base material with synthesis.In addition, this stock oil take normal paraffin as main component usually, but is not particularly limited for the amount of normal paraffin, is generally more than 60 quality %, is preferably more than 70 quality %.In addition, the amount of oxygenatedchemicals and alkene is not particularly limited, and with stock oil total amount for benchmark, is preferably respectively below 20 quality %.When the content of the one or both of oxygenatedchemicals or alkene is more than 20 quality %, then often hydrofinishing time thermal discharge increase, be difficult to control temperature of reaction.
In 1st embodiment, before carrying out hydrofinishing, to be in frontier point within the scope of 130 ~ 160 DEG C for boundary, the 2nd cut of to be the 1st cut of below above-mentioned frontier point and the initial boiling point of distillation proterties by separating of oil for the above-mentioned raw materials terminal for distillation proterties be more than above-mentioned frontier point.1st cut utilizes air distillation to carry out with the water distilling apparatus such as can using such as distillation tower that is separated of the 2nd cut.
The frontier point of the 1st cut and the 2nd cut is selected from the scope of 130 ~ 160 DEG C as mentioned above, is preferably 135 ~ 150 DEG C, is more preferably 140 ~ 145 DEG C.More preferred example is that the frontier point of the 1st cut and the 2nd cut is set as 145 DEG C, and the terminal being separated into distillation proterties is less than the 1st cut (petroleum naphtha) of 145 DEG C and distills the mode that the initial boiling point of proterties is the 2nd cut (middle runnings) of more than 145 DEG C.Be explained, the initial boiling point of the 1st cut is not particularly limited, for being generally more than 5 DEG C during naphtha fraction.In addition, the terminal of the 2nd cut is not particularly limited, and is generally less than 360 DEG C.Here, naphtha fraction preferably uses as oil base material, and in addition, middle runnings preferably uses as light oil base material.
By making the 1st of this separation the and the 2nd cut contact with special catalyst respectively, carry out hydrofinishing.
In the hydrofinishing of the 1st cut, use containing containing the carrier of solid acid and being carried on the 1st catalyzer of the periodictable group VIII metal on this carrier.The solid acid contained by carrier of the 1st catalyzer can enumerate the amorphous solid acid such as silica-alumina, silica-zirconia, alumina-boron oxide (aluminaboria), silica-magnesias, heteropolyacid, zirconium sulfate, the crystallinity aluminosilicate etc. of aluminate or phosphate (SAPO-11), USY, mordenite, ferrierite, ZSM-22, ZSM-23, beta-zeolite.
The carrier of the 1st catalyzer also can contain for shaping tackiness agent further.Tackiness agent is not particularly limited, and preferred tackiness agent can enumerate aluminum oxide or silicon-dioxide.The proterties of carrier is not particularly limited, and can make shapes such as granular, cylindric (particles).In addition, when carrier contains phosphorus and/or boron, isomerization reaction is easy to effectively carry out, and the content of phosphorus and/or boron is not particularly limited, and the total content of preferred phosphorus and boron is 0.1 ~ 2.0 % by weight.When the total content of phosphorus and boron is less than 0.1 quality %, there is the tendency that the facilitation effect of isomerization reaction is insufficient, in addition, during more than 2.0 quality %, have the tendency that the intensity of shaping catalyzer becomes insufficient.Phosphorus introduction method in the catalyst such as can enumerate the method for adding the P contained compound such as phosphoric acid, five phosphorus oxide in the tackiness agent before burning till (being the state of boehmite when tackiness agent is aluminum oxide, below equally).In addition, the method for adding the boron-containing compounds such as boric acid in the tackiness agent before burning till can such as be enumerated as the method importing boron in the catalyst.Be explained, as during as solid acid use alumina-boron oxide, when solid acid is for during containing phosphorus or boron, the introduction method of the above-mentioned phosphorus of non-essential employing or boron, the introduction method of above-mentioned phosphorus or boron is useful in the adjustment phosphorus of catalyzer or the content of boron.
In addition, in the 1st catalyzer, the group VIII metal as the periodictable being carried on above-mentioned carrier such as can enumerate nickel, rhodium, palladium, iridium, platinum etc., wherein preferred palladium and platinum.The amount of metal of load is not particularly limited, with catalyzer total amount for benchmark is preferably 0.1 ~ 2.0 quality %.
The hydrofinishing of the 1st cut can use the fixed-bed reactor being filled with above-mentioned 1st catalyzer to carry out.The temperature of reaction of carrying out the hydrofinishing of the 1st cut is not particularly limited, and is preferably the scope of 200 ~ 380 DEG C.When temperature of reaction is less than 200 DEG C, the isomerization ability of normal paraffin significantly reduces, during more than 380 DEG C, and the 1st cut generation lighting, the tendency having the yield of desired fuel base material to reduce.In addition, reaction pressure when carrying out the hydrofinishing of the 1st cut is not particularly limited, and is preferably 1 ~ 12MPa, is more preferably 2 ~ 6MPa.When reaction pressure is less than 1MPa, catalyzer is had to be easy to the tendency of deterioration, in addition, during more than 12MPa, the tendency that the temperature that responds rises.In addition, liquid space speed when carrying out the 1st cut hydrofinishing is not particularly limited, and is preferably 0.1 ~ 5.0h
-1.In addition, the ratio of the total hydrogen amount supplied relative to oil is not particularly limited, and is preferably 100 ~ 850NL/L.
In addition, the hydrofinishing of the 2nd cut uses the carrier containing solid acid and is carried on the 2nd catalyzer of the periodictable group VIII metal on this carrier.The solid acid contained by carrier of the 2nd catalyzer can enumerate the crystallinity aluminosilicates such as the acid of the amorphous solid such as silica-alumina, silica-zirconia and SAPO-11, USY, ZSM-22.Be explained, when using acid catalyst other than the above, because the middle runnings yield after hydrofinishing has the extreme tendency reduced, therefore not preferred.
The carrier of the 2nd catalyzer also can contain for shaping tackiness agent further.Tackiness agent is not particularly limited, and preferred tackiness agent can enumerate aluminum oxide or silicon-dioxide.The shape of carrier is not particularly limited, and can make shapes such as granular, cylindric (particles).In addition, when carrier contains phosphorus and/or boron, isomerization reaction is easy to effectively carry out, and the content of phosphorus and/or boron is not particularly limited, and the total content of preferred phosphorus and boron is 0.1 ~ 2.0 % by weight.When the total content of phosphorus and boron is less than 0.1 quality %, there is the tendency that the facilitation effect of isomerization reaction is insufficient, during more than 2.0 quality %, have the tendency that the intensity of shaping catalyzer becomes insufficient.The method importing phosphorus in catalyzer such as can enumerate the method for adding the P contained compound such as phosphoric acid, five phosphorus oxide in the tackiness agent before burning till (being the state of boehmite when tackiness agent is aluminum oxide, below equally).In addition, the method for adding the boron-containing compounds such as boric acid in the tackiness agent before burning till can such as be enumerated as the method importing boron in the catalyst.Be explained, as during as solid acid use alumina-boron oxide, when solid acid is for during containing phosphorus or boron, the introduction method of the above-mentioned phosphorus of non-essential employing or boron, the introduction method of above-mentioned phosphorus or boron is useful in the adjustment phosphorus of catalyzer or the content of boron.
In addition, in the 2nd catalyzer, as the group VIII metal of periodictable being carried on above-mentioned carrier, concrete example as nickel, rhodium, palladium, iridium, platinum etc. can be enumerated, wherein preferably palladium and platinum.The amount of metal of load is not particularly limited, with catalyzer total amount for benchmark is preferably 0.1 ~ 2.0 quality %.
The hydrofinishing of the 2nd cut can use the fixed-bed reactor being filled with above-mentioned 2nd catalyzer to carry out.Temperature of reaction when carrying out the hydrofinishing of the 2nd cut is not particularly limited, and is preferably the scope of 180 ~ 360 DEG C.When temperature of reaction is less than 180 DEG C, the isomerization ability of normal paraffin significantly reduces, on the other hand, during more than 360 DEG C, and the 2nd cut generation lighting, the tendency having the yield of desired fuel base material to reduce.In addition, reaction pressure when carrying out the hydrofinishing of the 2nd cut is not particularly limited, and is preferably 1 ~ 12MPa, is more preferably 2 ~ 6MPa.When reaction pressure is less than 1MPa, catalyzer is had to be easy to the tendency of deterioration, in addition, during more than 12MPa, the tendency that the temperature that responds rises.In addition, liquid space speed when carrying out the 2nd cut hydrofinishing is not particularly limited, and is preferably 0.1 ~ 4.0h
-1.In addition, the ratio of the total hydrogen amount supplied relative to oil is not particularly limited, and is preferably 100 ~ 850NL/L.
As mentioned above, according to the 1st embodiment, by to be in frontier point within the scope of 130 ~ 160 DEG C for boundary, will containing normal paraffin, 2nd cut of the terminal that oxygenatedchemicals and alkene and the stock oil that the terminal of distillation proterties is less than 360 DEG C are separated into distillation proterties to be the 1st cut of below above-mentioned frontier point and the initial boiling point that distills proterties be more than above-mentioned frontier point, use and with the catalyzer (the 1st catalyzer and the 2nd catalyzer) being carried on the periodictable group VIII metal on this carrier, respectively hydrofinishing is carried out to the above-mentioned 1st and the 2nd cut containing the carrier containing solid acid, thus the fuel base being rich in isoparaffin can be manufactured well by yield.Particularly, the fuel base obtained by the hydrofinishing of the 1st cut is preferably as oil base material.In addition, the fuel base obtained by the hydrofinishing of the 2nd cut is preferably as light oil base material.Be explained, the fuel base obtained by the hydrofinishing of the 2nd cut can contain lam-oil cut (cuts that boiling spread is 145 ~ 260 DEG C) and light oil distillate (boiling spread 260 ~ 360 DEG C) usually, after hydrofinishing, water distilling apparatus can also be used to be separated into lam-oil cut and light oil distillate.
Be explained, the 1st manufacture method of the present invention is not defined in above-mentioned 1st embodiment.Such as, in the 1st manufacture method, the technology of aftermentioned 2nd embodiment can be used.
[the 2nd embodiment]
2nd embodiment shown below is the preferred implementation of above-mentioned 2nd manufacture method.In 2nd embodiment, use the catalyzer containing carrier and platinum, wherein said carrier contains crystallinity aluminosilicate and amorphous solid acid, and described platinum is used as the not chloride platinic compound of constitution element to be carried on carrier.Crystallinity aluminosilicate refers to the crystallinity metal oxide formed with the element of aluminium, silicon and oxygen.Be explained, also can coexist other metallic elements in the scope not hindering effect of the present invention, and other metallographic phase are preferably below 5 quality % for the ratio of aluminum oxide or silicon-dioxide total mass with oxide compound conversion, are more preferably below 3 quality %.The metallic element coexisted can enumerate titanium, lanthanum, manganese, gallium, zinc etc., wherein from the preferred titanium of viewpoint and the lanthanum that improve middle runnings yield.
The crystallinity of aluminosilicate can be assessed with the ratio of 4 coordination aluminium atoms in total aluminium atom, and this ratio can be used
27al solid NMR measures.In the present invention, crystallinity aluminosilicate refers to that 4 coordination aluminium atoms are the aluminosilicate of more than 70% relative to the ratio of total aluminium atom.That is, when this ratio is more than 70%, the crystallinity aluminosilicate that all can be used as the 2nd embodiment uses.Usually this ratio can be used to be more than 80%, preferably more than 85%.
Crystallinity aluminosilicate can use so-called zeolite.Crystallinity aluminosilicate is preferably Y type or hyperstabilized Y type (USY type) zeolite, zeolite beta, mordenite, more preferably uses hyperstabilized Y type (USY type) zeolite.In addition, also may be combined with use crystallinity aluminosilicate of more than two kinds as required.
The median size of crystallinity aluminosilicate is not particularly limited, and is preferably less than 1.0 μm, is particularly preferably less than 0.5 μm.The particle diameter of crystallinity aluminosilicate is less, then the yield of the middle runnings in cracking generation oil has the tendency of increase, therefore preferably.
The content of crystallinity aluminosilicate is not particularly limited, usually with the total mass of carrier for benchmark can use in the scope of 0.1 ~ 20 quality %.
In addition, silica-alumina, silica-zirconia, silica-titania, silica-magnesias, silica-zirconia, alumina-boron oxide can be enumerated as amorphous solid acid contained by carrier.Wherein, from the view point of degrading activity and the middle runnings yield of taking into account catalyzer with high level, preferential oxidation silicon-aluminum oxide and alumina-boron oxide.
The amount of amorphous solid acid is not particularly limited, usually with the total mass of carrier for benchmark can use in the scope of 5 ~ 70 quality %.
Carrier containing above-mentioned crystallinity aluminosilicate and amorphous solid acid can not use the shaping above-mentioned crystallinity aluminosilicate of tackiness agent and amorphous solid acid, can use tackiness agent carry out shaping, this formed body is used as carrier.The tackiness agent used is not particularly limited, and can use aluminum oxide, silicon-dioxide etc., wherein preferential oxidation aluminium.The ratio of shaping used tackiness agent is not particularly limited, with the total mass of carrier for benchmark is preferably 20 ~ 90 quality %, is more preferably 40 ~ 80 quality %.When the ratio of tackiness agent is less than 20 quality %, the intensity of carrier has the tendency weakened; During more than 90 quality %, there is the tendency that fully cannot obtain effect of the present invention.
Catalyzer has platinum at the supported on carriers containing above-mentioned crystallinity aluminosilicate and amorphous solid acid.
For the selection particularly important of the platinic compound at supported on carriers platinum, use platinic compound not chloride as constitution element in the 2nd embodiment.As long as compound not chloride in platinic compound constitution element is then not particularly limited, preferably four ammino platinum nitrates (II) and dinitrobenzene two ammino platinum (II) particularly.
Be explained, above-mentioned platinic compound is not preferably as far as possible containing the chlorine as impurity.The catalyzer that cl concn fully reduces can be modulated thus.
The carrying method of platinum is not particularly limited, and usually can use pickling process, just wet dipping (incipientwetness) method, ion exchange method.Platinum is 0.1 ~ 2.0 quality % relative to the charge capacity of carrier relative to the quality optimization of carrier, is more preferably 0.4 ~ 1.2 quality %.When the charge capacity of platinum is less than 0.1 quality %, there is the tendency that the yield of middle runnings reduces; When the charge capacity of platinum is more than 2.0 quality %, there is the tendency that the degrading activity of catalyzer reduces.
Be explained, use except palladium also can be carried on carrier by above-mentioned platinum.The carrying method of palladium is not particularly limited, such as, side by side can be carried on carrier with platinum.Be explained, also during supported palladium, be importantly used as the palladium compound that constitution element is not chloride.Palladous nitrate, palladium, four ammino platinum nitrates (II) and dinitrobenzene two ammino platinum (II) etc. can be used particularly.
When catalyzer contains platinum and palladium, palladium is preferably less than 1.5 relative to the ratio (palladium/platinum, mol ratio) of platinum, is more preferably 0.2 ~ 0.8.When this ratio is more than 1.5, there is the tendency that the yield of middle runnings reduces.
As stock oil, the hydrocarbon ils of petroleum and synthesis system can be used, preferred paraffins.Paraffins mentioned here refers to the hydrocarbon ils of the normal paraffin containing more than 70 quality %.As stock oil, the carbonatoms in a part more preferably can be used to be more than 18, to be the paraffins of solid under normal temperature, be i.e. the paraffins of so-called paraffin.And then the boiling point particularly preferably under use normal pressure is the wax of more than 360 DEG C.
The method for making of the paraffins contained by stock oil is not particularly limited, and preferably utilizes the FT wax that the Fiscber-Tropscb synthesis as Carbon monoxide reduction reaction generates.
During hydrogenolysis, fixed-bed reactor in the past can be used.The stock oil of fixed-bed reactor and the reaction conditions of catalyzer are preferably the liquid space speed 0.1 ~ 10/h of temperature 200 ~ 450 DEG C, hydrogen-pressure 0.5 ~ 15MPa, stock oil, are more preferably the liquid space speed 0.3 ~ 5.0/h of temperature 250 ~ 370 DEG C, hydrogen pressure 2.0 ~ 8.0MPa, stock oil.
The cracking obtained by hydrogenolysis process generates oil except as except the middle runnings (cuts that boiling spread is 145 ~ 360 DEG C) of main component, also containing cut (LPG, naphtha fraction etc.), the cut of boiling point more than 360 DEG C that boiling point is less than 145 DEG C.In addition, middle runnings can utilize distillation etc. to be separated into lam-oil cut (cuts that boiling spread is 145 ~ 260 DEG C) and light oil distillate (cuts that boiling spread is 260 ~ 360 DEG C).
Be explained, the present invention the 2nd manufacture method is not defined in above-mentioned 2nd embodiment.Such as in the 2nd manufacture method, the technology of above-mentioned 1st embodiment can be used.
Embodiment
More specifically describe the present invention according to embodiment and comparative example below, but the present invention is not defined in following examples.
[embodiment 1-1]
(modulation of stock oil, the 1st with being separated of the 2nd cut)
Load on the silica supports of particle diameter 1.5mm there is the FT synthetic catalyst 20g of the Zr of the Co of 20 quality %, 2.4 quality % to be filled in fixed-bed reactor, carry out the reduction reaction (FT synthesis) of carbon monoxide.Reaction conditions is now GHSV=1500h
-1, pressure 2.5MPa, temperature 225 DEG C.Except after anhydrating from product, utilize air distillation, obtain as the naphtha fraction of the 1st cut and the middle runnings as the 2nd cut.The proterties of naphtha fraction and middle runnings is shown in table 1.
Table 1
(hydrofinishing)
Load on silicaalumina carrier there is the catalyzer of platinum (alumina content 14 quality %, platinum 0.4 quality %) 20g to be filled in fixed-bed reactor, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 1st cut.Temperature of reaction is now 300 DEG C, pressure 3.5MPa, liquid space speed 2.0h
-1.In addition, the catalyzer of platinum (alumina content 14 quality %, platinum 0.4 quality %) 20g load on silicaalumina carrier is had to be filled in other fixed-bed reactor, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 2nd cut.Temperature of reaction is now 300 DEG C, pressure 3.5MPa, liquid space speed 2.0h
-1.Each generations utilizing gas chromatographic analysis to be obtained by the hydrofinishing of the 1st cut and the 2nd cut is oily, tries to achieve the ratio that gas (compositions that boiling spread is less than 5 DEG C), the yield of naphtha fraction (cuts that boiling spread is 5 ~ 145 DEG C) and middle runnings (cuts that boiling spread is 145 ~ 360 DEG C) and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, table 2 is in order to compared with aftermentioned comparative example 1-1 etc., as the generation oil utilizing the hydrofinishing of the 1st cut to obtain and the mixture (mixture of mass ratio 50:50) utilizing the hydrofinishing of the 2nd cut to obtain generation oil, the value (for embodiment 1-2,1-3 too) of equalization is shown.In addition, in the present embodiment, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected, hydrogenation carries out fully.
(comparative example 1-1)
Carry out FT synthesis in the same manner as embodiment 1-1, reach 50:50 mixing gained the 1st cut and the 2nd cut with mass ratio.Then, the catalyzer of platinum (alumina content 14 quality %, platinum 0.4 quality %) 20g load on silicaalumina carrier is had to be filled in fixed-bed reactor, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of above-mentioned mixing raw material.Temperature of reaction is now 300 DEG C, pressure 3.5MPa, liquid space speed 2.0h
-1.Utilize gas chromatographic analysis gained to generate oil, try to achieve the ratio that gas, the yield of naphtha fraction and middle runnings and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, in this comparative example, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected.
(embodiment 1-2)
First equally with embodiment 1-1 carry out FT synthesis, obtain the 1st and the 2nd cut with proterties shown in table 1.Then, the catalyzer 20g of the platinum of 0.5 quality % is had to be filled in fixed-bed reactor by the supported on carriers be made up of USY zeolite (mol ratio 36 of silica/alumina) 3 quality % and alumina adhesive 97 quality %, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 1st cut.Temperature of reaction is now 295 DEG C, pressure 3MPa, liquid space speed 2.0h
-1.In addition, the catalyzer 20g of the platinum of 0.5 quality % is had to be filled in fixed-bed reactor by the supported on carriers be made up of USY zeolite (mol ratio 36 of silica/alumina) 3 quality % and alumina adhesive 97 quality %, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 2nd cut.Temperature of reaction is now 295 DEG C, pressure 3MPa, liquid space speed 2.0h
-1.The each generation oil utilizing gas chromatographic analysis to utilize the hydrofinishing of the 1st cut and the 2nd cut to obtain, tries to achieve the ratio that gas, the yield of naphtha fraction and middle runnings and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, in the present embodiment, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected, hydrogenation carries out fully.
(comparative example 1-2)
Carry out FT synthesis in the same manner as embodiment 1-1, reach 50:50 mixing gained the 1st cut and the 2nd cut with mass ratio.Then, the catalyzer 20g of the platinum of 0.5 quality % is had to be filled in fixed-bed reactor by the supported on carriers be made up of USY zeolite (mol ratio 36 of silica/alumina) 3 quality % and alumina adhesive 97 quality %, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of above-mentioned mixing raw material.Temperature of reaction is now 295 DEG C, pressure 3MPa, liquid space speed 2.0h
-1.Utilize gas chromatographic analysis gained to generate oil, try to achieve the ratio that gas, the yield of naphtha fraction and middle runnings and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, in this comparative example, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected.
(embodiment 1-3)
First equally with embodiment 1-1 carry out FT synthesis, obtain the 1st and the 2nd cut with proterties shown in table 1.Then, the catalyzer 20g of the platinum of 0.8 quality % is had to be filled in fixed-bed reactor by the supported on carriers be made up of 70 quality % and the alumina adhesive 30 quality % of SAPO-11, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 1st cut.Temperature of reaction is now 290 DEG C, pressure 4MPa, liquid space speed 1.5h
-1.In addition, the catalyzer 20g of platinum 0.8 quality % is had to be filled in fixed-bed reactor by the supported on carriers be made up of 70 quality % and the alumina adhesive 30 quality % of SAPO-11, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of the 2nd cut.Temperature of reaction is now 290 DEG C, pressure 4MPa, liquid space speed 1.5h
-1.The each generation oil utilizing gas chromatographic analysis to utilize the hydrofinishing of the 1st cut and the 2nd cut to obtain, tries to achieve the ratio that gas, the yield of naphtha fraction and middle runnings and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, in the present embodiment, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected, hydrogenation carries out fully.
(comparative example 1-3)
Carry out FT synthesis in the same manner as embodiment 1-1, reach 50:50 mixing gained the 1st cut and the 2nd cut with mass ratio.Then, the catalyzer 20g of platinum 0.8 quality % is had to fill in fixed-bed reactor by the supported on carriers be made up of 70 quality % and the alumina adhesive 30 quality % of SAPO-11, use this fixed-bed reactor, under hydrogen stream, carry out the hydrofinishing of above-mentioned mixing raw material.Temperature of reaction is now 290 DEG C, pressure 4MPa, liquid space speed 1.5h
-1.Utilize gas chromatographic analysis gained to generate oil, try to achieve the ratio that gas, the yield of naphtha fraction and middle runnings and isoparaffin account for naphtha fraction and middle runnings.Acquired results is shown in table 2.Be explained, in this comparative example, carry out the result of the gas Chromatographic Determination generating oil for oxygenatedchemicals and olefin(e) compound not detected.
Table 2
As shown in table 2, embodiment 1-1 ~ 1-3 is compared with comparative example 1-1 ~ 1-3, the isomerization to isoparaffin of the removing of oxygenatedchemicals, the hydrogenation of alkene and normal paraffin can be realized with high level, in addition, desired fuel base material (naphtha fraction and middle runnings) can be obtained well by yield.
(modulation of catalyst A)
(silica/alumina (mol ratio): 31) 30g, silica-alumina (alumina content: 14 quality %) 500g and boehmite 400g uses this mixture to obtain the cylindric formed body of diameter 1/16 inch (about 1.6mm) to hyperstabilized Y type (USY type) zeolite of mixing median size 0.6 μm.In atmosphere, burn till this cylindric formed body 1 hour at 500 DEG C, obtain carrier.Utilize just wet pickling process to reach 0.8 quality % according to platinum with the quality criteria of carrier on this carrier and flood four ammino platinum nitrate (II) aqueous solution.After dipping, drying 3 hours at 120 DEG C, then 1 hour is burnt till at 500 DEG C, obtain catalyst A.
(modulation of catalyst B)
Except replacing silica-alumina (alumina content: 14 quality %) to use except alumina-boron oxide (boron oxide content 15 quality %), obtain catalyst B equally with the modulation of catalyst A.
(modulation of catalyzer C)
Wet pickling process at the beginning of the carrier obtained same with the modulation of catalyst A utilizes reaches 0.6 quality % according to platinum with the quality criteria of carrier, palladium reaches 0.2 quality % and floods the aqueous solution (palladium/platinum (mol ratio)=0.61) containing four ammino platinum nitrates (II) and Palladous nitrate.After dipping, drying 3 hours at 120 DEG C, then 1 hour is burnt till at 500 DEG C, obtain catalyzer C.
(modulation of catalyzer D)
Except replacing four ammino platinum nitrates (II) to use except Platinic chloride, obtain catalyzer D equally with the modulation of catalyst A.
(modulation of catalyzer E)
Except replacing four ammino platinum nitrates (II) to use except Platinic chloride, obtain catalyzer E equally with the modulation of catalyst B.
(embodiment 2-1)
The interior supply of flow through reactors to the fixed bed being filled with catalyst A (100ml) carries out hydrogen treatment as the FT wax (normal paraffin content: 95 quality %, carbon number distribution: 21 ~ 60, the content of the cut of boiling point more than 360 DEG C: 100 quality %) of stock oil.Hydrogen pressure during hydrogen treatment is 3MPa, the liquid space speed of stock oil is 2.0/h.Try to achieve by this hydrogenolysis process obtain relative to stock oil be under the temperature of reaction (80 quality % decomposition temperature) of the degradation production (cuts that boiling point is less than 360 DEG C) of 80 quality % and this temperature of reaction middle runnings (cuts that boiling spread is 145 ~ 360 DEG C) relative to the yield of stock oil.Acquired results is shown in table 3.
(embodiment 2-2)
Except replacing catalyst A to use except catalyst B, carrying out hydrogenolysis process in the same manner as embodiment 2-1, trying to achieve the yield of 80 quality % decomposition temperatures and middle runnings.Acquired results is shown in table 3.
(embodiment 2-3)
Except replacing catalyst A to use except catalyzer C, carrying out hydrogenolysis process in the same manner as embodiment 2-1, trying to achieve the yield of 80 quality % decomposition temperatures and middle runnings.Acquired results is shown in table 3.
(comparative example 2-1)
Except replacing catalyst A to use except catalyzer D, carrying out hydrogenolysis process in the same manner as embodiment 2-1, trying to achieve the yield of 80 quality % decomposition temperatures and middle runnings.Acquired results is shown in table 3.
(comparative example 2-2)
Except replacing catalyst A to use except catalyzer E, carrying out hydrogenolysis process in the same manner as embodiment 2-1, trying to achieve the yield of 80 quality % decomposition temperatures and middle runnings.Acquired results is shown in table 3.
Table 3
| 80 quality % decomposition temperatures (DEG C) | Middle runnings yield (quality %) | |
| Embodiment 2-1 | 299 | 56.0 |
| Embodiment 2-2 | 300 | 62.0 |
| Embodiment 2-3 | 297 | 56.8 |
| Comparative example 2-1 | 302 | 54.8 |
| Comparative example 2-2 | 305 | 60.4 |
As shown in table 3, embodiment 2-1 ~ 2-3 compares with comparative example 2-1 with 2-2, and 80 quality % decomposition temperatures are low, and the yield of middle runnings is high in addition.
Claims (4)
1. a manufacture method for liquid fuel, is characterized in that, possesses following operation:
To be in frontier point within the scope of 130 ~ 160 DEG C for boundary, by containing normal paraffin, oxygenatedchemicals and alkene and the terminal that the stock oil that the terminal of distillation proterties is less than 360 DEG C is separated into distillation proterties is the 1st cut of below foregoing boundary point and the initial boiling point that distills proterties is the step of the 2nd cut of more than foregoing boundary point;
The carrier containing solid acid and the 1st catalyzer being carried on the periodictable group VIII metal on this carrier is used aforementioned 1st cut to be carried out to the step of hydrofinishing;
The carrier containing solid acid and the 2nd catalyzer being carried on the periodictable group VIII metal on this carrier is used aforementioned 2nd cut to be carried out to the step of hydrofinishing.
2. the manufacture method of liquid fuel according to claim 1, is characterized in that, aforementioned 1st catalyzer and the 2nd catalyzer are respectively containing as the palladium of the group VIII metal of preceding cycles table and/or platinum.
3. the manufacture method of liquid fuel according to claim 1 and 2, is characterized in that, aforementioned 1st catalyzer and the 2nd catalyzer are respectively containing boron or phosphorus.
4. the manufacture method of the liquid fuel according to any one of claims 1 to 3, is characterized in that, aforementioned base materials oil utilizes the reduction reaction of carbon monoxide to manufacture.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007006210A JP4861838B2 (en) | 2007-01-15 | 2007-01-15 | Method for producing liquid fuel |
| JP2007-006215 | 2007-01-15 | ||
| JP2007-006210 | 2007-01-15 | ||
| JP2007006215A JP2008169356A (en) | 2007-01-15 | 2007-01-15 | Method for producing liquid fuel |
| CNA2008800013593A CN101568623A (en) | 2007-01-15 | 2008-01-11 | Processes for production of liquid fuel |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2008800013593A Division CN101568623A (en) | 2007-01-15 | 2008-01-11 | Processes for production of liquid fuel |
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| CN201510314020.0A Pending CN105038844A (en) | 2007-01-15 | 2008-01-11 | Processes for production of liquid fuel |
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| CN (1) | CN105038844A (en) |
| AU (1) | AU2008206002B2 (en) |
| MY (1) | MY150403A (en) |
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| WO (1) | WO2008087897A1 (en) |
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| JP5676344B2 (en) * | 2011-03-31 | 2015-02-25 | Ｊｘ日鉱日石エネルギー株式会社 | Kerosene manufacturing method |
| RU2536585C1 (en) * | 2013-09-27 | 2014-12-27 | Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук | Catalyst, method of manufacturing thereof and process of diesel fuel hydroisomerisation |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378348A (en) * | 1993-07-22 | 1995-01-03 | Exxon Research And Engineering Company | Distillate fuel production from Fischer-Tropsch wax |
| CA2173599C (en) * | 1993-10-08 | 2004-07-20 | Johannes Wilhelmus Maria Sonnemans | Hydrocracking and hydrodewaxing process |
| US5865988A (en) * | 1995-07-07 | 1999-02-02 | Mobil Oil Corporation | Hydrocarbon upgrading process |
| US5660714A (en) * | 1995-07-14 | 1997-08-26 | Exxon Research And Engineering Company | Hydroconversion process utilizing a supported Ni-Cu hydroconversion catalyst |
| US5994607A (en) * | 1996-02-05 | 1999-11-30 | Institut Francais Du Petrole | Paraffin isomerization process comprising fractionation having at least two draw-off levels associated with at least two isomerization zones |
| US6569315B2 (en) * | 2000-04-17 | 2003-05-27 | Exxonmobil Research And Engineering Company | Cycle oil conversion process |
| FR2826971B1 (en) * | 2001-07-06 | 2003-09-26 | Inst Francais Du Petrole | PROCESS FOR PRODUCING MEDIUM DISTILLATES BY HYDROISOMERIZATION AND HYDROCRACKING OF FILLERS ARISING FROM THE FISCHER-TROPSCH PROCESS |
| ITMI20011441A1 (en) * | 2001-07-06 | 2003-01-06 | Agip Petroli | PROCESS FOR THE PRODUCTION OF MEDIUM PARAFFINIC DISTILLATES |
| FR2828205B1 (en) * | 2001-08-06 | 2004-07-30 | Inst Francais Du Petrole | PROCESS FOR ISOMERIZING A C5-C8 CUTTING USING TWO PARALLEL REACTORS |
| US7122494B2 (en) * | 2003-02-05 | 2006-10-17 | Exxonmobil Chemical Patents Inc. | Combined cracking and selective hydrogen combustion for catalytic cracking |
| JP4313237B2 (en) * | 2004-03-29 | 2009-08-12 | 新日本石油株式会社 | Hydrocracking catalyst and method for producing liquid hydrocarbon |
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| RU2009131081A (en) | 2011-02-27 |
| AU2008206002B2 (en) | 2011-11-17 |
| RU2443756C2 (en) | 2012-02-27 |
| MY150403A (en) | 2014-01-15 |
| AU2008206002A1 (en) | 2008-07-24 |
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