CN101410487B - Method of hydrotreating wax and process for producing fuel base - Google Patents
Method of hydrotreating wax and process for producing fuel base Download PDFInfo
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- CN101410487B CN101410487B CN200780011369.0A CN200780011369A CN101410487B CN 101410487 B CN101410487 B CN 101410487B CN 200780011369 A CN200780011369 A CN 200780011369A CN 101410487 B CN101410487 B CN 101410487B
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
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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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1022—Fischer-Tropsch products
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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
- C10G2300/4006—Temperature
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Abstract
A method of hydrotreating a wax, characterized by comprising: a step in which a wax produced by FT synthesis is used as a raw material and the wax is hydrocracked in the presence of hydrogen with a catalyst comprising a support comprising zeolite and, deposited thereon, a metal in Group VIII of the Periodic Table; a step in which the raw material is temporarily switched from the wax to a distillate oil obtained by distillating a mixture of the product of wax hydrocracking obtained in the first step and the product of hydrocracking of an intermediate fraction produced by FT synthesis, and the distillate oil is hydrocracked in the presence of hydrogen at a reaction temperature of 160-330 DEG C; and a step in which the raw material is switched from the distillate oil to the wax and the wax is hydrocracked in the presence of hydrogen.
Description
Technical field
The present invention relates to the method for manufacture of the hydroprocessing process and the fuel base of wax.
Background technology
In recent years, from the position of environment protection, to the restriction of sulphur content in the liquid fuels such as gasoline or the light oil strictness that becomes rapidly.Therefore, increasingly high to the expectation of the low clean fuel liquid of sulphur content or aromaticity content.As one of method of manufacture of this clean fuel, can enumerate the carbon monoxide that obtains with coal or bituminous gasification or gas renormalizing etc. and hydrogen fischer-tropsch (FT) synthesis method as raw material.
The fuel base that adopts the FT synthesis method to obtain; With the normal paraffin is staple; Contain some oxygenatedchemicals in addition; Therefore, be difficult to, need remove oxygenatedchemicals or carry out changing into the isomerizing processing of isoparaffin through unifining by normal paraffin with its use that directly acts as a fuel.In addition, adopt the FT synthesis method can generate the wax slop (FT wax) of heavy simultaneously, this FT wax generally need make it change the middle runnings (kerosene or light oil base material) of being rich in isoparaffin into through hydrogen cracking.
When hydrogen cracking that will be through FT wax or the synthetic middle runnings that makes of FT act as a fuel base material when using; Consider from the viewpoint of process economy; High yield is important, but considers from the viewpoint of fuel performance, hopes that normal paraffin content is low and isoparaffin content is high.For example with regard to light oil, if normal paraffin content is too much, low-temperature fluidity variation then when the low-temperature fluidity deterioration, just is restricted as the use of commodity.Because the light oil that in FT is synthetic, generates nearly all is normal paraffin, therefore, is difficult to its direct use.
Should explain that up to now, people are studying through FT wax is carried out the technology that fuel base is made in hydrogen cracking always, for example, following patent documentation 1～3 has been put down in writing with the method for hydrogen cracking of FT wax as raw material.
No. 2004/028688 pph of [patent documentation 1] International Publication
[patent documentation 2] spy opens the 2004-255241 communique
[patent documentation 3] spy opens the 2004-255242 communique
Summary of the invention
The problem that invention will solve
Yet according to the method for hydrogen cracking of the wax of above-mentioned patent documentation 1～3 record, when carrying out the hydrogen cracking of wax for a long time, the catalytic activity of catalyzer can be in time and deterioration causes the normal paraffin content of the fuel base that obtains to increase, and this is the problem of existence.
Past always is that to develop a kind of high performance catalyzer that is used for wax is carried out hydrogen cracking be the center, and not about improving activity of such catalysts in the running, promptly prolonging the report of catalyst life etc.In the field of petroleum refinement, as the method for manufacture of middle runnings, be representative with the method for decompression light oil being carried out hydrogen cracking, can make low-sulfur light oil through this technology.In this technology, when the deterioration ahead of estimate of catalyzer,, generally take to cut down the feed rate of raw material, or reduce disposal such as cleavage rate in order during predetermined, to turn round.Yet,, be not preferred therefore because this disposal can make running efficiency reduce.Therefore, people hope strongly to develop a kind of can suppress catalyst degradation, promptly can be to the method for the catalyst regeneration of the situation such as deterioration ahead of estimate of catalyzer.
The present invention carries out in view of above-mentioned technological in the past existing problem; Its purpose is; Provide a kind of when carrying out the hydrogen cracking of FT wax for a long time; Can improve through the time deterioration activity of such catalysts, and can obtain hydroprocessing process and the method for manufacture of fuel base of the wax of the fuel base that normal paraffin content fully reduces.
Solve the means of problem
To achieve these goals; The present invention provides the hydroprocessing process of wax; It is characterized in that; This method comprises following operation: to adopt the synthetic wax that obtains of fischer-tropsch is raw material, in the presence of hydrogen, makes above-mentioned wax and contacts the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite; Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer.
Hydroprocessing process according to this wax; When the catalyzer that the metal of duty cycle table group VIII forms on using through the carrier that is containing zeolite carries out hydrogen cracking to FT wax; Raw material is temporarily switched to above-mentioned distilled oil, under above-mentioned temperature condition, through this distilled oil being carried out hydrogen cracking with above-mentioned catalyzer; When before can improving FT wax being carried out hydrogen cracking through the time deterioration the catalytic activity of above-mentioned catalyzer; Then, once more raw material is switched to FT wax, can obtain the fuel base that normal paraffin content fully reduces chronically like this.
In addition, in the hydroprocessing process of wax of the present invention, above-mentioned zeolite is preferably overstable y-type zeolite (according to circumstances following, as to be sometimes referred to as " USY zeolite ").
In addition; The present invention provides the method for manufacture of fuel base; It is characterized in that; This method comprises following operation: to adopt the synthetic wax that obtains of fischer-tropsch is raw material, in the presence of hydrogen, makes above-mentioned wax and contacts the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite; Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Make the 4th operation of middle runnings by the handled thing that obtains in above-mentioned the 1st～the 3rd operation.According to this method of manufacture, when carrying out the hydrogen cracking of wax for a long time, can improve through the time deterioration the catalytic activity of catalyzer, and can obtain the fuel base that normal paraffin content fully reduces with high yield.
The invention effect
According to the present invention; Can provide a kind of when carrying out the hydrogen cracking of FT wax for a long time; Can improve through the time deterioration the catalytic activity of catalyzer, and can obtain hydroprocessing process and the method for manufacture of fuel base of the wax of the fuel base that normal paraffin content fully reduces.
Description of drawings
Fig. 1 is the schema of a routine fuel base manufacturing installation that the method for manufacture of the fuel base that is applicable to embodiment of the present invention is shown.
Nomenclature
10... reaction tower, 12... hydrocracking catalyst layer, 20... distillation tower, 100... fuel base manufacturing installation.
Embodiment
Below with preferred embodiment the present invention is described at length.
The hydroprocessing process of wax of the present invention; It is characterized in that; Comprise following operation: to adopt the synthetic wax that obtains of fischer-tropsch is raw material; In the presence of hydrogen, make above-mentioned wax and contact the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite; Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer.
Among the present invention, the hydrotreatment of wax for example can be adopted, and the fixed-bed reactor that is filled with catalyzer carries out.To import in the fixed-bed reactor as the FT wax of raw material, make its hydrogen cracking, obtain to generate oil through under nitrogen atmosphere, contacting with catalyzer.
As the catalyzer that the hydrogen cracking of filling in the reaction unit is used, use the catalyzer that forms through at the metal that contains duty cycle table group VIII on the carrier of zeolite here.In addition, as zeolite, for example can enumerate, USY zeolite, mordenite, SAPO-11 etc. wherein, preferably use the USY zeolite.They can use a kind of separately, perhaps combination more than 2 kinds are used.
In addition, when using the USY zeolite as zeolite, silicon-dioxide in the USY zeolite and the mol ratio of aluminum oxide (silica/alumina) are preferably 20～96, and more preferably 25～60, further be preferably 30～45.
In addition, the higher limit of the median size of USY zeolite is preferably 1.0 μ m, more preferably 0.5 μ m.On the other hand, the lower value of the median size of USY zeolite is preferably 0.05 μ m.
In addition, carrier also can contain amorphous solid acid such as silica alumina, silicon-dioxide zirconium white, aluminum oxide boron oxide, silicon-dioxide Natural manganese dioxide.
In addition, as carrier, preferably use those through with zeolite and the amorphous solid acid of using as required etc. be shaped to granular carrier with tackiness agent.As tackiness agent, for example can use, silicon-dioxide, aluminum oxide etc. preferably use aluminum oxide.
In addition, as the metal of the periodictable group VIII of load on the carrier, for example can enumerate, nickel, rhodium, palladium, iridium, platinum etc. wherein, preferably use palladium, platinum.They can use a kind of separately, perhaps combination more than 2 kinds are used.
In the 1st operation and the 3rd operation of the hydroprocessing process of wax of the present invention; Wax as the raw material use; Be to adopt the synthetic wax (FT wax) that obtains of fischer-tropsch (FT), it is to contain the above carbon number of 70 quality % 16 or more, the preferred wax of the normal paraffin of carbon number more than 20.The carbon number distribution of FT wax depends on FT synthetic condition, the FT wax that uses among the present invention, and its carbon number distribution does not have particular restriction.
In the 2nd operation of the hydroprocessing process of wax of the present invention; The distilled oil that uses as raw material is for distilling the distilled oil that obtains through the mixture to the isocrackate of the FT wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch.
Through the hydrogen cracking of the synthetic middle runnings of making of FT, can use fixed-bed reactor to carry out.The reaction conditions of this moment does not have particular restriction, and hope is can fully suppress the generation of gas or petroleum naphtha, remove oxygenatedchemicals or carry out the condition of hydrogenation of olefins efficiently.In addition, as catalyzer, preferred for example the use is through at the metal that contains duty cycle table group VIII on the carrier of solid acid, the catalyzer that the metal of from nickel, rhodium, palladium, iridium, platinum, selecting particularly more than a kind forms.
Mixture for by above-mentioned each isocrackate does not have particular restriction through the distilled oil that distillation obtains, and its carbon number is preferably 9～25, and more preferably 10～20.In addition, when said mixture is distilled,, also can their suitably be mixed and use in the situation of light oil distillate that with its fractionation is kerosene(oil)fraction and the carbon number 16～20 of for example carbon number 10～15.
Should explain in the 1st operation, do not have particular restriction for the temperature of reaction before being about to carry out the 2nd operation, when temperature more than 340 ℃ the time, the recovery extent of catalyst activity reduces in the 2nd operation, therefore preferably is lower than 340 ℃.In other words, preferably the temperature of reaction in the 1st operation reached before 340 ℃ that can make catalyst degradation, carried out the switching (beginning the 2nd operation) of raw material.
In addition, as the reaction conditions of the 2nd operation, preferably making temperature of reaction usually is 160～330 ℃, more preferably 170～320 ℃.Perhaps surpass 330 ℃ if temperature of reaction is lower than 160 ℃, then the recovery of catalyst activity can not fully be carried out.
In addition, in the 2nd operation, with respect to the catalyzer in the fixed-bed reactor, the liquid hourly space velocity of light paraffins (LHSV) is preferably 0.1～10.0h
-1, 0.5～5.0h more preferably
-1If liquid hourly space velocity is less than 0.1h
-1, then must take a long time and fully improve activity of such catalysts, be not preferred therefore.
And then in the 2nd operation, reaction pressure is preferably 1～12MPa, more preferably 2～6MPa.
In addition, in the 2nd operation, hydrogen/oil ratio does not have particular restriction, is preferably 100～850NL/L usually, more preferably 200～650NL/L.
Through coming wax is carried out hydrotreatment with the 1st～the 3rd above-mentioned operation, can when carrying out the 2nd operation, improve through the time deterioration the catalytic activity of catalyzer, thereby can obtain the fuel base that normal paraffin content fully reduces chronically.
The method of manufacture of fuel base of the present invention is described below.The method of manufacture of fuel base of the present invention; It is characterized in that; This method comprises following operation: to adopt the synthetic wax that obtains of fischer-tropsch is raw material; In the presence of hydrogen, make above-mentioned wax and contact the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite; Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer; Make the 4th operation of middle runnings by the handled thing that obtains in above-mentioned the 1st～the 3rd operation.
, carry out above-mentioned the 1st～the 3rd operation of raw material hydrogen cracking here, preferably according to carrying out with the same method of hydroprocessing process of the wax of the invention described above.
As the middle runnings that obtains in the 4th operation, can enumerate boiling point and be in the cut in 145～360 ℃ of scopes.
Explanation is used for the fuel base manufacturing installation of embodiment of the present invention fuel base method of manufacture below.Fig. 1 is the schema that a routine fuel base manufacturing installation that is applicable to embodiment of the present invention fuel base method of manufacture is shown.Fuel base manufacturing installation 100 shown in Figure 1 comprises: reaction tower 10, the reaction product (handled thing that is obtained by the raw material hydrogen cracking) that is used for reaction tower 10 is obtained are carried out distillatory distillation tower 20.Reaction tower 10 is the fixed-bed type reaction tower, and portion is provided with the hydrocracking catalyst layer 12 of preceding text explanation within it, contains the catalyzer that forms through at the metal that contains duty cycle table group VIII on the carrier of zeolite in this hydrocracking catalyst layer 12.In this reaction tower 10,, raw material is implemented hydrogen cracking according to the hydroprocessing process of the invention described above.In addition,, be connected with the pipeline L1 that is used for base feed in reaction tower 10, be connected with the pipeline L2 that is used to supply with hydrogen at the upstream side of the connection section of pipeline L1 and reaction tower 10 at the top of reaction tower 10.On the other hand, be connected with in the bottom of reaction tower 10 and be used for pipeline L3 that reaction product is taken out from reaction tower 10, the other end of pipeline L3 links to each other with non-pressurized distillation tower 20.
It is each cut of specific boiling spread through the reaction product fractionation that reaction generates that distillation tower 20 is used for reaction tower 10.Utilize distillation tower 20 with the reaction product fractionation for gas fraction (light hydrocarbon of carbon number below 4), heavy naphtha cut (cuts that boiling point is 80～145 ℃), kerosene(oil)fraction (cuts that boiling point is 145～260 ℃), light oil distillate (cuts that boiling point is 260～360 ℃) and residual oil fraction (cut of boiling point more than 360 ℃), can obtain desirable fuel base.Each cut that in distillation tower 20, fractionates out is through the pipeline (L4～L8) be delivered to respectively in the follow-up operation that links to each other with distillation tower 20.
Embodiment
Below based on embodiment and comparative example the present invention is described more specifically, but the present invention does not receive the qualification of following examples.
(embodiment 1)
Prepare FT wax (carbon number 20～80, normal paraffin content: 96 quality %) as the raw material of hydrogen cracking.In addition; With USY zeolite, silica alumina (alumina content: 17 moles of %) and alumina adhesive mix according to mass ratio 3:57:40; After being shaped to the about 1.5mm of diameter, long 3mm cylindrical,, obtain support of the catalyst 500 ℃ of following roastings 1 hour.Should explain that as above-mentioned USY zeolite, using silicon-dioxide and the mol ratio of aluminum oxide in this USY zeolite is 37, median size is the USY zeolite of 0.82 μ m.Make the aqueous solution of the support of the catalyst dipping dichloro four ammino platinum (II) that obtain; After under 120 ℃ dry 3 hours; 500 ℃ of following roastings 1 hour, being prepared in thus on the support of the catalyst with the catalyzer total amount was the hydrocracking catalyst that benchmark load 0.8 quality % platinum forms.
Then, above-mentioned catalyzer 300ml is filled in the fixed bed reaction tower, before reaction, in hydrogen stream, under 345 ℃, carries out the reduction of 4 hours metal (platinum) and handle.Then, be 2.0h according to above-mentioned raw materials with respect to the liquid hourly space velocity of above-mentioned catalyzer
-1The condition of (flow rate of liquid is 600ml/h), pressure 3.0MPa, hydrogen/oil ratio 570NL/L reaches the condition of 70 quality % according to the cleavage rate that can make raw material, Yi Bian conditioned reaction temperature frequently, Yi Bian raw material carried out hydrotreatment (the 1st operation) in continuous 45 days.Be collected in the generation oil that obtains during this period and it is distilled, obtain the isocrackate A (normal paraffin content: 60 quality %) of carbon number 10～20.
On the other hand, use the aluminium oxide catalyst that forms as benchmark load 0.2 quality % platinum with the catalyzer total amount, at 230 ℃ of temperature, liquid hourly space velocity 1.0h
-1, pressure 2.8MPa, hydrogen/oil ratio 380NL/L condition under, to carrying out unifining through the synthetic middle runnings that obtains of FT.Product to obtaining thus distills, and obtains the isocrackate B (normal paraffin content: 60 quality %) of carbon number 10～20.Then, isocrackate A is mixed according to mass ratio 40:60 with isocrackate B, the mixture that obtains is distilled, obtain distilled oil (carbon number 10～20, normal paraffin content: 60 quality %) thus.
After the hydrotreatment running of above-mentioned the 1st operation begins 45 days, raw material is switched to above-mentioned distilled oil by FT wax, this distilled oil is carried out hydrotreatment in 2 days (the 2nd operation).The reaction conditions of this processing is: 310 ℃ of temperature of reaction, liquid hourly space velocity 2.5h
-1, pressure 3.0MPa, hydrogen/oil ratio 350NL/L.
After distilled oil is carried out hydrotreatment, once more raw material is reverted to FT wax, with the same condition of the 1st operation under carry out hydrotreatment (the 3rd operation).
As the temperature of reaction of above-mentioned a series of hydrotreatment, with the temperature (reaction beginning temperature) in when beginning reaction, face raw material is switched to the temperature (temperature before the 2nd operation) before the distilled oil and just raw material has been shown in table 1 by the temperature (temperature after the 2nd operation) that distilled oil (light paraffins) switches to behind the FT wax once more by FT wax.This temperature of reaction is the index of catalyst activity, and temperature of reaction is low more, and the expression catalyst activity is good more.In addition, in the generation oil that obtains through the hydrotreatment after raw material is switched to FT wax by distilled oil once more, the normal paraffin content in the generation oil of carbon number 10～20 (isomerized index) is shown in table 1.
(comparative example 1)
Except the temperature of reaction of the hydrotreatment in the 2nd operation, distilled oil carried out is 130 ℃, all the other and embodiment 1 likewise carry out the hydrotreatment of above-mentioned the 1st～the 3rd operation.The olefiant normal paraffin content of life (isomerized index) of each temperature of reaction of above-mentioned a series of hydrotreatment, carbon number 10～20 is shown in table 1.
(comparative example 2)
Raw material as the 2nd operation; Use the unpurified middle runnings (carbon number 10～20, the pure content: 8.2 quality %, normal paraffin content: 80.6 quality %) replace distilled oil that in FT is synthetic, generate separately; In addition, likewise carry out the hydrotreatment of above-mentioned the 1st～the 3rd operation with embodiment 1.Each temperature of reaction of above-mentioned a series of hydrotreatment, the normal paraffin content in the generation oil of carbon number 10～20 (isomerized index) are shown in table 1.
[table 1]
| Reaction beginning temperature (℃) | Temperature before the 2nd operation (℃) | Temperature after the 2nd operation (℃) | Normal paraffin content (quality %) | |
| Embodiment 1 | 302 | 324 | 303 | 29 |
| Comparative example 1 | 302 | 324 | 314 | 57 |
| Comparative example 2 | 302 | 324 | 320 | 42 |
Can confirm from result shown in the table 1; When carrying out the hydrogen cracking of wax for a long time; Through the temporary transient specific distilled oil (isocrackate to the isocrackate of FT wax and the middle runnings that in FT is synthetic, obtains distills the distilled oil that obtains simultaneously) of supplying with in hydrogen cracking running under given conditions; Can improve through the time deterioration activity of such catalysts, and can obtain to be rich in isoparaffin (normal paraffin be'ss few) fuel base.
Industrial applicability
As described above; According to the present invention; Can provide a kind of when for a long time FT wax being carried out hydrogen cracking, can improve through the time deterioration activity of such catalysts, can obtain simultaneously hydroprocessing process and the method for manufacture of fuel base of the wax of the fuel base that normal paraffin content fully reduces.
Claims (3)
1. the hydroprocessing process of wax is characterized in that, comprises following operation:
To adopt the synthetic wax that obtains of fischer-tropsch is raw material; In the presence of hydrogen, make above-mentioned wax and be filled in the fixed-bed reactor, contact the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite;
Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer;
Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer.
2. the hydroprocessing process of the described wax of claim 1 is characterized in that, above-mentioned zeolite is overstable y-type zeolite.
3. the method for manufacture of fuel base is characterized in that, comprises following operation:
To adopt the synthetic wax that obtains of fischer-tropsch is raw material; In the presence of hydrogen, make above-mentioned wax and be filled in the fixed-bed reactor, contact the 1st operation of carrying out hydrogen cracking through the catalyzer that forms at the metal that contains duty cycle table group VIII on the carrier of zeolite;
Above-mentioned raw materials temporarily switched to through the mixture to the isocrackate of the above-mentioned wax that obtained by above-mentioned the 1st operation and the isocrackate that adopts the synthetic middle runnings that obtains of fischer-tropsch by above-mentioned wax distill the distilled oil that obtains; In the presence of hydrogen; Under the condition of 160～330 ℃ of temperature of reaction, make above-mentioned distilled oil contact the 2nd operation of carrying out hydrogen cracking with above-mentioned catalyzer;
Above-mentioned raw materials is switched to above-mentioned wax by above-mentioned distilled oil, in the presence of hydrogen, make above-mentioned wax contact the 3rd operation of carrying out hydrogen cracking with above-mentioned catalyzer;
Make the 4th operation of middle runnings by the handled thing that obtains in above-mentioned the 1st～the 3rd operation.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2006100177A JP4714066B2 (en) | 2006-03-31 | 2006-03-31 | Method for hydrotreating wax |
| JP100177/2006 | 2006-03-31 | ||
| PCT/JP2007/053933 WO2007113962A1 (en) | 2006-03-31 | 2007-03-01 | Method of hydrotreating wax and process for producing fuel base |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101410487A CN101410487A (en) | 2009-04-15 |
| CN101410487B true CN101410487B (en) | 2012-06-27 |
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| CN200780011369.0A Active CN101410487B (en) | 2006-03-31 | 2007-03-01 | Method of hydrotreating wax and process for producing fuel base |
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| Country | Link |
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| JP (1) | JP4714066B2 (en) |
| CN (1) | CN101410487B (en) |
| AU (1) | AU2007232010B2 (en) |
| MY (1) | MY146925A (en) |
| RU (1) | RU2443757C2 (en) |
| WO (1) | WO2007113962A1 (en) |
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| JP5737981B2 (en) | 2011-02-04 | 2015-06-17 | 独立行政法人石油天然ガス・金属鉱物資源機構 | Method for producing hydrocarbon oil |
| JP5998127B2 (en) * | 2012-03-30 | 2016-09-28 | Ｊｘエネルギー株式会社 | Manufacturing method of base oil for lubricating oil |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2723946A (en) * | 1950-05-29 | 1955-11-15 | Universal Oil Prod Co | Hydrocarbon conversion process |
| US3158563A (en) * | 1962-03-27 | 1964-11-24 | Standard Oil Co | Process for rejuvenation of hydrocracking catalysts |
| US3376218A (en) * | 1965-03-17 | 1968-04-02 | Standard Oil Co | Refining of lubricating oil and reactivation of the catalyst |
| JPS5670840A (en) * | 1979-11-12 | 1981-06-13 | Chiyoda Chem Eng & Constr Co Ltd | Method of removing carbonaceous substances deposited on catalyst |
| GB9119504D0 (en) * | 1991-09-12 | 1991-10-23 | Shell Int Research | Process for the preparation of naphtha |
| MY139353A (en) * | 2001-03-05 | 2009-09-30 | Shell Int Research | Process to prepare a lubricating base oil and a gas oil |
| US6583186B2 (en) * | 2001-04-04 | 2003-06-24 | Chevron U.S.A. Inc. | Method for upgrading Fischer-Tropsch wax using split-feed hydrocracking/hydrotreating |
| WO2004028688A1 (en) * | 2002-09-24 | 2004-04-08 | Nippon Oil Corporation | Hydrocracking catalyst and process for production of liquid hydrocarbons |
| US7150823B2 (en) * | 2003-07-02 | 2006-12-19 | Chevron U.S.A. Inc. | Catalytic filtering of a Fischer-Tropsch derived hydrocarbon stream |
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2007270060A (en) | 2007-10-18 |
| MY146925A (en) | 2012-10-15 |
| CN101410487A (en) | 2009-04-15 |
| WO2007113962A1 (en) | 2007-10-11 |
| JP4714066B2 (en) | 2011-06-29 |
| RU2443757C2 (en) | 2012-02-27 |
| AU2007232010B2 (en) | 2011-09-01 |
| AU2007232010A1 (en) | 2007-10-11 |
| RU2008143259A (en) | 2010-05-10 |
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