CN101410486A - Process for hydrorefining fuel base material - Google Patents

Process for hydrorefining fuel base material Download PDF

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Publication number
CN101410486A
CN101410486A CN 200780010849 CN200780010849A CN101410486A CN 101410486 A CN101410486 A CN 101410486A CN 200780010849 CN200780010849 CN 200780010849 CN 200780010849 A CN200780010849 A CN 200780010849A CN 101410486 A CN101410486 A CN 101410486A
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Prior art keywords
fuel base
fuel
base
carrier
catalyzer
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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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Priority to CN201510279681.4A priority Critical patent/CN104987881A/en
Publication of CN101410486A publication Critical patent/CN101410486A/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/42—Platinum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/44—Palladium
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/12—Silica and alumina
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/28—Phosphorising
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

Disclosed is a process for hydrorefining a fuel base material wherein a fuel base material containing an oxygen-containing compound, an olefin and a normal paraffin is brought into contact with a hydrorefining catalyst, which is composed of a carrier containing silica-zirconia and a group VIII metal of the periodic table supported by the carrier, in the presence of hydrogen.

Description

The hydrofinishing process of fuel base
Technical field
[0001] the present invention relates in the presence of hydrogen the hydrofinishing process that fuel base is contacted with Hydrobon catalyst.
Background technology
[0002] in recent years, consider, require the liquid fuel of the low and environment amenable cleaning of the content of sulphur composition and aromatic hydrocarbons from the viewpoint that reduces carrying capacity of environment.Therefore, in the oil industry, as the manufacture method of clean fuel, people are studying with carbon monoxide and hydrogen fischer-tropsch (Fischer-Tropsch) synthesis method (being designated hereinafter simply as " FT synthesis method ") as raw material.According to the FT synthesis method, can make be rich in alkane and the liquid fuel base of sulfur-bearing composition not, so people are very big to its expectation.
[0003] yet, adopt in the fuel base that the FT synthesis method obtains owing to contain oxygenatedchemicals and alkene, therefore, directly using as fuel such as gasoline or light oil may not be suitable.Therefore, in order to be effective as the fuel utilization, must remove the oxygenatedchemicals in this fuel base, and make alkene change alkane into by hydrogenation.
[0004] in addition, the fuel base that adopts the FT synthesis method to obtain, because the normal paraffin content height in alkane, therefore, use should not directly act as a fuel this fuel base.More particularly, if this fuel base is used as motor spirit, then its octane value is insufficient, and in addition, if it is used as light oil, then its low-temperature fluidity is insufficient.Therefore, in order to improve the octane value that adopts the fuel base that the FT synthesis method obtains, to improve low-temperature fluidity etc., very important a kind of technology is the hydrofining technology that the normal paraffin in this fuel base is changed into isoparaffin.
[0005] as the catalyzer that uses in the hydrofining technology, the known catalyzer (reference example such as patent documentation 1) that is useful on the hexane hydroisomerization.In addition, disclose in the patent documentation 2 a kind of on the carrier that obtains by amorphous silica alumina with certain detail pore volume the catalyzer of supported palladium as Hydrobon catalyst.
No. 4637992 specification sheets of [patent documentation 1] United States Patent (USP)
[patent documentation 2] Europe patent application discloses specification sheets No. 587246
Summary of the invention
The problem that invention will solve
[0006] past with the fuel base that contains oxygenatedchemicals, alkene and normal paraffin is being raw material when carrying out hydrofining, can fully reach to remove oxygenatedchemicals and to hydrogenation of olefins.Yet, except removing oxygenatedchemicals and, still not knowing to be used for normal paraffin is fully changed into the hydrofinishing process of isoparaffin to the hydrogenation of olefins.
[0007] therefore, the present invention In view of the foregoing carries out, its purpose is, provides a kind of except removing oxygenatedchemicals and to the hydrogenation of olefins, can also fully normal paraffin being changed into the hydrofinishing process of the fuel base of isoparaffin.
Be used to solve the means of problem
[0008] in order to achieve the above object, the invention provides a kind of hydrofinishing process of fuel base, this method is in the presence of hydrogen, make the fuel base that wherein contains oxygenatedchemicals, alkene and normal paraffin with comprise contain the zirconic carrier of silicon-dioxide and on this carrier the Hydrobon catalyst of the periodictable group VIII metal of load contact.
[0009] according to the hydrofinishing process of described fuel base, can when fully removing oxygenatedchemicals, alkene is fully carried out hydrogenation, fully change normal paraffin into isoparaffin.Its result, the hydrofinishing process of fuel base of the present invention can be made the fuel base that is rich in isoparaffin with high yield, thereby has good economy.
[0010] in hydrofinishing process of the present invention, Hydrobon catalyst preferably contains palladium and/or platinum as above-mentioned metal.If use described Hydrobon catalyst, then can change normal paraffin into isoparaffin more effectively, and can further suppress catalyst degradation.
[0011] in hydrofinishing process of the present invention, Hydrobon catalyst preferably also contains phosphorus.Can change normal paraffin into isoparaffin more effectively thus.
[0012] in hydrofinishing process of the present invention, fuel base preferably contains the composition that adopts the FT reaction and generate.Fuel base by will containing mentioned component is as raw material, can be more effectively and positively given play to adopt hydrofinishing process of the present invention remove oxygenatedchemicals, to hydrogenation of olefins and the effect that normal paraffin changed into isoparaffin etc.
The invention effect
[0013], can provide a kind of except removing oxygenatedchemicals and, can also fully reaching the hydrofinishing process that normal paraffin is changed into the fuel base of isoparaffin to the hydrogenation of olefins according to the present invention.
Embodiment
[0014] explains the preferred embodiments of the invention below.
[0015] hydrofinishing process of fuel base of the present invention is in the presence of hydrogen, make the fuel base that contains oxygenatedchemicals, alkene and normal paraffin with comprise contain the zirconic carrier of silicon-dioxide and on this carrier the Hydrobon catalyst of the periodictable group VIII metal of load contact.
[0016] base material that acts as a fuel as long as contain oxygenatedchemicals, alkene and normal paraffin, does not just have particular determination.For example, the base material that acts as a fuel can list oil system or synthetic gasoline base, kerosene base material, light oil base material or their the central mixtures more than 2 kinds that is.Therefore, the boiling range of fuel base is not had particular restriction yet, adjust as long as generate oil according to purpose.For example, when oil fuel was gasoline base, boiling range was generally room temperature～140 ℃; When oil fuel was light oil base material, boiling range was generally 140～360 ℃.
[0017] should illustrate, for example, gasoline base can be mixed with light oil base material,, but preferably gasoline base and light oil base material be carried out hydrofining respectively as the fuel base use of raw material.Therefore in the time will carrying out hydrofining by the base material that gasoline base and light oil base material mix, the part of gasoline base changes more light-weight gas fraction into, makes the yield of the gasoline base in the resultant that the tendency of minimizing is arranged.
[0018] when fuel base is gasoline base, oxygenatedchemicals mainly comprises the alcohols of carbon number 2～8.When fuel base was the kerosene base material, oxygenatedchemicals mainly comprised the alcohols of carbon number 8～13.When fuel base was light oil base material, oxygenatedchemicals mainly comprised the alcohols of carbon number 12～18.In addition, except above-mentioned alcohols, also can contain aldehydes and ketone in the fuel base.
[0019] when fuel base is gasoline base, alkene mainly comprises the unsaturated fatty hydrocarbons of carbon number 4～9.In addition, when fuel base was the kerosene base material, alkene mainly comprised the unsaturated fatty hydrocarbons of carbon number 10～14.When fuel base was light oil base material, alkene mainly comprised the unsaturated fatty hydrocarbons of carbon number 15～20.
[0020] when fuel base is gasoline base, normal paraffin mainly comprises the straight chain shape saturated aliphatic hydrocarbon of carbon number 4～9.In addition, when fuel base was the kerosene base material, normal paraffin mainly comprised the straight chain shape saturated aliphatic hydrocarbon of carbon number 10～14.When fuel base was light oil base material, normal paraffin mainly comprised the straight chain shape saturated aliphatic hydrocarbon of carbon number 15～20.
[0021] in fuel base as raw material, each composition contain the proportional particular determination that do not have.But in order to carry out the isomerization of normal paraffin to isoparaffin effectively, normal paraffin is proportional with respect to containing of fuel base total amount, is preferably more than the 30 quality %, more preferably more than the 50 quality %, is preferably especially more than the 70 quality %.
[0022] in addition, in order more effectively to have given play to above-mentioned effect of the present invention, the fuel base among the present invention preferably contains the composition that adopts the FT reaction to generate, and more preferably only contains the composition that adopts the FT reaction to generate.
[0023] Hydrobon catalyst that uses in the hydrofinishing process of the present invention so long as contain the silicon-dioxide zirconium white as carrier and contain the catalyzer of periodictable group VIII metal as the metal of load on this carrier, does not just have particular determination.
[0024] in the silicon-dioxide zirconium white as carrier, silicon-dioxide/zirconic mol ratio does not have particular determination, is preferably below 10.If this mol ratio surpasses 10, then the activity of Hydrobon catalyst has the tendency of reduction.
[0025] in addition, the Hydrobon catalyst that uses among the present invention can also contain the tackiness agent that is useful on the carrier moulding.Tackiness agent is not had particular restriction,, can list aluminum oxide or silicon-dioxide as preferred adhesive.Shape to carrier does not have particular restriction, can form granular, cylindric shapes such as (particles).
[0026] on above-mentioned carrier, as reactive metal, duty cycle table group VIII metal.As the group VIII metal, can enumerate particularly tap a blast furnace, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium, platinum etc.In these metals, as the metal of load on the carrier, the preferred metal of from nickel, rhodium, palladium, iridium and platinum, selecting more than a kind that uses.In addition,, more preferably use palladium and/or platinum, especially preferably use the mixture of palladium and platinum as the metal of load on the carrier.Thus, when containing the sulphur composition in the fuel base of raw material, can more effectively suppress catalyst degradation.
[0027] these metal loads not being had particular restriction to the method on the carrier, for example can be, the aqueous solution that contains above-mentioned metal is contained be dipped in the carrier, is dried, the method for roasting again.In the Hydrobon catalyst, the charge capacity of above-mentioned metal does not have particular restriction, generally, with respect to carrier 100 mass parts, is 0.1～2.0 mass parts.
[0028] in addition, Hydrobon catalyst of the present invention also preferably contains phosphorus, preferably adopts impregnation method etc. that phosphorus is added on the carrier.Thus, can further promote from the isomerization of normal paraffin to isoparaffin.Containing of phosphorus is proportional, with respect to carrier 100 mass parts, is preferably 0.02～10.0 mass parts.If phosphorus contain proportional 0.02 mass parts that is lower than, then be difficult to give full play to the additive effect of phosphorus.If phosphorus contain proportional 10.0 mass parts that surpass, then be accompanied by the lighting of resultant, the yield of desirable fuel base has the tendency of reduction.
[0029] hydro-refining unit that uses in the hydrofinishing process of fuel base of the present invention so long as can fuel base be contacted with Hydrobon catalyst and carry out hydrorefined device, just have particular determination.Therefore, for example, can use traditional fixed-bed reactor.
[0030] in addition, the temperature of reaction during hydrofining is preferably 180～320 ℃.If temperature of reaction is lower than 180 ℃, then to the isomerization of isoparaffin the tendency that can not fully produce is arranged from normal paraffin.In addition,, then be difficult to suppress the lighting of resultant, thereby make the yield of desirable fuel base that the tendency of reduction be arranged if temperature of reaction surpasses 320 ℃.
[0031] in addition, reaction pressure is not had particular restriction, still, the hydrogen dividing potential drop is preferably 1～12MPa, more preferably 2～6MPa.If the hydrogen dividing potential drop is lower than 1MPa, then the deterioration of catalyzer has the tendency of carrying out easily; And if surpass 12MPa, the temperature of reaction that then is used to obtain desirable fuel base has the tendency of raising.(LHSV) do not have particular restriction to liquid hourly space velocity, generally, as long as be 0.1～5.0h -1, just can carry out the hydrofining of fuel base.In addition, total hydrogen amount of supplying with to catalyst layer is with respect to the ratio as the fuel base amount of raw material, and promptly hydrogen/oil ratio does not have particular restriction, is generally the scope of 100～850NL/L.
[0032], make above-mentioned Hydrobon catalyst and the fuel base that contains oxygenatedchemicals, alkene and normal paraffin in the presence of the hydrogen, under the reaction conditions of regulation, contact according to the hydrofinishing process of the fuel base of the invention described above.Can remove oxygenatedchemicalss such as alcohols contained in the fuel base thus effectively, alkene is carried out hydrogenation and will change isoparaffin (isomerization) into from itself contained normal paraffin in the normal paraffin of oxygenatedchemicals and the fuel base.
[0033] more particularly, contained oxygenatedchemicalss such as alcohols in the fuel base can be removed by being transformed into hydrocarbon.In addition, contained alkene itself and the alkene that is formed by the transformations such as enol class in the fuel base can be transformed into alkane by hydrogenation in the fuel base.And then, the normal paraffin in the alkane that forms by transformations such as alcohols from n-alkanol class etc., contained normal paraffin itself is transformed into isoparaffin in fuel base.Therefore, in the present invention, in above-mentioned hydrofining technology, also can suppress the lighting of fuel base.Thus, both can keep the yield of fuel base, can fully reach simultaneously the purpose of removing oxygenatedchemicals contained in the fuel base, alkene being carried out hydrogenation and normal paraffin being transformed into isoparaffin again.
The preferred embodiments of the invention have been described [0034], but the present invention is not subjected to the qualification of above-mentioned embodiment.
[embodiment]
[0035] below, illustrate in greater detail the present invention, but the present invention is not subjected to the qualification of these embodiment with embodiment.
[0036] [Preparation of catalysts]
(catalyzer 1)
0.7) and the alumina adhesive thorough mixing with silicon-dioxide zirconium white (silicon-dioxide/zirconic mol ratio:, the mixture forming that obtains is φ 1.6mm, is about 3mm cylindric (silicon-dioxide zirconium white/alumina adhesive=70/30 (mass ratio)).With the formed body that obtains in atmosphere, 500 ℃ of following roastings 1 hour, obtain carrier.Make the aqueous nitric acid of this carrier impregnation Platinic chloride, load is the platinum of 0.6 mass parts with respect to carrier 100 mass parts.With its 120 ℃ dry 3 hours down, then in atmosphere, 500 ℃ of following roastings 1 hour, obtain catalyzer 1.
[0037] (catalyzer 2)
Before making carrier loaded platinum, make carrier impregnation phosphate aqueous solution, load is the phosphorus of 0.2 mass parts with respect to carrier 100 mass parts, in addition, similarly obtains catalyzer 2 with the preparation of catalyzer 1.
[0038] (catalyzer 3)
The aqueous nitric acid of impregnation Platinic chloride and Palladous chloride, load is the platinum of 0.5 mass parts and the palladium of 0.1 mass parts with respect to carrier 100 mass parts, the aqueous nitric acid that replaces the impregnation Platinic chloride, load is the platinum of 0.6 mass parts with respect to carrier 100 mass parts, in addition, obtain catalyzer 3 similarly to Example 1.
[0039] (catalyzer 4)
(alumina amount: (silicon-dioxide/zirconic mol ratio: 0.7), the preparation of all the other and catalyzer 1 is similarly carried out, and obtains catalyzer 4 14 quality %) to replace the silicon-dioxide zirconium white except using silica alumina.
[0040] (catalyzer 5)
(alumina amount: (silicon-dioxide/zirconic mol ratio: 0.7), the preparation of all the other and catalyzer 1 is similarly carried out, and obtains catalyzer 5 84 quality %) to replace the silicon-dioxide zirconium white except using the aluminum oxide boron oxide.
[0041] (catalyzer 6)
Make the aqueous nitric acid of the carrier impregnation Platinic chloride that the spheric active carbon by the about 3mm of particle diameter constitutes, load is the platinum of 0.6 mass parts with respect to carrier 100 mass parts.It was descended dry 3 hours at 120 ℃, then in atmosphere, 500 ℃ of following roastings 1 hour, obtain catalyzer 6.
[0042] [hydrofining]
(embodiment 1)
(100mL) is filled in the flow through reactors of fixed bed with catalyzer 1.Then, in nitrogen atmosphere and under 340 ℃, this catalyzer 1 is implemented reduction in 3 hours handle, make catalyzer 1 activation.
[0043] then, the boiling range that will obtain as the employing FT synthesis method of raw material is that 140～360 ℃ fuel base (oxygenatedchemicals/alkene/isoparaffin/normal paraffin=10/14/4/72 quality %) supplies in the above-mentioned reactor, carries out hydrofining under 250 ℃ or 300 ℃ of temperature of reaction.Should illustrate that in the occasion of any temperature of reaction, the hydrogen dividing potential drop is 4.0MPa, the liquid hourly space velocity of raw material is 2.0h -1(liquid flow rate is 200mL/h), hydrogen flow are 250NL/h (that is, hydrogen/oil ratio is 1250NL/L).
[0044] reaction product is distilled gas Chromatographic Determination, it is proportional to obtain containing of light ends, oxygenatedchemicals, alkene and isoparaffin that boiling point is lower than 140 ℃.The results are shown in table 1 (250 ℃ of temperature of reaction) and the table 2 (300 ℃ of temperature of reaction).
[0045] [table 1]
250 ℃ of temperature of reaction Oxygenatedchemicals (quality %) Alkene (quality %) Isoparaffin (quality %) Light ends (quality %)
Embodiment 1 0 0 55 3
Embodiment 2 0 0 58 3
Embodiment 3 0 0 69 3
Comparative example 1 3 1 44 3
Comparative example 2 4 1 28 4
Comparative example 3 4 2 26 6
[0046] [table 2]
300 ℃ of temperature of reaction Oxygenatedchemicals (quality %) Alkene (quality %) Isoparaffin (quality %) Light ends (quality %)
Embodiment 1 0 0 69 7
Embodiment 2 0 0 74 7
Embodiment 3 0 0 80 7
Comparative example 1 0 0 60 8
Comparative example 2 0 0 38 8
Comparative example 3 0 0 36 9
[0047] (embodiment 2)
Except using catalyzer 2 to replace the catalyzer 1, all the other carry out hydrofining and similarly to Example 1 to the analysis of reaction product.The results are shown in the table 1,2.
[0048] (embodiment 3)
(100mL) is filled in the flow through reactors of fixed bed with catalyzer 3.Then, in nitrogen atmosphere and under 340 ℃, this catalyzer 3 is implemented reduction in 3 hours handle, make catalyzer 3 activation.
[0049] then, the boiling range that will obtain as the employing FT synthesis method of raw material is 140～360 ℃ fuel base (oxygenatedchemicals/alkene/isoparaffin/normal paraffin=10/14/4/72 quality %) and is the sweet oil of fuel base as the oil of 140～360 ℃ of boiling ranges, mass ratio according to 70: 30 mixes, the mixing oil (oxygenatedchemicals/alkene/isoparaffin/normal paraffin=7/11/15/52 quality %, sulphur composition 12 quality ppm) that obtains is supplied in the above-mentioned reactor, under 250 ℃ or 300 ℃ of temperature of reaction, carry out hydrofining.In the occasion of any temperature of reaction, the hydrogen dividing potential drop is 4.0MPa, and the liquid hourly space velocity of raw material is 2.0h -1(liquid flow rate is 200mL/h), hydrogen flow are 250NL/h (that is, hydrogen/oil ratio is 1250NL/L).
[0050] reaction product is distilled gas Chromatographic Determination, it is proportional to obtain containing of light ends, oxygenatedchemicals, alkene and isoparaffin that boiling point is lower than 140 ℃.The results are shown in the table 1,2.
[0051] (comparative example 1)
Except using catalyzer 4 to replace the catalyzer 1, all the other carry out hydrofining and similarly to Example 1 to the analysis of reaction product.The results are shown in the table 1,2.
[0052] (comparative example 2)
Except using catalyzer 5 to replace the catalyzer 1, all the other carry out hydrofining and similarly to Example 1 to the analysis of reaction product.The results are shown in the table 1,2.
[0053] (comparative example 3)
Except using catalyzer 6 to replace the catalyzer 1, all the other carry out hydrofining and similarly to Example 1 to the analysis of reaction product.The results are shown in the table 1,2.
[0054] can confirm from the result shown in the table 1,2, in embodiment 1～3, can fully reduce oxygenatedchemicals and alkene in the fuel base, simultaneously, the abundant isomery of normal paraffin can be turned to isoparaffin.
Industrial applicability
[0055] according to the present invention, can provide a kind of except removing oxygenatedchemicals and can carrying out fully to reach the hydrofinishing process that n-alkane is changed into the fuel base of isoparaffin the hydrogenation to alkene.

Claims (4)

1, the hydrofinishing process of fuel base, wherein, in the presence of hydrogen, make the fuel base that contains oxygenatedchemicals, alkene and normal paraffin with comprise contain the zirconic carrier of silicon-dioxide and on this carrier the Hydrobon catalyst of the periodictable group VIII metal of load contact.
2, the described hydrofinishing process of claim 1 wherein, in the above-mentioned Hydrobon catalyst, as above-mentioned metal, contains palladium and/or platinum.
3, claim 1 or 2 described hydrofinishing process wherein, also contain phosphorus in the above-mentioned Hydrobon catalyst.
4, each described hydrofinishing process of claim 1～3 wherein, contains the composition that adopts Fischer-Tropsch reaction to generate in the above-mentioned fuel base.
CN 200780010849 2006-03-30 2007-03-20 Process for hydrorefining fuel base material Pending CN101410486A (en)

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CN201510279681.4A CN104987881A (en) 2006-03-30 2007-03-20 Process for hydrorefining fuel base material

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Application Number Priority Date Filing Date Title
JP094669/2006 2006-03-30
JP2006094669A JP4834438B2 (en) 2006-03-30 2006-03-30 Method for hydrotreating fuel substrate

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CN104987881A (en) 2015-10-21
AU2007239954B2 (en) 2011-09-29
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MY146894A (en) 2012-10-15
RU2008143027A (en) 2010-05-10

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