CN110292938A - A kind of method and its special-purpose catalyst converting production mixing isoparaffin by synthesis gas - Google Patents
A kind of method and its special-purpose catalyst converting production mixing isoparaffin by synthesis gas Download PDFInfo
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- CN110292938A CN110292938A CN201810238824.0A CN201810238824A CN110292938A CN 110292938 A CN110292938 A CN 110292938A CN 201810238824 A CN201810238824 A CN 201810238824A CN 110292938 A CN110292938 A CN 110292938A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/8993—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with chromium, molybdenum or tungsten
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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
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
- C10G2/32—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts
- C10G2/33—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used
- C10G2/331—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals
- C10G2/333—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen with the use of catalysts characterised by the catalyst used containing group VIII-metals of the platinum-group
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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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- 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
- C10G2300/4012—Pressure
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
Abstract
The present invention provides a kind of converted by synthesis gas to produce the method and its special-purpose catalyst that mix isoparaffin, it is characterized in that, under synthesis gas conversion reaction conditions, raw material containing isomeric olefine, synthesis gas are contacted with catalyst, wherein, the catalyst includes carrier, synthesis syngas conversion reactor active component, and the active component is selected from at least one of at least one and selected from Section VI B and/or VIIB race the second metal component of the first metal component of the VIIIth race.Compared with the production isoparaffin method of the prior art, the method for the present invention is simpler, and isoparaffin selectivity with higher.
Description
Technical field
The present invention relates to a kind of methods and its special-purpose catalyst that mixing isoparaffin is directly produced by synthesis gas conversion.
Background technique
F- T synthesis is that the non-petroleum carbon resource such as coal, biomass, shale gas, biomass passes through synthesis in derived energy chemical field
The core process of gas conversion Optimum utilization.Hydrocarbon based on the manufacture of the technologies such as F- T synthesis is had excellent performance, can be direct
It is used in mixed way using or with the fuel of low quality crude oil production, to meet increasingly harsher environmental protection and oil property index
Requirement.However, current oil price is sluggish and has no improvements trend within a short period of time, " limit coal " policy leads to coal price simultaneously
Go up；Thus, the approach profit for carrying out ICL for Indirect Coal Liquefaction liquefaction using F- T synthesis technology is limited, and technology homogeneity is serious.
How these severe challenges to be transformed into the opportunity of syngas chemistry, realize the differentiation of synthesis gas conversion product, high-endization and
High added value is the problem of academia and industry are thought deeply jointly at this stage.
The hydrogenated isomerization of Fischer-Tropsch synthetic obtains top-grade lubricating oil base oil or isoparaffin solvent oil, realizes Fischer-Tropsch
Product is high-valued.CN105521818A discloses a kind of hydroisomerisation catalysts and its preparation method and application, described plus hydrogen
It, can be effectively by the length in Fischer Tropsch waxes when isomerization catalyst is used as the catalyst of Fischer Tropsch waxes hygrogenating isomerization reaction
Linear paraffin is converted into the isoparaffin of highly branched chain, obtains higher isomerization product yield, while obtained isomerization product
With lower pour point and higher viscosity index (VI), it is suitable for lube base oil.CN101921621A discloses a kind of different
The production method of structure alkane solvent oil, the method is with distillate or frivolous oil etc. for raw material, different using hydrotreating-plus hydrogen
Structure-hydrofining group technology produces isoparaffin solvent oil.
To sum up, mixing isoparaffin is the important foundation raw material of lube base oil and isoparaffin solvent oil, it is still necessary to
The method of the more simplified production mixing isoparaffin of development technology process.
Summary of the invention
The purpose of the present invention is to provide a kind of methods for converting production mixing isoparaffin by synthesis gas.
The present invention also provides the special-purpose catalysts and preparation method thereof for realizing the above method.
First aspect present invention provides a kind of method for converting production mixing isoparaffin by synthesis gas, and feature exists
In under synthesis gas conversion reaction conditions, the raw material containing isomeric olefine, synthesis gas are contacted with special-purpose catalyst.
The isomeric olefine is selected from one of C4~C10 isomeric olefine or a variety of.
The synthesis gas conversion reaction conditions include that temperature is 50-350 DEG C, pressure 0.1-15MPa, the H of synthesis gas2With
CO molar ratio is 0.4-3.
Second aspect of the present invention provides a kind of special-purpose catalyst that production mixing isoparaffin is converted by synthesis gas, described
Catalyst includes carrier and load active metal component on this carrier, which is characterized in that the active metal component includes
At least one is selected from the non-noble metal first metal component M of group VIII1With at least one selected from Section VI B and/or VIIB race gold
The the second metal component M belonged to2。
Compared with the production isoparaffin method of the prior art, synthesis gas conversion of the invention directly produces mixing isoparaffin
Method is simpler, and isoparaffin selectivity with higher.Obtained liquid product is because of the isomeric alkane containing high level
Hydrocarbon and become various high-quality oil products, for example, 150 DEG C of boiling range < of product component is high-quality naphtha or high-quality solvent naphtha, boiling range
It is fine-quality diesel oil in 200-320 DEG C of product component, the product component of boiling range > 320 DEG C is good Lube basic oil material feedstocks.
It is emphasized that boiling range > 320 DEG C product component contains the isoparaffin of high level, so that its subsequent isomerization-visbreaking processing
At the technique severity sharp fall of lube base oil, to become a kind of good Lube basic oil material feedstocks.With it is existing
There is technology to compare, this method is simpler, and isoparaffin selectivity with higher.Specifically, using the method for the present invention and specially
With catalyst in the case where keeping the close conversion ratio of conventional F- T synthesis and methane selectively, the selectivity of isoparaffin from
40.7% (being free of the second metal component) increases substantially to 65.4%.
These embodiment results explanation, method provided by the present invention and special-purpose catalyst can be very easily by synthesis gas
Conversion directly produces mixing isoparaffin, and isoparaffin selectivity with higher.
Other features and advantages of the present invention will the following detailed description will be given in the detailed implementation section.
Specific embodiment
Detailed description of the preferred embodiments below.It should be understood that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to restrict the invention.
The present invention provides a kind of methods for converting production mixing isoparaffin by synthesis gas, which is characterized in that is synthesizing
Under the conditions of syngas conversion reactor, the raw material containing isomeric olefine, synthesis gas are contacted with special-purpose catalyst.
The isomeric olefine is selected from C4~C10One of isomeric olefine is a variety of, preferably isobutene, iso-amylene, dissident
At least one of alkene, iso-heptene, isooctene, different nonene, isodecyl alkene, more preferable isobutene, 2-methyl-1-butene alkene, 2- methyl-
2- butylene, 3-methyl-1-butene, 2- Methyl-1-pentene, 3- Methyl-1-pentene, 4-methyl-1-pentene, 2- methyl -2- amylene,
At least one of 3- methyl -2- amylene, 4- methyl -2- amylene.
The synthesis gas conversion reaction conditions include temperature be 50-350 DEG C, preferably 100-280 DEG C, more preferable 180-250
DEG C, pressure 0.1-15MPa, preferably 1-5MPa, the H of synthesis gas2It is 0.4-3, preferably 1-2.5 with CO molar ratio.
The catalytic device is one kind of batch reactor or flow reactor.The batch reactor
Including batch autoclave reactor.The flow reactor includes that fixed bed reactors, paste state bed reactor, moving bed are anti-
Answer one kind of device or fluidized bed reactor.It is preferred that flow reactor.
The when null-rate of synthesis gas used in the flow reactor is 200-20000 hours-1, preferably 500-12000
Hour-1, the reaction time of the batch reactor is 1-200 hours, preferably 2-50 hours.
The molar ratio that the when null-rate of the isomeric olefine meets CO and isomeric olefine is 1-2000, preferably 2-1000,
More preferable 3-300, particularly preferred 5-100.
A kind of special-purpose catalyst converting production mixing isoparaffin by synthesis gas, the catalyst includes carrier and load
Active metal component on this carrier, which is characterized in that the active metal component includes at least one selected from group VIII
Non-noble metal first metal component M1With at least one the second metal component M selected from Section VI B and/or VIIB race metal2。
The catalyst meets (M2/M1)XPS/(M2/M1)XRF=1.5-20.0, preferably 2.5-10, further preferably
3-5.Wherein, (M2/M1)XPSBe with x-ray photoelectron spectroscopy characterization the second metal component of catalyst and the first metal component with
The weight ratio of element meter, (M2/M1)XRFIt is with the second metal component and the first metal in the catalyst of X-ray fluorescence spectra characterization
The weight ratio of component based on the element.
The first metal component of catalyst M1At least one selected from group VIII, preferably cobalt, iron, at least one in ruthenium
Kind.The second metal component of catalyst M2Selected from least one of group vib, VIIB race, preferably in Mo, W, Re, Mn element
At least one.
The first metal component M1Load capacity be 5-70 weight %, preferably 8-50 weight %, further preferably
10-30 weight %；The second metal component M2Content be 0.01-10 weight %, preferably 0.02-8 weight %, further
Preferably 0.05-5 weight %.
The catalyst also includes metal promoter, and the metal promoter is selected from Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu
At least one of.On the basis of the total weight of catalyst, the metal promoter is 0-10 weight with the content of elemental metal
Measure %, preferably 0.5-6 weight %.
The catalyst carrier can be the various various carriers that can be used as fischer-tropsch synthetic catalyst carrier, such as aoxidize
One of aluminium, silica, titanium oxide, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, active carbon are more
Kind, preferably one of aluminium oxide, silica, titanium oxide, active carbon or a variety of.The carrier can also for using phosphorus, silicon,
One of fluorine, boron, charcoal or it is a variety of be modified after one of above-mentioned carrier or a variety of.Above-mentioned modified carrier can be with
It is commercially available, can also be obtained using the modification of existing method.
The preparation method of the special-purpose catalyst, comprising the following steps:
The non-noble metal first metal component M of group VIII is selected from containing at least one1Compound and be selected from Section VI B
And/or the second metal component M of VIIB race2Compound solution impregnating carrier, then the carrier after dipping is successively carried out
Whether dry, roasting or not, obtains the loaded catalyst.
The preparation method of the special-purpose catalyst, preferably includes following steps:
(1) it is soaked with the solution containing at least one compound selected from the non-noble metal first metal component M1 of group VIII
Then carrier after dipping is successively dried, roasted or not roasted, reduction activation by stain carrier；
(2) under reduction or inert atmosphere, with the chemical combination containing the second metal component selected from Section VI B and/or VIIB race
The product that the solution impregnation steps (1) of object obtain obtains the loaded catalyst through dry and optional roasting.
The condition of the dipping includes that temperature can be 10-90 DEG C, and preferably 15-40 DEG C, the time can be 1-24 hours,
Preferably 2-6 hours.The condition of the drying includes that temperature can be for 60-350 DEG C, and preferably 100-200 DEG C, the time can be
1~24 hour, preferably 2-6 hours.When the catalyst is roasted, the temperature of the roasting is to realize described contain
The compound of active metal component is converted into for the purpose of its oxide, and preferred maturing temperature is 200-700 DEG C, and calcining time is
1-12 hours, further preferred temperature was 250-500 DEG C, and calcining time is 2-6 hours.
The introducing method of the catalyst metals auxiliary agent by one of following manner or a variety of can be implemented:
1) first with the solution impregnating carrier of the compound containing the metal promoter, then with containing active metal component
The solution impregnating carrier of compound；
2) it is first then used with the solution impregnating carrier of the compound containing active metal component containing the metal promoter
The solution impregnating carrier of compound；
3) molten with the solution of the compound containing active metal component and the compound containing the metal promoter simultaneously
Liquid impregnated carrier；
4) compound containing active metal component and the compound containing the metal promoter are configured to a kind of dipping
Liquid, then with the maceration extract impregnated carrier.
The catalyst is before use, reducibility gas such as hydrogen reducing need to be used.
Embodiment below facilitates a better understanding of the present invention, but does not limit the present invention.It is described in following embodiments
Percentage composition is unless otherwise instructed mass percentage.The CO for wherein defining conversion accounts for the ratio of air inlet CO as CO conversion
Rate XCO, it is methane selectively S that the CO for being converted to methane, which is accounted for and converted the mole percent of CO,CH4, the CO for producing isoparaffin accounts for
The mole percent for converting CO is isoparaffin selectivity Siso。
Wherein for the different fractions content and feature of intuitively comparing product, using petroleum distillate boiling Range Distribution Analysis measuring method
(ASTM D6352-12) and GC/MS structure analysis method determine 200-320 DEG C fine-quality diesel oil boiling range component and > 320 DEG C
The fraction weight content and isoparaffin selectivity S of High Quality Lube Base Oils raw material boiling range componentiso, S hereisoIt is defined as
Isoparaffin weight accounts for the percentage of the fraction overall weight in the fraction.
Embodiment 1
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
By metal salt content needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2(Japanese fuji silicon company puts down carrier
It is equal 40-80 micron of granularity, same as below), stir evenly standing after 4 hours at 20 DEG C, dried through 120 DEG C, 400 DEG C roasting 4 hours,
400 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.It is down to room temperature after reduction, and 55.1 millis are added in a hydrogen atmosphere
The ammonium metatungstate aqueous solution of 9.07 grams per liter of tungstenic is risen, stands 2 hours, then dried up with hydrogen.Then through O2/N2Volume ratio is
0.5% gaseous mixture is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R-CoW-1, composition, XPS and
XRF characterization result is shown in Table 1.Surface layer atomic ratio is obtained according to the corresponding peak area conversion of the electron binding energy of W 4f and Co 2p
(M2/M1)XPs。
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
It is fitted into fixed bed reactors after the quartz sand of the same partial size of R-CoW-1 catalyst is diluted.First with 160 millis
Liter/min hydrogen 400 DEG C restore 4 hours.After reduction, become H in 210 DEG C of groups 80 ml/mins2/CO/N2
The unstripped gas of=56%/28%/16% (percentage by volume) is passed through reactor, and (the when null-rate of synthesis gas is 10000 hours-1),
And reactor is passed through after 4-methyl-1-pentene liquid is mixed with 0.2 ml/hour of liquid feed rate and gas simultaneously
In, control pressure is 2.5MPa, starts to react, reacts 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Comparative example 1
The comparative example is for illustrating control methods.
(1) catalyst preparation and characterization
With embodiment 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
According to the method for embodiment 1, unlike, it is not passed through liquid.That is, unstripped gas is led at 210 DEG C after reduction
Enter reactor to start to react, but is not passed through 4-methyl-1-pentene liquid.Reaction result is listed in table 1.
Comparative example 2
The comparative example is for illustrating control methods.
(1) catalyst preparation and characterization
With embodiment 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
According to the method for embodiment 1, unlike, it is passed through 1- hexene liquid.That is, after reduction, at 210 DEG C by raw material
Gas is passed through reactor and starts to react, and 1- hexene liquid is mixed with 0.2 ml/hour of liquid feed rate and gas simultaneously
After be passed through and start to react in reactor, react 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Comparative example 3
The comparative example is used to illustrate the effect of comparative catalyst.
(1) catalyst preparation and characterization
According to the method for embodiment 1, unlike, catalyst does not introduce tungsten species.
By metal salt content needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2It is small to stir evenly standing 4 at 20 DEG C for carrier
Shi Hou, through 120 DEG C dry, 400 DEG C roast 4 hours, 400 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.After reduction
It is down to room temperature, then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalysis
Agent is denoted as R-Co, and composition, XPS and XRF characterization result are shown in Table 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
With embodiment 1.
Embodiment 2
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
The catalyst R-CoW-2 of component same as the catalyst R-CoW-1 of embodiment 1 is prepared using co-impregnation.
By metal salt content needed for equi-volume impregnating, be configured to 36.1 milliliters containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum,
The cobalt nitrate of 13.9 grams per liter of tungsten, tetraammineplatinum chloride, ammonium metatungstate dipping solution.Maceration extract is decanted into 42.5 grams of SiO2
Carrier stirs evenly standing at 20 DEG C after 4 hours, dries through 120 DEG C, roasts 4 hours at 400 DEG C, 400 DEG C hydrogen reducing 4 hours, hydrogen
Atmospheric pressure is 0.1 megapascal.Room temperature is down to after reduction, then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, is deposited
It is spare in drier.Obtained catalyst is denoted as R-CoW-2, and characterization result is shown in Table 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
With embodiment 1.
Embodiment 3
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
By metal salt content needed for equi-volume impregnating, 36.1 milliliters are configured to containing 208 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of γ-Al2O3Carrier (put down by Sasol aluminium oxide
It is equal 40-80 micron of granularity, same as below), stir evenly standing after 4 hours at 20 DEG C, dried through 120 DEG C, 400 DEG C roasting 4 hours,
400 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.It is down to room temperature after reduction, and is added 55.1 under logical hydrogen atmosphere
The ammonium molybdate aqueous solution of milliliter 4.54 grams per liter containing molybdenum, stands 2 hours, then dried up with hydrogen.Then through O2/N2Volume ratio is
0.5% gaseous mixture is passivated 0.5 hour, and it is spare to be stored in drier.Obtained catalyst is denoted as R-CoMo-1, and characterization result is shown in Table
1。
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
R-CoMo-1 catalyst is fitted into fixed bed reactors, first restores 4 at 400 DEG C with the hydrogen of 160 ml/mins
Hour.After reduction, become H in 210 DEG C of groups 90 ml/mins2/CO/N2/ isobutene=55%/27.5%/
The unstripped gas of 15.7%/1.8% (percentage by volume) is passed through reactor, and (the when null-rate of synthesis gas is 10000 hours-1), control
Pressure is 2.5MPa, starts to react, and reacts 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Embodiment 4
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
By metal salt content needed for equi-volume impregnating, 36.1 milliliters are configured to containing 104 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of SiO2It is small to stir evenly standing 4 at 20 DEG C for carrier
Shi Hou, through 120 DEG C dry, 400 DEG C roast 4 hours, 400 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.After reduction
It is down to room temperature, and the ammonium metatungstate aqueous solution of 55.1 milliliters of 9.07 grams per liters of tungstenic is added in a hydrogen atmosphere, stands 2 hours, then
It is dried up with hydrogen.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.What is obtained urges
Agent is denoted as R-CoW-3, and composition and characterization result are shown in Table 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
R-CoW-3 catalyst is fitted into fixed bed reactors, first restores 4 at 400 DEG C with the hydrogen of 160 ml/mins
Hour.After reduction, become H in 220 DEG C of groups 80 ml/mins2/CO/N2=56%/28%/16% (volume basis
Number) unstripped gas be passed through reactor (synthesis gas when null-rate be 10000 hours-1), and simultaneously 2- Methyl-1-pentene liquid
It is passed through in reactor after being mixed with 0.2 ml/hour of liquid feed rate and gas, control pressure is 2.5MPa, is started anti-
It answers, reacts 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Embodiment 5
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
With embodiment 3.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
The hydrogen of 320 ml/mins of R-CoMo catalyst is restored 4 hours at 400 DEG C.After reduction, pass through hand
Casing is transferred in the autoclave for filling 40 grams of medium waxes and 10 grams of 4- methylpentenes, is warming up to 210 DEG C after checking air-tightness, and
The group of 160 ml/mins is become H2/CO/N2The unstripped gas of=56%/28%/16% (percentage by volume) is passed through reactor
(the when null-rate of synthesis gas is 10000 hours-1), control pressure be 2.5MPa, and simultaneously 4-methyl-1-pentene liquid with
0.4 ml/hour of liquid feed rate is passed through after mixing with gas to be started to react in reactor, reacts 120 hours post analysis
Gas and fluid sample.Reaction result is listed in table 1.
Embodiment 6
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
By metal salt content needed for equi-volume impregnating, 34.2 milliliters are configured to containing 54 grams per liter of ruthenium, 5.22 grams per liter of zirconium
The dipping solution of nitrosyl ruthenium and two nitric hydrate oxygen zirconiums.Maceration extract is decanted into 40 grams of Y-Al2O3Carrier stirs evenly at 25 DEG C quiet
After setting 4 hours, through 120 DEG C dry, 350 DEG C roast 4 hours, 350 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.
It is down to room temperature after reduction, and the ammonium metatungstate aqueous solution of 55.1 milliliters of 1.59 grams per liters of tungstenic is added in a hydrogen atmosphere, stands 2
Hour, then dried up with hydrogen.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.
Obtained catalyst is denoted as R-RuW, and composition and characterization result are shown in Table 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
It is fitted into fixed bed reactors after the quartz sand of the same partial size of R-RuW catalyst is diluted.First with 160 milliliters/
The hydrogen of minute restores 4 hours at 400 DEG C.After reduction, become H in 210 DEG C of groups 80 ml/mins2/CO/N2=
The unstripped gas of 56%/28%/16% (percentage by volume) is passed through reactor, and (the when null-rate of synthesis gas is 10000 hours-1), and
It is passed through in reactor, controls after 4-methyl-1-pentene liquid is mixed with 2 mls/hour of liquid feed rate and gas simultaneously
Pressing pressure is 2.5MPa, starts to react, and reacts 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Embodiment 7
The embodiment is for illustrating method provided by the invention and its special-purpose catalyst.
(1) catalyst preparation and characterization
By metal salt content needed for equi-volume impregnating, 36.1 milliliters are configured to containing 104 grams per liter of cobalt, 1.38 grams per liter of platinum
The dipping solution of cobalt nitrate, tetraammineplatinum chloride.Maceration extract is decanted into 42.5 grams of γ-Al2O3Carrier stirs evenly standing 4 at 20 DEG C
Hour after, through 120 DEG C dry, 400 DEG C roast 4 hours, 400 DEG C hydrogen reducing 4 hours, Hydrogen Vapor Pressure be 0.1 megapascal.Reduction
After be down to room temperature, and the ammonium molybdate aqueous solution of 55.1 milliliters of 4.54 grams per liters containing molybdenum is added under logical hydrogen atmosphere, stands 2 hours,
It is dried up again with hydrogen.Then through O2/N2The gaseous mixture that volume ratio is 0.5% is passivated 0.5 hour, and it is spare to be stored in drier.It obtains
Catalyst is denoted as R-CoMo-2, and characterization result is shown in Table 1.
(2) method that gas conversion directly produces mixing isoparaffin is catalyzed and synthesized
R-CoMo-2 catalyst is fitted into fixed bed reactors, first restores 4 at 400 DEG C with the hydrogen of 160 ml/mins
Hour.After reduction, become H in 220 DEG C of groups 90 ml/mins2/CO/N2/ isobutene=55%/27.5%/
The unstripped gas of 15.7%/1.8% (percentage by volume) is passed through reactor, and (the when null-rate of synthesis gas is 10000 hours-1), control
Pressure is 2.5MPa, starts to react, and reacts 48 hours post analysis gases and fluid sample.Reaction result is listed in table 1.
Keeping conventional F- T synthesis close using the method for the present invention with it can be seen from the result of comparative example 1 by embodiment 1
In the case where conversion ratio and methane selectively, the selectivity of isoparaffin is increased substantially from 5.2% to 65.4%.By embodiment
1 and the result of comparative example 2 can be seen that seldom isoparaffin is substantially achieved using normal olefine such as 1- hexene.By embodiment 1
With the result of comparative example 3 can be seen that using special-purpose catalyst of the invention keep the close conversion ratio of conventional F- T synthesis and
In the case where methane selectively, the selectivity of isoparaffin from 40.7% (being free of the second metal component) increase substantially to
65.4%.By (M it can be seen from the result of embodiment 1 and embodiment 22/M1)xPS/(M2/M1)XRFWhen under optimum condition, isomery
The selectivity of alkane is higher.When the molar ratio of CO/ isomeric olefine is preferred it can be seen from the result of embodiment 1 and embodiment 6
Under the conditions of when, the selectivity of isoparaffin is higher.
These embodiment results explanation, method provided by the present invention and special-purpose catalyst can be very easily by synthesis gas
Conversion directly produces mixing isoparaffin, and isoparaffin selectivity with higher.
The preferred embodiment of the present invention has been described above in detail, still, during present invention is not limited to the embodiments described above
Detail within the scope of the technical concept of the present invention can be with various simple variants of the technical solution of the present invention are made, this
A little simple variants all belong to the scope of protection of the present invention.
It is further to note that specific technical features described in the above specific embodiments, in not lance
In the case where shield, it can be combined in any appropriate way.In order to avoid unnecessary repetition, the present invention to it is various can
No further explanation will be given for the combination of energy.
Claims (16)
1. a kind of method for converting production mixing isoparaffin by synthesis gas, which is characterized in that in synthesis gas conversion reaction conditions
Under, the raw material containing isomeric olefine, synthesis gas are contacted with catalyst, wherein the catalyst includes carrier and active component,
The active component includes the first metal component M selected from the VIIIth race1At least one of and be selected from Section VI B and/or VIIB race
The second metal component M2At least one.
2. according to the method for claim 1, wherein the isomeric olefine is selected from C4~C10One of isomeric olefine is more
Kind, preferably isobutene, 2-methyl-1-butene alkene, 2- methyl-2-butene, 3-methyl-1-butene, 2- Methyl-1-pentene, 3- methyl-
At least one of 1- amylene, 4-methyl-1-pentene, 2- methyl -2- amylene, 3- methyl -2- amylene, 4- methyl -2- amylene.
3. according to the method for claim 1, wherein the synthesis gas conversion reaction conditions include that temperature is 50-350 DEG C,
It is preferred that 100-280 DEG C, more preferable 180-250 DEG C and/or pressure are 0.1-15MPa, the H of preferably 1-5MPa and/or synthesis gas2
It is 0.4-3, preferably 1-2.5 with CO molar ratio.
4. according to the method for claim 1, wherein the catalytic device is that batch reactor or continous way are anti-
Answer one kind of device, wherein the when null-rate of synthesis gas used in the flow reactor is 200-20000 hours-1, preferably
500-12000 hours-1And/or the reaction time of the batch reactor is 1-200 hours, preferably 2-50 hours.
5. according to the method for claim 1, wherein the when null-rate of the isomeric olefine meets rubbing for CO and isomeric olefine
You are than being 1-2000, preferably 2-1000, more preferable 3-300, particularly preferred 5-100.
6. according to the method for claim 1, wherein the catalyst meets (M2/M1)XPS/(M2/M1)XRF=1.5-20.0,
Preferably 2.5-10, further preferably 3-5.
7. according to method described in claim 1 or 6, wherein the first metal component of catalyst M1In cobalt, iron, ruthenium
At least one and/or the second metal component of catalyst M2Selected from least one of Mo, W, Re, Mn element.
8. according to method described in claim 1 or 6, wherein the first metal component M1Load capacity be 5-70 weight %,
Preferably 8-50 weight %, further preferably 10-30 weight %；The second metal component M2Content be 0.01-10 weight
Measure %, preferably 0.02-8 weight %, further preferably 0.05-5 weight %.
9. according to the method for claim 1, wherein the catalyst carrier is selected from aluminium oxide, silica, titanium oxide, oxygen
Change magnesium, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, one of active carbon or a variety of, or using phosphorus, silicon, fluorine, boron,
One of charcoal or it is a variety of be modified after one of above-mentioned carrier or a variety of.
10. according to the method for claim 1, wherein the catalyst also includes metal promoter, and the metal promoter is selected from
At least one of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, and/or on the basis of the total weight of catalyst, the metal
Auxiliary agent is 10 weight % hereinafter, preferably 0.05-6 weight % with the content of elemental metal.
11. it is a kind of by synthesis gas convert production mixing isoparaffin special-purpose catalyst, wherein the catalyst include carrier and
Active component, the active component include the first metal component M selected from the VIIIth race1At least one of and selected from Section VI B and/
Or the second metal component M of VIIB race2At least one, wherein (M2/M1)XPS/(M2/M1)XRF=1.5-20.0.
12. catalyst according to claim 11, wherein the first metal component of catalyst M1In cobalt, iron, ruthenium
At least one and/or the second metal component of catalyst M2Selected from least one of Mo, W, Re, Mn element.
13. catalyst according to claim 11, wherein the first metal component M1Load capacity be 5-70 weight %,
Preferably 8-50 weight %, further preferably 10-30 weight %；The second metal component M2Content be 0.01-10 weight
Measure %, preferably 0.02-8 weight %, further preferably 0.05-5 weight %.
14. catalyst according to claim 11, wherein the catalyst carrier is selected from aluminium oxide, silica, oxidation
One of titanium, magnesia, zirconium oxide, thorium oxide, beryllium oxide, clay, molecular sieve, active carbon are a variety of, or using phosphorus, silicon,
One of fluorine, boron, charcoal or it is a variety of be modified after one of above-mentioned carrier or a variety of.
15. catalyst according to claim 11, wherein the catalyst also includes metal promoter, the metal promoter
It is described selected from least one of Pt, Pd, Ru, Rh, Ir, La, Zr, Ce, Y, Cu, and/or on the basis of the total weight of catalyst
Metal promoter is 10 weight % hereinafter, preferably 0.05-6 weight % with the content of elemental metal.
16. the preparation method of special-purpose catalyst described in one of claim 11-15, comprising the following steps: with containing at least one
Selected from the non-noble metal first metal component M of group VIII1Compound and the second metal selected from Section VI B and/or VIIB race
Component M2Compound solution impregnating carrier, then the carrier after dipping is successively dried, roasted or not roasted, is obtained
The loaded catalyst.
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| CN101921621A (en) * | 2009-06-09 | 2010-12-22 | 中国石油化工股份有限公司 | Method for manufacturing isoparaffin solvent oil |
| CN105087042A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
| CN105521818A (en) * | 2014-10-24 | 2016-04-27 | 中国石油化工股份有限公司 | Hydroisomerization catalyst, its preparation method and use and Fischer-Tropsch synthetic wax hydroisomerization method |
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| CN1703487A (en) * | 2001-11-06 | 2005-11-30 | 英国石油勘探运作有限公司 | Fischer tropsch composition and process |
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| CN101698152A (en) * | 2009-10-20 | 2010-04-28 | 武汉凯迪科技发展研究院有限公司 | Cobalt-based compounded catalyst and preparing method and application thereof |
| CN105087042A (en) * | 2014-05-09 | 2015-11-25 | 中国石油化工股份有限公司 | Fischer-Tropsch synthesis method |
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