CN105618051B - A kind of catalyst for being used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil and preparation method and application - Google Patents
A kind of catalyst for being used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil and preparation method and application Download PDFInfo
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Abstract
A kind of catalyst for being used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil and preparation method and application.The catalyst is using Co as active component, and using Si as auxiliary agent, using activated carbon as carrier, active component is 5~30wt% of catalyst weight, and auxiliary agent is 0.1~5wt% of catalyst weight.The catalyst prepared by the present invention by adding Si auxiliary agents, CO conversion ratios are improved, C1‑C4Gaseous state hydrocarbon-selective reduces, and synthol and naphtha and diesel oil selectively increase, the especially C of high added value6‑C18The selectivity of higher alcohols is improved significantly.
Description
Technical field
The invention belongs to technical field of chemical engineering catalysts, and in particular to one kind is used for CO hydrogenation synthesis higher alcohols coproduction stone brains
Catalyst of oil and diesel oil and preparation method and application, more particularly, to a kind of using activated carbon as carrier loaded cobalt-based
Catalyst, through Si auxiliary agent regulating catalyst performances.
Background technology
C6Above alcohol is referred to as higher alcohols, and added value is high, is widely used, its demand is at 13,000,000 tons or so at present.And I
State is that a higher alcohols consume big country, either plastic products, detergent, surfactant and other fine chemical products all
There is wide consumption market.At present, the technique of industrial chemical method synthesizing bigh carbon alcohol has two kinds.First, it is catalyzed using triethyl aluminum
Triethyl aluminum chain propagation reaction and oxidation, the technique productions detergent alcohol such as hydrolysis and rectifying, but the party are passed through in agent, i.e. ethylene raw
Method triethylaluminium catalyst consumption is big, and cost is high, and production security is poor.Second, with even phase cobalt-phosphine metallo-organic compound
For catalyst, higher olefins, carbon monoxide and hydrogen generates straight chain and side chain high-carbon aldehyde in the presence of the catalyst, then passes through
Higher alcohols are hydrogenated to, but the flow is complicated, and target product selectivity is poor.
By synthesis gas by the direct Synthesis of mixed alcohols of Fischer-Tropsch synthesis, have higher economic benefit and the utilization of resources excellent
Gesture.The carbon number of its mixed alcohol synthesized is than relatively low, generally C1-C6OH, can be used as high-grade fuel, clean gasoline additive and
Chemicals and industrial chemicals.US 4513100 discloses a kind of methanol synthesis catalyst being modified by alkali and alkaline earth metal ions
Cu-ZnO/Al2O3, the primary product of synthesis gas reaction generation is C1-C6Straight chain and branched-chain alcoho, accessory substance are a small amount of other contain
Oxygen compound and hydro carbons.France Petroleum Institute (IFP) have developed Cu-Co base CO hydrogenation synthesizing low carbon alcohol catalysts (US
4122110 and US 4291126).The formula of catalyst composition is CuxCoyMzAw, wherein M=Cr, Fe, V, Mn and rare earth,
A is alkali metal.The Cu-Co bases catalyst of Cr, Mn, Fe, La and K auxiliary agent modulation has activity and the selection of higher synthesizing alcohol
Property.U.S.'s Dow Chemical Companies in 1984 and connection C.-Chem AG find respectively, by the MoS of alkali-metal-doped2Raw catelyst can be with
Catalyzed conversion synthesis gas is low-carbon straight chain mixed alcohol.The addition of base agent greatly inhibits the generation of hydrocarbon on catalyst, promoted
The generation of alcohol product, the selectivity for generating alcohol are greatly improved (WO 8503073 and US 4882360).CN
01130481 discloses Mn-Ni-K-MoS2Catalyst, in MoS2Mn elements are introduced in the preparation of base catalyst so that catalyst is urged
Alcohol activity is combined to significantly improve, meanwhile, C2 +The selectivity of alcohol increases, and is up to 62%.CN 200610097869 is provided
A kind of catalyst for synthesizing low-carbon alcohol from synthetic gas and preparation method thereof, catalyst key component are CuO, ZnO, Cr2O3、
Al2O3With appropriate other auxiliary agents (V, Mo, Mn, Mg, Ce), there is higher CO conversion ratios and higher C2Above alcohol selectivity.
Above by the carbon number of F- T synthesis production mixed alcohol than relatively low, generally C1~C6, substantially cannot get high added value C6+It is high
Carbon alcohol, and low value-added methanol proportion is larger, reaches more than 40%, constrains the economy of the technique.
Dalian Chemical Physics Research Institute have developed for CO hydrogenation synthesis mixing primary alconols (C2-C18OH) coproduction liquid fuel
On activated carbon supported cobalt-base catalyst (Co/AC) (US 7670985 and CN101310865).Hydro carbons produces in its synthetic fluid product
Thing (predominantly naphtha and diesel oil) is 1 with the mass ratio for mixing primary alconol:1 or so, the high carbon primary alcohol (carbon number >=6) of high added value
Reach 50% or so in the distribution of alcoholic product.But a kind of CO that further improves is remained a need in the art and is hydrogenated with
The catalyst and its preparation method of synthesizing bigh carbon alcohol performance and application.
The content of the invention
It is an object of the invention to for deficiencies of the prior art, there is provided a kind of CO hydrogenation of excellent performance closes
Into catalyst of higher alcohols coproduction naphtha and diesel oil and preparation method thereof.The present invention activated carbon supported cobalt-based (metal Co and
Co2C) on the Research foundation of catalyst, by introducing Si auxiliary agent regulating catalyst performances, further improve catalyst activity and
Selectivity, by reducing C1-C4The selectivity of gaseous hydrocarbon improves the selectivity of synthol and naphtha and diesel oil, especially carries
High C6-C18The selectivity of higher alcohols, further to lift the economy of CO hydrogenation synthesis higher alcohols techniques, promote the catalytic process
Commercial Application.The catalyst of the present invention is used for CO hydrogenation one-step synthesis method higher alcohols coproduction naphthas and diesel oil, has higher
CO conversion ratios, relatively low C1-C4The selectivity of gaseous state hydrocarbon-selective, higher synthesizing bigh carbon alcohol coproduction naphtha and diesel oil
(C1-C18Alcohol and C5+Hydrocarbon-selective), especially there is higher synthesis C6-C18The selectivity of higher alcohols.
In order to realize the above-mentioned purpose of the present invention, the invention provides following technical scheme：
For CO hydrogenation synthesis higher alcohols coproduction naphtha and the catalyst of diesel oil, the catalyst using Co as active component,
Using Si as auxiliary agent, using activated carbon as carrier.
According to described catalyst, wherein activated carbon is apricot shell charcoal or coconut husk charcoal, the specific surface area of activated carbon for 500~
1500m2/ g, average pore size are 1~10nm, and pore volume is 0.3~1.0ml/g.
According to described catalyst, wherein Co active components are cobalt nitrate, cobalt oxalate or citric acid cobalt, and it is catalyst weight
5~30wt% of amount.
According to described catalyst, wherein Si auxiliary agents are 0.1~5wt% of catalyst weight.
According to described catalyst, wherein Co active components are 10~20wt% of catalyst weight.
According to described catalyst, catalyst CO conversion ratios are 60%, C1-C4Gaseous state hydrocarbon-selective is 17%, and synthesis is high
The selectivity of carbon alcohol coproduction naphtha and diesel oil is 82%, C6-C18Straight chain mixed alcohol is distributed as 60%, CO in alcohol product
In the alcohol being hydrogenated to, methanol distribution 2~8%.
Invention also provides a kind of system for CO hydrogenation synthesis higher alcohols coproduction naphtha and the catalyst of diesel oil
Preparation Method, it is characterised in that using activated carbon as carrier, at the hydrochloric acid solution boiling washing that activated carbon is first 5~15% through concentration
Reason, then processing is boiled through deionized water, dry 4~8 hours in air atmosphere at a temperature of 383~403K, then impregnated
Catalyst-loaded component prepares catalyst precursors；The ethanol solution of Co nitrate solution and tetraethyl orthosilicate is immersed in work
Property high-area carbon on, soak catalyst promoter component after the active component of catalyst is first soaked during dipping, or first soak catalyst promoter group
Catalyst activity component, or total immersion simultaneously are soaked after point；Dried in the shade at room temperature after catalyst dipping, it is empty at a temperature of 323~353K
Dried 8~24 hours in gas atmosphere, by drying sample, 373~393K is dried 2~10 hours in a nitrogen atmosphere, the pressure of nitrogen
For normal pressure, air speed 300h-1~1000h-1, 473~773K roastings 4~20 hours in a nitrogen atmosphere, its pressure is normal pressure,
Air speed is 300h-1~1000h-1, the finally reduction activation in hydrogeneous gaseous mixture；In hydrogeneous gaseous mixture hydrogen content be 30~
100%, other gases in hydrogeneous gaseous mixture beyond hydrogen are nitrogen, reduction activation temperature is 573~773K, pressure 0.1
~1MPa, air speed are 300~2000h-1, the time is 2~50 hours.
It is used for the preparation method of the catalyst of CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil as mentioned, reduction is lived
CO hydrogenation reactions are carried out after change, with conventional fixed bed reactors, or with paste state bed reactor, 473~513K of reaction temperature, reaction
1.5~4.0MPa of pressure, 300~3000h of air speed-1, H2With CO gaseous mixture, H2The synthesis gas that mol ratio with CO is 1~3 connects
Continuous charging, CO hydrogenation reactions are carried out in beds, reaction end gas and product are persistently discharged, and its heavy group is collected with hot tank
Point, then its light components is collected with cold-trap, hot tank temperature maintains 373~403K, and condenser temperature maintains 273~293K.
Present invention also offers the above-mentioned catalyst of the present invention in CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil
Application, for CO hydrogenation directly synthesis C2-C18In straight chain mixing primary alconol coproduction naphtha and diesel oil.
The catalyst prepared by the present invention has higher CO conversion ratios, relatively low C1-C4Gaseous state hydrocarbon-selective is higher
Selectivity (the C of synthesizing bigh carbon alcohol coproduction naphtha and diesel oil1-C18Alcohol and C5+Hydrocarbon-selective), especially there is higher conjunction
Into C6-C18The selectivity of higher alcohols.By the catalyst of the present invention, in the alcohol that CO is hydrogenated to, methanol is distributed low (2~8%), closes
It is high into the selectivity of higher alcohols coproduction naphtha and diesel oil, it is 82% or so, C6-C18Straight chain mixing primary alconol (including C6-C11Alcohol and
C12-C18Higher alcohols) distribution in alcohol is up to 60% or so；
The present invention is improved the activity of catalyst, is reduced C with the activated carbon supported cobalt-base catalyst of Si auxiliary agent modulations1-C4Gaseous state
Hydrocarbon-selective, to improve the selectivity of synthesizing bigh carbon alcohol coproduction naphtha and diesel oil, and improve synthesis C6-C18The selection of higher alcohols
Property, the further economy for lifting CO hydrogenation synthesis higher alcohols techniques.In the presence of the catalyst, the rise of CO conversion ratios, C1-
C4Gaseous state hydrocarbon-selective reduces, the selectivity (C of synthesizing bigh carbon alcohol coproduction naphtha and diesel oil1-C18Alcohol and C5+Hydrocarbon-selective)
Rise, C6-C18Higher alcohols selectively raise.
Present disclosure can be described as more detail：
Catalyst provided by the invention, wherein active component are metal Co, the compound containing cobalt be cobalt nitrate, cobalt oxalate and
One kind of citric acid cobalt, preferably cobalt nitrate.Its weight is the 5~30% of catalyst weight, and preferably cobalt element weight content is
10~20%.Adjuvant component is Si, and raw material is tetraethyl orthosilicate, and auxiliary agent weight is the 0.1~5% of catalyst weight.Catalyst
Carrier is activated carbon, and activated carbon can be almond charcoal or coconut husk charcoal, and the specific surface area of absorbent charcoal carrier is 500~1500m2/ g,
Average pore size is 1~10nm, and pore volume is 0.3~1mL/g, and preferable activated carbon specific surface area is 700~1200m2/ g, average hole
Footpath is 3~8nm, and pore volume is 0.5~0.8mL/g.Catalytic component is loaded on carrier using dipping method；For maceration extract
In contained component include catalyst activity component and adjuvant component.
The present invention provides a kind of catalyst and is used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil.Prepare catalyst
Specific method is as follows：Using activated carbon as carrier, activated carbon is first handled through the hydrochloric acid solution boiling washing that concentration is 5~15%, then
Processing is boiled through deionized water, is dried 4~8 hours in air atmosphere at a temperature of 383~403K, then carries out dipping and support to urge
Agent component prepares catalyst precursors；The ethanol solution of Co nitrate solution and tetraethyl orthosilicate is immersed in carried by active carbon
Catalyst promoter component is soaked after the active component of catalyst can be first soaked on body, during dipping, or after first soaking catalyst promoter component
Catalyst activity component is soaked, the method that total immersion can also be used；Dried in the shade at room temperature after catalyst dipping, 323~353K temperature
Dried 8~24 hours in lower air atmosphere.Sample will be dried, and 373~393K is dried 2~10 hours in a nitrogen atmosphere, nitrogen
Pressure is normal pressure, air speed 300h-1~1000h-1, 473~773K roastings 4~20 hours in a nitrogen atmosphere, its pressure is normal
Pressure, air speed 300h-1~1000h-1, the finally reduction activation in hydrogeneous gaseous mixture.In hydrogeneous gaseous mixture hydrogen content be 30~
100%, other gases in hydrogeneous gaseous mixture beyond hydrogen are nitrogen, reduction activation temperature is 573~773K, pressure 0.1
~1MPa, air speed are 300~2000h-1, the time is 2~50 hours.
The reaction of the present invention can use conventional fixed bed reactors, can also use paste state bed reactor.Reaction temperature：
473~500K, reaction pressure：1.5~4.0MPa, 300~3000h of air speed-1.Its heavy component is collected with hot tank, then uses cold-trap
Its light components is collected, hot tank temperature maintains 373~403K, and condenser temperature maintains 273~293K.
Using the catalyst prepared by the catalyst of the present invention or the preparation method of the present invention, CO conversion ratios are 60% left
The right side, C1-C4Gaseous state hydrocarbon-selective is 17% or so, and the selectivity of synthesizing bigh carbon alcohol coproduction naphtha and diesel oil is high, is 82% left
The right side, C6-C18Straight chain mixed alcohol is distributed as 60% or so in alcohol product.The catalyst can be used for the directly synthesis of CO hydrogenation
C2-C18Straight chain mixing primary alconol coproduction naphtha and diesel oil, there is higher CO conversion ratios, relatively low C1-C4Gaseous state hydrocarbon-selective,
Higher synthesizing bigh carbon alcohol coproduction naphtha and the selectivity (C of diesel oil1-C18Alcohol and C5+Hydrocarbon-selective), especially have compared with
High synthesis C6-C18The selectivity of straight chain mixing primary alconol.
Brief description of the drawings
Fig. 1 is the XRD spectra after catalyst reaction.
Embodiment
Below in conjunction with the accompanying drawings, by specific embodiment, the present invention will be further described, but does not limit this hair with this
It is bright.
Embodiment 1
The specific surface area and pore-size distribution of cocoanut active charcoal are determined on the AS-1 type adsorption instruments of QUANTACHROME companies
Carry out.The first degassing process 3h under 573K of sample, carries out N2 adsorption test, N under liquid nitrogen temperature2Molecular cross-sectional area takes
0.162nm2.The specific surface area of sample is calculated with BET method, pore size distribution is calculated with BJH methods.Measured cocoanut active charcoal compares surface
Product is 912m2/ g, average pore size 3.5nm, pore volume 0.43mL/g.
1000 grams of coconut activated high-area carbons using 10% hydrochloric acid solution boiling washing method carry out processing 1 time, then spend from
Sub- boiling boiling washing methods carries out processing 9 times, is then dried 8 hours at a temperature of 393K, standby, labeled as AC1.Specific method
For：1000 grams of cocoanut active charcoals are taken, add 5000 grams of hydrochloric acid solutions containing 10% mass concentration, are heated to seething with excitement and seething with excitement
Boil under state 0.5 hour, then pour out hot acid solution, add 5000 grams of deionized waters, be heated to boiling and in fluidized state
Under boil 0.5 hour, hot deionized water is poured out, deionized water is added again and carries out boiling washing next time.Deionized water is boiled
Washing is washed 9 times altogether.Washed activated carbon is dried 8 hours at a temperature of 393K, standby, labeled as AC1.Determined using above method
AC1 activated carbons specific surface area is 956m2/ g, average pore size 3.6nm, pore volume 0.49mL/g.
Catalyst A composition is 15Co0.1Si/AC1.The activated carbon treated using 20~40 mesh as carrier, press by catalyst
Prepared according to following step.Weigh 10 grams and handle activated carbon well, weigh 0.09 gram of tetraethyl orthosilicate and be dissolved in 5mL absolute ethyl alcohols,
Weigh 8.71 grams of Co (NO3)2·6H2O is dissolved in 12mL deionized waters, and two kinds of solution are mixed and stirred for uniform, Ran Houyong
Conventional impregnation method loads mixed solution on the activated carbon.Dry in the shade at room temperature, 24 are then dried at a temperature of air atmosphere 333K
Hour, then dried 4 hours at a temperature of 393K in nitrogen atmosphere；Finally 623K roasting temperatures 8 hours in nitrogen atmosphere,
Obtain the catalyst oxide precursor thing that Co weight contents are 15%, Si weight contents are 0.1%.After being reacted using XRD determining
Co crystalline phase in catalyst, XRD tests are carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1
Radiation source, pipe pressure 40KV, pipe stream 40mA, scanning range is -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst
XRD is shown in Fig. 1.
Embodiment 2
Catalyst B composition is 6Co0.1Si/AC1.Using 20~40 mesh treat activated carbon as carrier, catalyst according to
It is prepared by following step.Weigh 10 grams and handle activated carbon well, weigh 0.08 gram of tetraethyl orthosilicate and be dissolved in 3mL absolute ethyl alcohols, claim
Take 3.15 grams of Co (NO3)2·6H2O is dissolved in 10mL deionized waters, and two kinds of solution are mixed and stirred for uniform, then with normal
Infusion process is advised to load mixed solution on the activated carbon.Dry in the shade at room temperature, it is small that 20 are then dried at a temperature of air atmosphere 343K
When, then dried 6 hours at a temperature of 383K in nitrogen atmosphere；Finally 603K roasting temperatures 6 hours in nitrogen atmosphere, are obtained
To the catalyst oxide precursor thing that Co weight contents are 6%, Si weight contents are 0.1%.It is catalyzed after being reacted using XRD determining
Co crystalline phase in agent, XRD tests are carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1Radiation
Source, pipe pressure 40KV, pipe stream 40mA, scanning range is -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst XRD
Figure is shown in Fig. 1.
Embodiment 3
Catalyst C compositions are 15Co0.5Si/AC1.Using the cocoanut active charcoal handled well in embodiment 1 as carrier, catalyst
Prepare as steps described below.Weigh 10 grams and handle activated carbon well, weigh 0.44 gram of tetraethyl orthosilicate and be dissolved in 5mL absolute ethyl alcohols
In, weigh 8.76 grams of Co (NO3)2·6H2Two kinds of solution are mixed and stirred for uniform, Ran Houyong by O in 12mL deionized waters
Conventional impregnation method loads mixed solution on the activated carbon.Dry in the shade at room temperature, 12 are then dried at a temperature of air atmosphere 353K
Hour, then dried 8 hours at a temperature of 383K in nitrogen atmosphere；Finally 603K roasting temperatures 8 hours in nitrogen atmosphere,
Obtain the catalyst oxide precursor thing that Co weight contents are 15%, Si weight contents are 0.5%.After being reacted using XRD determining
Co crystalline phase in catalyst, XRD tests are carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1
Radiation source, pipe pressure 40KV, pipe stream 40mA, scanning range is -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst
XRD is shown in Fig. 1.
Embodiment 4
Catalyst D compositions are 15Co1Si/AC1.Using the cocoanut active charcoal handled well in embodiment 1 as carrier, catalyst is pressed
Prepared according to following step.10 grams of AC1 activated carbons are weighed, 0.89 gram of tetraethyl orthosilicate is weighed and is dissolved in 5mL absolute ethyl alcohols, weigh
8.81 grams of Co (NO3)2·6H2Two kinds of solution are mixed and stirred for uniform by O in 12mL deionized waters, then with conventional dipping
Method loads mixed solution on the activated carbon.Dry in the shade at room temperature, it is then dry 24 hours at a temperature of air atmosphere 343K, then
Dried 4 hours at a temperature of 383K in nitrogen atmosphere；Finally 623K roasting temperatures 4 hours in nitrogen atmosphere, obtain Co weights
Amount content is 15%, the catalyst oxide precursor thing that Si weight contents are 1%.Using Co in XRD determining post catalyst reaction
Crystalline phase, XRD test carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1Radiation source, pipe pressure
40KV, pipe stream 40mA, scanning range are -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst XRD is shown in Fig. 1.
Embodiment 5
Catalyst E compositions are 15Co2Si/AC1.Using the cocoanut active charcoal handled well in embodiment 1 as carrier, catalyst is pressed
Prepared according to following step.Weigh 10 grams and handle activated carbon well, weigh 1.79 grams of tetraethyl orthosilicates and be dissolved in 8mL absolute ethyl alcohols,
Weigh 4.50 grams of cobalt oxalate CoC2O4In 10mL deionized waters, they are mixed after 2 components are completely dissolved, with conventional dipping
Method supports obtained solution on the activated carbon.Dry in the shade, then dried 24 hours at a temperature of air atmosphere 333K at room temperature, with
Dried 2 hours at a temperature of 393K in nitrogen atmosphere afterwards；Finally 623K roasting temperatures 6 hours in nitrogen atmosphere, obtain Co
The catalyst that weight content is 15%, Si weight contents are 2%.Using the crystalline phase of Co in XRD determining post catalyst reaction, XRD
Test is carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1Radiation source, pipe pressure 40KV, Guan Liu
40mA, scanning range are -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst XRD is shown in Fig. 1.
Embodiment 6
The specific surface area and pore-size distribution of apricot shell activated carbon are determined on the AS-1 type adsorption instruments of QUANTACHROME companies
Carry out.The first degassing process 3h under 573K of sample, carries out N2 adsorption test, N under liquid nitrogen temperature2Molecular cross-sectional area takes
0.162nm2.The specific surface area of sample is calculated with BET method, pore size distribution is calculated with BJH methods.Measured apricot shell activated carbon compares surface
Product is 856m2/ g, average pore size 3.5nm, pore volume 0.58mL/g.
1000 grams of apricot shell absorbent charcoal carriers carry out processing 1 time using 7% hydrochloric acid solution boiling washing method, then use deionization
Boiling boiling washing methods carries out processing 12 times, is then dried 8 hours at a temperature of 393K, standby, labeled as AC1.Specific method
For：1000 grams of apricot shell activated carbons are taken, add 5000 grams of hydrochloric acid solutions containing 7% mass concentration, are heated to seething with excitement and seething with excitement
Boil under state 0.5 hour, then pour out hot acid solution, add 5000 grams of deionized waters, be heated to boiling and in fluidized state
Under boil 0.5 hour, hot deionized water is poured out, deionized water is added again and carries out boiling washing next time.Deionized water is boiled
Washing is washed 12 times altogether.Washed apricot shell activated carbon is dried 12 hours at a temperature of 393K, standby, labeled as AC2.Use with top
Method measure AC2 activated carbons specific surface area is 956m2/ g, average pore size 3.8nm, pore volume 0.62mL/g.
Catalyst F compositions are 20Co3Si/AC2.Using the apricot shell activated carbon AC2 handled well as carrier, catalyst is according to following
It is prepared by step.10 grams of AC2 activated carbons are weighed, 2.90 grams of tetraethyl orthosilicates is weighed and is dissolved in 10mL absolute ethyl alcohols, weigh 12.81
Gram Co (NO3)2·6H2Two kinds of solution are mixed and stirred for uniform by O in 8mL deionized waters, will be made with conventional impregnation method
Solution support on the activated carbon.Dry in the shade, then dried 36 hours at a temperature of air atmosphere 353K, then in nitrogen at room temperature
Dried 10 hours at a temperature of 383K in atmosphere；Finally 623K roasting temperatures 2 hours in nitrogen atmosphere, obtain Co weight contents
The catalyst for being 3% for 20%, Si weight contents.
Embodiment 7
Catalyst G compositions are 25Co4Si/AC2.Using the apricot shell activated carbon AC2 handled well in embodiment 6 as carrier, catalysis
Agent is prepared as steps described below.10 grams of activated carbon AC2 are weighed, 4.19 grams of tetraethyl orthosilicates is weighed and is dissolved in 12ml absolute ethyl alcohols
In, weigh 17.36 grams of Co (NO3)2·6H2Two kinds of solution are mixed and stirred for uniform, with routine by O in 12mL deionized waters
Infusion process supports obtained solution on the activated carbon.Dry in the shade at room temperature, it is small that 20 are then dried at a temperature of air atmosphere 343K
When, then dried 4 hours at a temperature of 393K in nitrogen atmosphere；Finally 603K roasting temperatures 6 hours in nitrogen atmosphere, are obtained
To the catalyst that Co weight contents are 25%, Si weight contents are 4%.Using the crystalline phase of Co in XRD determining post catalyst reaction,
XRD tests are carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1Radiation source, pipe pressure 40KV, pipe
40mA is flowed, scanning range is -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst XRD is shown in Fig. 1.
Comparative example 1
Catalyst H composition is 15Co/AC1.Using 20~40 mesh treat AC1 activated carbons as carrier, catalyst according to
It is prepared by following step.Weigh 10 grams and handle activated carbon well, weigh 8.7 grams of Co (NO3)2·6H2O is dissolved in 10mL deionized waters,
Then with conventional impregnation method by obtained solution loadings on the activated carbon.Dry in the shade at room temperature, then in air atmosphere 333K temperature
Lower drying 24 hours, then dried 4 hours at a temperature of 393K in nitrogen atmosphere；Finally roasted in nitrogen atmosphere at a temperature of 623K
Burn 8 hours, obtain the catalyst oxide precursor thing that Co weight contents are 15%.Using Co in XRD determining post catalyst reaction
Crystalline phase, XRD test carried out on PANalytical companies X ' Pert PRO type X-ray diffractometers.Cu kα1Radiation source, pipe pressure
40KV, pipe stream 40mA, scanning range are -75 ° of 2 θ=5 °, and sweep speed is 0.2 °/s.Reacted catalyst XRD is shown in Fig. 1.
Comparative example 2
Catalyst I composition is 15Co2Zr/AC2.The apricot shell charcoal AC2 treated using 20~40 mesh as carrier, press by catalyst
Prepared according to following step.Weigh 10 grams and handle activated carbon well, weigh 8.9 grams of Co (NO3)2·6H2O is dissolved in 10mL deionized waters
In, weigh 1.13 grams of Zr (NO3)4·5H2O is dissolved in the deionized water of 5mL, 373K temperature, and two kinds of solution are fully mixed to
Uniformly, then with conventional impregnation method by obtained solution loadings on the activated carbon.Dry in the shade at room temperature, then in air atmosphere 333K
At a temperature of dry 24 hours, then dried 6 hours at a temperature of 383K in nitrogen atmosphere；The finally 623K temperature in nitrogen atmosphere
Lower roasting 4 hours, obtains the catalyst oxide precursor thing that Co weight contents are 15%, Zr contents are 2%.
Catalyst A-I reaction evaluatings are carried out in fixed bed reactors.Catalyst 4mL is respectively taken to be seated in fixed bed reactors
In, a diameter of 10mm of fixed bed reactors, length 40mm.Catalyst carries out reduction activation before the reaction, reduction activation
Condition is pure hydrogen atmosphere, and pressure is normal pressure, air speed 1000h-1, temperature 703K, the time is 10 hours.That is winner's active component is
The catalyst of metallic cobalt.Reaction bed temperature is down to below 373K after activation, and switching and merging gas (contains 66.6 volume %
H2, 33.4 volume %CO), be 493K, reaction pressure 3.0MPa, air speed 500h in temperature-1It is anti-under conditions of continuous feed
Should.It is pretreatment phase and stationary phase to react early stage (TOS=48 hours).48 hours samples are collected after stationary phase to be analyzed and counted
Calculate.Reaction end gas and gas-phase product are persistently discharged, and its heavy component is collected with hot tank, and liquid product, hot tank temperature are collected with cold-trap
Spend for 373K, condenser temperature 278K.Reaction end gas is using HP-6890 gas chromatographs (Porapark QS packed columns, TCD inspections
Survey device) on-line analysis, product liquid includes oil phase and aqueous phase product, using HP-6890 gas chromatographs (HP-5 capillaries, FID
Detector) off-line analysis oil phase and aqueous phase product, water-phase product analyzed using sec-butyl alcohol as internal standard.According to Analysis result calculation CO's
The selectivity of conversion ratio and product.Catalyst A-H composition and evaluation result is listed in table 1.
Take respectively and gained catalyst E and F each 10mL of oxide precursor thing is prepared in above-described embodiment 5 and 6, be ground to 150
The following powder of mesh, is respectively placed in fluidized-bed reactor, a diameter of 20mm of fluidized-bed reactor, volume 100mL, is passed through hydrogen
Gas carries out reduction activation under fluidized state, is 703K, normal pressure, air speed 1000h in temperature-1Under conditions of activate 12 hours.Urge
Agent evaluation is carried out in paste state bed reactor.After catalyst temperature is down to 333K, the catalyst after the activation is adopted
It is transferred to the mode of purging in the 1 anti-stirred autoclave of liter stainless steel high pressure for being pre-loaded with 300mL atoleines.Purge gass
Body is H2, volume space velocity 2000h-1, purge time is 2 hours.H is passed through after the completion of transfer in autoclave2With CO gaseous mixtures
(contain 66.6 volume %H2, 33.4 volume %CO) reacted, reaction temperature 493K, reaction pressure 3.0MPa, air speed
For 500h-1.It is pretreatment phase and stationary phase to react early stage (TOS=48 hours).48 hours samples are collected after stationary phase to be divided
Analyse and calculate.Reaction end gas and gas-phase product persistently discharge, and collect its heavy component with hot tank, then collect its lightweight group with cold-trap
Point, hot tank temperature is 373K, condenser temperature 278K.Using HP-6890 gas chromatographs, (Porapark QS are filled out reaction end gas
Fill post, TCD detectors) on-line analysis, product liquid includes oil phase and aqueous phase product, using HP-6890 gas chromatographs (HP-5
Capillary, fid detector) off-line analysis oil phase and aqueous phase product, water-phase product analyzed using sec-butyl alcohol as internal standard.Tied according to analysis
Fruit calculates CO conversion ratio and the selectivity of product.Catalyst A-H composition and evaluation result is listed in table 1.
From table 1, good synthol performance is shown using the catalyst of Si auxiliary agent modulations in embodiment.With not
The 15Co/AC catalyst (comparative example 1) of addition auxiliary agent is compared, and the activity and selectivity for adding the catalyst synthol of Si auxiliary agents obtains
Obvious raising has been arrived, there is higher CO conversion ratios, relatively low C1-C4Gaseous state hydrocarbon-selective, higher synthesis C5+Hydrocarbon and alcohol
The selectivity of liquid organic product, especially synthesizes C6-C18The selectivity of higher alcohols is improved significantly, in alcohol component
Distribution is improved to 60% or so by 50%.Wherein, 15Co1Si/AC catalyst CO high conversion rates are up to 52.75%, C1-C4Gaseous hydrocarbon
Selectivity as little as 16.5%, C5+The selectivity of hydrocarbon and alcohol liquid organic product is 82.4% (C5+Hydrocarbon-selective and alcohol selectivity
With), C6-C18Distribution of the higher alcohols in alcohol is up to 58.6%, synthesizes C6-C18The selectivity and space-time yield of higher alcohols be
4.0g/kg*h, integrate, there is excellent synthol performance.Patent US 7670985 and CN101310856 discloses Zr etc.
The activated carbon supported catalyst synthesis C of auxiliary agent modulation1~C18The activity and selectivity of alcohol, does not provide C6~C18Point of higher alcohols
Cloth.The application comparative example 2 develops catalyst with Zr auxiliary agents representative in patent US 7670985 and CN101310856
15Co2Zr/AC2, table 1 show that the indices of 15Co2Zr/AC2 catalyst synthols are below above-mentioned 15Co1Si/AC catalysis
The index of agent synthol.
Fig. 1 is the XRD spectra after catalyst reaction, it can be seen that reacted catalyst contains Co2C and metal
Co crystalline phase, show that part metals cobalt in-situ carburization is Co to catalyst during the course of the reaction2C.From figure it can also be seen that, catalyst
After middle addition Si auxiliary agents, the Co of Co species2C and metal Co diffraction maximums die down, and show that the decentralization of catalyst is improved.This can
Can be catalyst addition Si auxiliary agents after synthol performance obtain improve the reason for.It is further with Co loadings and Si additions
Improve, its XRD diffraction maximum signal enhancing, illustrate that the crystal grain of Co species increases, this is (high with 25Co4Si/AC2 catalyst in table 1
Load capacity Co and high addition Si) on synthol performance reduce phenomenon it is consistent.
Claims (6)
1. for CO hydrogenation synthesis higher alcohols coproduction naphtha and the catalyst of diesel oil, it is characterised in that the catalyst is using Co as work
Property component, using Si as auxiliary agent, using activated carbon as carrier, activated carbon is apricot shell charcoal or coconut husk charcoal, and the specific surface area of activated carbon is 500
~1500m2/ g, average pore size are 1~10nm, and pore volume is 0.3~1.0ml/g, and Co active components are cobalt nitrate, cobalt oxalate or lemon
Lemon acid cobalt, its weight are 5~30wt% of catalyst weight, and Si auxiliary agents weight is 0.1~5wt% of catalyst weight.
2. according to the catalyst described in claim 1, it is characterised in that wherein Co active components for catalyst weight 10~
20wt%.
3. according to the catalyst described in claim 1, it is characterised in that catalyst CO conversion ratios are 60%, C1-C4Gaseous hydrocarbon
Selectivity is 17%, and the selectivity of synthesizing bigh carbon alcohol coproduction naphtha and diesel oil is 82%, C6-C18Straight chain mixed alcohol produces in alcohols
In the alcohol for being distributed as 60%, CO and being hydrogenated in thing, methanol distribution 2~8%.
4. the preparation method of the catalyst for being used for CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil described in claim 1,
Characterized in that, using activated carbon as carrier, activated carbon is first handled through the hydrochloric acid solution boiling washing that concentration is 5~15%, then is passed through
Deionized water boils processing, is dried 4~8 hours in air atmosphere at a temperature of 383~403K, then carries out dipping supported catalyst
Agent component prepares catalyst precursors；The ethanol solution of Co nitrate solution and tetraethyl orthosilicate is immersed in absorbent charcoal carrier
On, catalyst promoter component is soaked after the active component of catalyst is first soaked during dipping, or first soak to soak after catalyst promoter component and urge
Agent active component, or total immersion simultaneously；Dried in the shade at room temperature after catalyst dipping, at a temperature of 323~353K in air atmosphere
Drying 8~24 hours, by drying sample, 373~393K is dried 2~10 hours in a nitrogen atmosphere, and the pressure of nitrogen is normal pressure,
Air speed is 300h-1~1000h-1, 473~773K roastings 4~20 hours in a nitrogen atmosphere, its pressure is normal pressure, and air speed is
300h-1~1000h-1, the finally reduction activation in hydrogeneous gaseous mixture；Hydrogen content is 30~100% in hydrogeneous gaseous mixture, hydrogeneous
Other gases in gaseous mixture beyond hydrogen are nitrogen, reduction activation temperature is 573~773K, and pressure is 0.1~1MPa, empty
Speed is 300~2000h-1, the time is 2~50 hours.
5. the preparation side for CO hydrogenation synthesis higher alcohols coproduction naphtha and the catalyst of diesel oil as claimed in claim 4
Method, it is characterised in that CO hydrogenation reactions are carried out after reduction activation, with conventional fixed bed reactors, or with paste state bed reactor, instead
Answer 473~513K of temperature, 1.5~4.0MPa of reaction pressure, 300~3000h of air speed-1, H2With CO gaseous mixture, H2With rubbing for CO
Your ratio is 1~3 synthesis gas continuous feed, and CO hydrogenation reactions are carried out in beds, and reaction end gas and product persistently discharge,
Its heavy component is collected with hot tank, then its light components is collected with cold-trap, hot tank temperature maintains 373~403K, condenser temperature
Maintain 273~293K.
6. application of the catalyst in CO hydrogenation synthesis higher alcohols coproduction naphtha and diesel oil described in claim 1, its feature
It is that the catalyst is used for CO and is hydrogenated with directly synthesis C2-C18In straight chain mixing primary alconol coproduction naphtha and diesel oil.
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| CN101265149A (en) * | 2008-04-25 | 2008-09-17 | 北京化工大学 | Method for preparing low-carbon olefin from synthetic gas by two-stage process |
| CN101310856A (en) * | 2007-05-24 | 2008-11-26 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN103586060A (en) * | 2012-08-16 | 2014-02-19 | 中国科学院大连化学物理研究所 | Catalyst used for increasing selectivity of higher carbon alcohol production via Fischer-Tropsch synthesis, and preparation method and applications thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101310856A (en) * | 2007-05-24 | 2008-11-26 | 中国科学院大连化学物理研究所 | Catalyst for directly synthesizing high carbon primary alcohol using CO hydrogenation and preparation method thereof |
| CN101265149A (en) * | 2008-04-25 | 2008-09-17 | 北京化工大学 | Method for preparing low-carbon olefin from synthetic gas by two-stage process |
| CN103586060A (en) * | 2012-08-16 | 2014-02-19 | 中国科学院大连化学物理研究所 | Catalyst used for increasing selectivity of higher carbon alcohol production via Fischer-Tropsch synthesis, and preparation method and applications thereof |
Non-Patent Citations (1)
| Title |
|---|
| Reversible promotional effect of SiO2 modification to Co/Al2O3 catalyst for Fischer–Tropsch synthesis;Xiaoyu Sun et al.,;《Applied Catalysis A: General》;20100125;第377卷;第134–139页 * |
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