CN105618051A - Catalyst for CO hydrogenation synthesis of high-carbon alcohols and coproduction of naphtha and diesel oil, and preparation method and application of catalyst - Google Patents
Catalyst for CO hydrogenation synthesis of high-carbon alcohols and coproduction of naphtha and diesel oil, and preparation method and application of catalyst Download PDFInfo
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Abstract
The invention discloses a catalyst for CO hydrogenation synthesis of high-carbon alcohols and coproduction of naphtha and diesel oil, and a preparation method and an application of the catalyst. The catalyst takes Co as an active component, Si as an auxiliary agent and activated carbon as a carrier, the active component is 5-30 wt% of the catalyst weight, and the auxiliary agent is 0.1-5 wt% of the catalyst weight. With the catalyst prepared by adding the Si auxiliary agent, the CO conversion rate is improved, the C1-C4 gaseous hydrocarbon selectivity is reduced, selectivity of synthetic alcohol, naphtha and diesel oil is increased, and especially, the selectivity of the high-added-value C6-C18 high-carbon alcohols is improved obviously.
Description
Technical field
The invention belongs to chemical catalyst technical field, it is specifically related to a kind of Catalysts and its preparation method for CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil and application, more particularly, to a kind of with activated carbon for carrier loaded cobalt-base catalyst, through Si auxiliary agent regulating catalyst performance.
Background technology
C6Above alcohol is called higher alcohols, and added value is high, is widely used, and its demand is at about 13,000,000 tons at present. And China is higher alcohols consumption big country, it is that plastic, detergent, surfactant and other fine chemical product all have wide consumption market. At present, the technique of industrial chemical method synthesizing bigh carbon alcohol has two kinds. One is adopt triethylaluminium catalyst, and namely ethylene raw is through explained hereafter detergent alcohols such as triethyl aluminum chain propagation reaction and oxidation, hydrolysis and rectification, but the method triethylaluminium catalyst consumption is big, and cost is high, and production security is poor. Two is with even phase cobalt-phosphine metallo-organic compound for catalyst, higher olefins, carbon monoxide and hydrogen under the effect of this catalyst, generate straight chain and side chain high-carbon aldehyde, generate higher alcohols then through hydrogenation, but this flow process be complicated, target product selectivity is poor.
It is directly synthesized mixed alcohol by synthesis gas by Fischer-Tropsch synthesis, there is higher economic benefit and utilization of resources advantage. The carbon number of the mixed alcohol of its synthesis is relatively low, is generally C1-C6OH, it is possible to as high-grade fuel, clean gasoline additive and chemicals and industrial chemicals. US4513100 discloses a kind of methanol synthesis catalyst Cu-ZnO/Al modifiied by alkali and alkaline earth metal ions2O3, the primary product that synthesis gas reaction generates is C1-C6Straight chain and branched-chain alcoho, by-product is other a small amount of oxygenatedchemicals and hydro carbons. France Petroleum Institute (IFP) have developed Cu-Co base CO hydrogenation synthesizing low carbon alcohol catalyst (US4122110 and US4291126). The formula of this catalyst composition is CuxCoyMzAw, wherein M=Cr, Fe, V, Mn and rare earth, A is alkali metal. Cr, Mn, Fe, La and K auxiliary agent modulation the catalyst based activity and selectivity with higher synthesizing alcohol of Cu-Co. U.S.'s Dow Chemical Company in 1984 and connection C.-Chem AG find respectively, by the MoS of alkali-metal-doped2Raw catelyst can catalyzed conversion synthesis gas be low-carbon (LC) straight chain mixed alcohol. The interpolation of base agent greatly inhibits the generation of hydrocarbon on catalyst, has promoted the generation of alcohol product, and the selectivity generating alcohol is greatly improved (WO8503073 and US4882360). CN01130481 discloses Mn-Ni-K-MoS2Catalyst, at MoS2Catalyst based preparation introduces Mn element so that catalyst synthol activity significantly improves, meanwhile, C2 +The selectivity of alcohol increases, and is up to 62%. CN200610097869 provides a kind of Catalysts and its preparation method for synthesizing low-carbon alcohol from synthetic gas, and catalyst key component is CuO, ZnO, Cr2O3��Al2O3Other auxiliary agent (V, Mo, Mn, Mg, Ce) with appropriate, has higher CO conversion ratio and higher C2Above alcohol selectivity. The carbon number producing mixed alcohol above by F-T synthesis is relatively low, is generally C1��C6, substantially can not get high added value C6+Higher alcohols, and low value-added methanol proportion is relatively big, reaches more than 40%, constrains the economy of this technique.
Dalian Chemical Physics Research Institute have developed for CO hydrogenation synthesis mixing primary alconol (C2-C18OH) the activated carbon supported cobalt-base catalyst (Co/AC) of coproduction liquid fuel upper (US7670985 and CN101310865). In its synthetic fluid product, hydrocarbon product (being mainly Petroleum and diesel oil) is about 1:1 with the mass ratio mixing primary alconol, and the high carbon primary alcohol (carbon number >=6) of high added value reaches about 50% in the distribution of alcoholic product. But, remain a need for a kind of further catalyst improving CO hydrogenation synthesis higher alcohols performance and its preparation method and application in the art.
Summary of the invention
Present invention aims to prior art above shortcomings, it is provided that the CO hydrogenation synthesis higher alcohols coproduction Petroleum of a kind of excellent performance and the Catalysts and its preparation method of diesel oil. The present invention is at activated carbon supported cobalt-based (metal Co and Co2C) on the Research foundation of catalyst, by introducing Si auxiliary agent regulating catalyst performance, the activity and selectivity of catalyst is improved further, by reducing C1-C4The selectivity of gaseous hydrocarbon improves the selectivity of synthol and Petroleum and diesel oil, especially improves C6-C18The selectivity of higher alcohols, to promote the economy of CO hydrogenation synthesis higher alcohols technique further, promotes the commercial Application of this catalytic process. The catalyst of the present invention is hydrogenated with one-step synthesis method higher alcohols coproduction Petroleum and diesel oil for CO, has higher CO conversion ratio, relatively low C1-C4Gaseous hydrocarbon selectivity, higher synthesizing bigh carbon alcohol coproduction Petroleum and the selectivity (C of diesel oil1-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 the catalyst of CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil, this catalyst is with Co for active component, with Si for auxiliary agent, with activated carbon for carrier.
According to described catalyst, wherein activated carbon is Fructus Pruni shell charcoal or coconut husk charcoal, and the specific surface area of activated carbon is 500��1500m2/ g, average pore size is 1��10nm, and pore volume is 0.3��1.0ml/g.
According to described catalyst, wherein Co active component is cobalt nitrate, cobalt oxalate or citric acid cobalt, and it is 5��30wt% of catalyst weight.
According to described catalyst, wherein Si auxiliary agent is 0.1��5wt% of catalyst weight.
According to described catalyst, wherein Co active component is 10��20wt% of catalyst weight.
According to described catalyst, this catalyst CO conversion ratio is 60%, C1-C4Gaseous hydrocarbon selectivity is 17%, and the selectivity of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil is 82%, C6-C18Straight chain mixed alcohol is distributed as 60% in alcohol product, in the alcohol that CO hydrogenation generates, and methanol distribution 2��8%.
Invention also provides a kind of preparation method for CO hydrogenation synthesis higher alcohols coproduction Petroleum and the catalyst of diesel oil, it is characterized in that with activated carbon for carrier, activated carbon first processes through the hydrochloric acid solution boiling washing that concentration is 5��15%, process is boiled then through deionized water, at 383��403K temperature, air atmosphere dries 4��8 hours, then carry out impregnating catalyst-loaded component and prepare catalyst precursors; The alcoholic solution of the nitrate solution of Co and tetraethyl orthosilicate is immersed on absorbent charcoal carrier, during dipping, first soaks leaching catalyst promoter component after the active component of catalyst, or first leaching catalyst activity component after leaching catalyst promoter component, or total immersion simultaneously; At room temperature drying in the shade after catalyst soakage, dry 8��24 hours, drying sample 373��393K in a nitrogen atmosphere is dried 2��10 hours at 323��353K temperature in air atmosphere, the pressure of nitrogen is normal pressure, and air speed is 300h-1��1000h-1, 473��773K roasting 4��20 hours in a nitrogen atmosphere, its pressure is normal pressure, and air speed is 300h-1��1000h-1, finally reduction activation in hydrogeneous gaseous mixture; In hydrogeneous gaseous mixture, hydrogen content is 30��100%, and in hydrogeneous gaseous mixture, other gases beyond hydrogen are nitrogen, reduction activation temperature is 573��773K, and pressure is 0.1��1MPa, and air speed is 300��2000h-1, the time is 2��50 hours.
As mentioned for the preparation method of CO hydrogenation synthesis higher alcohols coproduction Petroleum and the catalyst of diesel oil, CO hydrogenation reaction is carried out after reduction activation, with conventional fixed bed reactors, or with paste state bed reactor, reaction temperature 473��513K, reaction pressure 1.5��4.0MPa, air speed 300��3000h-1, H2With the gaseous mixture of CO, H2With the synthesis gas continuous feed that the mol ratio of CO is 1��3, beds carry out CO hydrogenation reaction, reaction end gas and product continue discharging, its heavy component is collected with hot tank, collecting its light components with cold-trap again, hot tank temperature maintains 373��403K, and condenser temperature maintains 273��293K.
Present invention also offers the application in CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil of the above-mentioned catalyst of the present invention, be directly synthesized C for CO hydrogenation2-C18In straight chain mixing primary alconol coproduction Petroleum and diesel oil.
The catalyst prepared by the present invention has higher CO conversion ratio, relatively low C1-C4Gaseous hydrocarbon selectivity, higher synthesizing bigh carbon alcohol coproduction Petroleum and the selectivity (C of diesel oil1-C18Alcohol and C5+Hydrocarbon-selective), especially there is higher synthesis C6-C18The selectivity of higher alcohols. By the catalyst of the present invention, in the alcohol that CO hydrogenation generates, methanol is distributed low (2��8%), and the selectivity of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil is high, is about 82%, C6-C18Straight chain mixing primary alconol (includes C6-C11Alcohol and C12-C18Higher alcohols) distribution in alcohol is up to about 60%;
The present invention, with the Si activated carbon supported cobalt-base catalyst of auxiliary agent modulation, improves the activity of catalyst, reduces C1-C4Gaseous hydrocarbon selectivity, to improve the selectivity of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil, and improves synthesis C6-C18The selectivity of higher alcohols, promotes the economy of CO hydrogenation synthesis higher alcohols technique further. Under the effect of this catalyst, CO conversion ratio raises, C1-C4Gaseous hydrocarbon selectivity reduces, the selectivity (C of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil1-C18Alcohol and C5+Hydrocarbon-selective) raise, C6-C18Higher alcohols selectivity raises.
Present disclosure can more be described as detail:
Catalyst provided by the invention, wherein active component is metal Co, and the compound containing cobalt is the one of cobalt nitrate, cobalt oxalate and citric acid cobalt, it is preferred to cobalt nitrate. Its weight is the 5��30% of catalyst weight, it is preferable that 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, it is preferred that activated carbon specific surface area is 700��1200m2/ g, average pore size is 3��8nm, and pore volume is 0.5��0.8mL/g. Dipping method is adopted to load on carrier by catalytic component; Catalyst activity component and adjuvant component is included for component contained in impregnation liquid.
The present invention provides a kind of catalyst for CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil. The concrete grammar preparing catalyst is as follows: with activated carbon for carrier, activated carbon first processes through the hydrochloric acid solution boiling washing that concentration is 5��15%, process is boiled then through deionized water, at 383��403K temperature, air atmosphere dries 4��8 hours, then carry out impregnating catalyst-loaded component and prepare catalyst precursors; The alcoholic solution of the nitrate solution of Co and tetraethyl orthosilicate is immersed on absorbent charcoal carrier, catalyst promoter component is soaked after can first soaking the active component of catalyst during dipping, or soak catalyst activity component after first soaking catalyst promoter component, it would however also be possible to employ the method for total immersion; At room temperature dry in the shade after catalyst soakage, at 323��353K temperature, air atmosphere is dried 8��24 hours. Drying sample 373��393K in a nitrogen atmosphere is dried 2��10 hours, and the pressure of nitrogen is normal pressure, and air speed is 300h-1��1000h-1, 473��773K roasting 4��20 hours in a nitrogen atmosphere, its pressure is normal pressure, and air speed is 300h-1��1000h-1, finally reduction activation in hydrogeneous gaseous mixture. In hydrogeneous gaseous mixture, hydrogen content is 30��100%, and in hydrogeneous gaseous mixture, other gases beyond hydrogen are nitrogen, reduction activation temperature is 573��773K, and pressure is 0.1��1MPa, and air speed is 300��2000h-1, the time is 2��50 hours.
The reaction of the present invention can adopt conventional fixed bed reactors, it is possible to adopts paste state bed reactor. Reaction temperature: 473��500K, reaction pressure: 1.5��4.0MPa, air speed 300��3000h-1. Collecting its heavy component with hot tank, then collect its light components with cold-trap, hot tank temperature maintains 373��403K, and condenser temperature maintains 273��293K.
Adopting the catalyst of the present invention or the catalyst prepared by preparation method of the present invention, CO conversion ratio is about 60%, C1-C4Gaseous hydrocarbon selectivity is about 17%, and the selectivity of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil is high, is about 82%, C6-C18Straight chain mixed alcohol is distributed as about 60% in alcohol product. This catalyst may be used for CO hydrogenation and is directly synthesized C2-C18Straight chain mixing primary alconol coproduction Petroleum and diesel oil, have higher CO conversion ratio, relatively low C1-C4Gaseous hydrocarbon selectivity, higher synthesizing bigh carbon alcohol coproduction Petroleum and the selectivity (C of diesel oil1-C18Alcohol and C5+Hydrocarbon-selective), especially there is higher synthesis C6-C18The selectivity of straight chain mixing primary alconol.
Accompanying drawing explanation
Fig. 1 is the XRD spectra after catalyst reaction.
Detailed description of the invention
Below in conjunction with accompanying drawing, by specific embodiment, the present invention will be further described, but does not limit the present invention with this.
Embodiment 1
The specific surface area of cocoanut active charcoal and pore-size distribution measure and carry out on the AS-1 type adsorption instrument of QUANTACHROME company. Sample is degassed process 3h under 573K first, carries out N2 adsorption test, N under liquid nitrogen temperature2Molecular cross-sectional area takes 0.162nm2. Calculate the specific surface area of sample with BET method, calculate pore size distribution by BJH method. Measured cocoanut active charcoal specific surface area is 912m2/ g, average pore size is 3.5nm, and pore volume is 0.43mL/g.
1000 grams of coconut activated high-area carbon adopt 10% hydrochloric acid solution boiling washing method to carry out processing 1 time, then are undertaken processing 9 times by deionized water boiling washing method, then dry 8 hours at 393K temperature, standby, are labeled as AC1. Method particularly includes: take 1000 grams of cocoanut active charcoals, add 5000 grams of hydrochloric acid solutions containing 10% mass concentration, heating is to boiling and boils under fluidized state 0.5 hour, subsequently hot acid solution is poured out, add 5000 grams of deionized waters, heating is to boiling and boils under fluidized state 0.5 hour, is poured out by hot deionized water, again adds deionized water and carries out boiling washing next time. Deionized water boiling washing washes 9 times altogether. Washed activated carbon dries 8 hours at 393K temperature, standby, is labeled as AC1. Adopting above method to measure AC1 activated carbon specific surface area is 956m2/ g, average pore size is 3.6nm, and pore volume is 0.49mL/g.
Catalyst A consists of 15Co0.1Si/AC1. The activated carbon processed with 20��40 orders is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 0.09 gram of tetraethyl orthosilicate and be dissolved in 5mL dehydrated alcohol, weigh 8.71 grams of Co (NO3)2��6H2O is dissolved in 12mL deionized water, is mixed and stirred for by two kinds of solution to uniformly, then using conventional infusion process by mixed solution load on the activated carbon. Dry in the shade under room temperature, dry 24 hours at air atmosphere 333K temperature subsequently, dry 4 hours at 393K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 8 hours in nitrogen atmosphere, obtain Co weight content be 15%, Si weight content be 0.1% catalyst oxide precursor thing. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Embodiment 2
Catalyst B consists of 6Co0.1Si/AC1. The activated carbon processed with 20��40 orders is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 0.08 gram of tetraethyl orthosilicate and be dissolved in 3mL dehydrated alcohol, weigh 3.15 grams of Co (NO3)2��6H2O is dissolved in 10mL deionized water, is mixed and stirred for by two kinds of solution to uniformly, then using conventional infusion process by mixed solution load on the activated carbon. Dry in the shade under room temperature, dry 20 hours at air atmosphere 343K temperature subsequently, dry 6 hours at 383K temperature in nitrogen atmosphere subsequently; Last 603K roasting temperature 6 hours in nitrogen atmosphere, obtain Co weight content be 6%, Si weight content be 0.1% catalyst oxide precursor thing. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Embodiment 3
Catalyst C consists of 15Co0.5Si/AC1. The cocoanut active charcoal handled well in embodiment 1 is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 0.44 gram of tetraethyl orthosilicate and be dissolved in 5mL dehydrated alcohol, weigh 8.76 grams of Co (NO3)2��6H2Two kinds of solution, in 12mL deionized water, are mixed and stirred for uniformly, then using conventional infusion process by mixed solution load on the activated carbon by O. Dry in the shade under room temperature, dry 12 hours at air atmosphere 353K temperature subsequently, dry 8 hours at 383K temperature in nitrogen atmosphere subsequently; Last 603K roasting temperature 8 hours in nitrogen atmosphere, obtain Co weight content be 15%, Si weight content be 0.5% catalyst oxide precursor thing. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Embodiment 4
Catalyst D consists of 15Co1Si/AC1. The cocoanut active charcoal handled well in embodiment 1 is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams of AC1 activated carbons, weigh 0.89 gram of tetraethyl orthosilicate and be dissolved in 5mL dehydrated alcohol, weigh 8.81 grams of Co (NO3)2��6H2Two kinds of solution, in 12mL deionized water, are mixed and stirred for uniformly, then using conventional infusion process by mixed solution load on the activated carbon by O. Dry in the shade under room temperature, dry 24 hours at air atmosphere 343K temperature subsequently, dry 4 hours at 383K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 4 hours in nitrogen atmosphere, obtain Co weight content be 15%, Si weight content be 1% catalyst oxide precursor thing. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Embodiment 5
Catalyst E consists of 15Co2Si/AC1. The cocoanut active charcoal handled well in embodiment 1 is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 1.79 grams of tetraethyl orthosilicates and be dissolved in 8mL dehydrated alcohol, weigh 4.50 grams of cobalt oxalate CoC2O4In 10mL deionized water, after 2 components are completely dissolved, they are mixed, by conventional infusion process, prepared solution is supported on the activated carbon. Dry in the shade under room temperature, dry 24 hours at air atmosphere 333K temperature subsequently, dry 2 hours at 393K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 6 hours in nitrogen atmosphere, obtain Co weight content be 15%, Si weight content be the catalyst of 2%. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Embodiment 6
The specific surface area of Fructus Pruni shell activated carbon and pore-size distribution measure and carry out on the AS-1 type adsorption instrument of QUANTACHROME company. Sample is degassed process 3h under 573K first, carries out N2 adsorption test, N under liquid nitrogen temperature2Molecular cross-sectional area takes 0.162nm2. Calculate the specific surface area of sample with BET method, calculate pore size distribution by BJH method. Measured Fructus Pruni shell activated carbon specific surface area is 856m2/ g, average pore size is 3.5nm, and pore volume is 0.58mL/g.
1000 grams of Fructus Pruni shell absorbent charcoal carriers adopt 7% hydrochloric acid solution boiling washing method to carry out processing 1 time, then are undertaken processing 12 times by deionized water boiling washing method, then dry 8 hours at 393K temperature, standby, are labeled as AC1. Method particularly includes: take 1000 grams of Fructus Pruni shell activated carbons, add 5000 grams of hydrochloric acid solutions containing 7% mass concentration, heating is to boiling and boils under fluidized state 0.5 hour, subsequently hot acid solution is poured out, add 5000 grams of deionized waters, heating is to boiling and boils under fluidized state 0.5 hour, is poured out by hot deionized water, again adds deionized water and carries out boiling washing next time. Deionized water boiling washing washes 12 times altogether. Washed Fructus Pruni shell activated carbon dries 12 hours at 393K temperature, standby, is labeled as AC2. Adopting above method to measure AC2 activated carbon specific surface area is 956m2/ g, average pore size is 3.8nm, and pore volume is 0.62mL/g.
Catalyst F consists of 20Co3Si/AC2. With the Fructus Pruni shell activated carbon AC2 that handles well for carrier, catalyst is prepared as steps described below. Weigh 10 grams of AC2 activated carbons, weigh 2.90 grams of tetraethyl orthosilicates and be dissolved in 10mL dehydrated alcohol, weigh 12.81 grams of Co (NO3)2��6H2Two kinds of solution, in 8mL deionized water, are mixed and stirred for uniformly, being supported on the activated carbon by prepared solution by conventional infusion process by O. Dry in the shade under room temperature, dry 36 hours at air atmosphere 353K temperature subsequently, dry 10 hours at 383K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 2 hours in nitrogen atmosphere, obtain Co weight content be 20%, Si weight content be the catalyst of 3%.
Embodiment 7
Catalyst G consists of 25Co4Si/AC2. The Fructus Pruni shell activated carbon AC2 handled well in embodiment 6 is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams of activated carbon AC2, weigh 4.19 grams of tetraethyl orthosilicates and be dissolved in 12ml dehydrated alcohol, weigh 17.36 grams of Co (NO3)2��6H2Two kinds of solution, in 12mL deionized water, are mixed and stirred for uniformly, being supported on the activated carbon by prepared solution by conventional infusion process by O. Dry in the shade under room temperature, dry 20 hours at air atmosphere 343K temperature subsequently, dry 4 hours at 393K temperature in nitrogen atmosphere subsequently; Last 603K roasting temperature 6 hours in nitrogen atmosphere, obtain Co weight content be 25%, Si weight content be the catalyst of 4%. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Comparative example 1
Catalyst H consists of 15Co/AC1. The AC1 activated carbon processed with 20��40 orders is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 8.7 grams of Co (NO3)2��6H2O is dissolved in 10mL deionized water, then by conventional infusion process by prepared solution loadings on the activated carbon. Dry in the shade under room temperature, dry 24 hours at air atmosphere 333K temperature subsequently, dry 4 hours at 393K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 8 hours in nitrogen atmosphere, obtain the catalyst oxide precursor thing that Co weight content is 15%. Adopting the crystalline phase of Co in XRD determining post catalyst reaction, XRD test carries out on PANalytical company X ' PertPRO type X-ray diffractometer. Cuk��1Radiation source, pipe pressure 40KV, pipe flow 40mA, sweep limits is-75 ��, 2 ��=5 ��, and scanning speed is 0.2 ��/s. Reacted catalyst XRD figure is shown in Fig. 1.
Comparative example 2
Catalyst I consists of 15Co2Zr/AC2. The Fructus Pruni shell charcoal AC2 processed with 20��40 orders is for carrier, and catalyst is prepared as steps described below. Weigh 10 grams and handle activated carbon well, weigh 8.9 grams of Co (NO3)2��6H2O is dissolved in 10mL deionized water, weighs 1.13 grams of Zr (NO3)4��5H2O is dissolved in the deionized water of 5mL, 373K temperature, is fully mixed to uniformly by two kinds of solution, then by conventional infusion process by prepared solution loadings on the activated carbon. Dry in the shade under room temperature, dry 24 hours at air atmosphere 333K temperature subsequently, dry 6 hours at 383K temperature in nitrogen atmosphere subsequently; Last 623K roasting temperature 4 hours in nitrogen atmosphere, obtain Co weight content be 15%, Zr content be 2% catalyst oxide precursor thing.
Catalyst A-I reaction evaluating carries out in fixed bed reactors. Respectively taking catalyst 4mL and be seated in fixed bed reactors, the diameter of fixed bed reactors is 10mm, and length is 40mm. Catalyst carries out reduction activation before the reaction, and the condition of reduction activation is pure hydrogen atmosphere, and pressure is normal pressure, and air speed is 1000h-1, temperature 703K, the time is 10 hours. Namely winner's active component is the catalyst of metallic cobalt. After activation, reaction bed temperature is down to below 373K, and switching and merging gas is (containing 66.6 volume %H2, 33.4 volume %CO), be 493K in temperature, reaction pressure is 3.0MPa, and air speed is 500h-1React when continuous feed. Reaction early stage (TOS=48 hour) is pretreatment phase and stable phase. Collect 48 hr sample after stable phase be analyzed and calculate. Reaction end gas and gas-phase product continue discharging, collect its heavy component with hot tank, collect liquid product with cold-trap, and hot tank temperature is 373K, and condenser temperature is 278K. Reaction end gas adopts HP-6890 gas chromatograph (PoraparkQS packed column, TCD detector) on-line analysis, product liquid includes oil phase and aqueous phase product, adopt HP-6890 gas chromatograph (HP-5 capillary tube, fid detector) off-line analysis oil phase and aqueous phase product, water-phase product analysis is with sec-butyl alcohol for interior mark. Conversion ratio according to Analysis result calculation CO and the selectivity of product. The composition of catalyst A-H and evaluation result are listed in table 1.
Take respectively and above-described embodiment 5 and 6 is prepared gained catalyst E and each 10mL of F oxide precursor thing, it is ground to the 150 following powder of order, it is respectively placed in fluidized-bed reactor, the diameter of fluidized-bed reactor is 20mm, volume is 100mL, pass into hydrogen under fluidized state, carry out reduction activation, be 703K, normal pressure, air speed 1000h in temperature-1When, activates 12 hours. Evaluating catalyst carries out in paste state bed reactor. After treating that catalyst temperature is down to 333K, the mode purged is adopted to be transferred in the 1 liter anti-stirred autoclave of rustless steel high pressure being pre-loaded with 300mL liquid paraffin the catalyst after described activation. Purging gas is H2, volume space velocity is 2000h-1, purge time is 2 hours. In autoclave, H is passed into after having shifted2With CO gaseous mixture (containing 66.6 volume %H2, 33.4 volume %CO) react, reaction temperature is 493K, and reaction pressure is 3.0MPa, and air speed is 500h-1. Reaction early stage (TOS=48 hour) is pretreatment phase and stable phase. Collect 48 hr sample after stable phase be analyzed and calculate. Reaction end gas and gas-phase product continue discharging, collect its heavy component with hot tank, then collect its light components with cold-trap, and hot tank temperature is 373K, and condenser temperature is 278K. Reaction end gas adopts HP-6890 gas chromatograph (PoraparkQS packed column, TCD detector) on-line analysis, product liquid includes oil phase and aqueous phase product, adopt HP-6890 gas chromatograph (HP-5 capillary tube, fid detector) off-line analysis oil phase and aqueous phase product, water-phase product analysis is with sec-butyl alcohol for interior mark. Conversion ratio according to Analysis result calculation CO and the selectivity of product. The composition of catalyst A-H and evaluation result are listed in table 1.
From table 1, embodiment adopt the catalyst of Si auxiliary agent modulation show good synthol performance. Compared with the 15Co/AC catalyst (comparative example 1) being not added with auxiliary agent, the activity and selectivity of the catalyst synthol adding Si auxiliary agent is significantly improved, and has higher CO conversion ratio, relatively low C1-C4Gaseous hydrocarbon selectivity, higher synthesis C5+The selectivity of hydrocarbon and alcohol liquid organic product, especially synthesizes C6-C18The selectivity of higher alcohols is improved significantly, and the distribution in alcohol component is increased to about 60% by 50%. Wherein, 15Co1Si/AC catalyst CO conversion ratio up to 52.75%, C1-C4Gaseous hydrocarbon selectivity is low to moderate 16.5%, C5+The selectivity of hydrocarbon and alcohol liquid organic product is 82.4% (C5+Hydrocarbon-selective and alcohol selectivity sum), C6-C18Higher alcohols distribution in alcohol, up to 58.6%, synthesizes C6-C18The selectivity of higher alcohols and space-time yield are 4.0g/kg*h, integrate, and have the synthol performance of excellence. Patent US7670985 and CN101310856 discloses the activated carbon supported catalyst synthesis C of the auxiliary agent modulations such as Zr1��C18The activity and selectivity of alcohol, does not provide C6��C18The distribution of higher alcohols. The application comparative example 2 develops catalyst 15Co2Zr/AC2 with Zr auxiliary agent representative in patent US7670985 and CN101310856, table 1 shows, the indices of 15Co2Zr/AC2 catalyst synthol is below the index of above-mentioned 15Co1Si/AC catalyst synthol.
Fig. 1 is the XRD spectra after catalyst reaction, it can be seen that reacted catalyst all contains Co2The crystalline phase of C and metal Co, it was shown that catalyst part metals cobalt in-situ carburization in course of reaction is Co2C. From figure it can also be seen that, catalyst adds after Si auxiliary agent, the Co of Co species2C and metal Co diffraction maximum die down, it was shown that the dispersion of catalyst is improved. This is probably catalyst and adds the improved reason of synthol performance after Si auxiliary agent. Further raising along with Co loading and Si addition, its XRD diffraction maximum signal strengthens, illustrating that the crystal grain of Co species increases, this phenomenon reduced with the upper synthol performance of 25Co4Si/AC2 catalyst in table 1 (high capacity amount Co and high addition Si) is consistent.
Claims (9)
1. for the catalyst of CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil, it is characterised in that this catalyst is with Co for active component, with Si for auxiliary agent, with activated carbon for carrier.
2. the catalyst described in claim 1, it is characterised in that activated carbon is Fructus Pruni shell charcoal or coconut husk charcoal, and the specific surface area of activated carbon is 500��1500m2/ g, average pore size is 1��10nm, and pore volume is 0.3��1.0ml/g.
3. the catalyst described in claim 1, it is characterised in that Co active component is cobalt nitrate, cobalt oxalate or citric acid cobalt, and its weight is 5��30wt% of catalyst weight.
4. the catalyst described in claim 1, it is characterised in that Si auxiliary agent weight is 0.1��5wt% of catalyst weight.
5. the catalyst described in claim 1 or 3, it is characterised in that wherein Co active component is 10��20wt% of catalyst weight.
6. the catalyst described in claim 1, it is characterised in that this catalyst CO conversion ratio is 60%, C1-C4Gaseous hydrocarbon selectivity is 17%, and the selectivity of synthesizing bigh carbon alcohol coproduction Petroleum and diesel oil is 82%, C6-C18Straight chain mixed alcohol is distributed as 60% in alcohol product, in the alcohol that CO hydrogenation generates, and methanol distribution 2��8%.
7. the preparation method for CO hydrogenation synthesis higher alcohols coproduction Petroleum and the catalyst of diesel oil described in claim 1, it is characterized in that, with activated carbon for carrier, activated carbon first processes through the hydrochloric acid solution boiling washing that concentration is 5��15%, process is boiled then through deionized water, at 383��403K temperature, air atmosphere dries 4��8 hours, then carry out impregnating catalyst-loaded component and prepare catalyst precursors; The alcoholic solution of the nitrate solution of Co and tetraethyl orthosilicate is immersed on absorbent charcoal carrier, during dipping, first soaks leaching catalyst promoter component after the active component of catalyst, or first leaching catalyst activity component after leaching catalyst promoter component, or total immersion simultaneously; At room temperature drying in the shade after catalyst soakage, dry 8��24 hours, drying sample 373��393K in a nitrogen atmosphere is dried 2��10 hours at 323��353K temperature in air atmosphere, the pressure of nitrogen is normal pressure, and air speed is 300h-1��1000h-1, 473��773K roasting 4��20 hours in a nitrogen atmosphere, its pressure is normal pressure, and air speed is 300h-1��1000h-1, finally reduction activation in hydrogeneous gaseous mixture; In hydrogeneous gaseous mixture, hydrogen content is 30��100%, and in hydrogeneous gaseous mixture, other gases beyond hydrogen are nitrogen, reduction activation temperature is 573��773K, and pressure is 0.1��1MPa, and air speed is 300��2000h-1, the time is 2��50 hours.
8. the preparation method for CO hydrogenation synthesis higher alcohols coproduction Petroleum and the catalyst of diesel oil as claimed in claim 7, it is characterized in that, CO hydrogenation reaction is carried out after reduction activation, with conventional fixed bed reactors, or with paste state bed reactor, reaction temperature 473��513K, reaction pressure 1.5��4.0MPa, air speed 300��3000h-1, H2With the gaseous mixture of CO, H2With the synthesis gas continuous feed that the mol ratio of CO is 1��3, beds carry out CO hydrogenation reaction, reaction end gas and product continue discharging, its heavy component is collected with hot tank, collecting its light components with cold-trap again, hot tank temperature maintains 373��403K, and condenser temperature maintains 273��293K.
9. the application in CO hydrogenation synthesis higher alcohols coproduction Petroleum and diesel oil of the catalyst described in claim 1, it is characterised in that this catalyst is directly synthesized C for CO hydrogenation2-C18In straight chain mixing primary alconol coproduction Petroleum and diesel oil.
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| CN111375417A (en) * | 2018-12-29 | 2020-07-07 | 中国石油化工股份有限公司 | Catalyst for preparing high-carbon alcohol by CO hydrogenation and preparation method thereof |
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