CN104174443B - A kind of catalyst of nucleocapsid structure - Google Patents
A kind of catalyst of nucleocapsid structure Download PDFInfo
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- CN104174443B CN104174443B CN201410451832.5A CN201410451832A CN104174443B CN 104174443 B CN104174443 B CN 104174443B CN 201410451832 A CN201410451832 A CN 201410451832A CN 104174443 B CN104174443 B CN 104174443B
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Abstract
A kind of catalyst of nucleocapsid structure, this catalyst has the function of the methanol decomposition process of coupling heat absorption and the Fischer-Tropsch synthesis of heat release, methyl alcohol can be converted into diesel oil distillate, its kernel is the catalytic component with F-T synthesis function, outer shell is the catalytic component with Methanol Decomposition function, and the preparation method of this catalyst be infusion process in conjunction with the rolling method of forming, concrete, catalyst granules kernel adopts infusion process preparation, and outer shell realizes by shaping method of rolling.
Description
Technical field
The invention provides a kind of catalyst of nucleocapsid structure, be specifically related to a kind of solid catalyst with nucleocapsid structure for Methanol diesel oil.
Background technology
In chemical reaction, understand the generation with heat release or endothermic process.Solving the heat problem of transmission in course of reaction, is one of groundwork of chemical production technical.
Methanol Decomposition is the reaction (CH3OH → CO+2H2) of synthesis gas is a reaction of absorbing heat, and be the process of a heat release through the process that F-T synthesis produces diesel component by synthesis gas, cryogenic high pressure is conducive to F-T synthesis and produces diesel oil, in actual production operating process, F-T synthesis carries out between 200 DEG C to 250 DEG C, and takes reaction heat out of reactor by various heating picking process.
Synthesis gas Methanol Decomposition obtained changes diesel oil into through F-T synthesis, this process route is in the relatively oversaturated situation in ammonia from coal market, the methanol conversion of a part can be become diesel fuel, formed one parallel mutually with preparing gasoline by methanol technique, widen the new technology of the application surface of Coal Chemical Industry.The catalyst synergy that this technique needs two kinds to act on, namely carbinol resolving catalyst and fischer-tropsch synthetic catalyst, bifunctional catalyst is a kind of approach realizing this technique.The method preparing bifunctional catalyst has multiple, and the component Homogeneous phase mixing had plenty of having different catalysis is together shaping, the blended aftershaping of such as powder or the preparation of total immersion stain.The catalyst prepared by the way, influencing each other effect between wherein each kind of component often changes the function of original active component existed with independent form, the function of the catalyst that is formed after mixing is not the superposition of original catalysis separately, but there occurs the change of matter.Obviously for Methanol Decomposition preparing synthetic gas again F-T synthesis obtain the technique of diesel oil, such method for preparing catalyst is inappropriate.And combination adopts shaping method of rolling can prepare the catalyst with nucleocapsid structure.
Summary of the invention
The object of the present invention is to provide a kind of can be the catalyst with nucleocapsid structure of the high-quality diesel oil being rich in straight-chain hydrocarbons by methanol conversion.This catalyst adopts infusion process to combine the shaping method of rolling to prepare, and kernel is for having F-T synthesis function catalytic component, and outer shell is the catalytic active component with Methanol Decomposition function.
Be the process of diesel oil by methanol conversion, be the series processes be cascaded by two reactions in fact, being first that methyl alcohol is decomposed into synthesis gas on a catalyst, is and then that synthesis gas changes diesel oil into through Fischer-Tropsch synthesis.The catalyst of a kind of nucleocapsid structure provided by the invention, has decomposition methyl alcohol simultaneously and is the ability of synthesis gas and is the ability of diesel oil by Synthetic holography, so this catalyst provided by the invention has bifunctional catalyst.
Methanol Decomposition is the reaction of synthesis gas is a reaction of absorbing heat, and synthesis gas is the process of a heat release through the process that F-T synthesis changes diesel component into, the present invention is exactly by the method for infusion process in conjunction with roller forming, the component of two kinds of catalysis is incorporated into same catalyst particles intragranular, and make them while each autocatalysis of performance, the methanol decomposition reaction of carrying out in kernel is allowed to utilize the reaction heat discharged in F-T synthesis in shell, achieve the coupling of heat absorption and release process, thus while reducing whole process energy consumption, also improve the selective of equilibrium conversion and target product.Therefore, the catalyst of this nucleocapsid structure provided by the invention also has the heat exchange function of coupling Process of absorption or liberation of heat process.
The catalyst granules of nucleocapsid structure provided by the invention is in preparation process, first be adopt infusion process to be impregnated on carrier by the component relevant to fischer-tropsch process, and then it is shaping to continue to roll with the powder of the component with Methanol Decomposition function, after reaching required diameter, shapingly to complete to particle.After Overheating Treatment, become catalyst granules bead.
The invention provides a kind of catalyst with nucleocapsid structure, methyl alcohol can be converted into the product being rich in diesel component.Except the characteristic with double-function catalyzing, the present invention also has the heat exchange function of coupling Process of absorption or liberation of heat, therefore has better diesel oil selective.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is further detailed.
The following examples only for explaining explanation the present invention in detail, and limit the scope of the invention never in any form.
Embodiment 1
Configuration quality concentration is the aqueous solution of the cobalt nitrate of 34%, and flood in the mode of excessive dipping the ball-aluminium oxide that diameter is 5mm, taken out by ball-aluminium oxide after 5min from cobalt nitrate aqueous solution, room temperature puts into nodulizer after drying; To take density as the Alumina gel of 0.7g/ml and concentration be 5% aqueous solution of nitric acid be mixed with adhesive (Alumina gel and 5% aqueous solution of nitric acid volume ratio are 15:1), the powder (Cu:Zn:Al=1:1:6 mol ratio) of uniform for ground and mixed cupric oxide, zinc oxide and aluminium oxide is poured in nodulizer, bead after dipping dries rolls shaping with the powder added being atomized under the adhesive effect that sprays into, and being formed into diameter is terminate after the spheroid of 10mm.Now there is the kernel area of Active components distribution at radius≤2.5mm of F-T synthesis function, and the Active components distribution with Methanol Decomposition function is in the housing region between 2.5mm to 5mm at radius.Spheric granules roasting at 400 DEG C after shaping, after 2 hours, is obtained spherical catalyst particles.It is in the fixed bed reactors of 80mm that such catalyst granules is loaded internal diameter, height of formation is the beds of 320mm, methyl alcohol is passed into, at 225 DEG C, under the reaction condition of 5MPa with the flow of 1000ml/min, methanol conversion is 22%, in whole product, CO2 accounts for 25%, and in hydrocarbon product, methane selectively is 17%, and the selective of more than C10 (representing diesel oil with more than C10 component here, lower same) reaches 36%.
Embodiment 2
(wherein cobalt nitrate mass concentration is 34% to the mixed aqueous solution of configuration cobalt nitrate and potassium nitrate, potassium nitrate mass concentration is 7%), the ball-aluminium oxide that diameter is 5mm is flooded in the mode of excessive dipping, taken out from cobalt nitrate and potassium nitrate mixed aqueous solution by ball-aluminium oxide after 5min, room temperature puts into nodulizer after drying; To take density as the Alumina gel of 0.7g/ml and concentration be 5% aqueous solution of nitric acid be mixed with adhesive (Alumina gel and 5% aqueous solution of nitric acid volume ratio are 15:1), the powder (Cu:Zn:Al=1:1:6 mol ratio) of uniform for ground and mixed cupric oxide, zinc oxide and aluminium oxide is poured in nodulizer, bead after dipping dries rolls shaping with the powder added being atomized under the adhesive effect that sprays into, and being formed into diameter is terminate after the spheroid of 10mm.Now there is the kernel area of Active components distribution at radius≤2.5mm of F-T synthesis function, and the Active components distribution with Methanol Decomposition function is in the housing region between 2.5mm to 5mm at radius.Spheric granules roasting at 400 DEG C after shaping, after 2 hours, is obtained spherical catalyst particles.It is in the fixed bed reactors of 80mm that such catalyst granules is loaded internal diameter, height of formation is the beds of 320mm, methyl alcohol is passed into the flow of 1000ml/min, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 21%, in whole product, CO2 accounts for 21%, in hydrocarbon product, methane selectively is 13%, and the selective of more than C10 reaches 41%.
Comparative example 1
Pour in nodulizer after cupric oxide, zinc oxide, cobalt oxide and aluminium oxide is even according to the ratio ground and mixed of mol ratio 1:1:1:15, to spray into atomization, the adhesive (wherein Alumina gel and aqueous solution of nitric acid volume ratio are 15:1) that the aqueous solution of nitric acid take density as Alumina gel and the concentration of 0.7g/ml being 5% is mixed with contacts, roll and be shaped to the spherical particle that diameter is 10mm, through 400 DEG C of roastings globulate catalyst granules after 2 hours.It is in the fixed bed reactors of 80mm that such catalyst granules is loaded internal diameter, height of formation is the beds of 320mm, methyl alcohol is passed into the flow of 1000ml/min, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 3.5%, in whole product, CO2 accounts for 45%, in hydrocarbon product, the selective of methane is 23%, and the selective of more than C10 is 18%.
Claims (3)
1. the catalyst of a nucleocapsid structure, it is characterized in that, this catalyst has the function of the methanol decomposition process of coupling heat absorption and the Fischer-Tropsch synthesis of heat release, methyl alcohol can be converted into diesel oil distillate, its kernel is the catalytic component with F-T synthesis function, outer shell is the catalytic component with Methanol Decomposition function, and the preparation method of this catalyst is that infusion process is in conjunction with the rolling method of forming, concrete, catalyst granules kernel adopts infusion process preparation, and outer shell realizes by shaping method of rolling.
2. the catalyst of a kind of nucleocapsid structure according to claim 1, is characterized in that, the catalyst activity component in outer shell with Methanol Decomposition function contains one or several elements in Cu, Zn, Al and Si.
3. the catalyst of a kind of nucleocapsid structure according to claim 1, it is characterized in that, process prepared by kernel is with the salt solution impregnated carrier bead containing catalysis component, material as the bead of carrier is have the aluminium oxide of loose structure, silica or various molecular sieve, and maceration extract is the salting liquid having F-T synthesis function He have auxiliary agent function, comprises cobalt nitrate, ferric nitrate, potassium nitrate, lanthanum nitrate, more than one the salting liquid in magnesium nitrate.
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| US7422995B2 (en) * | 2004-04-30 | 2008-09-09 | Basf Catalysts Llc | Process for the preparation of a supported catalyst |
| KR101297599B1 (en) * | 2011-04-26 | 2013-08-19 | 한국화학연구원 | Fischer-tropsch synthesis catalyst having improved heat transfer capability |
| CN102489312B (en) * | 2011-11-24 | 2013-06-19 | 武汉凯迪工程技术研究总院有限公司 | Fischer-Tropsch synthesis cobalt-based nano-catalyst based on porous material confinement, and preparation method thereof |
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| CN103212418B (en) * | 2013-04-25 | 2015-05-20 | 太原理工大学 | Dual-function catalyst for directly preparing dimethyl ether from synthesis gas and preparation method of dual-function catalyst |
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