CN104152172B - A kind of is the technique of diesel oil by methanol conversion - Google Patents
A kind of is the technique of diesel oil by methanol conversion Download PDFInfo
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- CN104152172B CN104152172B CN201410451498.3A CN201410451498A CN104152172B CN 104152172 B CN104152172 B CN 104152172B CN 201410451498 A CN201410451498 A CN 201410451498A CN 104152172 B CN104152172 B CN 104152172B
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- methyl alcohol
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock
Abstract
A kind of is the technique of diesel oil by methanol conversion, this technique is a consecutive reaction, first be methanolysis be synthetic gas, then be that synthetic gas changes the product being rich in diesel component into through F-T synthesis, a kind of difunctional solid catalyst that with the addition of the nucleocapsid structure of heat conduction auxiliary agent in moulding process is used in this technique, what distribute in the outer shell of this catalyzer is the catalytic active component with methanolysis function, and kernel portion is the catalytic active component with F-T synthesis function; And using this catalytic conversion methyl alcohol to be diesel oil process initial period, what pass in reactor is the mixing raw material of synthetic gas and methyl alcohol, and along with reaction is carried out, the ratio of methyl alcohol in parallel feeding increases in time gradually, until all charging is all methyl alcohol.
Description
Technical field
The invention provides a kind of is the technique of diesel oil by methanol conversion, is specifically related to a kind of processing method using dual-function catalyst to be diesel oil by methanol conversion.
Background technology
In chemical reaction, understand the generation with heat release or endothermic process.Solving the heat problem of transmission in reaction process, is one of groundwork of chemical production technical.
Methanolysis is the reaction (CH3OH → CO+2H2) of synthetic gas is a reaction of absorbing heat.Consider from thermodynamics, high temperature is conducive to methyl alcohol to carry out to the direction being decomposed into synthetic gas.And be the process of a heat release through the process that F-T synthesis produces diesel component by synthetic 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.
Synthetic gas methanolysis obtained changes diesel oil into through F-T synthesis, this operational path is in the relatively oversaturated situation in ammonia from coal market, the methanol conversion of a part can be become diesel oil fuel, formed one parallel mutually with preparing gasoline by methanol technique, widen the novel process of the application surface of Coal Chemical Industry.The catalyzer synergy that this technique needs two kinds to act on, namely carbinol resolving catalyst and fischer-tropsch synthetic catalyst, dual-function catalyst is a kind of approach realizing this technique.The method preparing dual-function 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 catalyzer prepared by the way, between wherein each kind of component, reciprocal influence effect cannot be avoided, interaction often between each component changes the function of original active ingredient existed with independent form, the function of the catalyzer that is formed after mixing is not the superposition of original catalysis separately, but there occurs the change of matter.Obviously for methanolysis preparing synthetic gas again F-T synthesis obtain the technique of diesel oil, such method for preparing catalyst is inappropriate.And the method that another kind prepares dual-function catalyst is the catalyzer with nucleocapsid structure adopting shaping method of rolling to prepare.Rolling in shaping process, different time adds the powder containing different activities component, the structure with radially layered can be formed in granules of catalyst, different activities component is distributed in different radial depths, this also just defines the different zones in same granules of catalyst with multiple catalysis, and between the active ingredient of difference in functionality, only have the attaching space of a sphere, influencing each other between therefore different active ingredients is very little.Such preparation method is favourable for Methanol for diesel oil.Moreover, because the endothermic process of methanolysis and the exothermic process of F-T synthesis are limited in carrying out in same granules of catalyst, the coupling process of Process of absorption or liberation of heat also will inevitably improve equilibrium conversion and the selectivity of product of reaction.
Summary of the invention
The object of the present invention is to provide a kind of can be the processing method of the high-quality diesel oil being rich in straight chain hydrocarbon by methanol conversion.The catalyzer used in this technique adopts shaping method of rolling to prepare, and in moulding process, introduce the auxiliary agent with heat conduction function, and this catalyzer kernel is the component with F-T synthesis function, and outer shell is the component with methanolysis 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 synthetic gas on a catalyst, is and then that synthetic gas changes diesel oil into through Fischer-Tropsch synthesis.The catalyzer of a kind of eggshell type provided by the invention, has decomposition methyl alcohol simultaneously and is the ability of synthetic gas and is the ability of diesel oil by Synthetic holography, so this catalyzer provided by the invention has bifunctional catalyzer.
Methanolysis is the reaction of synthetic gas is a reaction of absorbing heat, and synthetic gas is the process of a heat release through the process that F-T synthesis changes diesel component into, the present invention is exactly the method by roller forming, the component of two kinds of catalysiss is incorporated into same catalyst particles intragranular, and make them while each self-catalysis 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 selectivity of equilibrium conversion and target product.Therefore, the catalyzer of this eggshell type provided by the invention, not only has double-function catalyzing performance, also has the heat exchange function of coupling Process of absorption or liberation of heat process.
Egg-shell catalyst particle provided by the invention is rolling in shaping process, the powder with the active ingredient of different catalysis successively adds according to time sequence, first be that the powder of the component by having F-T synthesis function adds in nodulizer together with heat conduction auxiliary agent, after the thickness formed when this component reaches required numerical value, rolling is continued together with heat conduction auxiliary agent more shaping with the powder of the component with methanolysis function, after reaching required diameter to particle, shapingly to complete.
The active ingredient with F-T synthesis function mainly comprises the metal component that Fe and Co etc. has F-T synthesis activity, and what have methanolysis function can be the metal components such as Cu, Zn.
When using this dual-function catalyst, the synthetic gas produced iff utilizing methanolysis enters into granules of catalyst kernel by diffusion and carries out F-T synthesis again, the heat release of the heat absorption of methanolysis and F-T synthesis not mating in time can be caused, so that affect the effect of whole consecutive reaction.Therefore, in the first stage of reaction, need the parallel feeding first passing into synthetic gas (gas mixture of CO and H2) and methyl alcohol in reactor.Such as, start only to pass into synthetic gas, and methyl alcohol not charging (or methyl alcohol proportion is little), when the Fischer-Tropsch synthesis in kernel portion proceeds to a certain degree, pass into methanol feedstock again, and progressively improve methyl alcohol proportion in combined feed total feed, until synthetic gas inlet amount is zero.When improving the ratio of methyl alcohol in charging, the rate-controlling that methanol ratio improves is between per hour 7% to per hour 45%.
The invention provides a kind of is the technique of diesel oil by methanol conversion, owing to using a kind of dual-function catalyst with heat exchange function, makes this processing method simply effective.
Embodiment
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
To take density as the Alumina gel of 0.7g/ml and concentration be 5% aqueous nitric acid be mixed with tackiness agent (wherein Alumina gel and aqueous nitric acid volume ratio are 15:1), by uniform for ground and mixed cobalt oxide, aluminum oxide and graphite (Co:Al=1:9 mol ratio, the mass ratio of graphite and Co and Al oxide compound is 1:100) powder pour in A nodulizer, the tackiness agent sprayed into atomization contacts, roll shaping, when shaping spherolite radius reaches 2.5mm, spherolite enters after rolling out from A nodulizer in B nodulizer, the uniform cupric oxide of ground and mixed is had in B nodulizer, zinc oxide and aluminum oxide, and the powder of graphite (Cu:Zn:Al=1:1:6 mol ratio, graphite and Cu, the mass ratio of Zn and Al oxide compound is 1:5), be atomized under the tackiness agent effect sprayed into, continue to roll and be formed into the spherical of diameter 10mm, leave B nodulizer.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 methanolysis function is in the housing region between 2.5mm to 5mm at radius, heat conduction auxiliary agent graphite is then be distributed in whole particle.Spheroidal particle roasting at 400 DEG C after shaping, after 2 hours, is obtained spherical catalyst particles.It is in the fixed-bed reactor of 80mm that such granules of catalyst is loaded internal diameter, and height of formation is the beds of 320mm, and initial time, with air speed 1000h
-1synthetic gas (H2:CO=2 volume ratio) is passed in reactor, and start from scratch and increase the ratio of methyl alcohol in charging with the speedup of per hour 10% and (measure total inlet amount with the total mole number of methyl alcohol and synthetic gas, methyl alcohol accounts for the molecular fraction that the ratio of combined feed total feed and methyl alcohol account for total feed), 10 hours rear feedings are all methyl alcohol, at 225 DEG C, under the reaction conditions of 5MPa, react 24 constantly little, methanol conversion is 30%, in whole product, CO2 accounts for 25%, in hydrocarbon product, methane selectively is 11%, and more than C10 (represents diesel oil with more than C10 component here, selectivity down together) reaches 52%.
Embodiment 2
Catalyzer is with embodiment 1.It is in the fixed-bed reactor of 80mm that such granules of catalyst is loaded internal diameter, and height of formation is the beds of 320mm, and initial time, with air speed 1000h
-1synthetic gas (H2:CO=2 volume ratio) is passed in reactor, and start from scratch and increase the ratio of methyl alcohol in charging with the speedup of per hour 45% and (measure total inlet amount with the total mole number of methyl alcohol and synthetic gas, methyl alcohol accounts for the molecular fraction that the ratio of combined feed total feed and methyl alcohol account for total feed), 2 hours rear feedings are all methyl alcohol, at 215 DEG C, under the reaction conditions of 5MPa, react 24 constantly little, methanol conversion is 25%, in whole product, CO2 accounts for 26%, in hydrocarbon product, methane selectively is 13%, and the selectivity of more than C10 reaches 48%.
Claims (4)
1. methanol conversion is the technique of diesel oil by one kind, this technique is a consecutive reaction, first be methanolysis be synthetic gas, then be that synthetic gas changes the product being rich in diesel component into through F-T synthesis, it is characterized in that, a kind of difunctional solid catalyst that with the addition of the nucleocapsid structure of heat conduction auxiliary agent in moulding process is used in this technique, what distribute in the outer shell of this catalyzer is the catalytic active component with methanolysis function, and kernel portion is the catalytic active component with F-T synthesis function; And using this catalytic conversion methyl alcohol to be diesel oil process initial period, what pass in reactor is the mixing raw material of synthetic gas and methyl alcohol, and along with reaction is carried out, the ratio of methyl alcohol in parallel feeding increases in time gradually, until all charging is all methyl alcohol.
2. according to claim 1 a kind of be the technique of diesel oil by methanol conversion, it is characterized in that, the catalyst activity component with methanolysis function in the outer shell of the catalyst with core-casing structure of use contains one or several elements in Cu, Zn, Al and Si.
3. according to claim 1 a kind of be the technique of diesel oil by methanol conversion, it is characterized in that, the catalyst activity component with F-T synthesis function in the kernel of the catalyst with core-casing structure of use contains one or several elements in Co, Fe, Al and Si.
4. according to claim 1 a kind of be the technique of diesel oil by methanol conversion, it is characterized in that, the speed that the ratio of methyl alcohol in parallel feeding increases in time is gradually per hour 7% to per hour 45%.
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| CN104152172B true CN104152172B (en) | 2016-01-06 |
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| CN104162430A (en) * | 2014-09-09 | 2014-11-26 | 安徽工程大学 | Egg shell type catalyst |
| CN104162431A (en) * | 2014-09-09 | 2014-11-26 | 安徽工程大学 | Roll forming type egg shell type catalyst |
Citations (5)
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| CN101775310A (en) * | 2010-02-04 | 2010-07-14 | 山西天和煤气化科技有限公司 | Method of producing gasoline by fluidized bed process methanol |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN103071528A (en) * | 2013-01-21 | 2013-05-01 | 浙江大学 | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method |
| CN103212418A (en) * | 2013-04-25 | 2013-07-24 | 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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| US8137531B2 (en) * | 2003-11-05 | 2012-03-20 | Chevron U.S.A. Inc. | Integrated process for the production of lubricating base oils and liquid fuels from Fischer-Tropsch materials using split feed hydroprocessing |
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Patent Citations (5)
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| CN101775310A (en) * | 2010-02-04 | 2010-07-14 | 山西天和煤气化科技有限公司 | Method of producing gasoline by fluidized bed process methanol |
| CN101850259A (en) * | 2010-06-01 | 2010-10-06 | 上海华谊丙烯酸有限公司 | Preparation method of catalyst of acrolein through propylene oxidation at high airspeed |
| CN101947467A (en) * | 2010-09-14 | 2011-01-19 | 辽宁石油化工大学 | Preparation process for synthesizing catalyst for low-carbon olefin by carbon dioxide hydrogenation one-step method |
| CN103071528A (en) * | 2013-01-21 | 2013-05-01 | 浙江大学 | Core-shell structure catalyst and method for preparing low-carbon olefin by using synthetic gas one-step method |
| CN103212418A (en) * | 2013-04-25 | 2013-07-24 | 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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Inventor after: Zhao Jinling Inventor after: Wang Hongming Inventor after: Wang Anqiao Inventor before: Zhao Jinling Inventor before: Wang Hongming |
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Effective date of registration: 20151203 Address after: Jinghu Century City Jinghu District 241000 Anhui city of Wuhu province in the new Eaton mansion 23-1-3102 room Applicant after: WUHU NIUTAI INTELLECTURAL PROPERTY INFORMATION CONSULTANT CO., LTD Address before: 241000, green land No. 5, Jinghu District, Anhui, Wuhu, 23-1-3102 Applicant before: Zhao Jinling |
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