CN104162430A - Egg shell type catalyst - Google Patents
Egg shell type catalyst Download PDFInfo
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- CN104162430A CN104162430A CN201410451831.0A CN201410451831A CN104162430A CN 104162430 A CN104162430 A CN 104162430A CN 201410451831 A CN201410451831 A CN 201410451831A CN 104162430 A CN104162430 A CN 104162430A
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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
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- 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
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Abstract
The invention relates to an egg shell type catalyst which has a core-shell structure; the catalyst can be used in a methanolysis process with coupling heat absorption and a Fischer-Tropsch synthesis process with heat release, so that methyl alcohol is directly converted into diesel fraction; and a shell layer of the egg shell type catalyst is made of a catalyst component with a methanolysis function, and an inner core of the egg shell type catalyst is made of a catalyst component with a Fischer-Tropsch synthesis function.
Description
Technical field
The invention provides a kind of catalyst of eggshell type, be specifically related to a kind of solid catalyst with nucleocapsid structure for Methanol diesel oil.
Background technology
In chemical reaction, can be with the generation of 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 that the reaction (CH3OH → CO+2H2) of synthesis gas is the reaction of a heat absorption, on Cu-series catalyst, carries out.Consider from thermodynamics, high temperature is conducive to methyl alcohol to carry out to the direction that is decomposed into synthesis gas, but rising temperature need to consume more heat energy, therefore in actual industrial process, from application of engineering project, methyl alcohol is decomposed into the reaction temperature of synthesis gas between 200 DEG C to 280 DEG C under catalyst action.
The process of a heat release by synthesis gas through the synthetic process of producing diesel component of Fischer-Tropsch, how on Co series catalysts, to carry out, consider from improving the selective angle of diesel component, cryogenic high pressure is conducive to the synthetic diesel oil of producing of Fischer-Tropsch, so in actual production operating process, Fischer-Tropsch is synthetic also between 200 DEG C to 250 DEG C, and takes reaction heat out of reactor by various heating picking process.
The synthesis gas that Methanol Decomposition is obtained is through the synthetic diesel oil that changes into of Fischer-Tropsch, this process route is in the relatively oversaturated situation in coal methyl alcohol processed market, a part of methanol conversion can be become to diesel fuel, form one parallel mutually with preparing gasoline by methanol technique, widen the new technology of the application surface of Coal Chemical Industry.This technique needs the catalyst synergy of two kinds of effects, namely carbinol resolving catalyst and fischer-tropsch synthetic catalyst, and bifunctional catalyst is a kind of approach that realizes this technique.The method of preparing bifunctional catalyst has multiple, has plenty of the component with different catalysis is evenly mixed to moulding, for example powder blend aftershaping or the preparation of total immersion stain.The catalyst of preparing by the way, the effect of influencing each other between wherein each kind of component has often changed the function of original active component existing with independent form, the function that is to say the catalyst forming after mixing is not the original stack of catalysis separately, but the change of matter has occurred.Obviously for Methanol Decomposition preparing synthetic gas again Fischer-Tropsch synthetic the technique of diesel oil, such method for preparing catalyst is inappropriate.And the another kind of method of preparing bifunctional catalyst is the catalyst with nucleocapsid structure that adopts the method for rolling moulding to prepare.In the process of rolling moulding, different time adds the powder that contains different activities component, can in catalyst granules, form the structure with radially layered, different activities component is distributed in different radial depths, this has also just formed the zones of different in same catalyst granules with multiple catalysis, and between the active component of difference in functionality, only have the attaching space of a sphere, therefore between different active components influence each other very little.Such preparation method is favourable for Methanol for diesel oil.
Summary of the invention
The object of the present invention is to provide a kind of can be the egg-shell catalyst with nucleocapsid structure that is rich in the high-quality diesel oil of straight-chain hydrocarbons by methanol conversion.This catalyst is to adopt the method for rolling moulding to prepare, and kernel is for having Fischer-Tropsch complex functionality catalytic component, and outer shell is the catalytic active component with Methanol Decomposition function.
Methyl alcohol being changed into the process of diesel oil, is the consecutive process being cascaded by two reactions in fact, is first that methyl alcohol is decomposed into synthesis gas on catalyst, is and then that synthesis gas changes diesel oil into through Fischer-Tropsch synthesis.The catalyst of a kind of eggshell type provided by the invention has the ability of decomposing the ability that methyl alcohol is synthesis gas and synthesis gas being converted into diesel oil, so this catalyst provided by the invention is to have bifunctional catalyst simultaneously.
Methanol Decomposition is that the reaction of synthesis gas is the reaction of a heat absorption, and synthesis gas is the process of a heat release through the synthetic process that changes diesel component into of Fischer-Tropsch, the present invention is exactly the method by roller forming, the component of two kinds of catalysis is incorporated into same catalyst particles intragranular, and make them in the each autocatalysis of performance, the reaction heat that allows the methanol decomposition reaction of carrying out in kernel utilize Fischer-Tropsch in shell to discharge in synthetic, realize the coupling of heat absorption and release process, thereby in reducing whole process energy consumption, improve the selective of equilibrium conversion and target product.Therefore, the catalyst 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 in the process of rolling moulding, the powder with the active component of different catalysis successively adds according to time sequencing, first be that the powder of the component with Fischer-Tropsch complex functionality is added in nodulizer, the thickness forming when this component reaches after required numerical value, continue rolling moulding with the powder of the component with Methanol Decomposition function again, reach after required diameter to particle, moulding completes.
The catalyst that the invention provides a kind of eggshell type can be converted into methyl alcohol the product that is rich in diesel component.Except having the characteristic of double-function catalyzing, be coupled the in addition heat exchange function of Process of absorption or liberation of heat of the present invention, 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 are only for the present invention that explains in detail, and limit the scope of the invention never in any form.
Embodiment 1
Aluminium colloidal sol taking density as 0.7g/ml and concentration are mixed with adhesive (wherein aluminium colloidal sol and aqueous solution of nitric acid volume ratio are 15:1) as 5% aqueous solution of nitric acid, the powder of uniform ground and mixed cobalt oxide and aluminium oxide (Co:Al=1:9 mol ratio) is poured in A nodulizer, the adhesive spraying into atomization contacts, rolling moulding, in the time that the spherolite radius of moulding reaches 2.5mm, spherolite enters in B nodulizer after rolling out from A nodulizer, in B nodulizer, there is the uniform cupric oxide of ground and mixed, the powder (Cu:Zn:Al=1:1:6 mol ratio) of zinc oxide and aluminium oxide, under the adhesive effect spraying in atomization, continue to roll and be formed into the spherical of diameter 10mm, leave B nodulizer.Now there is the Active components distribution of Fischer-Tropsch complex functionality in the kernel area of radius≤2.5mm, and the Active components distribution with Methanol Decomposition function at radius in the shell region between 2.5mm to 5mm.The roasting at 400 DEG C of spheric granules after moulding, after 2 hours, is obtained to spheric catalyst particle.Such catalyst granules is packed in the fixed bed reactors that internal diameter is 80mm, height of formation is the beds of 320mm, flow with 1000ml/min passes into methyl alcohol, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 28%, all in product, CO2 accounts for 21%, and in hydrocarbon product, methane selectively is 14%, and C10 above (represent diesel oil with the above component of C10 here, lower together) selectively reach 45%.
Comparative example 1
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, pour in nodulizer, spray into atomization, the adhesive (wherein aluminium colloidal sol is 15:1 with aqueous solution of nitric acid volume ratio) that aluminium colloidal sol taking density as 0.7g/ml is mixed with as 5% aqueous solution of nitric acid with concentration contacts, rolling is shaped to the spherical particle that diameter is 10mm, through 400 DEG C of roastings globulate catalyst granules after 2 hours.Such catalyst granules is packed in the fixed bed reactors that internal diameter is 80mm, height of formation is the beds of 320mm, flow with 1000ml/min passes into methyl alcohol, at 225 DEG C, under the reaction condition of 5MPa, methanol conversion is 3.5%, all in product, CO2 accounts for 45%, in hydrocarbon product, methane be selectively 23%, and more than C10 be selectively 18%.
Claims (3)
1. the catalyst of an eggshell type, there is 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 building-up process of heat release, methyl alcohol can be converted into diesel oil distillate, its outer shell is the catalytic component with Methanol Decomposition function, and kernel is the catalytic component with Fischer-Tropsch complex functionality.
2. the catalyst of a kind of eggshell type 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 eggshell type according to claim 1, is characterized in that, the active component in kernel with Fischer-Tropsch complex functionality catalyst contains one or several elements in Co, Fe, Al and Si.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410451831.0A CN104162430A (en) | 2014-09-09 | 2014-09-09 | Egg shell type catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410451831.0A CN104162430A (en) | 2014-09-09 | 2014-09-09 | Egg shell type catalyst |
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| Publication Number | Publication Date |
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| CN104162430A true CN104162430A (en) | 2014-11-26 |
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| CN201410451831.0A Pending CN104162430A (en) | 2014-09-09 | 2014-09-09 | Egg shell type catalyst |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824197A (en) * | 2017-02-04 | 2017-06-13 | 厦门大学 | A kind of synthesis gas prepares catalyst of MAS and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492074A (en) * | 2011-04-26 | 2014-01-01 | 韩国化学研究院 | Catalyst for fischer-tropsch synthesis having excellent heat transfer capability |
| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
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2014
- 2014-09-09 CN CN201410451831.0A patent/CN104162430A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103492074A (en) * | 2011-04-26 | 2014-01-01 | 韩国化学研究院 | Catalyst for fischer-tropsch synthesis having excellent heat transfer capability |
| CN103920496A (en) * | 2014-04-22 | 2014-07-16 | 武汉凯迪工程技术研究总院有限公司 | Mesoporous material coated cobalt-based fischer-tropsch synthesis catalyst and preparation method thereof |
| CN104152172A (en) * | 2014-09-08 | 2014-11-19 | 赵锦玲 | Process for converting methanol into diesel |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106824197A (en) * | 2017-02-04 | 2017-06-13 | 厦门大学 | A kind of synthesis gas prepares catalyst of MAS and preparation method thereof |
| CN106824197B (en) * | 2017-02-04 | 2019-03-05 | 厦门大学 | A kind of catalyst and preparation method thereof of synthesis gas preparation low carbon mixed alcohol |
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Application publication date: 20141126 |