CN100435926C - Multiple molecule contacting catalytic reaction apparatus and method - Google Patents
Multiple molecule contacting catalytic reaction apparatus and method Download PDFInfo
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- CN100435926C CN100435926C CNB200610123282XA CN200610123282A CN100435926C CN 100435926 C CN100435926 C CN 100435926C CN B200610123282X A CNB200610123282X A CN B200610123282XA CN 200610123282 A CN200610123282 A CN 200610123282A CN 100435926 C CN100435926 C CN 100435926C
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Abstract
The present invention relates to multiple molecules contacting catalysis reaction, and provides multiple molecules contacting catalysis reaction apparatus and method with inhibition on catalyst poisoning and high reaction rate. The apparatus is provided with a reaction container, a catalyst bed in the middle inside the container, and at least one material duct, which is set vertically inside the container with the bottom on the catalyst bed. The material duct has holes in the end near to the catalyst bed. During reaction, the catalyst bed is filled with catalyst, the material duct has the holes located inside the catalyst bed, the material is divided into two parts including one part flowing out through the outlet continuously and the other part flowing into the catalyst bed through the duct, and the reaction conditions are set properly.
Description
Technical field
The present invention relates to a kind of multiple molecule contacting catalytic reaction unit and reaction method.
Background technology
" polymolecular " refers to the molecular species that is transformed and has two kinds at least in chemical reaction, " contact catalysis " refers at least a molecule that is transformed and contacts with catalyst and become atom (to comprise ion by cracking catalyst, together following) or atomic radical, this atom or atomic radical contact generation novel species quasi-molecule with atom or the atomic radical that other molecules or its cracking form again.As everyone knows, the multiple molecule contacting catalytic that carries out in the reactor of reaction mass continuous-flow generally is to carry out in the following manner: the material that all reaction moleculars are formed at first mixes again and flows to reactor outlet by reactor inlet through beds, and require mixed material to tend to piston flow (claiming laminar flow again) flowing of beds as far as possible, make each material micelle reach unanimity, to improve general reaction efficient in the time of staying of beds.The multiple molecule contacting catalytic method that the reverse flow of patent proposition reaction mass is arranged recent years, as patent CN02133135.9, CN03133543.8 and CN03133565.9.Specifically be, contain two class materials in the reaction mass, a class material is " liquid " state under reaction condition, and another kind of material is " gas " state, liquid material flows to the reactor below by the reactor top, and gas material flows to the reactor top by the reactor below.But which kind of material all travels through whole beds, if contain the poisonous substance that can make catalyst poisoning in a certain material, then the catalyst of whole bed all will be poisoned, and reactivity is descended significantly.For example, reaction has very high activity to the metallic nickel catalyst for aromatic hydrogenation, but when containing micro-organic sulfur such as thiophene in the aromatic hydrocarbons material, catalyst will be caused reactivity to descend by poisoning.
Summary of the invention
Purpose of the present invention aims to provide a kind of multiple molecule contacting catalytic reaction unit and reaction method thereof that suppresses catalyst poisoning, improves catalyst reaction efficient.
A kind of multiple molecule contacting catalytic reaction unit of the present invention is provided with cylindricality reaction vessel, at least 1 material conduit and catalyst bed, the material conduit is arranged in the reaction vessel from the upper end edge vertical direction of reaction vessel, material conduit bottom is fixed on the catalyst bed, and catalyst bed is positioned at the reaction vessel middle part.Establish at least 2 perforates by on the material catheter wall of catalyst bed one end, perforate is presented along material conduit vertical direction and is dredged close distribution down, then is symmetrical distribution on the horizontal direction; Opening diameter is less than catalyst granules.
The concrete quantity of material conduit is determined by reaction vessel sectional area size; The reaction vessel sectional area is big more, and then required material conduit quantity is many more.Perforate quantity is determined by the material catheter outer surface is long-pending, for concerning along becoming.
A kind of multiple molecule contacting catalytic reaction method of the present invention the steps include:
1) loading catalyst on the catalyst bed of multiple molecule contacting catalytic reaction unit allows the supravasal perforate of material be in the catalyst layer;
2) reaction mass is divided into two strands, and enter beds in the reaction vessel by different way, wherein one material adopts common axial continuous-flow mode to be flowed out from the device outlet via beds by reactor inlet again, and another strand material directly enters beds by the material conduit;
3) requiring that according to reaction reaction condition is set reacts.
Material share split principle is: wherein one material (being made as A-share) contains the poisonous substance that makes catalyst poisoning, and another strand (being made as the B thigh) then do not contain the poisonous substance that makes catalyst poisoning.The A-share material is continuously flowed into by the reaction unit inlet, and B thigh material is then imported continuously by the material conduit.So, form a special area at every material catheter wall tapping; In this zone, the low and B thigh material concentration height of A-share material concentration (comprising TC), thereby the poisonous substance in the A-share material reduces significantly in this regional poisoning effect.
For organic hydrogenation catalyst reaction, multiple molecule contacting catalytic reaction unit provided by the invention has following advantage:
1. the modulation of distribution by material conduit position of opening and hydrogen temperature of charge can be controlled the Temperature Distribution of reaction bed flexibly.
2. the perforate of material conduit distributes to adopt and goes up the reaction efficiency that thin close mode down can promote catalyst rear portion bed.
3. the catalyst poisoning effect reduces significantly.
Description of drawings
Fig. 1 is a multiple molecule contacting catalytic reaction unit structural representation of the present invention.
The experimental provision structural representation that Fig. 2 uses conventional axial to mix and flow for comparative example.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
Referring to Fig. 1, described multiple molecule contacting catalytic reaction unit comprises cylindricality reaction vessel 1, material conduit 2 and catalyst bed 3, material conduit 2 is arranged in the reaction vessel from the upper end edge vertical direction of reaction vessel 1, material conduit 2 bottoms are fixed on the catalyst bed 3, and catalyst bed 3 is positioned at the reaction vessel middle part.Establish at least 2 perforates 4 by on the catheter wall of catalyst bed one end, perforate 4 is presented along material conduit 2 vertical direction and is dredged close distribution down, then is symmetrical distribution on the horizontal direction; Perforate 4 diameters are less than catalyst granules.
Reaction is adopted and is contained B
2O
3The nickel-base catalyst of 4.7% (wt) during loading catalyst, is respectively adorned a small amount of quartz sand or porcelain ring (ball) 5 in two ends up and down at beds, and the perforate 4 on the material conduit 2 is in the catalyst layer.Be 30000h at first in 300 ℃, 0.5MPa and gas volume air speed
-1The following reduction 3h of hydrogen.Reaction raw materials is for containing 300 μ gg
-1The ethylbenzene A of thiophene adopts common axial continuous-flow mode from top to bottom to be flowed out from the device outlet via beds by reactor inlet again, and another strand material hydrogen B then directly enters beds by material conduit 2.200 ℃ of reaction temperatures, pressure 1.0MPa, ethylbenzene liquid volume air speed is 30h
-1, the hydrogen volume air speed is 30000h
-1, sample analysis behind the reaction 2.5h, purpose product ethyl cyclohexane C yield is listed in table 1.
The aromatic hydrocarbons that contains organic sulfur during reaction is as the A-share material, and hydrogen is as B thigh material.Form an aromatic hydrocarbons and organic sulfur concentration is low and zone that density of hydrogen is high at every material catheter wall tapping, the probability that the metal hydrogenation catalyst in this zone is poisoned by organic sulfur in the aromatic hydrocarbons greatly descends.Again because the existence of hydrogen overflow effect, hydrogen is moved to the outer and aromatic hydrocarbons in zone boundary or zone and is carried out haptoreaction, thereby improved aromatic hydrogenation catalytic reaction efficient on the whole after absorption on this regional catalyst is dissociated.
Adopt the multiple molecule contacting catalytic reaction unit of embodiment 1 to react, change the hydrogen volume air speed and be respectively 15000h
- 1And 45000h
-1, the remaining reaction condition is with embodiment 1, and the ethyl cyclohexane yield is listed in table 1.
Comparative example 1
Conventional apparatus is as shown in Figure 2 adopted in reaction, during reaction hydrogen B with contain 300 μ gg
-1The ethylbenzene A of thiophene is mixed together the back by reactor 6 inlet axially and flow to into beds 7, and the remaining reaction condition is with embodiment 1, and the ethyl cyclohexane yield is listed in table 1.
Comparative example 2～3
Change the hydrogen volume air speed and be respectively 15000h
-1And 45000h
-1, all the other are with Comparative Examples 1, and the ethyl cyclohexane yield is listed in table 1.
Table 1. embodiment 1～3 and comparative example 1～3 result of the test
| Embodiment | Hydrogen volume air speed/h -1 | Ethyl cyclohexane yield/% | Comparative example | Hydrogen volume air speed/h -1 | Ethyl cyclohexane yield/% |
| Embodiment 1 | 30000 | 82.6 | Comparative example 1 | 30000 | 75.1 |
| |
15000 | 79.9 | Comparative example 2 | 15000 | 72.8 |
| Embodiment 3 | 45000 | 86.0 | Comparative example 3 | 45000 | 79.6 |
Claims (1)
1. multiple molecule contacting catalytic reaction unit, it is characterized in that being provided with cylindricality reaction vessel, at least 1 material conduit and catalyst bed, the material conduit is arranged in the reaction vessel from the upper end edge vertical direction of reaction vessel, material conduit bottom is fixed on the catalyst bed, catalyst bed is positioned at the reaction vessel middle part, establishes at least 2 perforates by on the material catheter wall of catalyst bed one end; Perforate on the material catheter wall is presented along material conduit vertical direction and is dredged close distribution down, then is symmetrical distribution on the horizontal direction; Opening diameter on the material catheter wall is less than catalyst granules.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610123282XA CN100435926C (en) | 2006-11-03 | 2006-11-03 | Multiple molecule contacting catalytic reaction apparatus and method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200610123282XA CN100435926C (en) | 2006-11-03 | 2006-11-03 | Multiple molecule contacting catalytic reaction apparatus and method |
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| CN1973985A CN1973985A (en) | 2007-06-06 |
| CN100435926C true CN100435926C (en) | 2008-11-26 |
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| CNB200610123282XA Expired - Fee Related CN100435926C (en) | 2006-11-03 | 2006-11-03 | Multiple molecule contacting catalytic reaction apparatus and method |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0442164A1 (en) * | 1990-01-10 | 1991-08-21 | Shell Internationale Researchmaatschappij B.V. | Fixed bed reactor |
| JPH03238036A (en) * | 1990-02-14 | 1991-10-23 | Toshiba Corp | Fuel reforming apparatus |
| US5112578A (en) * | 1988-04-12 | 1992-05-12 | Mitsubishi Gas Chemical Company, Inc. | Reactor for reforming hydrocarbon and process for reforming hydrocarbon |
| CN1527742A (en) * | 2000-12-22 | 2004-09-08 | 环球油品公司 | Simplified plate channel reactor design |
| CN1788835A (en) * | 2004-12-14 | 2006-06-21 | 杭州林达化工技术工程有限公司 | Transverse pipe type heat transfer reaction unit |
-
2006
- 2006-11-03 CN CNB200610123282XA patent/CN100435926C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5112578A (en) * | 1988-04-12 | 1992-05-12 | Mitsubishi Gas Chemical Company, Inc. | Reactor for reforming hydrocarbon and process for reforming hydrocarbon |
| EP0442164A1 (en) * | 1990-01-10 | 1991-08-21 | Shell Internationale Researchmaatschappij B.V. | Fixed bed reactor |
| JPH03238036A (en) * | 1990-02-14 | 1991-10-23 | Toshiba Corp | Fuel reforming apparatus |
| CN1527742A (en) * | 2000-12-22 | 2004-09-08 | 环球油品公司 | Simplified plate channel reactor design |
| CN1788835A (en) * | 2004-12-14 | 2006-06-21 | 杭州林达化工技术工程有限公司 | Transverse pipe type heat transfer reaction unit |
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| CN1973985A (en) | 2007-06-06 |
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Granted publication date: 20081126 Termination date: 20111103 |