CN103301786A - Fluidized bed reactor, butadiene and preparation method thereof - Google Patents
Fluidized bed reactor, butadiene and preparation method thereof Download PDFInfo
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- CN103301786A CN103301786A CN201210068959XA CN201210068959A CN103301786A CN 103301786 A CN103301786 A CN 103301786A CN 201210068959X A CN201210068959X A CN 201210068959XA CN 201210068959 A CN201210068959 A CN 201210068959A CN 103301786 A CN103301786 A CN 103301786A
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Abstract
The invention relates to a fluidized bed reactor, butadiene and a preparation method thereof. The fluidized bed reactor comprises a body, wherein at least two reaction spaces are defined in the body along the longitudinal direction; the adjacent reaction spaces are communicated with each other; catalysts are arranged in the reaction spaces; and the filling amount and the reaction temperature of the catalysts in the adjacent reaction spaces can be different. By utilizing the fluidized bed reactor, the raw material conversion rate and the product selectivity can be improved.
Description
Technical field
The present invention relates to chemical field, especially relate to fluidized-bed reactor, butadiene and preparation method thereof.
Background technology
Butadiene is a kind of important petrochemical industry basic organic material and polymer monomer, and the status in the petrochemical industry olefin feedstock is only second to ethene and propylene, and purposes is very extensive.It not only can be for the production of multiple rubber and naval stores such as synthetic butadiene rubber (BR), butadiene-styrene rubber (SBR), acrylonitrile-butadiene rubber, SBS elastomer (SBS), acrylonitrile-butadiene-styrene (ABS) (ABS) resins, can also be for the production of Organic chemical products such as adiponitrile, BDO, anthraquinone, sulfolane, THPA, higher alcohol and macrocyclic musks.Therefore, produce efficiently butadiene significant.
Present stage, butadiene derives from oil C
4The extracting of cut.Because the petroleum resources of China are day by day deficient, cause the butadiene price to rise steadily and supply having risk.Along with the continuous maturation of coal acetylene new technology processed, acetylene might become cheap industrial chemicals.At present, acetylene is except mainly for the production of the vinyl chloride, the vinylacetylene that its dimerization reaction makes, can be used for the production of the chemical products such as neoprene, 4-chloro-benzoic anhydride and vinyl polymer, and vinylacetylene selects hydrogenation can obtain butadiene, and this technique can realize being that raw material is produced butadiene take coal as the source by acetylene.In addition, oil C
4In the extractive process of cut, also can obtain the higher vinylacetylene of concentration, can produce butadiene by selecting hydrogenation equally.
Yet the means of producing at present butadiene still remain to be improved.
Summary of the invention
The present invention is intended to solve at least one of technical problem that exists in the prior art.
The present invention is based on that inventor's following discovery finishes: the vinylacetylene hydrogenation reaction is strong exothermal reaction, traditional fixed bed device makes the catalyst granules temperature far above the temperature in the reactor owing to moving the heat difficulty, accelerate thus the inactivation of catalyst, increased the production cost of butadiene.Simultaneously, catalyst is tight in the fixed bed, and bed pressure drop is high, and raw material passes in the reactor with higher pressure usually, and vinylacetylene easy polymerization reaction take place under elevated pressures.Compare with fixed bed reactors, the fluidized-bed reactor heat transfer efficiency is high, and bed temperature is easily controlled, but common fluidised bed material back-mixing is serious, and the poor selectivity of product easily produces accessory substance.
For this reason, the present invention proposes a kind of fluidized-bed reactor, butadiene goods and method for preparing butadiene that can be used for the vinylacetylene hydrogenation reaction.
In one aspect of the invention, the present invention proposes a kind of fluidized-bed reactor.According to embodiments of the invention, this fluidized-bed reactor comprises: body longitudinally be limited with at least two reaction compartments in described body, and adjacent reaction compartment communicates with each other.Thus, can in this fluidized-bed reactor, realize the multistage chemical reaction, improve reaction efficiency.Especially, when this fluidized-bed reactor being applied to the vinylacetylene hydrogenation reaction preparing butadiene, can avoid excessive hydrogenation, thereby improve the selective of product butadiene.
In a second aspect of the present invention, the present invention proposes a kind of method for preparing butadiene.According to embodiments of the invention, the method comprises: make vinylacetylene and hydrogen carry out hydrogenation reaction at least two reaction compartments, in order to obtain butadiene, wherein, be provided with catalyst in the described reaction compartment, and the adjacent reaction space requires to arrange best reaction temperature and loaded catalyst according to kinetics, can improve reaction efficiency thus, and the fluidised mode of operation of segmentation can reduce the material back-mixing, and then can avoid excessive hydrogenation, thereby improve the selective of product butadiene.
In a third aspect of the present invention, the present invention proposes a kind of butadiene goods.According to of the present invention be example, these butadiene goods prepare according to foregoing method.
According to embodiments of the invention, to compare with fluidized-bed process with traditional fixed bed, fluidized-bed reactor of the present invention has one of following advantages at least:
1. compare with traditional fixed-bed process, heat-transfer capability is stronger, does not have catalyst over-heat inside phenomenon, can suppress the catalyst activity component and run off, and has improved catalyst life.
2. compare with traditional fixed-bed process, the beds pressure drop is little, and is low to the feed pressure requirement, thereby is conducive to reduce the polymerization of raw material vinylacetylene, and then strengthened the security of operation.
3. compare with traditional fluidized-bed process, be provided with a plurality of reaction compartments in the fluidized-bed reactor of the present invention, can reduce the back-mixing of material, make and react to carry out near plug flow mode, thereby can reduce the generation of accessory substance, and then improve the selective of product.
4. compare with traditional fluidized-bed process, be provided with a plurality of reaction compartments in the fluidized-bed reactor of the present invention, by regulating catalyst that each reaction compartment holds and the reaction temperature of employing, can control feed stock conversion and the selectivity of product of each reaction compartment, thereby can strengthen the operating flexibility of technique, be conducive to improve reaction efficiency.
Additional aspect of the present invention and advantage in the following description part provide, and part will become obviously from the following description, or recognize by practice of the present invention.
Description of drawings
Above-mentioned and/or additional aspect of the present invention and advantage are from obviously and easily understanding becoming the description of embodiment in conjunction with following accompanying drawing, wherein:
Fig. 1 is the structural representation of fluidized-bed reactor according to an embodiment of the invention.
The specific embodiment
The below describes embodiments of the invention in detail, and the example of described embodiment is shown in the drawings, and wherein same or similar label represents same or similar element or the element with identical or similar functions from start to finish.Be exemplary below by the embodiment that is described with reference to the drawings, only be used for explaining the present invention, and can not be interpreted as limitation of the present invention.
In description of the invention, term " vertically ", " laterally ", " on ", orientation or the position relationship of the indications such as D score, 'fornt', 'back', " left side ", " right side ", " vertically ", " level ", " top ", " end " be based on orientation shown in the drawings or position relationship, only be for convenience of description the present invention rather than require the present invention with specific orientation structure and operation, therefore can not be interpreted as limitation of the present invention.Employed term " a plurality of " refers to two or more in this article.Term used in the present invention " upstream ", " downstream " refer to the upstream and downstream of technological process.
With reference to figure 1, the present invention proposes a kind of fluidized-bed reactor 1000.According to embodiments of the invention, this fluidized-bed reactor 1000 comprises body 100 and at least two reaction compartments 101.Wherein, these reaction compartments be arranged in the body 100 vertically on, and adjacent reaction compartment 101 communicates with each other.According to embodiments of the invention, in each reaction compartment 101, be provided with catalyst, and the reaction condition in the adjacent reaction space 101 can be different.According to embodiments of the invention, the reaction condition difference here can be different for reaction temperature, perhaps the amount of setting of catalyst difference.Preferably, according to embodiments of the invention, along the longitudinal direction, from bottom to top, the amount of setting of catalyst or temperature raise successively in the reaction compartment.
Utilize this fluidized-bed reactor, can avoid catalyst overheating to delay its inactivation by fluidised reactive mode, in addition, owing to useful load and the reaction temperature of catalyst can be regulated and control, thereby can realize improving the purpose of reaction efficiency.Especially, when this fluidized-bed reactor being applied to the vinylacetylene hydrogenation reaction preparing butadiene, can improve the vinylacetylene conversion ratio, can avoid excessive hydrogenation simultaneously, thereby improve the selective of product butadiene.
According to embodiments of the invention, in body 100, limit the means of a plurality of reaction compartments 101 and be not particularly limited.According to one embodiment of present invention, can be by 100 kinds of bodies a plurality of gas distribution grids 200 being set, in order in body 100, form a plurality of reaction compartments 101, and according to embodiments of the invention, be formed with through hole 300 at gas distribution grid 200, thus, can be so that adjacent reaction compartment communicates with each other.In addition, according to embodiments of the invention, catalyst can be arranged on the gas distribution grid 200.According to embodiments of the invention, the type of gas distribution grid and number also are not particularly limited, and according to examples more of the present invention, are provided with three gas distribution grids 200 in the body 100, thus, and can be easily at three reaction compartments 101 of body 100 interior formation.According to embodiments of the invention, the type of gas distribution grid 200 can include but not limited to straight hole sieve plate, matrix straight hole sieve plate, straight hole bubble cap distribution grid, bar shaped latasuture distribution grid, cone cap latasuture distribution grid.It will be appreciated by persons skilled in the art that the combination that to adopt the multiple gases distribution grid, in order to form a plurality of reaction compartments 101.
According to embodiments of the invention, can be applied to the embodiment of the invention fluid bed catalyst type and be not particularly limited.According to embodiments of the invention, can adopt load type metal catalyst.According to embodiments of the invention, the reactive metal of load type metal catalyst is be selected from Pd, Cu, Ni, Pt, Ir, Ru, Mo, Co, Ga, Sn, Ag, Pt, Au, In, Sb, Ge, Bi, Fe and Pb at least a, and the carrier of load type metal catalyst is for being selected from Al
2O
3, SiO
2, TiO
2, ZnO, MgO, CaCO
3, molecular sieve, Graphene, carbon pipe and active carbon at least a, the preferred load type metal catalyst that adopts is Pd/ α-Al
2O
3Catalyst.Thus, can effectively in the fluidized-bed reactor of the embodiment of the invention, realize the vinylacetylene hydrogenation, thereby obtain butadiene.According to embodiments of the invention, for load type metal catalyst, in different reaction compartments, the loadings of catalyst can be different.In according to example of the present invention, in body 100, longitudinally be limited with three reaction compartments 101, longitudinally from bottom to top, and in the reaction compartment 101, Pd/ α-Al
2O
3The loadings of catalyst is respectively 400kg, 500kg and 600kg.
Fluidized-bed reactor 1000 can also have other annexes according to an embodiment of the invention, in order to provide extra beneficial effect for fluidized-bed reactor.According to one embodiment of present invention, in each reaction compartment 101, be respectively arranged with temperature control modules 700.Thus, can easily control and regulate the temperature in each reaction compartment 101, effectively carry out in order to realize the reaction in each reaction compartment 101.According to embodiments of the invention, the type of temperature control modules also is not particularly limited, and according to a particular embodiment of the invention, temperature control modules 700 can be serpentine heat exchanger or tube bundle heat exchanger.Thus, can regulate the temperature in each reaction compartment 101 easily.According to embodiments of the invention, the setting position of temperature control modules 700 also is not particularly limited, can select easily setting position according to the type of temperature control modules, for coil heat exchanger, can be arranged on the sidewall of reaction compartment, for tube bundle heat exchanger, reaction compartment inside can be set.It will be appreciated by persons skilled in the art that the combination that to adopt the various temperature control module.
According to embodiments of the invention, longitudinally from bottom to top, the temperature in the reaction compartment 101 can be different.Thus, can be according to the reaction temperature in preferred each reaction compartment of kinetics feature, thus realize improving the purpose of feed stock conversion and target product selectivity.According to a particular embodiment of the invention,, be provided with three reaction compartments 101 longitudinally from bottom to top, and the temperature in the reaction compartment is respectively 26 degrees centigrade, 28 degrees centigrade and 30 degrees centigrade.Thus, can effectively carry out the vinylacetylene hydrogenation, thereby obtain butadiene.
According to embodiments of the invention, feed(raw material)inlet 500 and catalyst outlet 800 can be arranged on the bottom of body 100.According to embodiments of the invention, the discharging opening 600 of reaction product gas can be arranged on the top of body 100.Thus, can effectively improve the efficient of reaction.In addition, according to embodiments of the invention, discharging opening 600 may further include gas-solid separating device, can further improve thus the purity of resulting product gas.According to embodiments of the invention, the type of gas-solid separating device also is not particularly limited, and can be cyclone separator, sack cleaner or electric cleaner.In addition, can also in each reaction compartment 101, be provided with catalyst charging hole, so that loading catalyst in reaction compartment easily.
According to embodiments of the invention, overflow pipe 900 can be arranged on inside or the outside of reactor 1000 cylindrical shells.When the catalyst height surpasses this section reaction compartment overflow pipe top, turned back to the reaction compartment of bottommost on the reactor longitudinal direction by corresponding overflow pipe, randomly, also can catalyst be back in other reaction compartments by overflow pipe.
In another aspect of this invention, a kind of method for preparing butadiene has been proposed.According to embodiments of the invention, the method comprises makes vinylacetylene and hydrogen carry out hydrogenation reaction at least two reaction compartments, in order to obtain butadiene, wherein, is provided with catalyst in the reaction compartment.According to embodiments of the invention, the reaction condition in the adjacent space can be different, and according to embodiments of the invention, the reaction condition difference can be that reaction temperature is different, also can be the amount of the setting difference of catalyst.
According to embodiments of the invention, can be applied to according to the catalyst type of the method for preparing butadiene of the embodiment of the invention and be not particularly limited.According to embodiments of the invention, can adopt load type metal catalyst.According to example of the present invention, catalyst is load type metal catalyst.According to embodiments of the invention, the reactive metal of load type metal catalyst is be selected from Pd, Cu, Ni, Pt, Ir, Ru, Mo, Co, Ga, Sn, Ag, Pt, Au, In, Sb, Ge, Bi, Fe and Pb at least a, and the carrier of load type metal catalyst is for being selected from Al
2O
3, SiO
2, TiO
2, ZnO, MgO, CaCO
3, molecular sieve, Graphene, carbon pipe and active carbon at least a, the preferred load type metal catalyst that adopts is Pd/ α-Al
2O
3Catalyst.Thus, can effectively, realize the vinylacetylene hydrogenation, thereby obtain butadiene.
In addition, according to embodiments of the invention, along the direction of technological process, to the downstream, the temperature in the described reaction compartment can be optimized regulation and control from the upstream.According to a specific embodiment, from the upstream to the downstream, three reaction compartments are set, and the temperature in the reaction compartment can be respectively 22-28 degree centigrade, 25-30 degree centigrade and 30-35 degree centigrade, and the temperature in preferred three reaction compartments is respectively 26 degrees centigrade, 28 degrees centigrade and 30 degrees centigrade.Thus, can effectively carry out the vinylacetylene hydrogenation, thereby obtain butadiene.
According to embodiments of the invention, in the method for preparing butadiene of the present invention, vinylacetylene is with form and the hydrogen generation hydrogenation reaction of the mixture of vinylacetylene and inert gas, and wherein, this mixture can comprise: the vinylacetylene of 20-90 parts by volume; And the inert gas of 10-80 parts by volume.According to embodiments of the invention, the type of inert gas is not particularly limited.According to concrete examples more of the present invention, inert gas can be for being selected from least a of nitrogen, argon gas and butane.
According to embodiments of the invention, carry out hydrogenation reaction a plurality of reaction compartments setting and be not particularly limited, both can be a plurality of reaction compartments that directly link to each other, also can be a plurality of reaction compartments that indirectly link to each other.According to one embodiment of present invention, can adopt fluidized-bed reactor described above, form a plurality of reaction compartments that are interconnected and realize above-mentioned preparation method.Thereby, the present invention proposes a kind of method of utilizing multiple stage fluidized-bed reactor of the present invention to prepare butadiene.Particularly, according to embodiments of the invention, the method that adopts fluidized-bed reactor shown in Figure 1 to prepare butadiene comprises:
I, with load type metal catalyst by being arranged on catalyst charging hole on the reaction compartment corresponding reaction compartment of packing into.
II, catalyst is all packed into behind the fluid bed, passed into the mist of vinylacetylene, nitrogen and hydrogen by feed(raw material)inlet 500, keeping the vinylacetylene air speed is 50-500mlgcat
-1H
-1, catalyst is carried by gas, to the motion of fluid bed top, above baffle plate, pile up, form the close phase of catalyst and be in fluidized state, in snakelike heat exchange tube, pass into the cooling medium (water that temperature is lower simultaneously, gas or oil), make and keep suitable temperature in the fluid bed in each reaction compartment.
After III, mixed material gas entered respectively in the catalyst emulsion zone in the reaction compartment, what obtain was the product gas mixture that contains vinylacetylene, left fluid bed through gas-solid separating device from the gas vent of fluid bed.Preferably, by follow-up conventional separator product gas mixture (except butadiene, also may contain nitrogen, hydrogen, butadiene, normal butane, 1-butylene, suitable 2-butylene and anti-2-butylene) is carried out the butadiene purifying.
IV, behind catalysqt deactivation, discharge from the catalyst outlet of fluid bed bottom, load simultaneously new catalyst and react.
The below describes embodiments of the invention in detail, need to prove that the embodiment that the following describes is exemplary, only is used for explaining the present invention, and can not be interpreted as limitation of the present invention.
Embodiment 1:
Adopt fluidized-bed reactor shown in Figure 1, prepare butadiene according to the following step, wherein the distance between the gas distribution grid (height of reaction compartment) is 3 times of fluid bed diameter:
Nitrogen is entered reactor with 1.5l/min from the feed(raw material)inlet, simultaneously with 0.06%Pd/ α-Al
2O
3(mass fraction) catalyst is entered in the respective reaction space by the catalyst inlet filling of each reaction compartment, and the loadings of each reaction compartment is 500kg.Filling passes into the mist that consists of 30 volume % vinylacetylenes, 40 volume % hydrogen and 30 volume % nitrogen after finishing from the feed(raw material)inlet, keeping the vinylacetylene air speed is 200ml.gcat
-1.h
-1After the reaction beginning,, pass into the cooling water of 15 ℃, 20 ℃ and 25 ℃ from bottom to top in the coil heat exchanger of each reaction compartment, the flow by the control cooling water makes the temperature of reaction compartment maintain respectively 26 ℃, 28 ℃ and 30 ℃ from bottom to top.Behind catalysqt deactivation, discharge from the catalyst outlet of fluid bed bottom, load simultaneously new catalyst and react.
Embodiment 2:
Prepare butadiene according to embodiment 1 described method, wherein difference from Example 1 is: the loadings along each reaction compartment inner catalyst on the axial direction from bottom to top of reactor is respectively 400kg, 500kg and 600kg.
Embodiment 3:
Prepare butadiene according to embodiment 1 described method, wherein difference from Example 1 is: all pass into 25 ℃ cooling water in the coil heat exchanger of each reaction compartment, and the temperature of each reaction compartment is all maintained 30 ℃.
In above-described embodiment, adopt Agilent 1790 type gas-chromatographies to analyze to the gaseous product of discharging after processing through cyclone separator, so that the gaseous sample medium vinyl acetylene that acquisition is collected and the amount of butadiene.Wherein, the chromatographic column of employing is 30m * 0.53mm glass fiber buttress shaft, Al
2O
3-PLOT adopts hydrogen flame detector.The heating schedule of hydrogen flame detector is: 120 ℃ kept 10 minutes, then with 5 ℃ of min
-1Speed rise to 190 ℃, keep 20min.Then, the vinylacetylene conversion ratio and the butadiene that calculate respectively among the butadiene preparation method of the various embodiments described above are selective, the results are shown in following table 1, and therein ethylene ethyl-acetylene conversion ratio and butadiene optionally computing formula are as follows:
Table 1 butadiene preparation method evaluation result
| Embodiment | Vinylacetylene conversion ratio (%) | Butadiene selective (%) |
| Embodiment 1 | 55.0 | 88.5 |
| Embodiment 2 | 59.8 | 84.4 |
| Embodiment 3 | 52.2 | 81.8 |
Comparative example 1 and embodiment 2 can find out, when axially the loadings of catalyst increased successively in each reaction compartment of (vertically) direction from bottom to top along reactor, the vinylacetylene conversion ratio was improved.Comparative example 1 and embodiment 3 can find out, the set-up mode of preferred reaction temperature is axially constantly to increase on from bottom to top the direction along reactor.
In the description of this specification, the description of reference term " embodiment ", " some embodiment ", " example ", " concrete example " or " some examples " etc. means to be contained at least one embodiment of the present invention or the example in conjunction with specific features, structure, material or the characteristics of this embodiment or example description.In this manual, the schematic statement of above-mentioned term not necessarily referred to identical embodiment or example.And the specific features of description, structure, material or characteristics can be with suitable mode combinations in any one or more embodiment or example.
Although illustrated and described embodiments of the invention, those having ordinary skill in the art will appreciate that: in the situation that do not break away from principle of the present invention and aim can be carried out multiple variation, modification, replacement and modification to these embodiment, scope of the present invention is limited by claim and equivalent thereof.
Claims (10)
1. vinylacetylene hydrogenation fluidized-bed reactor, it is characterized in that, in body, longitudinally be limited with at least two reaction compartments, and adjacent reaction compartment communicates with each other, the height of preferred described reaction compartment is 2-10 times of described body diameter, wherein, be provided with catalyst in the described reaction compartment
Randomly, the loadings of described reaction compartment inner catalyst is different,
Randomly, at least two gas distribution grids are set longitudinally in described body, in order to longitudinally be limited with at least two reaction compartments in described body, adjacent reaction compartment communicates with each other,
Randomly, in described body, longitudinally be limited with three reaction compartments,
Randomly, the reactive metal of described load type metal catalyst is be selected from Pd, Cu, Ni, Pt, Ir, Ru, Mo, Co, Ga, Sn, Ag, Pt, Au, In, Sb, Ge, Bi, Fe and Pb at least a,
Randomly, the carrier of described load type metal catalyst is for being selected from Al
2O
3, SiO
2, TiO
2, ZnO, MgO, CaCO
3, molecular sieve, Graphene, carbon pipe and active carbon at least a,
Randomly, described load type metal catalyst is Pd/ α-Al
2O
3
2. fluidized-bed reactor according to claim 1 is characterized in that, is respectively arranged with temperature control modules in each reaction compartment,
Randomly, described temperature control modules is serpentine heat exchanger.
3. fluidized-bed reactor according to claim 1 is characterized in that, is provided with gas-solid separating device at the top of described body,
Randomly, described gas-solid separating device is cyclone separator.
4. fluidized-bed reactor according to claim 1 is characterized in that, is provided with feed(raw material)inlet and catalyst outlet in the bottom of described body.
5. fluidized-bed reactor according to claim 1 is characterized in that, each reaction compartment all has catalyst feeds.
6. fluidized-bed reactor according to claim 1 is characterized in that, is provided with the catalyst overflow pipe at described body barrel, and described catalyst overflow pipe is connected reaction compartments different in the body.
7. a method for preparing butadiene is characterized in that, makes vinylacetylene and hydrogen carry out hydrogenation reaction at least two reaction compartments, in order to obtain butadiene, wherein, is provided with catalyst in the described reaction compartment,
Randomly, the loadings of described reaction compartment interior reaction temperature and catalyst one of at least different,
Randomly, the reactive metal of described load type metal catalyst is be selected from Pd, Cu, Ni, Pt, Ir, Ru, Mo, Co, Ga, Sn, Ag, Pt, Au, In, Sb, Ge, Bi, Fe and Pb at least a,
Randomly, the carrier of described load type metal catalyst is for being selected from Al
2O
3, SiO
2, TiO
2, ZnO, MgO, CaCO
3, molecular sieve, Graphene, carbon pipe and active carbon at least a,
Randomly, described load type metal catalyst is Pd/ α-Al
2O
3Catalyst,
Randomly, vinylacetylene and hydrogen carry out hydrogenation reaction in three reaction compartments,
Randomly, to the downstream, the temperature in the described reaction compartment is respectively 22-28 degree centigrade, 25-30 degree centigrade and 30-35 degree centigrade from the upstream.
8. method according to claim 7 is characterized in that, described vinylacetylene is with form and the hydrogen generation hydrogenation reaction of the mixture of vinylacetylene and inert gas,
Wherein, described mixture comprises:
The vinylacetylene of 20-90 parts by volume; And
The inert gas of 10-80 parts by volume;
Randomly, described inert gas is be selected from nitrogen, argon gas and butane at least a.
9. method according to claim 7 is characterized in that, described hydrogenation reaction is being carried out in each described fluidized-bed reactor according to claim 1-6.
10. butadiene goods is characterized in that, described butadiene goods are that each described method prepares according to claim 7-9.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104971667A (en) * | 2014-04-01 | 2015-10-14 | 清华大学 | Fluidized bed equipment and method for preparing poly-methoxy-dimethyl ether from dimethoxymethane and paraformaldehyde |
| CN114950127A (en) * | 2022-03-31 | 2022-08-30 | 成都达奇环境科技有限公司 | Catalytic flue gas desulfurization tower |
| CN115254170A (en) * | 2022-08-19 | 2022-11-01 | 浙江师范大学 | Cobalt-based catalyst for 1,3-butadiene selective hydrogenation and preparation method and application thereof |
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| CN115254170B (en) * | 2022-08-19 | 2023-05-16 | 浙江师范大学 | Cobalt-based catalyst for selective hydrogenation of 1, 3-butadiene and preparation method and application thereof |
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Application publication date: 20130918 |