CN105413670A - Solid acid catalyst for preparing butane through normal butanol dehydration and preparation method thereof - Google Patents
Solid acid catalyst for preparing butane through normal butanol dehydration and preparation method thereof Download PDFInfo
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- CN105413670A CN105413670A CN201510696506.5A CN201510696506A CN105413670A CN 105413670 A CN105413670 A CN 105413670A CN 201510696506 A CN201510696506 A CN 201510696506A CN 105413670 A CN105413670 A CN 105413670A
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- butanol
- butylene
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Abstract
The invention provides a supported catalyst, a method for preparing the catalyst, use of the catalyst, a method for preparing butane and equipment for preparing butane. The supported catalyst comprises a gamma-Al2O3 carrier and active ingredients, wherein the active ingredients are supported on the gamma-Al2O3 carrier, and the active ingredients contain zinc oxide, manganese oxide and cobaltous oxide. Thereofe, through effective support of the active ingredients on the carrier, the stability of the supported catalyst is improved, the service life of the supported catalyst is prolonged, and efficient catalytic effect is achieved.
Description
Technical field
The present invention relates to chemical field, particularly, the present invention relates to for the solid acid catalyst and preparation method thereof of n-butanol Dehydration for butylene.
Background technology
Butylene is a kind of important petrochemical materials, by multiple petrochemicals of preparation such as alkylated reaction, polymerisation, catalytic oxidations.If 1-butylene and 2-butylene are without the need to being separated, can be used for producing sec-butyl alcohol, methyl ethyl ketone, butadiene etc., 2-butylene can be used in producing crosslinking agent, polymer gasoline etc., isobutene is mainly used to manufacture butyl rubber, Oppanol, in addition, can be used for preparing liquid fuel by polymerization by butanols the obtained butylene that dewaters.Industrial production butylene to be mainly separated with the C-4-fraction of petrochemical plant by-product from oil plant and to obtain, and the method raw material depends on petroleum resources, and product separation system is complicated, and energy consumption is large, invests high.Along with the aggravation of environmental problem and the day by day exhausted of petroleum resources, Biomass Energy Development is the green approach realizing chemical industry sustainable development.
Utilize fermentable can effectively by saccharide converted for butanols, butanols can obtain butylene by further catalytic dehydration.Compared with traditional method, bioanalysis does not rely on petroleum resources and raw material is renewable, and technique is simple, and small investment, cost is low.Therefore, utilize renewable resource, rely on the biological butanol butylene technique of environmental friendly catalysis technology to have very large development potentiality.Prepare in the process of butylene utilizing biological butanol, the catalyst that exploitation has high catalytic efficiency is key biological butanol being converted into butylene, catalyst needs higher stability and longer life-span, and the dehydration that butylene is prepared in catalysis will have higher butanols conversion ratio and butylene is selective, the technique that biological butanol prepares butylene can be realized and promote.
But, still have much room for improvement for the catalyst of butylene and the method that utilizes butanols to prepare butylene for catalysis butanols Dehydration at present.
Summary of the invention
The present invention is intended to solve one of technical problem in correlation technique at least to a certain extent.For this reason, one object of the present invention is to propose that a kind of catalytic efficiency is high, the selective high loaded catalyst of good stability, long service life, butanols conversion ratio and butylene.
The application makes the discovery of the following fact and problem and understanding based on inventor: at present for the preparation of the catalyst of butylene, ubiquity catalyst stability is low, the life-span is short, the problem such as the development of evil in febrile disease rate of butanols and the selective lower of butylene in catalysis n-butanol dehydration.Further, carry out in butylene production at the above-mentioned catalyst of use, the problem such as have that material concentration is low, air speed is low, energy consumption is high and butylene output is undesirable.Inventor finds through further investigation, and this is due in existing catalyst, the kind of carried metal and load capacity can not abundant catalysis n-butanol generation dehydrations, and optionally generation butylene causes.
In view of this, in one aspect of the invention, the present invention proposes a kind of loaded catalyst.According to embodiments of the invention, this loaded catalyst comprises: γ-Al
2o
3carrier; And active component, described active component load is at described γ-Al
2o
3on carrier, and described active component contains zinc oxide, manganese oxide and cobalt oxide.Thus, by the pay(useful) load of active component on carrier, stability and the service life of this loaded catalyst can be improved, and realizes efficient catalytic effect.
According to embodiments of the invention, described loaded catalyst is used for the dehydration of catalysis n-butanol to obtain butylene.Thus, the conversion ratio of n-butanol can be improved, and improve the selective of n-butanol dehydration generation butylene.
According to embodiments of the invention, in this loaded catalyst, described γ-Al
2o
3the content of carrier is 60 ~ 99.7 quality %, and the content of described zinc oxide is 0.1 ~ 5 quality %, and the content of described manganese oxide is 0.1 ~ 20 quality %, and the content of described cobalt oxide is 0.1 ~ 15 quality %.Thus, can by regulating the content of mentioned component, improve this loaded catalyst catalysis n-butanol Dehydration further for the conversion ratio of butylene and selective.
In another aspect of this invention, the present invention proposes a kind of method preparing previously described loaded catalyst.According to embodiments of the invention, the method comprises: make active component be carried on γ-Al
2o
3on carrier, to obtain described loaded catalyst, wherein, described active component contains zinc oxide, manganese oxide and cobalt oxide.Thus, above-mentioned loaded catalyst can be prepared easily, and then the efficiency utilizing the method Kaolinite Preparation of Catalyst can be improved.
According to embodiments of the invention, the method comprises: (1) is by described γ-Al
2o
3carrier with containing Zn
2+, Mn
2+and Co
2+solution mixing; (2) mixture obtained in step (1) is carried out hydro-thermal reaction 2 ~ 6 hours at the temperature of 130 ~ 180 degrees Celsius; And (3) solid product to the described hydro-thermal reaction obtained in step (2) carries out calcination process, to obtain described loaded catalyst, optionally, described γ-Al
2o
3by carrying out calcination process acquisition to boehmite, optionally, described containing Zn
2+, Mn
2+and Co
2+solution be containing the following aqueous solution: based on the gross mass of the described aqueous solution, the Zn (NO of 1 quality %
3)
2, the Mn (NO of 4 quality %
3)
2and 3 Co (NO of quality %
3)
2, optionally, by described γ-Al
2o
3and it is described containing Zn
2+, Mn
2+and Co
2+solution be (1 ~ 5) according to mass ratio: (5 ~ 20) mix.Thus, can pass through above-mentioned steps, preparation has the loaded catalyst of suitable active composition load capacity, and then can improve the catalytic effect of catalyst in catalysis n-butanol dehydration generation butylene utilizing the method to prepare.
According to embodiments of the invention, described hydro-thermal reaction is reacted 4 hours under 150 degrees Celsius.Thus, can effectively by active component load at γ-Al
2o
3on carrier, and then the catalytic effect of loaded catalyst in catalysis n-butanol dehydration generation butylene utilizing the method to prepare can be improved.
According to embodiments of the invention, carrying out described calcination process to the solid product of described hydro-thermal reaction is 600 degrees Celsius of lower roastings 5 hours.Thus, the catalytic effect of loaded catalyst in catalysis n-butanol dehydration generation butylene utilizing the method to prepare can be improved further.
According to embodiments of the invention, before described calcination process is carried out to the solid product of described hydro-thermal reaction, in advance washing and dry process are carried out to described solid product.Thus, the catalytic effect of loaded catalyst in catalysis n-butanol dehydration generation butylene utilizing the method to prepare can be improved further.
In still another aspect of the invention, the present invention proposes previously described loaded catalyst and preparing the purposes in butylene, wherein, described butylene of preparing comprises n-butanol is dewatered.Thus, can by previously described loaded catalyst for the preparation of butylene, and then can improve by n-butanol Dehydration for the efficiency of butylene and effect.
In still another aspect of the invention, the present invention proposes a kind of method preparing butylene.According to embodiments of the invention, the method comprises: adopt foregoing loaded catalyst, makes n-butanol generation dehydration, to obtain butylene.Thus, previously described loaded catalyst can be utilized, improve the conversion ratio of n-butanol and dehydration generates the selective of butylene, and then efficiency and the effect that the method prepares butylene can be improved.
According to embodiments of the invention, the method comprises: butanol solution is carried out heating and gasifying by (1), to obtain gasification n-butanol; And (2) are under 350 ~ 450 degrees Celsius, described gasification n-butanol is contacted with described loaded catalyst, make described gasification n-butanol generation dehydration, to obtain butylene.Thus, in advance n-butanol is gasified to make n-butanol contact better with previously described catalyst, and then the effect of catalysis can be improved, and by selecting suitable temperature to complete catalytic and dehydration reaction, and then the efficiency and the effect that utilize the method to prepare butylene can be improved further.
According to embodiments of the invention, the particle diameter of described loaded catalyst is 0.4 ~ 0.9mm, and described butanol solution contains one of following: the n-butanol of 5 ~ 7.7 quality % and the water of surplus; Or the n-butanol of 80 ~ 100 quality % and the water of surplus.Thus, can to improve the efficiency and the effect that utilize the method to prepare butylene further.
According to embodiments of the invention, by peristaltic pump, described butanol solution is injected fixed bed reactors, described immobilization reactor comprises bringing-up section and catalytic dehydration section, wherein, in described bringing-up section, heating and gasifying is carried out to described butanol solution, to obtain described gasification n-butanol; In described catalytic dehydration section, adopt nitrogen as carrier gas, described gasification n-butanol is contacted with described loaded catalyst, to obtain the dehydration reaction product containing butylene, the flow of described nitrogen is 40 ~ 100ml/min, and the mass space velocity of described gasification n-butanol is 0.2 ~ 4h
-1; And the described dehydration reaction product containing butylene is passed in condenser, condensation process is carried out, to obtain butylene to the described dehydration reaction product containing butylene.Thus, can to improve the efficiency and the effect that utilize the method to prepare butylene further.
According to embodiments of the invention; before carrying out step (2), carry out activation process in advance to described loaded catalyst, described activation process comprises: under the protection of nitrogen; at the temperature of 450 degrees Celsius, heating is carried out 1 hour to described loaded catalyst.Thus, the efficiency and the effect that utilize the method to prepare butylene can be improved further.
In still another aspect of the invention, the present invention proposes a kind of equipment for the preparation of butylene.According to embodiments of the invention, this equipment comprises: fixed bed reactors, described fixed bed reactors comprise bringing-up section and catalytic dehydration section, described bringing-up section is set to be suitable for carrying out heating and gasifying to described butanol solution, to obtain described gasification n-butanol, foregoing catalyst is provided with in described catalytic dehydration section, and described catalytic dehydration section is set to be suitable for adopting nitrogen as carrier gas, make described gasification n-butanol and described catalyst exposure, to obtain the dehydration reaction product containing butylene; Peristaltic pump, described peristaltic pump is connected with described fixed bed reactors, for supplying butanol solution in described bringing-up section; And condenser, described condenser is connected with described fixed bed reactors, for carrying out condensation process, to obtain butylene to the described dehydration reaction product containing butylene.Thus, this equipment can be utilized, improve and utilize n-butanol Dehydration for the efficiency of butylene and effect.
Accompanying drawing explanation
Fig. 1 shows the flow chart of the method preparing loaded catalyst according to an embodiment of the invention;
Fig. 2 shows the flow chart of the method preparing butylene according to an embodiment of the invention; And
Fig. 3 shows the structural representation of the equipment preparing butylene according to an embodiment of the invention.
Reference numeral:
100: fixed bed reactors
110: bringing-up section
120: catalytic dehydration section
200: peristaltic pump
300: condenser
10: loaded catalyst
Detailed description of the invention
Be described below in detail embodiments of the invention, the example of described embodiment is shown in the drawings.Be exemplary below by the embodiment be described with reference to the drawings, be intended to for explaining the present invention, and can not limitation of the present invention be interpreted as.
In one aspect of the invention, the present invention proposes a kind of loaded catalyst.According to embodiments of the invention, this loaded catalyst comprises: γ-Al
2o
3carrier and active component, active component load is at γ-Al
2o
3on carrier.Wherein, active component contains zinc oxide, manganese oxide and cobalt oxide.Thus, the catalytic activity of this loaded catalyst can be improved by the active component containing three kinds of metal oxides.
Inventor finds, although γ is-Al through further investigation and great many of experiments
2o
3as solid acid catalyst, there is good stability and the advantage such as catalytic life is longer, and under certain condition, such as, in 320 ~ 350 degree Celsius range, there is certain catalytic activity, the dehydration of catalysis n-butanol can generate butylene, but be used alone γ-Al
2o
3often there is the problems such as the conversion ratio of reaction is on the low side, reaction selectivity is not high in the catalytic reaction as catalyst.Therefore, need γ-Al
2o
3carry out modification, to improve γ-Al
2o
3as catalytic efficiency and the effect of catalyst.Inventor finds, by γ-Al
2o
3as carrier, and when adding the active component containing metal oxide wherein, the reaction conversion ratio of catalyst chemical reaction can be improved.Further, when containing zinc oxide, manganese oxide and cobalt oxide in active component, the catalytic effect of this loaded catalyst significantly improves.Thus, can by γ-Al
2o
3as carrier, by by zinc oxide, manganese oxide and cobalt oxide as active component, load on carrier, realize the synergy of above-mentioned three kinds of metal oxides when catalyzed chemical reaction, and then realize the catalytic efficiency and the effect that improve this loaded catalyst.
According to embodiments of the invention, in this loaded catalyst, based on the gross mass of this loaded catalyst, γ-Al
2o
3the content of carrier is 60 ~ 99.7 quality %, and the content of zinc oxide is 0.1 ~ 5 quality %, and the content of manganese oxide is 0.1 ~ 20 quality %, and the content of cobalt oxide is 0.1 ~ 15 quality %.Thus, the content of metal oxide in active component can be regulated, make the load capacity of zinc oxide, manganese oxide and cobalt oxide within above-mentioned scope, and then catalytic efficiency and the effect of this loaded catalyst can be improved further.
According to embodiments of the invention, this loaded catalyst may be used for catalysis n-butanol Dehydration for butylene.Thus, the conversion ratio preparing n-butanol and dehydration can be improved and generate the selective of butylene.Inventor finds through great many of experiments, adopts in the n-butanol dehydration of this loaded catalyst catalysis, and the conversion ratio of n-butanol up to 100%, can generate the selective of butylene and reach as high as 99.33%.Thus, the utilization rate of raw material and the output of butylene can significantly be improved.
In another aspect of this invention, the present invention proposes a kind of method preparing previously described loaded catalyst.According to embodiments of the invention, the method comprises makes active component be carried on γ-Al
2o
3on carrier, to obtain loaded catalyst.Wherein, active component contains zinc oxide, manganese oxide and cobalt oxide.Thus, the previously described loaded catalyst of the present invention can be obtained easily, and then the efficiency and the effect that utilize the method to prepare above-mentioned loaded catalyst can be improved.
Particularly, according to embodiments of the invention, with reference to figure 1, the method can realize through the following steps:
S100: mixing
According to embodiments of the invention, in this step, by γ-Al
2o
3carrier with containing Zn
2+, Mn
2+and Co
2+solution mixing.Thus, the metal ion of metal oxide in active component will can be formed, i.e. Zn easily
2+, Mn
2+and Co
2+add γ-Al to
2o
3mixed solution is formed, to complete active component at γ-Al in subsequent step in carrier
2o
3load on carrier, and then the method can be utilized easily to prepare above-mentioned loaded catalyst.
Particularly, γ-Al
2o
3carrier is by carrying out calcination process acquisition to boehmite.Those skilled in the art can select the actual conditions of calcination process according to actual conditions, as long as boehmite can be converted into γ-Al
2o
3.Such as, according to one embodiment of present invention, under 600 degrees Celsius, roasting can be carried out to boehmite, to obtain γ-Al
2o
3carrier.
In this step, according to embodiments of the invention, containing Zn
2+, Mn
2+and Co
2+solution be containing the following aqueous solution: based on the gross mass of the described aqueous solution, the Zn (NO of 1 quality %
3)
2, the Mn (NO of 4 quality %
3)
2and 3 Co (NO of quality %
3)
2.In other words, containing Zn
2+, Mn
2+and Co
2+solution can be Zn (NO
3)
2, Mn (NO
3)
2and Co (NO
3)
2mixed solution, and, based on the gross mass of mixed solution, Zn (NO
3)
2content be 1 quality %, Mn (NO
3)
2content be 4 quality %, Co (NO
3)
2content be 3 quality %.Thus, can prepare containing Zn easily
2+, Mn
2+and Co
2+solution.The salt of zinc nitrate, manganese nitrate and cobalt nitrate can be dissolved in and having in the aqueous solution of certain mass by those skilled in the art, and regulates the quality of zinc nitrate, manganese nitrate and the cobalt nitrate added, and makes Zn (NO in the solution of preparation
3)
2, Mn (NO
3)
2and Co (NO
3)
2content be above-mentioned content, can obtain containing Zn easily
2+, Mn
2+and Co
2+solution, and with γ-Al
2o
3carrier mixes.
According to embodiments of the invention, by γ-Al
2o
3carrier with containing Zn
2+, Mn
2+and Co
2+solution when mixing, can according to γ-Al
2o
3and the mass ratio of above-mentioned solution is (1 ~ 5): (5 ~ 20) mix.Thus, the metal ion of metal oxide in active component will can be formed, i.e. Zn easily
2+, Mn
2+and Co
2+add γ-Al to
2o
3mixed solution is formed in carrier.
S200: hydro-thermal
According to embodiments of the invention, in this step, will containing γ-Al
2o
3carrier and containing Zn
2+, Mn
2+and Co
2+mixed solution at the temperature of 130 ~ 180 degrees Celsius, carry out hydro-thermal reaction, the reaction time is 2 ~ 6 hours.Thus, can easily by Zn
2+, Mn
2+and Co
2+be converted into corresponding metal oxide, i.e. zinc oxide, manganese oxide and cobalt oxide, and load is at γ-Al
2o
3on carrier.
It should be noted that, those skilled in the art can according to Zn in mixed solution
2+, Mn
2+and Co
2+actual content, regulate the actual temp of hydro-thermal reaction and time, as long as above-mentioned metal ion can be converted into metal oxide and load at γ-Al
2o
3on carrier.Such as, according to one embodiment of present invention, can in airtight hydrothermal reaction kettle, will containing γ-Al
2o
3carrier and containing Zn
2+, Mn
2+and Co
2+mixed solution be heated to 150 degrees Celsius, and keep having carried out hydro-thermal reaction in 4 hours.
S300: roasting
According to embodiments of the invention, in this step, calcination process is carried out, to obtain the loaded catalyst according to the embodiment of the present invention to the solid product that hydro-thermal reaction obtains.Thus, the loaded catalyst according to the embodiment of the present invention can be obtained easily.
Particularly, according to embodiments of the invention, in this step, within 5 hours, above-mentioned loaded catalyst can be obtained by the solid product obtained hydro-thermal reaction 600 degrees Celsius of lower roastings.Thus, the effect of the loaded catalyst utilizing the method to prepare can be improved.
In addition, before the solid product obtained hydro-thermal reaction carries out above-mentioned calcination process, first washing and dry process can be carried out to solid product.Particularly, by carrying out suction filtration process to the product of hydro-thermal reaction, to make product Separation of Solid and Liquid, solid product can be obtained.Subsequently the solid product that suction filtration obtains is washed, and washed solid product is carried out drying at one hundred and twenty degrees centigrade.Thus, the effect of the loaded catalyst utilizing the method to prepare can be improved further.
In still another aspect of the invention, the present invention proposes previously described loaded catalyst and prepare the purposes in butylene.Wherein, prepare butylene to comprise n-butanol is dewatered.The feature of this loaded catalyst and advantage have carried out detailed description above, do not repeat them here.Thus, above-mentioned loaded catalyst can be applied to and adopt n-butanol to prepare in the reaction of butylene, to improve efficiency and the effect of preparing butylene.
In still another aspect of the invention, the present invention proposes a kind of method preparing butylene.According to embodiments of the invention, the method comprises: adopt previously described loaded catalyst, makes n-butanol generation dehydration, to obtain butylene.Owing to the process employs previously described loaded catalyst, therefore this method preparing butylene has higher n-butanol conversion ratio, and there is the selective of higher generation butylene, the conversion ratio of n-butanol and the selective of butylene when preparing butylene about the previously described loaded catalyst of employing, be previously detailed description, do not repeat them here.Particularly, according to embodiments of the invention, with reference to figure 2, the method can realize through the following steps:
S100: gasification n-butanol
According to embodiments of the invention, in this step, by butanol solution heating and gasifying, to obtain gasification n-butanol.Thus, contact area and the contact range of n-butanol and catalyst can be strengthened, and then improve catalytic reaction efficiency and the effect of subsequent step.
Particularly, according to embodiments of the invention, in this step, butanol solution can select the water of n-butanol containing 5 ~ 7.7 quality % and surplus, or the butanol solution of the n-butanol of 80 ~ 100 quality % and the water of surplus.In other words, in above-mentioned butanol solution, based on the gross mass of butanol solution, the content of n-butanol is 5 ~ 7.7 quality %, namely, by the configuration butanol solution that is added to the water by appropriate n-butanol, and the amount of the n-butanol added can be regulated, make the content of n-butanol in butanol solution be 5 ~ 7.7 quality %.Or, select the gross mass based on butanol solution, the solution of the n-butanol containing 80 ~ 100 quality % and the water of surplus is as butanol solution, namely, by suitable quantity of water is joined in n-butanol, regulate the amount of the water added, make in the butanol solution of configuration containing the n-butanol of 80 ~ 100 quality % and the water of surplus.Thus, suitable solution can be selected as butanol solution according to actual conditions, and then the effect utilizing the method to prepare butylene can be improved.
It should be noted that, in this step, the method that n-butanol is gasified is not particularly limited, and those skilled in the art can according to concrete conditions such as the devices in actual production, select suitable method to heat n-butanol, produce gasification n-butanol to make n-butanol gasify.Such as, according to embodiments of the invention, peristaltic pump can be adopted to be injected in fixed bed reactors by above-mentioned n-butanol aqueous solution, wherein, fixed bed reactors comprise bringing-up section and catalytic dehydration section.Peristaltic pump can be adopted n-butanol aqueous solution to be injected into the bringing-up section of these fixed bed reactors, butanol solution is heated, to obtain gasification n-butanol.Thus, gasification n-butanol can be obtained easily, and then the catalytic efficiency that can improve in subsequent step and effect.
S200: dehydration
According to embodiments of the invention, in this step, under 350 ~ 450 degrees Celsius, gasification n-butanol is contacted with previously described loaded catalyst, make gasification n-butanol generation dehydration, to obtain butylene.Owing to the process employs previously described loaded catalyst, therefore this method preparing butylene has higher n-butanol conversion ratio, and has the selective of higher generation butylene.
Particularly, according to embodiments of the invention, particle diameter can be selected to be the loaded catalyst of 0.4 ~ 0.9mm, and the catalytic dehydration section inserted in previously described fixed bed reactors, make the gasification n-butanol obtained above under the condition of nitrogen as carrier gas, contact with above-mentioned loaded catalyst, so that catalytic gasification n-butanol generation dehydration, and generate butylene.Wherein, according to embodiments of the invention, the flow of nitrogen can be 40 ~ 100ml/min, and the mass space velocity of described gasification n-butanol is 0.2 ~ 4h
-1.Thus, under 350 ~ 450 degrees Celsius, the dehydration of gasification n-butanol can be completed efficiently, and preferably generates butylene, and then the efficiency and the effect that utilize the method to prepare butylene can be improved.Adopt the previously described loaded catalyst according to the embodiment of the present invention to carry out catalysis to n-butanol dehydration, the conversion ratio of n-butanol up to 100%, can generate the selective of butylene and reaches as high as 99.33%.The product of dehydration can carry out condensation process by condenser, and collects gas-phase product, to obtain butylene.
In addition, according to embodiments of the invention, before being contacted with previously described loaded catalyst by gasification n-butanol, activation process can also be carried out to loaded catalyst in advance.Particularly, under the protection of nitrogen, at the temperature of 450 degrees Celsius, 1 hour can be heated to loaded catalyst, and then be cooled to the temperature that gasification n-butanol and loaded catalyst carry out contacting, and complete catalytic and dehydration reaction.Thus, catalytic efficiency and the effect of this catalyst can be improved further, and then raising utilizes the method to prepare efficiency and the effect of butylene further.
In still another aspect of the invention, the present invention proposes a kind of equipment for the preparation of butylene.According to embodiments of the invention, with reference to figure 3, this equipment comprises: fixed bed reactors 100, peristaltic pump 200 and condenser 300.Particularly, fixed bed reactors comprise bringing-up section 110 and catalytic dehydration section 120, and bringing-up section 110 is for carrying out heat vaporized to butanol solution, so that acquisition gasification n-butanol; Being provided with previously described loaded catalyst 10 in catalytic dehydration section 120, to adopt nitrogen as carrier gas, by making gasification n-butanol contact with catalyst 10, obtaining the dehydration reaction product containing butylene.Peristaltic pump 200 is connected with fixed bed reactors 100, for supplying butanol solution in bringing-up section 110.Condenser 300 is connected with fixed bed reactors 100, for carrying out condensation process to the dehydration reaction product containing butylene, to obtain butylene.Thus, this equipment can be utilized, improve and utilize n-butanol to prepare efficiency and the effect of butylene.Owing to being provided with previously described loaded catalyst 10 in this equipment, therefore utilizing this equipment to prepare butylene and can obtain previously described beneficial effect, do not repeat them here.
Below by specific embodiment, the present invention will be described, and those skilled in the art are it is understood that specific embodiment is below only used to the object illustrated, and the scope do not limited the present invention in any way.In addition, in the following embodiments, unless stated otherwise, the material and facility adopted is all commercially available.If in embodiment below, concrete treatment conditions and processing method are not clearly described, then condition as known in the art and method can be adopted to process.
Embodiment 1
Boehmite 600 degrees Celsius of roasting 5h in Muffle furnace are obtained γ-Al
2o
3, by 20g γ-Al
2o
3with the Zn (NO containing 1 quality %
3)
2, the Mn (NO of 4 quality %
3)
2and 3 Co (NO of quality %
3)
2the aqueous solution add hydrothermal reaction kettle with solid-liquid mass ratio 1:10, hydrothermal reaction kettle is heated to 150 degrees Celsius under airtight state, and keeps 4h; Then suction filtration also fully washing, by solid dry 12h under 120 degrees Celsius; Dried catalyst is placed in Muffle furnace roasting 5h, and temperature is 600 degrees Celsius; Obtain load Zn
2+, Mn
2+, Co
2+γ-Al
2o
3solid acid catalyst.
Embodiment 2
Boehmite 600 degrees Celsius of roasting 5h in Muffle furnace are obtained γ-Al
2o
3, by 20g γ-Al
2o
3with the Zn (NO containing 1 quality %
3)
2, the Mn (NO of 4 quality %
3)
2and 3 Co (NO of quality %
3)
2the aqueous solution add hydrothermal reaction kettle with solid-liquid mass ratio 1:20, hydrothermal reaction kettle is heated to 150 degrees Celsius under airtight state, and keeps 4h; Then suction filtration also fully washing, by solid dry 12h under 120 degrees Celsius; Dried catalyst is placed in Muffle furnace roasting 5h, and temperature is 600 degrees Celsius; Obtain load Zn
2+, Mn
2+, Co
2+γ-Al
2o
3solid acid catalyst.
Embodiment 3
Boehmite 600 degrees Celsius of roasting 5h in Muffle furnace are obtained γ-Al
2o
3, by 20g γ-Al
2o
3with the Zn (NO containing 0.1 quality %
3)
2, the Mn (NO of 0.1 quality %
3)
2and 0.1 Co (NO of quality %
3)
2the aqueous solution add hydrothermal reaction kettle with solid-liquid mass ratio 1:10, hydrothermal reaction kettle is heated to 150 degrees Celsius under airtight state, and keeps 4h; Then suction filtration also fully washing, by solid dry 12h under 120 degrees Celsius; Dried catalyst is placed in Muffle furnace roasting 5h, and temperature is 600 degrees Celsius; Obtain load Zn
2+, Mn
2+, Co
2+γ-Al
2o
3solid acid catalyst.
Embodiment 4
Getting catalyst obtained in 1.3g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 400 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.0h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Gas-phase product is analyzed by Shimadzu GC-2010 gas-chromatography.Gas chromatograph condition: Al
2o
3/ NaSO
4capillary column 30m*0.53mm*10um, fid detector, detector 150 degrees Celsius, injector temperature 120 degrees Celsius, column temperature 100 degrees Celsius; Liquid product liquid chromatograph analysis, chromatographic condition: chromatographic column HPX-87H organic acid analysis column, column temperature 65 degrees Celsius, mobile phase 0.5mmol/L dilute sulfuric acid, detector RID-10A.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 99.33%.
Embodiment 5
Getting catalyst obtained in 1.3g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 450 degrees Celsius after; temperature remains on 450 degrees Celsius; pure butanol solution is by peristaltic pump injecting reactor gasification section, and the mass space velocity of n-butanol is 2.5h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 99.7%, and the selective of butylene reaches 90.81%.
Embodiment 6
Getting catalyst obtained in 1.3g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 40mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 394 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.63h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 93.52%.
Embodiment 7
Getting catalyst obtained in 1.3g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 350 degrees Celsius.Concentration be the butanol solution of 5wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 0.2h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 92.85%.
Embodiment 8
Getting catalyst obtained in 1.5g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 400 degrees Celsius after, cool the temperature to 350 degrees Celsius.Concentration be the butanol solution of 7.7wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 0.3h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 87.06%.
Embodiment 9
Getting catalyst obtained in 10g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 20mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 80mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 380 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.5h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 86.02%.
Embodiment 10
Getting catalyst obtained in 10g embodiment 1 loads in stainless steel fixed-bed tube reactor (Ф 20mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 400 degrees Celsius after, cool the temperature to 380 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.5h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 90.22%.
Embodiment 11
Getting catalyst obtained in 1.3g embodiment 2 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 400 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.0h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Gas-phase product is analyzed by Shimadzu GC-2010 gas-chromatography.Gas chromatograph condition: Al
2o
3/ NaSO
4capillary column 30m*0.53mm*10um, fid detector, detector 150 degrees Celsius, injector temperature 120 degrees Celsius, column temperature 100 degrees Celsius; Liquid product liquid chromatograph analysis, chromatographic condition: chromatographic column HPX-87H organic acid analysis column, column temperature 65 degrees Celsius, mobile phase 0.5mmol/L dilute sulfuric acid, detector RID-10A.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 90%, and the selective of butylene reaches 90%.
Embodiment 12
Getting catalyst obtained in 1.3g embodiment 3 loads in stainless steel fixed-bed tube reactor (Ф 8mm*2mm*400mm); inert ceramic balls or quartz sand is loaded under catalyst; under the protection of flow 100mL/min nitrogen; activate 1h under 450 degrees Celsius after, cool the temperature to 400 degrees Celsius.Concentration be the butanol solution of 80wt% by peristaltic pump injecting reactor gasification section, the mass space velocity of n-butanol is 1.0h
-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is after gas-liquid separator, and collection gas phase and liquid product are analyzed respectively.Gas-phase product is analyzed by Shimadzu GC-2010 gas-chromatography.Gas chromatograph condition: Al
2o
3/ NaSO
4capillary column 30m*0.53mm*10um, fid detector, detector 150 degrees Celsius, injector temperature 120 degrees Celsius, column temperature 100 degrees Celsius; Liquid product liquid chromatograph analysis, chromatographic condition: chromatographic column HPX-87H organic acid analysis column, column temperature 65 degrees Celsius, mobile phase 0.5mmol/L dilute sulfuric acid, detector RID-10A.Calculate by analysis, modification γ-Al
2o
3the conversion ratio of solid acid catalyst catalysis n-butanol Dehydration butylene is 100%, and the selective of butylene reaches 95%.
In the present invention, unless otherwise clearly defined and limited, the term such as term " installation ", " being connected ", " connection ", " fixing " should be interpreted broadly, and such as, can be fixedly connected with, also can be removably connect, or integral; Can be mechanical connection, also can be electrical connection or each other can communication; Can be directly be connected, also indirectly can be connected by intermediary, can be the connection of two element internals or the interaction relationship of two elements, unless otherwise clear and definite restriction.For the ordinary skill in the art, above-mentioned term concrete meaning in the present invention can be understood as the case may be.
In the description of this description, specific features, structure, material or feature that the description of reference term " embodiment ", " some embodiments ", " example ", " concrete example " or " some examples " etc. means to describe in conjunction with this embodiment or example are contained at least one embodiment of the present invention or example.In this manual, to the schematic representation of above-mentioned term not must for be identical embodiment or example.And the specific features of description, structure, material or feature can combine in one or more embodiment in office or example in an appropriate manner.In addition, when not conflicting, the feature of the different embodiment described in this description or example and different embodiment or example can carry out combining and combining by those skilled in the art.
Although illustrate and describe embodiments of the invention above, be understandable that, above-described embodiment is exemplary, can not be interpreted as limitation of the present invention, and those of ordinary skill in the art can change above-described embodiment within the scope of the invention, revises, replace and modification.
Claims (10)
1. a loaded catalyst, is characterized in that, comprising:
γ-Al
2o
3carrier; And
Active component, described active component load is at described γ-Al
2o
3on carrier, and described active component contains zinc oxide, manganese oxide and cobalt oxide.
2. loaded catalyst according to claim 1, is characterized in that, described loaded catalyst is used for the dehydration of catalysis n-butanol to obtain butylene.
3. loaded catalyst according to claim 1, is characterized in that, described γ-Al
2o
3the content of carrier is 60 ~ 99.7 quality %, and the content of described zinc oxide is 0.1 ~ 5 quality %, and the content of described manganese oxide is 0.1 ~ 20 quality %, and the content of described cobalt oxide is 0.1 ~ 15 quality %.
4. prepare a method for the loaded catalyst described in any one of claims 1 to 3, it is characterized in that, comprising:
Active component is made to be carried on γ-Al
2o
3on carrier, to obtain described loaded catalyst, wherein, described active component contains zinc oxide, manganese oxide and cobalt oxide.
5. method according to claim 4, is characterized in that, comprising:
(1) by described γ-Al
2o
3carrier with containing Zn
2+, Mn
2+and Co
2+solution mixing;
(2) mixture obtained in step (1) is carried out hydro-thermal reaction 2 ~ 6 hours at the temperature of 130 ~ 180 degrees Celsius; And
(3) calcination process is carried out to the solid product of the described hydro-thermal reaction obtained in step (2), to obtain described loaded catalyst,
Optionally, described γ-Al
2o
3by carrying out calcination process acquisition to boehmite,
Optionally, described containing Zn
2+, Mn
2+and Co
2+solution be containing the following aqueous solution: based on the gross mass of the described aqueous solution, the Zn (NO of 1 quality %
3)
2, the Mn (NO of 4 quality %
3)
2and 3 Co (NO of quality %
3)
2,
Optionally, by described γ-Al
2o
3and it is described containing Zn
2+, Mn
2+and Co
2+solution be (1 ~ 5) according to mass ratio: (5 ~ 20) mix,
Optionally, described hydro-thermal reaction is reacted 4 hours under 150 degrees Celsius,
Optionally, carrying out described calcination process to the solid product of described hydro-thermal reaction is 600 degrees Celsius of lower roastings 5 hours,
Optionally, before described calcination process is carried out to the solid product of described hydro-thermal reaction, in advance washing and dry process are carried out to described solid product.
6. the loaded catalyst described in any one of claims 1 to 3 is preparing the purposes in butylene, and wherein, described butylene of preparing comprises n-butanol is dewatered.
7. prepare a method for butylene, it is characterized in that, comprising:
Adopt the loaded catalyst described in any one of claims 1 to 3, make n-butanol generation dehydration, to obtain butylene.
8. method according to claim 7, is characterized in that, comprising:
(1) butanol solution is carried out heating and gasifying, to obtain gasification n-butanol; And
(2) under 350 ~ 450 degrees Celsius, described gasification n-butanol is contacted with described loaded catalyst, make described gasification n-butanol generation dehydration, to obtain butylene.
9. method according to claim 8, is characterized in that, the particle diameter of described loaded catalyst is 0.4 ~ 0.9mm, and described butanol solution contains one of following: the n-butanol of 5 ~ 7.7 quality % and the water of surplus; Or the n-butanol of 80 ~ 100 quality % and the water of surplus,
Optionally, by peristaltic pump, described butanol solution is injected fixed bed reactors, described immobilization reactor comprises bringing-up section and catalytic dehydration section, wherein, in described bringing-up section, heating and gasifying is carried out to described butanol solution, to obtain described gasification n-butanol; In described catalytic dehydration section, adopt nitrogen as carrier gas, described gasification n-butanol is contacted with described loaded catalyst, to obtain the dehydration reaction product containing butylene, the flow of described nitrogen is 40 ~ 100ml/min, and the mass space velocity of described gasification n-butanol is 0.2 ~ 4h
-1; And the described dehydration reaction product containing butylene is passed in condenser, and condensation process is carried out to the described dehydration reaction product containing butylene, to obtain butylene,
Optionally, before carrying out step (2), carry out activation process in advance to described loaded catalyst, described activation process comprises: under the protection of nitrogen, at the temperature of 450 degrees Celsius, carries out heating 1 hour to described loaded catalyst.
10. for the preparation of an equipment for butylene, it is characterized in that, comprising:
Fixed bed reactors, described fixed bed reactors comprise bringing-up section and catalytic dehydration section, described bringing-up section is set to be suitable for carrying out heating and gasifying to described butanol solution, to obtain described gasification n-butanol, the catalyst described in any one of claims 1 to 3 is provided with in described catalytic dehydration section, and described catalytic dehydration section is set to be suitable for adopting nitrogen as carrier gas, makes described gasification n-butanol and described catalyst exposure, to obtain the dehydration reaction product containing butylene;
Peristaltic pump, described peristaltic pump is connected with described fixed bed reactors, for supplying butanol solution in described bringing-up section; And
Condenser, described condenser is connected with described fixed bed reactors, for carrying out condensation process, to obtain butylene to the described dehydration reaction product containing butylene.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2021200689A1 (en) * | 2020-03-31 | 2021-10-07 | 三菱ケミカル株式会社 | Catalyst, method for producing isobutylene, method for producing methacrylic acid, and method for producing methyl methacrylate |
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| CN105413670B (en) | 2018-05-29 |
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