CN105413670B - It is a kind of to prepare solid acid catalyst of butylene and preparation method thereof for n-butanol dehydration - Google Patents
It is a kind of to prepare solid acid catalyst of butylene and preparation method thereof for n-butanol dehydration Download PDFInfo
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- CN105413670B CN105413670B CN201510696506.5A CN201510696506A CN105413670B CN 105413670 B CN105413670 B CN 105413670B CN 201510696506 A CN201510696506 A CN 201510696506A CN 105413670 B CN105413670 B CN 105413670B
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- butanol
- butylene
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- dehydration
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- 239000003054 catalyst Substances 0.000 title claims abstract description 137
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 title claims abstract description 114
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 title claims description 289
- 238000006297 dehydration reaction Methods 0.000 title claims description 60
- 230000018044 dehydration Effects 0.000 title claims description 49
- 239000011973 solid acid Substances 0.000 title description 16
- 238000002360 preparation method Methods 0.000 title description 4
- 238000000034 method Methods 0.000 claims abstract description 74
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 claims abstract description 35
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000004480 active ingredient Substances 0.000 claims abstract description 28
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 28
- 239000011787 zinc oxide Substances 0.000 claims abstract description 14
- 229910000428 cobalt oxide Inorganic materials 0.000 claims abstract description 13
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 51
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 230000002572 peristaltic effect Effects 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001994 activation Methods 0.000 claims description 14
- 239000012265 solid product Substances 0.000 claims description 14
- 239000007795 chemical reaction product Substances 0.000 claims description 13
- 238000009834 vaporization Methods 0.000 claims description 12
- 230000008016 vaporization Effects 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 239000011701 zinc Substances 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 9
- 229910001593 boehmite Inorganic materials 0.000 claims description 8
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 8
- 239000011572 manganese Substances 0.000 claims description 7
- 239000012159 carrier gas Substances 0.000 claims description 6
- 238000009833 condensation Methods 0.000 claims description 6
- 230000005494 condensation Effects 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 238000012545 processing Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052593 corundum Inorganic materials 0.000 abstract description 8
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract description 8
- 238000002309 gasification Methods 0.000 description 36
- 230000000694 effects Effects 0.000 description 26
- 238000006555 catalytic reaction Methods 0.000 description 24
- 239000007788 liquid Substances 0.000 description 19
- 239000007789 gas Substances 0.000 description 16
- 238000004458 analytical method Methods 0.000 description 15
- 239000000463 material Substances 0.000 description 14
- 239000012263 liquid product Substances 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 229910002651 NO3 Inorganic materials 0.000 description 11
- 230000004913 activation Effects 0.000 description 10
- 239000006004 Quartz sand Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 239000000919 ceramic Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- 238000007171 acid catalysis Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(II) nitrate Inorganic materials [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical class S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 description 2
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 208000015220 Febrile disease Diseases 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000011953 bioanalysis Methods 0.000 description 1
- 229920005549 butyl rubber Polymers 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
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- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
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- -1 poly- isobutyl Alkene Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention proposes a kind of loaded catalyst, the method for preparing catalyst, the purposes of catalyst, the method for preparing butylene and the equipment for preparing butylene, and the loaded catalyst includes：γ‑Al2O3Carrier；And active ingredient, the active ingredient are supported on the γ Al2O3On carrier, and the active ingredient contains zinc oxide, manganese oxide and cobalt oxide.Thus, it is possible to which the payload by active ingredient on carrier, improves the stability and service life of the loaded catalyst, and realize efficient catalytic effect.
Description
Technical field
The present invention relates to chemical field, in particular it relates to which the solid acid that butylene is prepared for n-butanol dehydration is urged
Agent and preparation method thereof.
Background technology
Butylene is a kind of important petrochemical materials, can pass through alkylated reaction, polymerisation, catalytic oxidation etc.
Prepare a variety of petrochemicals.If 1- butylene and 2- butylene are without separation, available for production sec-butyl alcohol, methyl ethyl ketone, fourth
Diene etc., 2- butylene can be used in producing crosslinking agent, polymer gasoline etc., and isobutene is mainly used to manufacture butyl rubber, poly- isobutyl
Alkene rubber, in addition, liquid fuel was prepared can be used for by polymerization by being dehydrated obtained butylene by butanol.Industrial production butylene
Mainly being obtained from the separation of the C-4-fraction of oil plant and petrochemical plant by-product, the method raw material depends on petroleum resources, and
Product separation system is complicated, and energy consumption is big, and investment is high.With the aggravation of environmental problem and the increasingly depleted of petroleum resources, development life
The substance energy is the green approach for realizing chemical industry sustainable development.
Can be effectively by saccharide converted for butanol using microbial fermentation, butanol can be made by further catalytic dehydration
Obtain butylene.Compared with traditional method, bioanalysis do not depend on petroleum resources and raw material it is renewable, simple for process, small investment,
It is at low cost.Therefore, using renewable resource, the biological butanol butylene technique of environmental friendly catalysis technology is relied on very big
Development potentiality.During butylene is prepared using biological butanol, catalyst of the exploitation with high catalytic efficiency is by biological fourth
Alcohol is converted into the key of butylene, and catalyst needs higher stability and longer service life, and catalysis prepares the de- of butylene
Water reaction will have higher butanol conversion ratio and butylene selectivity, can realize that biological butanol prepares the technique of butylene and pushes away
Extensively.
However, it prepares the catalyst of butylene currently used for catalysis butanol dehydration and prepares the method for butylene still using butanol
Have much room for improvement.
The content of the invention
It is contemplated that it solves at least some of the technical problems in related technologies.For this purpose, the present invention
One purpose is to propose that a kind of high catalytic efficiency, stability are good, service life is long, butanol conversion ratio and butylene high selectivity
Loaded catalyst.
The application is that the discovery of following facts and problem and understanding are made based on inventor：Currently used for preparing butylene
Catalyst, generally existing catalyst stability is low, short life, catalysis n-butanol dehydration in butanol development of evil in febrile disease rate and fourth
The problems such as selectivity of alkene is relatively low.Also, in above-mentioned catalyst is used to carry out butylene production, there are material concentration is low, air speed
The problems such as low, high energy consumption and undesirable butylene yield.Inventor has found by further investigation, this is because existing catalyst
In, the species and load capacity of carried metal can not sufficiently catalytic n-butanol dehydration occurs, and be selectively generating fourth
Caused by alkene.
In view of this, in one aspect of the invention, the present invention proposes a kind of loaded catalyst.Reality according to the present invention
Example is applied, which includes：γ-Al2O3Carrier；And active ingredient, the active ingredient be supported on the γ-
Al2O3On carrier, and the active ingredient contains zinc oxide, manganese oxide and cobalt oxide.Thus, it is possible to pass through active ingredient
Payload on carrier improves the stability and service life of the loaded catalyst, and realizes efficient catalysis effect
Fruit.
According to an embodiment of the invention, the loaded catalyst is dehydrated to obtain butylene for being catalyzed n-butanol.By
This, can improve the conversion ratio of n-butanol, and improve the selectivity of n-butanol dehydration generation butylene.
According to an embodiment of the invention, in the loaded catalyst, the γ-Al2O3The content of carrier is 60~99.7
Quality %, the content of the zinc oxide are 0.1~5 mass %, and the content of the manganese oxide is 0.1~20 mass %, the oxygen
The content for changing cobalt is 0.1~15 mass %.Thus, it is possible to the content by adjusting mentioned component, further improves the support type
Catalyst n-butanol dehydration prepares the conversion ratio and selectivity of butylene.
In another aspect of this invention, the present invention proposes a kind of method for preparing previously described loaded catalyst.
According to an embodiment of the invention, this method includes：Active ingredient is made to be carried on γ-Al2O3On carrier, to obtain the load
Type catalyst, wherein, the active ingredient contains zinc oxide, manganese oxide and cobalt oxide.Thus, it is possible to it easily prepares above-mentioned
Loaded catalyst, and then the efficiency that catalyst is prepared using this method can be improved.
According to an embodiment of the invention, this method includes：(1) by the γ-Al2O3Carrier is with containing Zn2+, Mn2+And
Co2+Solution mixing；(2) that obtained mixture in step (1) is carried out hydro-thermal at a temperature of 130~180 degrees Celsius is anti-
Answer 2~6 it is small when；And (3) carry out calcination process to the solid product of the obtained hydro-thermal reaction in step (2), so as to
The loaded catalyst is obtained, optionally, the γ-Al2O3Be by boehmite carry out calcination process acquisition,
Optionally, it is described to contain Zn2+, Mn2+And Co2+Solution to contain following aqueous solution：Total matter based on the aqueous solution
Amount, the Zn (NO of 1 mass %3)2, the Mn (NO of 4 mass %3)2And 3 mass % Co (NO3)2, optionally, by the γ-
Al2O3And described contain Zn2+, Mn2+And Co2+Solution according to mass ratio be (1~5)：(5~20) are mixed.As a result,
The loaded catalyst with suitable active ingredient load capacity can be prepared by above-mentioned steps, and then can improve to utilize and be somebody's turn to do
The catalytic effect of catalyst prepared by method in catalysis n-butanol dehydration generation butylene.
According to an embodiment of the invention, when the hydro-thermal reaction is that reaction 4 is small under 150 degrees Celsius.Thus, it is possible to effectively
Active ingredient is supported on γ-Al by ground2O3On carrier, and then the loaded catalyst prepared using this method can be improved and urged
Change the catalytic effect in n-butanol dehydration generation butylene.
According to an embodiment of the invention, carrying out the calcination process to the solid product of the hydro-thermal reaction is taken the photograph 600
When roasting 5 is small under family name's degree.It is taken off thus, it is possible to further improve using loaded catalyst prepared by this method in catalysis n-butanol
Catalytic effect in water generation butylene.
According to an embodiment of the invention, before the calcination process is carried out to the solid product of the hydro-thermal reaction, in advance
First the solid product is washed and drying process.Thus, it is possible to further improve the support type prepared using this method
Catalytic effect of the catalyst in catalysis n-butanol dehydration generation butylene.
In still another aspect of the invention, the present invention proposes use of the previously described loaded catalyst in butylene is prepared
On the way, wherein, the butylene for preparing includes being dehydrated n-butanol.Thus, it is possible to previously described loaded catalyst is used to make
Standby butylene, and then the efficiency and effect that butylene is prepared by n-butanol dehydration can be improved.
In still another aspect of the invention, the present invention proposes a kind of method for preparing butylene.According to an embodiment of the invention,
This method includes：Using foregoing loaded catalyst, make n-butanol that dehydration occur, to obtain butylene.As a result,
Previously described loaded catalyst can be utilized, improves the selection of the conversion ratio and dehydration generation butylene of n-butanol
Property, and then efficiency and effect that this method prepares butylene can be improved.
According to an embodiment of the invention, this method includes：(1) butanol solution is subjected to heating and gasifying, to obtain gas
Change n-butanol；And (2) make the gasification n-butanol be contacted with the loaded catalyst, make under 350~450 degrees Celsius
Dehydration occurs for the gasification n-butanol, to obtain butylene.N-butanol is gasified to make n-butanol with before in advance as a result,
The catalyst of face description better contacts with, and then can improve the effect of catalysis, and passes through and appropriate temperature is selected to complete catalysis
Dehydration, and then the efficiency and effect that butylene is prepared using this method can be further improved.
According to an embodiment of the invention, the grain size of the loaded catalyst be 0.4~0.9mm, the butanol solution
Containing one of following：The n-butanol of 5~7.7 mass % and the water of surplus；Or 80~100 mass % n-butanol and surplus
Water.Thus, it is possible to further improve efficiency and effect that butylene is prepared using this method.
According to an embodiment of the invention, the butanol solution is injected in fixed bed reactors by peristaltic pump, it is described
Immobilization reactor includes bringing-up section and catalytic dehydration section, wherein, in the bringing-up section, the butanol solution is carried out
Heating and gasifying, to obtain the gasification n-butanol；In the catalytic dehydration section, employ nitrogen as carrier gas, make the gas
Change n-butanol to contact with the loaded catalyst, to obtain the dehydration reaction product containing butylene, the flow of the nitrogen
For 40~100ml/min, the mass space velocity of the gasification n-butanol is 0.2~4h-1；It is and the dehydration containing butylene is anti-
Product is answered to be passed through in condenser, condensation process is carried out to the dehydration reaction product containing butylene, to obtain butylene.By
This, can be to further improve efficiency and effect that butylene is prepared using this method.
According to an embodiment of the invention, before step (2) is carried out, the loaded catalyst is carried out at activation in advance
Reason, the activation process include：Under the protection of nitrogen, at a temperature of 450 degrees Celsius, the loaded catalyst is carried out
Heat 1 it is small when.Thus, it is possible to further improve the efficiency and effect that butylene is prepared using this method.
In still another aspect of the invention, the present invention proposes a kind of equipment for being used to prepare butylene.Reality according to the present invention
Example is applied, which includes：Fixed bed reactors, the fixed bed reactors include bringing-up section and catalytic dehydration section, the heating
Section is arranged to be suitable for carrying out heating and gasifying to the butanol solution, and to obtain the gasification n-butanol, the catalysis is de-
It is provided with foregoing catalyst in water section, and the catalytic dehydration section is arranged to be suitable for employ nitrogen as carrier gas,
The gasification n-butanol is made to be contacted with the catalyst, to obtain the dehydration reaction product containing butylene；Peristaltic pump, it is described compacted
Dynamic pump is connected with the fixed bed reactors, for supplying butanol solution into the bringing-up section；And condenser, it is described cold
Condenser is connected with the fixed bed reactors, for carrying out condensation process to the dehydration reaction product containing butylene, so as to
Obtain butylene.Thus, it is possible to using the equipment, the efficiency and effect that butylene is prepared using n-butanol dehydration are improved.
Description of the drawings
Fig. 1 shows the flow chart of the method according to an embodiment of the invention for preparing loaded catalyst；
Fig. 2 shows the flow chart of the method according to an embodiment of the invention for preparing butylene；And
Fig. 3 shows the structure diagram of the equipment according to an embodiment of the invention for preparing butylene.
Reference numeral：
100：Fixed bed reactors
110：Bringing-up section
120：Catalytic dehydration section
200：Peristaltic pump
300：Condenser
10：Loaded catalyst
Specific embodiment
The embodiment of the present invention is described below in detail, the example of the embodiment is shown in the drawings.Below with reference to
The embodiment of attached drawing description is exemplary, it is intended to for explaining the present invention, and is not considered as limiting the invention.
In one aspect of the invention, the present invention proposes a kind of loaded catalyst.According to an embodiment of the invention, should
Loaded catalyst includes：γ-Al2O3Carrier and active ingredient, active ingredient are supported on γ-Al2O3On carrier.Wherein, it is living
Property ingredient contains zinc oxide, manganese oxide and cobalt oxide.Thus, it is possible to it is carried by the active ingredient contained there are three types of metal oxide
The catalytic activity of the high loaded catalyst.
Inventor has found by further investigation and many experiments, although γ-Al2O3As solid acid catalyst, have compared with
The advantages that good stability and longer catalytic life, and under certain condition, for example, in 320~350 degree Celsius ranges
It is interior, there is certain catalytic activity, n-butanol dehydration generation butylene can be catalyzed, but γ-Al are used alone2O3As catalyst
Catalytic reaction often exist reaction conversion ratio is relatively low, the problems such as reaction selectivity is not high.Therefore, it is necessary to γ-Al2O3Into
Row modification, to improve γ-Al2O3As the catalytic efficiency and effect of catalyst.Inventor has found, by γ-Al2O3Make
For carrier, and when adding the active ingredient containing metal oxide thereto, the anti-of catalyst chemical reaction can be improved
Answer conversion ratio.Also, when containing zinc oxide, manganese oxide and cobalt oxide in active ingredient, the catalysis of the loaded catalyst
Significant effect improves.Thus, it is possible to by γ-Al2O3As carrier, by by zinc oxide, manganese oxide and cobalt oxide as activity
Ingredient is loaded on carrier, is realized synergistic effect of the above-mentioned three kinds of metal oxides when catalytic chemistry reacts, and then is realized and carry
The catalytic efficiency and effect of the high loaded catalyst.
According to an embodiment of the invention, in the loaded catalyst, the gross mass based on the loaded catalyst, γ-
Al2O3The content of carrier is 60~99.7 mass %, and the content of zinc oxide is 0.1~5 mass %, the content of manganese oxide for 0.1~
20 mass %, the content of cobalt oxide is 0.1~15 mass %.Thus, it is possible to the content of metal oxide in active ingredient is adjusted,
Make the load capacity of zinc oxide, manganese oxide and cobalt oxide within above range, and then the support type can be further improved and urged
The catalytic efficiency and effect of agent.
According to an embodiment of the invention, the loaded catalyst can be used for be catalyzed n-butanol dehydration prepare butylene.As a result,
The selectivity of the conversion ratio for preparing n-butanol and dehydration generation butylene can be improved.Inventor sends out by many experiments
Existing, in the n-butanol dehydration using loaded catalyst catalysis, the conversion ratio of n-butanol can be up to 100%, generation
The selectivity of butylene reaches as high as 99.33%.Thus, it is possible to greatly improve the utilization rate of raw material and the yield of butylene.
In another aspect of this invention, the present invention proposes a kind of method for preparing previously described loaded catalyst.
According to an embodiment of the invention, this method includes active ingredient is made to be carried on γ-Al2O3On carrier, to obtain supported catalyst
Agent.Wherein, active ingredient contains zinc oxide, manganese oxide and cobalt oxide.Thus, it is possible to it is previously mentioned easily to obtain the present invention
Loaded catalyst, and then the efficiency and effect that above-mentioned loaded catalyst is prepared using this method can be improved.
Specifically, according to an embodiment of the invention, with reference to figure 1, this method can be realized through the following steps：
S100：Mixing
According to an embodiment of the invention, in this step, by γ-Al2O3Carrier is with containing Zn2+, Mn2+And Co2+It is molten
Liquid mixes.Thus, it is possible to it will easily form the metal ion of metal oxide in active ingredient, i.e. Zn2+, Mn2+And Co2+
It is added to γ-Al2O3Mixed solution is formed in carrier, to complete active ingredient in subsequent step in γ-Al2O3On carrier
Load, and then easily can prepare above-mentioned loaded catalyst using this method.
Specifically, γ-Al2O3Carrier is by carrying out calcination process acquisition to boehmite.Those skilled in the art
The actual conditions of calcination process can be selected according to actual conditions, as long as boehmite can be converted into γ-Al2O3.
For example, according to one embodiment of present invention, can be roasted under 600 degrees Celsius to boehmite, so as to obtain γ-
Al2O3Carrier.
In this step, according to an embodiment of the invention, containing Zn2+, Mn2+And Co2+Solution to contain following water
Solution：Based on the gross mass of the aqueous solution, the Zn (NO of 1 mass %3)2, the Mn (NO of 4 mass %3)2And 3 mass % Co
(NO3)2.In other words, containing Zn2+, Mn2+And Co2+Solution can be Zn (NO3)2、Mn(NO3)2And Co (NO3)2It is mixed
Close solution, also, the gross mass based on mixed solution, Zn (NO3)2Content be 1 mass %, Mn (NO3)2Content be 4 matter
Measure %, Co (NO3)2Content be 3 mass %.Contain Zn thus, it is possible to easily prepare2+, Mn2+And Co2+Solution.Ability
The salt of zinc nitrate, manganese nitrate and cobalt nitrate can be dissolved in the aqueous solution with certain mass by field technique personnel, and be adjusted
The quality of the zinc nitrate of addition, manganese nitrate and cobalt nitrate, makes Zn (NO in the solution of preparation3)2、Mn(NO3)2And Co (NO3)2
Content be above-mentioned content, you can easily obtain contain Zn2+, Mn2+And Co2+Solution, and with γ-Al2O3Carrier carries out
Mixing.
According to an embodiment of the invention, by γ-Al2O3Carrier is with containing Zn2+, Mn2+And Co2+Solution mixed
When, it can be according to γ-Al2O3And the mass ratio of above-mentioned solution is (1~5)：(5~20) are mixed.It is thus, it is possible to easy
Ground will form the metal ion of metal oxide in active ingredient, i.e. Zn2+, Mn2+And Co2+It is added to γ-Al2O3Shape in carrier
Into mixed solution.
S200：Hydro-thermal
According to an embodiment of the invention, in this step, γ-Al will be contained2O3Carrier and contain Zn2+, Mn2+And
Co2+Mixed solution carry out hydro-thermal reaction at a temperature of 130~180 degrees Celsius, the reaction time for 2~6 it is small when.As a result, may be used
With easily by Zn2+, Mn2+And Co2+Corresponding metal oxide, i.e. zinc oxide, manganese oxide and cobalt oxide are converted into, and
It is supported on γ-Al2O3On carrier.
It should be noted that those skilled in the art can be according to Zn in mixed solution2+, Mn2+And Co2+Reality contain
Amount, adjusts actual temp and the time of hydro-thermal reaction, as long as can above-mentioned metal ion be converted into metal oxide and born
It is loaded in γ-Al2O3On carrier.For example, according to one embodiment of present invention, it can be in closed hydrothermal reaction kettle, it will
Contain γ-Al2O3Carrier and contain Zn2+, Mn2+And Co2+Mixed solution be heated to 150 degrees Celsius, and keep 4 it is small when come
Complete hydro-thermal reaction.
S300：Roasting
According to an embodiment of the invention, in this step, calcination process is carried out to the solid product that hydro-thermal reaction obtains, with
Just loaded catalyst according to embodiments of the present invention is obtained.Thus, it is possible to easily obtain according to embodiments of the present invention bear
Supported catalyst.
It specifically, according to an embodiment of the invention, in this step, can be by the solid product that is obtained to hydro-thermal reaction
Above-mentioned loaded catalyst is obtained when roasting 5 is small under 600 degrees Celsius.It is born thus, it is possible to improve using prepared by this method
The effect of supported catalyst.
In addition, before the solid product obtained to hydro-thermal reaction carries out above-mentioned calcination process, it can be first to solid product
It is washed and drying process.Specifically, can suction filtration processing be carried out by the reaction product to hydro-thermal reaction, to make reaction
Product separation of solid and liquid obtains solid product.It is then washed to filtering the solid product obtained, and washed solid is produced
Object is dried at one hundred and twenty degrees centigrade.Thus, it is possible to further improve the effect of the loaded catalyst prepared using this method
Fruit.
In still another aspect of the invention, the present invention proposes use of the previously described loaded catalyst in butylene is prepared
On the way.Wherein, preparing butylene includes being dehydrated n-butanol.The feature and advantage of the loaded catalyst carry out in front
Description in detail, details are not described herein.Butylene is prepared using n-butanol thus, it is possible to be applied to above-mentioned loaded catalyst
In reaction, to improve the efficiency and effect that prepare butylene.
In still another aspect of the invention, the present invention proposes a kind of method for preparing butylene.According to an embodiment of the invention,
This method includes：Using previously described loaded catalyst, make n-butanol that dehydration occur, to obtain butylene.Due to
The process employs previously described loaded catalyst, therefore there is the method for preparing butylene higher n-butanol to convert
Rate, and with the selectivity of higher generation butylene, on when preparing butylene using previously described loaded catalyst just
The conversion ratio of butanol and the selectivity of butylene, before have been carried out describing in detail, details are not described herein.Specifically, root
According to the embodiment of the present invention, with reference to figure 2, this method can be realized through the following steps：
S100：Gasify n-butanol
According to an embodiment of the invention, in this step, by butanol solution heating and gasifying, to obtain the positive fourth of gasification
Alcohol.Thus, it is possible to enhance the contact area and contact range of n-butanol and catalyst, and then the catalysis for improving subsequent step is anti-
Answer efficiency and effect.
Specifically, according to an embodiment of the invention, in this step, butanol solution can be selected containing 5~7.7 matter
Measure the butanol solution of the water of the n-butanol and surplus of the n-butanol of % and the water or 80~100 mass % of surplus.In other words
It says, in above-mentioned butanol solution, the gross mass based on butanol solution, the content of n-butanol is 5~7.7 mass %, i.e. can
To configure butanol solution by the way that appropriate n-butanol is added to the water, and the amount of the n-butanol of addition is adjusted, make n-butanol molten
The content of n-butanol is 5~7.7 mass % in liquid.Alternatively, selecting the gross mass based on butanol solution, contain 80~100 matter
The solution of the n-butanol of % and the water of surplus is measured as butanol solution, i.e. by the way that suitable quantity of water is added in n-butanol, adjust
The amount of the water added in makes the water of the n-butanol and surplus containing 80~100 mass % in the butanol solution of configuration.As a result,
Appropriate solution can be selected according to actual conditions as butanol solution, and then can improve and prepare butylene using this method
Effect.
It should be noted that in this step, it is not particularly limited the method that n-butanol gasifies, those skilled in the art
According to concrete conditions such as the devices in actual production appropriate method can be selected to heat n-butanol, to make positive fourth
Alcohol gasification generates gasification n-butanol.For example, according to an embodiment of the invention, peristaltic pump may be employed by above-mentioned n-butanol aqueous solution
It is injected into fixed bed reactors, wherein, fixed bed reactors include bringing-up section and catalytic dehydration section.Peristaltic pump may be employed
N-butanol aqueous solution is injected into the bringing-up section of the fixed bed reactors, butanol solution is heated, to be gasified
N-butanol.Thus, it is possible to easily obtain gasification n-butanol, and then catalytic efficiency and effect in subsequent step can be improved
Fruit.
S200：Dehydration
According to an embodiment of the invention, in this step, under 350~450 degrees Celsius, gasification n-butanol is made to be retouched with front
The loaded catalyst contact stated, makes gasification n-butanol that dehydration occur, to obtain butylene.Since the process employs preceding
The loaded catalyst of face description, therefore the method for preparing butylene has higher n-butanol conversion ratio, and with higher
Generation butylene selectivity.
Specifically, according to an embodiment of the invention, loaded catalyst of the grain size for 0.4~0.9mm can be selected, and is filled out
Enter the catalytic dehydration section in previously described fixed bed reactors, make previously obtained gasification n-butanol in nitrogen as carrier gas
Under the conditions of, it is contacted with above-mentioned loaded catalyst, so that dehydration occurs for catalytic gasification n-butanol, and generates butylene.Wherein,
According to an embodiment of the invention, the flow of nitrogen can be 40~100ml/min, and the mass space velocity of the gasification n-butanol is
0.2~4h-1.Thus, it is possible under 350~450 degrees Celsius, the dehydration of gasification n-butanol is efficiently completed, and it is preferably raw
Into butylene, and then the efficiency and effect that butylene is prepared using this method can be improved.Using it is previously described according to the present invention
The loaded catalyst of embodiment is catalyzed n-butanol dehydration, and the conversion ratio of n-butanol can be up to 100%, generate butylene
Selectivity reach as high as 99.33%.The reaction product of dehydration can carry out condensation process by condenser, and collect gas
Phase product, to obtain butylene.
In addition, according to an embodiment of the invention, that will gasify, n-butanol connects with previously described loaded catalyst
Before touching, can also activation process be carried out to loaded catalyst in advance.Specifically, can be taken the photograph under the protection of nitrogen 450
At a temperature of family name's degree, when small to loaded catalyst heating 1, then it be cooled to gasification n-butanol and carried out with loaded catalyst
The temperature of contact, and complete catalytic and dehydration reaction.Thus, it is possible to the catalytic efficiency and effect of the catalyst are further improved,
And then further improve the efficiency and effect that butylene is prepared using this method.
In still another aspect of the invention, the present invention proposes a kind of equipment for being used to prepare butylene.Reality according to the present invention
Example is applied, with reference to figure 3, which includes：Fixed bed reactors 100, peristaltic pump 200 and condenser 300.Specifically, fixed bed
Reactor includes bringing-up section 110 and catalytic dehydration section 120, and bringing-up section 110 is used to carry out heating vaporization to butanol solution, with
Just gasification n-butanol is obtained；Previously described loaded catalyst 10 is provided in catalytic dehydration section 120, to employ nitrogen as
For carrier gas, by the way that gasification n-butanol is made to be contacted with catalyst 10, the dehydration reaction product containing butylene is obtained.Peristaltic pump
200 are connected with fixed bed reactors 100, for supplying butanol solution into bringing-up section 110.Condenser 300 and fixed bed are anti-
Device 100 is answered to be connected, for carrying out condensation process to the dehydration reaction product containing butylene, to obtain butylene.It is thus, it is possible to sharp
With the equipment, the efficiency and effect that butylene is prepared using n-butanol are improved.It is previously described negative due to being provided in the equipment
Supported catalyst 10, therefore prepare butylene using the equipment and can obtain previously described advantageous effect, details are not described herein.
Below by specific embodiment, the present invention will be described, it will be appreciated to those of skill in the art that below
The purpose that is merely to illustrate that of specific embodiment, without limiting the scope of the invention in any way.In addition, below
Embodiment in, unless stated otherwise, used material and facility is commercially available.If in embodiment below
In, specific treatment conditions and processing method are not expressly recited, then condition as known in the art and side may be employed
Method is handled.
Embodiment 1
By boehmite, 600 degrees Celsius of roasting 5h obtain γ-Al in Muffle furnace2O3, by 20g γ-Al2O3With containing 1
Zn (the NO of quality %3)2, the Mn (NO of 4 mass %3)2And 3 mass % Co (NO3)2Aqueous solution with solid-liquid mass ratio 1:10
Hydrothermal reaction kettle is added in, hydrothermal reaction kettle in the state of closed is heated to 150 degrees Celsius, and keeps 4h；Then filter simultaneously
Solid is dried 12h by fully washing under 120 degrees Celsius；Dried catalyst is placed in Muffle kiln roasting 5h, and temperature is
600 degrees Celsius；Obtain load Zn2+、Mn2+、Co2+γ-Al2O3Solid acid catalyst.
Embodiment 2
By boehmite, 600 degrees Celsius of roasting 5h obtain γ-Al in Muffle furnace2O3, by 20g γ-Al2O3With containing 1
Zn (the NO of quality %3)2, the Mn (NO of 4 mass %3)2And 3 mass % Co (NO3)2Aqueous solution with solid-liquid mass ratio 1:20
Hydrothermal reaction kettle is added in, hydrothermal reaction kettle in the state of closed is heated to 150 degrees Celsius, and keeps 4h；Then filter simultaneously
Solid is dried 12h by fully washing under 120 degrees Celsius；Dried catalyst is placed in Muffle kiln roasting 5h, and temperature is
600 degrees Celsius；Obtain load Zn2+、Mn2+、Co2+γ-Al2O3Solid acid catalyst.
Embodiment 3
By boehmite, 600 degrees Celsius of roasting 5h obtain γ-Al in Muffle furnace2O3, by 20g γ-Al2O3With containing
Zn (the NO of 0.1 mass %3)2, the Mn (NO of 0.1 mass %3)2And 0.1 mass % Co (NO3)2Aqueous solution with solid-liquid matter
Measure ratio 1:10 add in hydrothermal reaction kettle, and hydrothermal reaction kettle in the state of closed is heated to 150 degrees Celsius, and keeps 4h；So
It filters and fully washs afterwards, solid is dried into 12h under 120 degrees Celsius；Dried catalyst is placed in Muffle kiln roasting 5h,
Temperature is 600 degrees Celsius；Obtain load Zn2+、Mn2+、Co2+γ-Al2O3Solid acid catalyst.
Embodiment 4
Catalyst obtained in 1.3g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 400 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.0h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.Gas-phase product is carried out by Shimadzu GC-2010 gas-chromatographies
Analysis.Gas chromatograph condition：Al2O3/NaSO4Capillary column 30m*0.53mm*10um, fid detector, detector 150 are Celsius
Degree, 120 degrees Celsius of injector temperature, 100 degrees Celsius of column temperature；Liquid product is analyzed with liquid chromatograph, chromatographic condition：Chromatographic column
HPX-87H organic acid analysis columns, 65 degrees Celsius of column temperature, mobile phase 0.5mmol/L dilute sulfuric acids, detector RID-10A.Through analysis meter
It calculates, modified γ-Al2O3The conversion ratio that solid acid catalyst catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches
To 99.33%.
Embodiment 5
Catalyst obtained in 1.3g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, temperature is maintained at 450 degrees Celsius, and pure butanol solution injects reactor gasification section by peristaltic pump, n-butanol
Mass space velocity is 2.5h-1.Raw material after gasification is reacted by catalyst layer, and reactor outlet material is through gas-liquid separator
Afterwards, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid catalyst is catalyzed positive fourth
The conversion ratio of dehydration of alcohols butylene is 99.7%, and the selectivity of butylene reaches 90.81%.
Embodiment 6
Catalyst obtained in 1.3g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 40mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 394 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.63h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid catalysis
The conversion ratio that agent catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches 93.52%.
Embodiment 7
Catalyst obtained in 1.3g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 350 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 5wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 0.2h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid catalysis
The conversion ratio that agent catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches 92.85%.
Embodiment 8
Catalyst obtained in 1.5g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 400 degrees Celsius
After lower activation 1h, 350 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 7.7wt% injects reactor gas by peristaltic pump
Change section, the mass space velocity of n-butanol is 0.3h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid is urged
The conversion ratio that agent catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches 87.06%.
Embodiment 9
Catalyst obtained in 10g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 20mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 80mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 380 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.5h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid catalysis
The conversion ratio that agent catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches 86.02%.
Embodiment 10
Catalyst obtained in 10g embodiments 1 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 20mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 400 degrees Celsius
After lower activation 1h, 380 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.5h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.It is calculated through analysis, modified γ-Al2O3Solid acid catalysis
The conversion ratio that agent catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches 90.22%.
Embodiment 11
Catalyst obtained in 1.3g embodiments 2 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 400 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.0h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.Gas-phase product is carried out by Shimadzu GC-2010 gas-chromatographies
Analysis.Gas chromatograph condition：Al2O3/NaSO4Capillary column 30m*0.53mm*10um, fid detector, detector 150 are Celsius
Degree, 120 degrees Celsius of injector temperature, 100 degrees Celsius of column temperature；Liquid product is analyzed with liquid chromatograph, chromatographic condition：Chromatographic column
HPX-87H organic acid analysis columns, 65 degrees Celsius of column temperature, mobile phase 0.5mmol/L dilute sulfuric acids, detector RID-10A.Through analysis meter
It calculates, modified γ-Al2O3The conversion ratio that solid acid catalyst catalysis n-butanol is dehydrated butylene processed is 90%, and the selectivity of butylene reaches
90%.
Embodiment 12
Catalyst obtained in 1.3g embodiments 3 is taken to be packed into stainless steel fixed-bed tube reactor (Ф 8mm*2mm*
In 400mm), inert ceramic balls or quartz sand are loaded under catalyst, under the protection of flow 100mL/min nitrogen, at 450 degrees Celsius
After lower activation 1h, 400 degrees Celsius are cooled the temperature to.The butanol solution that concentration is 80wt% injects reactor gasification by peristaltic pump
Section, the mass space velocity of n-butanol is 1.0h-1.Raw material after gasification is reacted by catalyst layer, reactor outlet material warp
After gas-liquid separator, collect gas phase respectively and liquid product is analyzed.Gas-phase product is carried out by Shimadzu GC-2010 gas-chromatographies
Analysis.Gas chromatograph condition：Al2O3/NaSO4Capillary column 30m*0.53mm*10um, fid detector, detector 150 are Celsius
Degree, 120 degrees Celsius of injector temperature, 100 degrees Celsius of column temperature；Liquid product is analyzed with liquid chromatograph, chromatographic condition：Chromatographic column
HPX-87H organic acid analysis columns, 65 degrees Celsius of column temperature, mobile phase 0.5mmol/L dilute sulfuric acids, detector RID-10A.Through analysis meter
It calculates, modified γ-Al2O3The conversion ratio that solid acid catalyst catalysis n-butanol is dehydrated butylene processed is 100%, and the selectivity of butylene reaches
To 95%.
In the present invention, unless otherwise clearly defined and limited, term " installation ", " connected ", " connection ", " fixation " etc.
Term should be interpreted broadly, for example, it may be being fixedly connected or being detachably connected or integral；Can be that machinery connects
It connects or is electrically connected or can communicate each other；It can be directly connected, can also be indirectly connected by intermediary, it can be with
It is the interaction relationship of connection inside two elements or two elements, unless otherwise restricted clearly.For this field
For those of ordinary skill, the concrete meaning of above-mentioned term in the present invention can be understood as the case may be.
In the description of this specification, reference term " one embodiment ", " some embodiments ", " example ", " specifically show
The description of example " or " some examples " etc. means specific features, structure, material or the spy for combining the embodiment or example description
Point is contained at least one embodiment of the present invention or example.In the present specification, schematic expression of the above terms is not
It must be directed to identical embodiment or example.Moreover, particular features, structures, materials, or characteristics described can be in office
It is combined in an appropriate manner in one or more embodiments or example.In addition, without conflicting with each other, the skill of this field
Art personnel can tie the different embodiments described in this specification or example and different embodiments or exemplary feature
It closes and combines.
Although the embodiment of the present invention has been shown and described above, it is to be understood that above-described embodiment is example
Property, it is impossible to limitation of the present invention is interpreted as, those of ordinary skill in the art within the scope of the invention can be to above-mentioned
Embodiment is changed, changes, replacing and modification.
Claims (16)
1. a kind of be used to be catalyzed n-butanol dehydration to obtain the loaded catalyst of butylene, which is characterized in that including：
γ-Al2O3Carrier；And
Active ingredient, the active ingredient are supported on the γ-Al2O3On carrier, and the active ingredient contain zinc oxide,
Manganese oxide and cobalt oxide, the γ-Al2O3The content of carrier is 60~99.7 mass %, and the content of the zinc oxide is 0.1
~5 mass %, the content of the manganese oxide is 0.1~20 mass %, and the content of the cobalt oxide is 0.1~15 mass %.
A kind of 2. method for preparing loaded catalyst described in claim 1, which is characterized in that including：
Active ingredient is made to be carried on γ-Al2O3On carrier, to obtain the loaded catalyst, wherein, the active ingredient
Contain zinc oxide, manganese oxide and cobalt oxide.
3. according to the method described in claim 2, it is characterised in that it includes：
(1) by the γ-Al2O3Carrier is with containing Zn2+, Mn2+And Co2+Solution mixing；
(2) by obtained mixture in step (1) when progress hydro-thermal reaction 2~6 is small at a temperature of 130~180 degrees Celsius；
And
(3) calcination process is carried out to the solid product of the obtained hydro-thermal reaction in step (2), to obtain the load
Type catalyst.
4. the according to the method described in claim 3, it is characterized in that, γ-Al2O3It is by being roasted to boehmite
Burn what processing obtained.
5. according to the method described in claim 3, it is characterized in that, described contain Zn2+, Mn2+And Co2+Solution be containing
Following aqueous solution：Based on the gross mass of the aqueous solution, the Zn (NO of 1 mass %3)2, the Mn (NO of 4 mass %3)2And 3 matter
Measure the Co (NO of %3)2。
6. according to the method described in claim 3, it is characterized in that, by the γ-Al2O3And described contain Zn2+, Mn2+With
And Co2+Solution according to mass ratio be (1~5)：(5~20) are mixed.
7. according to the method described in claim 3, it is characterized in that, the hydro-thermal reaction is that reaction 4 is small under 150 degrees Celsius
When.
8. according to the method described in claim 3, it is characterized in that, the roasting is carried out to the solid product of the hydro-thermal reaction
When processing is that roasting 5 is small under 600 degrees Celsius.
9. according to the method described in claim 3, it is characterized in that, carry out the roasting in the solid product to the hydro-thermal reaction
Before burning processing, the solid product is washed in advance and drying process.
10. purposes of the loaded catalyst described in claim 1 in butylene is prepared, wherein, the butylene for preparing includes making
N-butanol is dehydrated.
A kind of 11. method for preparing butylene, which is characterized in that including：
Using loaded catalyst described in claim 1, make n-butanol that dehydration occur, to obtain butylene.
12. according to the method for claim 11, which is characterized in that including：
(1) butanol solution is subjected to heating vaporization, to obtain vaporization n-butanol；And
(2) under 350~450 degrees Celsius, the vaporization n-butanol is made to be contacted with the loaded catalyst, makes the vaporization
Dehydration occurs for n-butanol, to obtain butylene.
13. according to the method for claim 12, which is characterized in that the grain size of the loaded catalyst for 0.4~
0.9mm, the butanol solution contain one of following：The n-butanol of 5~7.7 mass % and the water of surplus；Or 80~100 matter
Measure the n-butanol of % and the water of surplus.
14. according to the method for claim 13, which is characterized in that the butanol solution is injected by peristaltic pump and is fixed
In bed reactor, the immobilization reactor includes bringing-up section and catalytic dehydration section, wherein, in the bringing-up section, to institute
It states butanol solution and carries out heating vaporization, to obtain the vaporization n-butanol；In the catalytic dehydration section, using nitrogen
As carrier gas, the vaporization n-butanol is made to be contacted with the loaded catalyst, to obtain the dehydration production containing butylene
Object, the flow of the nitrogen is 40~100ml/min, and the mass space velocity of the vaporization n-butanol is 0.2~4h-1；And by institute
It states the dehydration reaction product containing butylene to be passed through in condenser, the dehydration reaction product containing butylene is carried out at condensation
Reason, to obtain butylene.
15. according to the method for claim 13, which is characterized in that before step (2) is carried out, in advance to the support type
Catalyst carries out activation process, and the activation process includes：Under the protection of nitrogen, at a temperature of 450 degrees Celsius, to described
Loaded catalyst carry out heating 1 it is small when.
16. a kind of equipment for being used to prepare butylene, which is characterized in that including：
Fixed bed reactors, the fixed bed reactors include bringing-up section and catalytic dehydration section, and the bringing-up section is arranged to suitable
In carrying out heating vaporization to the butanol solution, to obtain the vaporization n-butanol, set in the catalytic dehydration section
The catalyst having the right described in requirement 1, and the catalytic dehydration section is arranged to be suitable for employing nitrogen as carrier gas, makes described
Vaporization n-butanol is contacted with the catalyst, to obtain the dehydration reaction product containing butylene；
Peristaltic pump, the peristaltic pump are connected with the fixed bed reactors, for supplying butanol solution into the bringing-up section；
And
Condenser, the condenser are connected with the fixed bed reactors, for the dehydration reaction product containing butylene
Condensation process is carried out, to obtain butylene.
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| "Zn-Mn-CoZSM-5催化低浓度乙醇脱水制乙烯";罗亮;《中国优秀硕士学位论文全文数据库 工程科技Ι辑》;20111215(第S1期);第41页第4.2节，第30页第1段，第25页第1段，第25页第2段、图2-2 * |
| "响应面法优化Zn-Mn-Co/HZSM-5催化乙醇脱水制乙烯";王伟等;《生物工程学报》;20110325;第27卷(第3期);第412-418页 * |
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