CN103157503A - Synthesis and regeneration method of catalyst for preparing ethylene from ethanol - Google Patents
Synthesis and regeneration method of catalyst for preparing ethylene from ethanol Download PDFInfo
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- CN103157503A CN103157503A CN2013101047354A CN201310104735A CN103157503A CN 103157503 A CN103157503 A CN 103157503A CN 2013101047354 A CN2013101047354 A CN 2013101047354A CN 201310104735 A CN201310104735 A CN 201310104735A CN 103157503 A CN103157503 A CN 103157503A
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- ethyl alcohol
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000005977 Ethylene Substances 0.000 title claims abstract description 31
- 238000011069 regeneration method Methods 0.000 title abstract description 4
- 238000001308 synthesis method Methods 0.000 title abstract 2
- 230000015572 biosynthetic process Effects 0.000 title 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002808 molecular sieve Substances 0.000 claims abstract description 19
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000002002 slurry Substances 0.000 claims abstract description 16
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 11
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000010457 zeolite Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 40
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 40
- 235000019441 ethanol Nutrition 0.000 claims description 35
- 239000004411 aluminium Substances 0.000 claims description 31
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 25
- 239000001301 oxygen Substances 0.000 claims description 25
- 229910052760 oxygen Inorganic materials 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- 238000010189 synthetic method Methods 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011888 foil Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 239000003085 diluting agent Substances 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 230000004048 modification Effects 0.000 claims description 6
- 238000012986 modification Methods 0.000 claims description 6
- 238000009418 renovation Methods 0.000 claims description 6
- 239000012153 distilled water Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 238000010926 purge Methods 0.000 claims description 2
- 239000003643 water by type Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 230000009849 deactivation Effects 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000010306 acid treatment Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 150000004965 peroxy acids Chemical class 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000035800 maturation Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- -1 normal pressure Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a synthesis method of a catalyst for preparing ethylene from ethanol. The method comprises the following steps: (1) based on parts by mass, firstly taking 5 to 30 parts of alumina sol, wherein the content of the alumina in the alumina sol is from 5wt% to 25wt%, thereby obtaining a slurry A; (2) stirring and slowly adding 70 to 95 parts of hydrogen-type Pentasil-based zeolite molecular sieve powder by mass into the slurry A, wherein the silicon-aluminum molar ratio of the molecular sieve powder is between 25 and 200, thereby obtaining a slurry B; and (3) after heating and modifying the slurry B, washing and drying the slurry B and standing the slurry B in a muffle furnace for roasting, thereby obtaining the catalyst for preparing the ethylene from the ethanol. The invention further discloses a regeneration method of the catalyst. The catalyst synthesized by using the method has the characteristics of high hydrothermal stability, adjustable silicon-aluminum ratio, high dispensability and the like, and also has the advantages of low reaction temperature, high activity and selectivity and the like. In addition, the catalyst can be regenerated for many times. Thus, the catalyst is superior in performance.
Description
Technical field
The invention belongs to catalyst field, relate in particular to a kind of for the synthetic method with the catalyst of producing ethylene with ethyl alcohol, and the renovation process of this catalyst.
Background technology
Ethene is important petrochemical industry basic material, can be in order to produce multiple important Organic Chemicals.Yet in short supply due to oil supply, the rise of crude oil price and traditional petroleum path are produced the environmental problem that ethene brings, and non-traditional petroleum path is produced ethene will very large market prospects.The bio-ethanol industry obtains flourish these needs that catered to just, and along with the maturation of bio-ethanol technology, the continuous reduction of bio-ethanol cost makes the alcohol production ethylene process have more economic advantages simultaneously.
At present, molecular sieve catalyst due to its heat endurance and hydrothermal stability high, the framework silicon-aluminum mol ratio can regulate and control in a big way, has simultaneously strong acid and weak acid center, usually product is had higher activity and selectivity.Be its catalytic performance of raising in the producing ethylene with ethyl alcohol reaction, often needing that it is carried out surface acidity processes, method of modifying mainly contains steam treatment and acid treatment etc., and reduce acid strength or increase total acid content by removing framework aluminum, number be described in 201010608182.2 as Chinese patent application, but understand like this saboteur and sieve lattice, thereby form the skeleton defective, finally cause catalyst activity and stability decreases, if frequent regeneration, also can destroy its skeleton structure, shorten its service life.
Summary of the invention
the objective of the invention is in order to overcome the prior art above shortcomings, a kind of synthetic method of catalyst of producing ethylene with ethyl alcohol is provided, take aluminium colloidal sol as the modifier synthetic catalyst, this catalyst is after the peracid modification, the acid strength that it is suitable and acid total amount are very favourable to the producing ethylene from dehydration of ethanol reaction, containing in addition al composition is scattered in molecular sieve with high dispersion state, this high dispersive contains al composition can form new meso-hole structure, improved the diffusivity of reaction medium, improve its catalytic performance, molecular sieve has high hydrothermal stability, silica alumina ratio is adjustable and the feature such as polymolecularity, reaction temperature is low, catalyst activity and selectivity is high, repeatedly renewable, superior performance.In addition, the present invention also provides a kind of renovation process of described catalyst.
To achieve these goals, the present invention adopts following technical proposals:
A kind of synthetic method of the catalyst for producing ethylene with ethyl alcohol comprises the following steps:
(1) first take in mass the aluminium colloidal sol of 5 parts～30 parts, in aluminium colloidal sol, take the aluminium content of aluminium oxide as 5wt%～25wt%, this is slurries A;
(2) be 25～200 Hydrogen Pentasil type zeolite molecular sieve powder while stirring the silica alumina ratio of 70 parts～95 parts that slowly adds in the slurries A in mass, obtain homogeneous slurry B;
(3) with after the processing of slurries B heat modification, washing, drying, then be placed in the Muffle furnace roasting, namely get the catalyst of producing ethylene with ethyl alcohol.
Aluminium colloidal sol preparation method is take metal aluminum foil as raw material, and adding concentration is at least aly in hydrochloric acid, nitric acid, oxalic acid or the acetic acid of 0.1mol/L～10mol/L to keep 4～12h in 60 ℃～100 ℃ thermostat water baths.
In step (3), the modification of slurries B is to process 4～36h in 60 ℃～90 ℃ waters bath with thermostatic control, constantly stirs simultaneously.
Washing described in step (3) refers to wash to filtrate pH value as 6.5～7.5 take deionized water or distilled water.
Drying described in step (3) refers to dry 2～24h in the blast dry oven of 100 ℃～120 ℃.
Roasting described in step (3) refers to 400 ℃～550 ℃ lower roasting 4～24h in Muffle furnace.
The renovation process of described catalyst for producing ethylene with ethyl alcohol is characterized in that: comprise the following steps:
(1) control 220 ℃～320 ℃ of bed temperatures, with 10～100mL/min flow velocity, 1%～21%(? data in embodiment are 40%, please check) oxygen blow 0.5～6h;
(2) be warmed up to 420 ℃～440 ℃, with the oxygen blow 0.5～6h of 10～100mL/min flow velocity 1%～21%;
(3) be warmed up to 460 ℃～500 ℃, with the oxygen blow 1～18h of 10～100mL/min flow velocity 1%～21%;
(4) purge the reaction temperature of reaction bed temperature to 220 ℃～300 ℃ with 99.9% above high pure nitrogen, and guarantee that in reactor, oxygen content is down to below 0.5%.
Be nitrogen beyond oxygen in step (1)--(3), nitrogen is diluent gas.
Existing multinomial disclosed patent relates to the catalyst based on zeolite molecular sieve in recent years, and be applied to producing ethylene from dehydration of ethanol reaction, such as the patent No. is 200810244135.7 patents that are called " a kind of catalyst for ethanol delydration to ethylene and its preparation method and application ", but continuous product yield easily fluctuates, less stable, regenerability are not good enough yet.The inventive method has been avoided employing steam treatment and acid treatment to remove framework aluminum reducing acid strength or increase total acid content simultaneously; protected the molecular sieve lattice be not damaged and form the skeleton defective; the destruction that its good catalytic performance finally also avoids frequent regeneration to cause its skeleton structure fundamentally guarantees the service life that it is long.
Catalyst of the present invention is at 60% concentration of alcohol, air speed 0.6 h
-1～1.8h
-1Reach under 220 ℃～300 ℃ reaction conditions, the ethanol average conversion reaches more than 96%; At 0.6h
-1Reach under 275 ℃ of reaction conditions, ethanol conversion still can keep more than 95% after reaction 2000h, and catalytic performance is splendid.
Compared with prior art, the invention has the beneficial effects as follows:
The present invention adopts Pentasil type zeolite molecular sieve as catalyst, take molecular sieve powder as basic material, is prepared from through the heat treatment of aluminium colloidal sol, and specific surface area of catalyst is 305 m
2/ g～370m
2/ g, suitable with molecular screen primary powder, and this catalyst is after the peracid modification, the acid strength that it is suitable and acid total amount are very favourable to the producing ethylene from dehydration of ethanol reaction, containing al composition is scattered in molecular sieve with high dispersion state, this high dispersive contains al composition can form new meso-hole structure, has improved the diffusivity of reaction medium, improves its catalytic performance.The catalyst of the inventive method preparation has high hydrothermal stability, silica alumina ratio is adjustable and the feature such as polymolecularity, has that reaction temperature is low, the catalyst activity and selectivity advantages of higher, and is renewable more than 6 times, superior performance.
The specific embodiment
Below in conjunction with the specific embodiment, foregoing invention content of the present invention is described in further detail.But this should be interpreted as that the scope of the above-mentioned theme of the present invention only limits to following embodiment.Not breaking away from the above-mentioned technological thought situation of the present invention, according to ordinary skill knowledge and customary means, make various replacements and change, all should comprise within the scope of the invention.
Embodiment 1
Take metal aluminum foil as raw material, add in three-neck flask together with hydrochloric acid that the concentration that configures is 1mol/L, then keep 8h in 80 ℃ of thermostat water baths, get aluminium colloidal sol, wherein in aluminium colloidal sol, the content of aluminium is counted 20wt% with aluminium oxide.Then taking respectively 5 parts of aluminium colloidal sols and silica alumina ratio and be 50 the Hydrogen Pentasil type zeolite molecular sieve of 95 parts is positioned in three-neck flask, process 8h again in 80 ℃ of thermostat water baths, and constantly stir, then with deionized water wash to filtrate pH value be 6.5～7.5.Dry 16h in the blast dry oven of 110 ℃ again, then in Muffle furnace 550 ℃ of lower roasting 6h, namely get required catalyst for producing ethylene with ethyl alcohol.
Embodiment 2
Take metal aluminum foil as raw material, add in three-neck flask together with oxalic acid that the concentration that configures is 10mol/L, then keep 8h in 100 ℃ of thermostat water baths, get aluminium colloidal sol, wherein in aluminium colloidal sol, the content of aluminium is counted 5wt% with aluminium oxide.Then taking respectively 30 parts of aluminium colloidal sols and silica alumina ratio and be 200 the Hydrogen Pentasil type zeolite molecular sieve of 70 parts is positioned in three-neck flask, process 12h again in 75 ℃ of thermostat water baths, and constantly stir, then with deionized water wash to filtrate pH value be 6.5～7.5.Dry 24h in the blast dry oven of 100 ℃ again, then in Muffle furnace 500 ℃ of lower roasting 6h, namely get required catalyst for producing ethylene with ethyl alcohol.
Embodiment 3
Take metal aluminum foil as raw material, add in three-neck flask together with acetic acid that the concentration that configures is 8mol/L, then keep 12h in 60 ℃ of thermostat water baths, get aluminium colloidal sol, wherein in aluminium colloidal sol, the content of aluminium is counted 15wt% with aluminium oxide.Then taking respectively 10 parts of aluminium colloidal sols and silica alumina ratio and be 140 the Hydrogen Pentasil type zeolite molecular sieve of 90 parts is positioned in three-neck flask, process 36h again in 60 ℃ of thermostat water baths, and constantly stir, then being washed with distilled water to filtrate pH value is 6.5～7.5.Dry 2h in the blast dry oven of 120 ℃ again, then in Muffle furnace 400 ℃ of lower roasting 24h.Both required producing ethylene with ethyl alcohol catalyst.
Embodiment 4
Take metal aluminum foil as raw material, add in three-neck flask together with nitric acid that the concentration that configures is 0.1mol/L, then keep 4h in 100 ℃ of thermostat water baths, get aluminium colloidal sol, wherein in aluminium colloidal sol, the content of aluminium is counted 25wt% with aluminium oxide.Then taking respectively 15 parts of aluminium colloidal sols and silica alumina ratio and be 25 the Hydrogen Pentasil type zeolite molecular sieve of 85 parts is positioned in three-neck flask, process 4h again in 90 ℃ of thermostat water baths, and constantly stir, then being washed with distilled water to filtrate pH value is 6.5～7.5.Dry 8h in the blast dry oven of 110 ℃ again, then in Muffle furnace 550 ℃ of lower roasting 4h.Both required producing ethylene with ethyl alcohol catalyst.
Embodiment 5
Take metal aluminum foil as raw material, add in three-neck flask together with acetic acid mixed solution that the concentration that configures is the hydrochloric acid of 1mol/L and 1mol/L, keep 6h in 100 ℃ of thermostat water baths again, get aluminium colloidal sol, wherein in aluminium colloidal sol, the content of aluminium is counted 15wt% with aluminium oxide.Then taking respectively 10 parts of aluminium colloidal sols and silica alumina ratio and be 45 the Hydrogen Pentasil type zeolite molecular sieve of 90 parts is positioned in three-neck flask, process 24h again in 70 ℃ of thermostat water baths, and constantly stir, then being washed with distilled water to filtrate pH value is 6.5～7.5.Dry 18h in the blast dry oven of 110 ℃ again, then in Muffle furnace 450 ℃ of lower roasting 8h.Both required producing ethylene with ethyl alcohol catalyst.
Embodiment 6
After catalysqt deactivation in embodiment 5 (ethanol conversion drops to below 96%), this catalyst is regenerated, control 220 ℃ of bed temperatures, with the oxygen blow 6h of 100mL/min flow velocity 1%; Be warmed up to 420 ℃, with the oxygen blow 6h of 100mL/min flow velocity 1%; Being warmed up to 500 ℃, with the oxygen blow 1h of 10mL/min flow velocity 21%, is wherein nitrogen beyond oxygen, and nitrogen is diluent gas.Then logical 99.9% above high pure nitrogen is down to 220 ℃ of reaction temperatures with reaction bed temperature, and guarantees that in reactor, oxygen content is down to below 0.5%.
Embodiment 7
After catalysqt deactivation in embodiment 5 (ethanol conversion drops to below 96%), this catalyst is regenerated, control 320 ℃ of bed temperatures, with the oxygen blow 0.5h of 10mL/min flow velocity 21%; Be warmed up to 440 ℃, with the oxygen blow 0.5h of 10mL/min flow velocity 21%; Be warmed up to 460 ℃, with the oxygen blow 18h of 100mL/min flow velocity 1%, be wherein nitrogen beyond oxygen, nitrogen is diluent gas, then logical 99.9% above high pure nitrogen is down to 300 ℃ of reaction temperatures with reaction bed temperature, and guarantees that in reactor, oxygen content is down to below 0.5%.
Embodiment 8
After catalysqt deactivation in embodiment 5 (ethanol conversion drops to below 96%), this catalyst is regenerated, control 280 ℃ of bed temperatures, with the oxygen blow 3.5h of 40mL/min flow velocity 12%; Be warmed up to 430 ℃, with the oxygen blow 4h of 50mL/min flow velocity 15%; Be warmed up to 480 ℃, with the oxygen blow 8h of 60mL/min flow velocity 15%, be wherein nitrogen beyond oxygen, nitrogen is diluent gas, then logical 99.9% above high pure nitrogen is down to 260 ℃ of reaction temperatures with reaction bed temperature, and guarantees that in reactor, oxygen content is down to below 0.5%.
Above each embodiment catalyst activity appreciation condition is: the fixed bed isothermal reactor, and loaded catalyst 10g, take ethanol as raw material, water (content is 40%) is diluent, normal pressure, gas space velocity is 0.6 h
-1～1.8h
-1, 220 ℃～300 ℃ of bed temperatures.Table 1 is the activity data after evaluating catalyst 400h.
The activity rating table of table 1 catalyst
As seen from the above table, the present invention is all better in aspect performances such as ethanol conversion, ethylene selectivities.
In sum, the present invention adopts Pentasil type zeolite molecular sieve as catalyst, take molecular sieve powder as basic material, be prepared from through the heat treatment of aluminium colloidal sol, the acid strength that it is suitable and acid total amount are very favourable to the producing ethylene from dehydration of ethanol reaction, and high dispersive contains al composition can improve its catalytic performance, have high hydrothermal stability, silica alumina ratio is adjustable and polymolecularity, have that reaction temperature is low, the catalyst activity and selectivity advantages of higher, renewable more than 6 times, superior performance.
Claims (8)
1. synthetic method that is used for the catalyst of producing ethylene with ethyl alcohol is characterized in that comprising the following steps:
(1) first take in mass the aluminium colloidal sol of 5 parts～30 parts, in aluminium colloidal sol, take the aluminium content of aluminium oxide as 5 wt%～25wt%, this is slurries A;
(2) be 25～200 Hydrogen Pentasil type zeolite molecular sieve powder while stirring the silica alumina ratio of 70 parts～95 parts that slowly adds in the slurries A in mass, obtain homogeneous slurry B;
(3) with after the processing of slurries B heat modification, washing, drying, then be placed in the Muffle furnace roasting, namely get the catalyst of producing ethylene with ethyl alcohol.
2. be used for the synthetic method of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: aluminium colloidal sol preparation method, be take metal aluminum foil as raw material, adding concentration is at least aly in hydrochloric acid, nitric acid, oxalic acid or the acetic acid of 0.1mol/L～10mol/L to keep 4～12h in 60 ℃～100 ℃ thermostat water baths.
3. be used for the synthetic method of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: in step (3), the modification of slurries B for processing 4～36h in 60 ℃～90 ℃ waters bath with thermostatic control, constantly stirs simultaneously.
4. be used for the synthetic method of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: washing described in step (3) refers to wash to filtrate pH value as 6.5～7.5 take deionized water or distilled water.
5. be used for the synthetic method of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: the drying described in step (3) refers to dry 2～24h in the blast dry oven of 100 ℃～120 ℃.
6. be used for the synthetic method of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: the roasting described in step (3) refers to 400 ℃～550 ℃ lower roasting 4～24h in Muffle furnace.
7. be used for the renovation process of the catalyst of producing ethylene with ethyl alcohol described in claim 1, it is characterized in that: comprise the following steps:
(1) control 220 ℃～320 ℃ of bed temperatures, with the oxygen blow 0.5～6h of 10～100mL/min flow velocity 1%～21%;
(2) be warmed up to 420 ℃～440 ℃, with the oxygen blow 0.5～6h of 10～100mL/min flow velocity 1%～21%;
(3) be warmed up to 460 ℃～500 ℃, with the oxygen blow 1～18h of 10～100mL/min flow velocity 1%～21%;
(4) purge the reaction temperature of reaction bed temperature to 220 ℃～300 ℃ with 99.9% above high pure nitrogen, and guarantee that in reactor, oxygen content is down to below 0.5%.
8. be used for the renovation process of the catalyst of producing ethylene with ethyl alcohol described in claim 7, it is characterized in that: be nitrogen in step (1)--(3) beyond oxygen, nitrogen is diluent gas.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540736A (en) * | 2016-10-14 | 2017-03-29 | 太原理工大学 | A kind of hierarchical pore molecular sieve catalyst of Ethanol Dehydration ethylene and its preparation method and application |
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|---|---|---|---|---|
| EP0022640A1 (en) * | 1979-07-09 | 1981-01-21 | Commonwealth Scientific And Industrial Research Organisation | Improved zeolite catalysts, method for their preparation and their use in the conversion of ethanol into ethylene and of both into higher hydrocarbons |
| CN102059137A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene (MTP) from methanol, preparation method and regeneration method thereof |
| CN102294263A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | In-situ regeneration method for ethanol dehydration ZSM-5 zeolite catalyst |
| CN102527426A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Preparation method for catalyst for preparing ethylene by dehydrating ethanol |
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2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0022640A1 (en) * | 1979-07-09 | 1981-01-21 | Commonwealth Scientific And Industrial Research Organisation | Improved zeolite catalysts, method for their preparation and their use in the conversion of ethanol into ethylene and of both into higher hydrocarbons |
| CN102294263A (en) * | 2010-06-24 | 2011-12-28 | 中国石油化工股份有限公司 | In-situ regeneration method for ethanol dehydration ZSM-5 zeolite catalyst |
| CN102059137A (en) * | 2010-11-18 | 2011-05-18 | 大唐国际化工技术研究院有限公司 | ZSM-5 zeolite catalyst for preparing propylene (MTP) from methanol, preparation method and regeneration method thereof |
| CN102527426A (en) * | 2011-12-15 | 2012-07-04 | 西南化工研究设计院 | Preparation method for catalyst for preparing ethylene by dehydrating ethanol |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106540736A (en) * | 2016-10-14 | 2017-03-29 | 太原理工大学 | A kind of hierarchical pore molecular sieve catalyst of Ethanol Dehydration ethylene and its preparation method and application |
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| CN103157503B (en) | 2015-09-30 |
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