CN103157503B - A kind of synthesis of the catalyst for producing ethylene with ethyl alcohol and renovation process - Google Patents
A kind of synthesis of the catalyst for producing ethylene with ethyl alcohol and renovation process Download PDFInfo
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- CN103157503B CN103157503B CN201310104735.4A CN201310104735A CN103157503B CN 103157503 B CN103157503 B CN 103157503B CN 201310104735 A CN201310104735 A CN 201310104735A CN 103157503 B CN103157503 B CN 103157503B
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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 81
- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 235000019441 ethanol Nutrition 0.000 title claims abstract description 34
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 239000005977 Ethylene Substances 0.000 title claims abstract description 27
- 238000000034 method Methods 0.000 title claims abstract description 20
- 230000008569 process Effects 0.000 title claims abstract description 16
- 238000009418 renovation Methods 0.000 title claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 title abstract description 4
- 238000003786 synthesis reaction Methods 0.000 title abstract description 4
- 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 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- 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 18
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 14
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 12
- 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
- 239000004411 aluminium Substances 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 8
- 230000004048 modification Effects 0.000 claims abstract description 7
- 238000012986 modification Methods 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims abstract description 6
- 238000010189 synthetic method Methods 0.000 claims abstract description 6
- 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 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 7
- 239000011888 foil Substances 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
- 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
- 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
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000010926 purge Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 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
- 238000010306 acid treatment Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 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
- 238000011069 regeneration method Methods 0.000 description 2
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 description 1
- 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
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 kind of synthetic method of the catalyst for producing ethylene with ethyl alcohol, comprise the following steps: (1) first takes the Alumina gel of 5 parts ~ 30 parts in mass, in Alumina gel in the aluminium content of aluminium oxide for 5wt% ~ 25wt%, this is slurries A; (2) stir while the silica alumina ratio slowly adding 70 parts ~ 95 parts in mass in slurries A is the Hydrogen Pentasil type zeolite molecular sieve powder of 25 ~ 200, obtain homogeneous slurry B; (3) by after the process of slurries B heat modification, washing, dry, then be placed in Muffle furnace roasting, obtain the catalyst of producing ethylene with ethyl alcohol.The present invention discloses a kind of renovation process of this catalyst.The inventive method synthesis catalyst has high hydrothermal stability, silica alumina ratio is adjustable and the feature such as polymolecularity, have that reaction temperature is low, catalyst activity and selectivity advantages of higher, repeatedly renewable, superior performance.
Description
Technical field
A kind of synthesis of the catalyst for producing ethylene with ethyl alcohol and renovation process
Technical field
The invention belongs to catalyst field, particularly relate to a kind of for the synthetic method of the catalyst of producing ethylene with ethyl alcohol, and the renovation process of this catalyst.
Background technology
Ethene is important basic petrochemical raw material, can in order to produce multiple important Organic Chemicals.But in short supply due to oil supply, the rise of crude oil price and conventional petroleum route produce the environmental problem that ethene brings, and non-traditional petroleum path produces ethene will have very large market prospects.The acquisition of bio-ethanol industry is flourish has catered to these needs just, and simultaneously along with the maturation of bio-ethanol technology, the continuous reduction of bio-ethanol cost, makes alcohol production ethylene process have more economic advantages.
At present, molecular sieve catalyst due to its heat endurance and hydrothermal stability high, framework silicon-aluminum mol ratio can regulate and control in a big way, has strong acid and weak acid center simultaneously, usually has higher activity and selectivity to product.For improving its catalytic performance in producing ethylene with ethyl alcohol reaction, often need to carry out surface acidity process to it, method of modifying mainly contains steam treatment and acid treatment etc., reduces acid strength by removing framework aluminum or increases total acid content, if Chinese Patent Application No. is for described in 201010608182.2, but saboteur can sieve lattice like this, thus form skeleton defect, finally cause catalyst activity and stability to decline, if frequent regeneration, also can destroy its skeleton structure, shorten its service life.
Summary of the invention
The object of the invention is to overcome prior art above shortcomings, a kind of synthetic method of catalyst of producing ethylene with ethyl alcohol is provided, take Alumina gel as modifier synthetic catalyst, this catalyst is after peracid modification, its suitable acid strength and acid total amount react very favourable to producing ethylene from dehydration of ethanol, be scattered in molecular sieve containing al composition with high dispersion state in addition, this high dispersive can form new meso-hole structure containing al composition, improve 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, present invention also offers a kind of renovation process of described catalyst.
To achieve these goals, the present invention adopts following technical proposals:
For a synthetic method for the catalyst of producing ethylene with ethyl alcohol, comprise the following steps:
(1) first take the Alumina gel of 5 parts ~ 30 parts in mass, in Alumina gel in the aluminium content of aluminium oxide for 5wt% ~ 25wt%, this is slurries A;
(2) stir while the silica alumina ratio slowly adding 70 parts ~ 95 parts in mass in slurries A is the Hydrogen Pentasil type zeolite molecular sieve powder of 25 ~ 200, obtain homogeneous slurry B;
(3) by after the process of slurries B heat modification, washing, dry, then be placed in Muffle furnace roasting, obtain the catalyst of producing ethylene with ethyl alcohol.
Alumina gel preparation method is raw material with metal aluminum foil, adds at least one in hydrochloric acid, nitric acid, oxalic acid or the acetic acid that concentration is 0.1mol/L ~ 10mol/L and keep 4 ~ 12h in 60 DEG C ~ 100 DEG C thermostat water baths.
In step (3), the modification of slurries B is in 60 DEG C ~ 90 DEG C water bath with thermostatic control process 4 ~ 36h, constantly stirs simultaneously.
Described in step (3) washing refer to deionized water or distilled water washing to filtrate pH value for 6.5 ~ 7.5.
Drying described in step (3) refers to dry 2 ~ 24h in the blast dry oven of 100 DEG C ~ 120 DEG C.
Roasting described in step (3) to refer in Muffle furnace roasting 4 ~ 24h at 400 DEG C ~ 550 DEG C.
The renovation process of the described catalyst for producing ethylene with ethyl alcohol, is characterized in that: comprise the following steps:
(1) bed temperature 220 DEG C ~ 320 DEG C is controlled, with the oxygen blow 0.5 ~ 6h of 10 ~ 100mL/min flow velocity 1% ~ 21%;
(2) 420 DEG C ~ 440 DEG C are warmed up to, with the oxygen blow 0.5 ~ 6h of 10 ~ 100mL/min flow velocity 1% ~ 21%;
(3) 460 DEG C ~ 500 DEG C are warmed up to, 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 DEG C ~ 300 DEG C with more than 99.9% high pure nitrogen, and ensure that in reactor, oxygen content is down to less than 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, the such as patent No. is 200810244135.7 patents being called " a kind of catalyst for ethanol delydration to ethylene and its preparation method and application ", but continuous print product yield easily fluctuates, less stable, regenerability is not good enough yet.The inventive method avoids simultaneously and adopts steam treatment and acid treatment to remove framework aluminum to reduce acid strength or to increase total acid content; protect molecular sieve lattice be not damaged and form skeleton defect; its excellent catalytic performance finally also avoids frequent regeneration to cause the destruction of its skeleton structure, fundamentally ensures its longer service life.
Catalyst of the present invention, at 60% concentration of alcohol, air speed 0.6 h
-1~ 1.8h
-1and under 220 DEG C ~ 300 DEG C reaction conditions, ethanol average conversion reaches more than 96%; At 0.6h
-1and under 275 DEG C 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, and raw material based on molecular sieve powder, is prepared from through Alumina gel heat treatment, 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 peracid modification, its suitable acid strength and acid total amount react very favourable to producing ethylene from dehydration of ethanol, be scattered in molecular sieve containing al composition with high dispersion state, this high dispersive can form new meso-hole structure containing al composition, improves the diffusivity of reaction medium, improves its catalytic performance.Catalyst prepared by the inventive method has high hydrothermal stability, silica alumina ratio is adjustable and the feature such as polymolecularity, has that reaction temperature is low, catalyst activity and selectivity advantages of higher, renewable more than 6 times, superior performance.
Detailed description of the invention
Below in conjunction with detailed description of the invention, 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 is only limitted to following embodiment.Without departing from the idea case in the present invention described above, according to ordinary skill knowledge and customary means, make various replacement 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 the hydrochloric acid that the concentration configured is 1mol/L, then keep 8h in 80 DEG C of thermostat water baths, obtain Alumina gel, wherein in Alumina gel, the content of aluminium counts 20wt% with aluminium oxide.Then taking 5 parts of Alumina gel and silica alumina ratio is respectively that the Hydrogen Pentasil type zeolite molecular sieve of 50 95 parts is positioned in three-neck flask, 8h is processed again in 80 DEG C of thermostat water baths, and constantly stir, then spending deionized water to filtrate pH value is 6.5 ~ 7.5.Dry 16h in the blast dry oven of 110 DEG C again, then in Muffle furnace roasting 6h at 550 DEG C, obtain the required catalyst for producing ethylene with ethyl alcohol.
embodiment 2
Take metal aluminum foil as raw material, add in three-neck flask together with the oxalic acid that the concentration configured is 10mol/L, then keep 8h in 100 DEG C of thermostat water baths, obtain Alumina gel, wherein in Alumina gel, the content of aluminium counts 5wt% with aluminium oxide.Then taking 30 parts of Alumina gel and silica alumina ratio is respectively that the Hydrogen Pentasil type zeolite molecular sieve of 200 70 parts is positioned in three-neck flask, 12h is processed again in 75 DEG C of thermostat water baths, and constantly stir, then spending deionized water to filtrate pH value is 6.5 ~ 7.5.Dry 24h in the blast dry oven of 100 DEG C again, then in Muffle furnace roasting 6h at 500 DEG C, obtain the required catalyst for producing ethylene with ethyl alcohol.
embodiment 3
Take metal aluminum foil as raw material, add in three-neck flask together with the acetic acid that the concentration configured is 8mol/L, then keep 12h in 60 DEG C of thermostat water baths, obtain Alumina gel, wherein in Alumina gel, the content of aluminium counts 15wt% with aluminium oxide.Then taking 10 parts of Alumina gel and silica alumina ratio is respectively that the Hydrogen Pentasil type zeolite molecular sieve of 140 90 parts is positioned in three-neck flask, 36h is processed again in 60 DEG C of thermostat water baths, and constantly stir, being then washed with distilled water to filtrate pH value is 6.5 ~ 7.5.Dry 2h in the blast dry oven of 120 DEG C again, then in Muffle furnace roasting 24h at 400 DEG C.Both required producing ethylene with ethyl alcohol catalyst had been obtained.
embodiment 4
Take metal aluminum foil as raw material, add in three-neck flask together with the nitric acid that the concentration configured is 0.1mol/L, then keep 4h in 100 DEG C of thermostat water baths, obtain Alumina gel, wherein in Alumina gel, the content of aluminium counts 25wt% with aluminium oxide.Then taking 15 parts of Alumina gel and silica alumina ratio is respectively that the Hydrogen Pentasil type zeolite molecular sieve of 25 85 parts is positioned in three-neck flask, 4h is processed again in 90 DEG C of thermostat water baths, and constantly stir, being then washed with distilled water to filtrate pH value is 6.5 ~ 7.5.Dry 8h in the blast dry oven of 110 DEG C again, then in Muffle furnace roasting 4h at 550 DEG C.Both required producing ethylene with ethyl alcohol catalyst had been obtained.
embodiment 5
Take metal aluminum foil as raw material, being 1mol/L with the concentration configured, hydrochloric acid adds in three-neck flask together with the acetic acid mixed solution of 1mol/L, keep 6h in 100 DEG C of thermostat water baths again, obtain Alumina gel, wherein in Alumina gel, the content of aluminium counts 15wt% with aluminium oxide.Then taking 10 parts of Alumina gel and silica alumina ratio is respectively that the Hydrogen Pentasil type zeolite molecular sieve of 45 90 parts is positioned in three-neck flask, 24h is processed again in 70 DEG C of thermostat water baths, and constantly stir, being then washed with distilled water to filtrate pH value is 6.5 ~ 7.5.Dry 18h in the blast dry oven of 110 DEG C again, then in Muffle furnace roasting 8h at 450 DEG C.Both required producing ethylene with ethyl alcohol catalyst had been obtained.
embodiment 6
In embodiment 5 after catalysqt deactivation (ethanol conversion drops to less than 96%), this catalyst is regenerated, control bed temperature 220 DEG C, with the oxygen blow 6h of 100mL/min flow velocity 1%; Be warmed up to 420 DEG C, with the oxygen blow 6h of 100mL/min flow velocity 1%; Be warmed up to 500 DEG C, with the oxygen blow 1h of 10mL/min flow velocity 21%, be wherein nitrogen beyond oxygen, nitrogen is diluent gas.Then reaction bed temperature is down to reaction temperature 220 DEG C by logical more than 99.9% high pure nitrogen, and ensures that in reactor, oxygen content is down to less than 0.5%.
embodiment 7
In embodiment 5 after catalysqt deactivation (ethanol conversion drops to less than 96%), this catalyst is regenerated, control bed temperature 320 DEG C, with the oxygen blow 0.5h of 10mL/min flow velocity 21%; Be warmed up to 440 DEG C, with the oxygen blow 0.5h of 10mL/min flow velocity 21%; Be warmed up to 460 DEG C, with the oxygen blow 18h of 100mL/min flow velocity 1%, be wherein nitrogen beyond oxygen, nitrogen is diluent gas, then reaction bed temperature is down to reaction temperature 300 DEG C by logical more than 99.9% high pure nitrogen, and ensures that in reactor, oxygen content is down to less than 0.5%.
embodiment 8
In embodiment 5 after catalysqt deactivation (ethanol conversion drops to less than 96%), this catalyst is regenerated, control bed temperature 280 DEG C, with the oxygen blow 3.5h of 40mL/min flow velocity 12%; Be warmed up to 430 DEG C, with the oxygen blow 4h of 50mL/min flow velocity 15%; Be warmed up to 480 DEG C, with the oxygen blow 8h of 60mL/min flow velocity 15%, be wherein nitrogen beyond oxygen, nitrogen is diluent gas, then reaction bed temperature is down to reaction temperature 260 DEG C by logical more than 99.9% high pure nitrogen, and ensures that in reactor, oxygen content is down to less than 0.5%.
Each embodiment catalyst activity appreciation condition is above: fixed bed isothermal reactor, loaded catalyst 10g, and take ethanol as raw material, water (content is 40%) is diluent, normal pressure, gas space velocity is 0.6 h
-1~ 1.8h
-1, bed temperature 220 DEG C ~ 300 DEG C.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's performance in ethanol conversion, ethylene selectivity etc. is all better.
In sum, the present invention adopts Pentasil type zeolite molecular sieve as catalyst, raw material based on molecular sieve powder, be prepared from through Alumina gel heat treatment, its suitable acid strength and acid total amount react very favourable to producing ethylene from dehydration of ethanol, and high dispersive can improve its catalytic performance containing al composition, there is high hydrothermal stability, silica alumina ratio is adjustable and polymolecularity, have that reaction temperature is low, catalyst activity and selectivity advantages of higher, renewable more than 6 times, superior performance.
Claims (3)
1., for a synthetic method for the catalyst of producing ethylene with ethyl alcohol, it is characterized in that comprising the following steps:
(1) first take the Alumina gel of 5 parts ~ 30 parts in mass, the aluminium content in aluminium oxide in Alumina gel is 5 wt% ~ 25wt%, and this is slurries A;
(2) stir while the silica alumina ratio slowly adding 70 parts ~ 95 parts in mass in slurries A is the Hydrogen Pentasil type zeolite molecular sieve powder of 25 ~ 200, obtain homogeneous slurry B;
(3) by after the process of slurries B heat modification, washing, dry, then be placed in Muffle furnace roasting, obtain the catalyst of producing ethylene with ethyl alcohol;
Alumina gel preparation method is raw material with metal aluminum foil, adds at least one in hydrochloric acid, nitric acid, oxalic acid or the acetic acid that concentration is 0.1mol/L ~ 10mol/L and keep 4 ~ 12h in 60 DEG C ~ 100 DEG C thermostat water baths;
In step (3), the modification of slurries B is in 60 DEG C ~ 90 DEG C water bath with thermostatic control process 4 ~ 36h, constantly stirs simultaneously; Described washing refer to deionized water or distilled water washing to filtrate pH value for 6.5 ~ 7.5; Described drying refers to dry 2 ~ 24h in the blast dry oven of 100 DEG C ~ 120 DEG C; Described roasting to refer in Muffle furnace roasting 4 ~ 24h at 400 DEG C ~ 550 DEG C.
2. the as described in claim 1 renovation process of the catalyst for producing ethylene with ethyl alcohol that obtains of synthetic method, is characterized in that: comprise the following steps:
(1) bed temperature 220 DEG C ~ 320 DEG C is controlled, with the oxygen blow 0.5 ~ 6h of 10 ~ 100mL/min flow velocity 1% ~ 21%;
(2) 420 DEG C ~ 440 DEG C are warmed up to, with the oxygen blow 0.5 ~ 6h of 10 ~ 100mL/min flow velocity 1% ~ 21%;
(3) 460 DEG C ~ 500 DEG C are warmed up to, 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 DEG C ~ 300 DEG C with more than 99.9% high pure nitrogen, and ensure that in reactor, oxygen content is down to less than 0.5%.
3. as stated in claim 2 for the renovation process of the catalyst of producing ethylene with ethyl alcohol, it is characterized in that: be nitrogen beyond oxygen in step (1)--(3), nitrogen is diluent gas.
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Citations (3)
| 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 |
| 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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Patent Citations (3)
| 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 |
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