CN107213913A - A kind of preparation method of low-carbon alkanes producing light olefins catalyst - Google Patents
A kind of preparation method of low-carbon alkanes producing light olefins catalyst Download PDFInfo
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- CN107213913A CN107213913A CN201710338128.2A CN201710338128A CN107213913A CN 107213913 A CN107213913 A CN 107213913A CN 201710338128 A CN201710338128 A CN 201710338128A CN 107213913 A CN107213913 A CN 107213913A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
- C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
- C07C5/333—Catalytic processes
- C07C5/3335—Catalytic processes with metals
- C07C5/3337—Catalytic processes with metals of the platinum group
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/44—Noble metals
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- 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
Abstract
The invention provides a kind of preparation method for low-carbon alkanes producing light olefins catalyst：Supported on carriers has the activity component metal element of carrier quality 0.01 5%, 0.01 10% assistant metal element, 0.01 10% alkali metal, 0.2 15% halogen and 0.01 3% element sulphur, and surplus is carrier.The present invention has the advantages that anti-carbon, long lifespan, high stability, high selectivity.
Description
Technical field
The present invention relates to a kind of preparation method for low-carbon alkanes producing light olefins catalyst.
Background technology
Low-carbon alkanes (C2-C5) dehydrogenation producing light olefins are one of important channels of its Optimum utilization, can be with by the process
A large amount of low-carbon alkanes catalytic dehydrogenations that the techniques such as catalytic cracking, naphtha steam cracking, MTO/MTP are produced generate corresponding alkene
Hydrocarbon and hydrogen.As the whole world is growing for the demand of low-carbon alkene, the process is increasingly valued by people.Mesh
Before, low-carbon alkanes are burned off mainly as fuel, dehydrogenating low-carbon alkane producing light olefins technology are developed, for making full use of low-carbon
Alkane resource and the new low-carbon alkene source of exploitation have great importance.The related process of alkane direct dehydrogenation mainly includes
The Olfiex techniques, the Catfin techniques of Air Product＆Chemical companies, the Star works of Phillips companies of Uop Inc.
Skill and the Linde techniques of German Linde Co etc., but it is domestic still without dehydrogenating low-carbon alkane producing light olefins so far
Industrialized unit, its key of the process is to develop the catalyst with high activity and stability, therefore the research and development of catalyst
It is significant for the industrialization and large-scale application that promote the process.
Dehydrogenating low-carbon alkane reaction under high temperature, lower pressure carry out, with reaction carry out catalyst surface carbon distribution from
And causing catalyst inactivation, catalyst needs timely regeneration or replacing repeatedly, is the main cause for limiting its large-scale application.
The catalyst for including platinum group in alkane dehydrogenating catalyst for main active component, addition all kinds auxiliary agent is it
In a mostly important class, using Al2O3, Y type molecular sieve, ZSM-5 etc. as carrier, then drawn by different synthetic methods
Enter Sn elements, while add alkali and alkaline earth metal ions etc. has carried out modulation, but catalyst as auxiliary agent to the performance of catalyst
Carbon distribution situation is still than more serious, and catalyst is after decarbonizing is lived again, and activity occurs in that obvious decline.
Above-mentioned catalyst, as active component, passes through different synthetic methods and addition different type using precious metals pt
Auxiliary agent so that the performance of catalyst has obtained a certain degree of improvement, but the problem of fundamentally do not solve catalyst carbon deposition,
Thus the usage cycles of catalyst are shorter, it is necessary to which timely regeneration repeatedly, considerably increases production cost.
The content of the invention
The invention provides a kind of preparation method for low-carbon alkanes producing light olefins catalyst, the catalyst has anti-
The characteristics of carbon distribution, long lifespan, high stability, high selectivity.
The composition of catalyst of the present invention is：
0.01-5% activity component metal element, 0.01-10% assistant metal element, 0.01-10% alkali metal
Element, 0.2-15% halogen and 0.01-3% element sulphur, surplus is carrier.
Activity component metal as described above is the one or more in platinum, palladium, iridium, rhodium, osmium or rhenium, wherein using platinum as most
It is good.
Promoter metal as described above is one or more of elements in Si, Ge, Sn or Pb.
Alkali metal as described above is one or more of elements in Li, Na, K, Rb, Cs or Fr.
Halogen as described above is F, Cl, Br, I or At halogen.
Element sulphur as described above is S.
Carrier as described above is ZSM-5 molecular sieve.
The method for preparing catalyst that the present invention is provided comprises the following steps：
(1) carrier is warming up to 600-900 DEG C with 3-5 DEG C/min, is calcined 10-12h, obtains pretreated carrier；
(2) the soluble predecessor of auxiliary agent is configured to the aqueous solution that concentration is 0.01-10mol/L, then by catalyst
Composition, which adds carrier in solution, impregnates stirred in water bath of the carrier after 8-10h, dipping at 80-100 DEG C, then in 120-
140 DEG C of drying 12-24h, resulting sample is warming up to after 600-800 DEG C, roasting 10-12h with 2-4 DEG C/min, born
Carry the carrier of auxiliary agent oxide；
(3) the 0.01-50mol/L aqueous solution is configured to the soluble predecessor of active component again, is constituted by catalyst
On carrier obtained by being impregnated in step (2), stand and upper strata raffinate is removed after 12-15h, and after 120-140 DEG C of dry 10-
12h, is warming up to 600-800 DEG C of roasting 12-16h with 2-4 DEG C/min, the load of oxide containing active component and auxiliary agent oxide is made
Body；
(4) soluble-salt of alkali metal is configured to the 0.01-10mol/L aqueous solution, then added by the composition of catalyst
Enter into step (3) in obtained carrier, stand after 9-12h, 24-48h is dried in 120-140 DEG C, by resulting sample with
2-4 DEG C/min is warming up to after 600-800 DEG C, roasting 10-12h, and taking-up is cooled to room temperature；
(5) soluble-salt of halogen element is configured to the 0.2-15mol/L aqueous solution, then added by the composition of catalyst
Into step (4) in obtained carrier, stand after 9-12h, 24-48h is dried in 120-140 DEG C, by resulting sample with 2-4
DEG C/min is warming up to 600-800 DEG C, after roasting 10-12h, taking-up is cooled to room temperature；
(6) soluble-salt of element sulphur is configured to the 0.01-3mol/L aqueous solution, then added by the composition of catalyst
Into step (5) in obtained carrier, stand after 9-12h, 24-48h is dried in 120-140 DEG C, by resulting sample with 2-4
DEG C/min is warming up to 600-800 DEG C, after roasting 10-12h, taking-up is cooled to room temperature；
(7) with the H containing 0.1-5ppm2Sample obtained by mixed gas reduction step (6), mixture pressure is
1-2.5MPa, the temperature of processing is 200-400 DEG C, and the air speed of gas is 10000-15000/h, and heating rate is 2-4 DEG C/min,
Sample is handled after 5-8h under this condition, is cooled to room temperature, that is, is obtained catalyst.
The present invention has the following advantages that compared with prior art：
(1) it is characteristic of the invention that increasing halogen in active component, its anti-carbon performance is strengthened, so as to strengthen it
Stability, reduce its frequency lived again, improve production efficiency.
(2) catalyst that the present invention is provided is on the premise of olefine selective is ensured, conversion per pass is also of a relatively high, because
And with great potential industrial application value.
(3) catalyst is handled by element sulphur in preparation process, and catalyst is during the course of the reaction for the pure of unstripped gas
Change and require reduction, simplify the related process links such as purification.
Embodiment
The following examples are that the present invention is further illustrated, rather than limitation of the present invention, unless otherwise specified, institute
There is the percentage composition in embodiment to be weight percentage.
Embodiment 1
(1) first by the advance 600 DEG C of roasting 10h in Muffle furnace of carrier ZSM-5, heating rate is 3 DEG C/min.Then match somebody with somebody
The SnCl that concentration is 0.01mol/L is put2Solution is added rapidly on pretreated carrier, after dipping 8h, is placed in 80 DEG C
Stirred in water bath, after dry 12h at 120 DEG C, resulting sample is warming up to 600 DEG C of roastings in Muffle furnace with 2 DEG C/min
10h。
(2) platinum acid chloride solution for having configured 0.01mol/L is then added dropwise to Sn/Al2O3On carrier, stand after 12h,
Treat that the colourless hypsokinesis of upper liquid goes to impregnate raffinate, be then placed in 120 DEG C of drying 10h of baking oven.Sample after drying is placed in Muffle furnace with 2
DEG C/min be warming up to 600 DEG C roasting 12h.
(3) by 0.01mol/L KNO3The aqueous solution is dipped in Pt-Sn/Al2O3On, stand after 9h, 24h is dried in 120 DEG C.Dry
Sample after dry is placed in Muffle furnace and is warming up to 2 DEG C/min after 600 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(4) by 0.2mol/L AlCl3The aqueous solution is dipped in K-Pt-Sn/Al2O3On,
Stand after 9h, 24h is dried in 120 DEG C, the sample after drying is placed in Muffle furnace and is warming up to 600 DEG C of roasting 10h with 2 DEG C/min
Afterwards, take out and be cooled to room temperature.
(5) by 0.01mol/L H2SO4The aqueous solution is dipped in Cl-K-Pt-Sn/Al2O3On, stand after 9h, in 120 DEG C of drying
24h, the sample after drying is placed in Muffle furnace and is warming up to 2 DEG C/min after 600 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(6) by S-Cl-K-Pt-Sn/Al2O3It is placed in tube furnace, the H containing 0.1ppm2Mixed gas is in 200 DEG C of processing
5h, heating rate is 2 DEG C/min, and mixture pressure is 1.0MPa, and air speed is 10000/h.Resulting sample is cooled to room
Temperature is to obtain catalyst.
The performance of the catalyst dehydrogenating propane is as shown in table 1.
The catalyst dehydrogenating propane reaction experiment result of table 1
| Reaction time (h) | Conversion of propane (%) | Olefine selective (%) | Olefin yields (%) |
| Initially | 56.2 | 90.3 | 50.3 |
| 4 | 55.8 | 88.9 | 49.1 |
| 8 | 54.6 | 87.3 | 47.9 |
| 12 | 52.9 | 86.8 | 46.1 |
| 16 | 50.4 | 86.3 | 44.8 |
| 20 | 48.1 | 84.9 | 42.7 |
| 30 | 46.8 | 83.8 | 40.6 |
The catalyst has preferable dehydrogenating propane performance, and preferable reactivity is still kept after reaction 30h.
Embodiment 2
(1) first by the advance 700 DEG C of roasting 11h in Muffle furnace of carrier ZSM-5, heating rate is 4 DEG C/min.Then match somebody with somebody
The SnCl that concentration is 0.05mol/L is put2Solution is added rapidly on pretreated carrier, after dipping 9h, is placed in 90 DEG C
Stirred in water bath, after dry 14h at 130 DEG C, resulting sample is warming up to 700 DEG C of roastings in Muffle furnace with 3 DEG C/min
12h。
(2) platinum acid chloride solution for having configured 5mol/L is then added dropwise to Sn/Al2O3On carrier, stand after 13h, treat
The layer colourless hypsokinesis of liquid goes to impregnate raffinate, is then placed in 130 DEG C of drying 10h of baking oven.Sample after drying be placed in Muffle furnace with 3 DEG C/
Min is warming up to 700 DEG C of roasting 12h.
(3) by 5mol/L KNO3The aqueous solution is dipped in Pt-Sn/Al2O3On, stand after 10h, 28h is dried in 130 DEG C.Drying
Sample afterwards is placed in Muffle furnace and is warming up to 3 DEG C/min after 700 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(4) by 5mol/L AlCl3The aqueous solution is dipped in K-Pt-Sn/Al2O3On,
Stand after 10h, 24h is dried in 130 DEG C, the sample after drying is placed in Muffle furnace and is warming up to 700 DEG C of roastings with 3 DEG C/min
After 10h, taking-up is cooled to room temperature.
(5) by 1mol/L H2SO4The aqueous solution is dipped in Cl-K-Pt-Sn/Al2O3On, stand after 9h, in 130 DEG C of drying
24h, the sample after drying is placed in Muffle furnace and is warming up to 4 DEG C/min after 700 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(6) by S-Cl-K-Pt-Sn/Al2O3It is placed in tube furnace, the H containing 0.5ppm2Mixed gas is in 300 DEG C of processing
5h, heating rate is 2 DEG C/min, and mixture pressure is 1.0MPa, and air speed is 12000/h.Resulting sample is cooled to room
Temperature is to obtain catalyst.
The performance of the catalyst dehydrogenating propane is as shown in table 2.
The catalyst dehydrogenating propane reaction experiment result of table 2
| Reaction time (h) | Conversion of propane (%) | Olefine selective (%) | Olefin yields (%) |
| Initially | 54.9 | 89.9 | 52.3 |
| 4 | 54.1 | 88.8 | 51.1 |
| 8 | 53.7 | 87.7 | 50.9 |
| 12 | 53.1 | 86.8 | 49.1 |
| 16 | 52.5 | 85.3 | 47.8 |
| 20 | 51.6 | 84.6 | 45.7 |
| 30 | 50.3 | 83.3 | 44.6 |
The catalyst has preferable dehydrogenating propane performance, and preferable reactivity is still kept after reaction 30h.
Embodiment 3
(1) first by the advance 800 DEG C of roasting 11h in Muffle furnace of carrier ZSM-5, heating rate is 4 DEG C/min.Then match somebody with somebody
The SnCl that concentration is 7mol/L is put2Solution is added rapidly on pretreated carrier, after dipping 9h, is placed in 95 DEG C of water-bath
Middle stirring, after 18h are dried at 130 DEG C, resulting sample is warming up to 800 DEG C of roasting 10h in Muffle furnace with 4 DEG C/min.
(2) platinum acid chloride solution for having configured 15mol/L is then added dropwise to Sn/Al2O3On carrier, stand after 12h, treat
The colourless hypsokinesis of upper liquid goes to impregnate raffinate, is then placed in 140 DEG C of drying 12h of baking oven.Sample after drying is placed in Muffle furnace with 2
DEG C/min be warming up to 800 DEG C roasting 12h.
(3) by 6mol/L KNO3The aqueous solution is dipped in Pt-Sn/Al2O3On, stand after 10h, 24h is dried in 120 DEG C.Drying
Sample afterwards is placed in Muffle furnace and is warming up to 4 DEG C/min after 800 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(4) by 10mol/L AlCl3The aqueous solution is dipped in K-Pt-Sn/Al2O3On,
Stand after 9h, 24h is dried in 120 DEG C, the sample after drying is placed in Muffle furnace and is warming up to 800 DEG C of roasting 10h with 2 DEG C/min
Afterwards, take out and be cooled to room temperature.
(5) by 2.5mol/L H2SO4The aqueous solution is dipped in Cl-K-Pt-Sn/Al2O3On, stand after 9h, in 120 DEG C of drying
24h, the sample after drying is placed in Muffle furnace and is warming up to 4 DEG C/min after 800 DEG C of roasting 10h, and taking-up is cooled to room temperature.
(6) by S-Cl-K-Pt-Sn/Al2O3It is placed in tube furnace, the H containing 5ppm2Mixed gas handles 6h in 300 DEG C,
Heating rate is 4 DEG C/min, and mixture pressure is 1.0MPa, and air speed is 15000/h.Resulting sample is cooled to room temperature i.e.
To obtain catalyst.
The performance of the catalyst dehydrogenating propane is as shown in table 3.
The catalyst dehydrogenating propane reaction experiment result of table 3
| Reaction time (h) | Conversion of propane (%) | Olefine selective (%) | Olefin yields (%) |
| Initially | 55.8 | 91.3 | 50.3 |
| 4 | 54.3 | 89.9 | 49.1 |
| 8 | 53.6 | 87.3 | 47.9 |
| 12 | 52.3 | 86.8 | 46.1 |
| 16 | 51.4 | 86.3 | 44.8 |
| 20 | 48.9 | 84.9 | 42.7 |
| 30 | 47.8 | 83.8 | 40.6 |
The catalyst has preferable dehydrogenating propane performance, and preferable reactivity is still kept after reaction 30h.
Embodiment 3
(1) first by the advance 900 DEG C of roasting 12h in Muffle furnace of carrier ZSM-5, heating rate is 4 DEG C/min.Then match somebody with somebody
The SnCl that concentration is 10mol/L is put2Solution is added rapidly on pretreated carrier, after dipping 10h, is placed in 100 DEG C
Stirred in water bath, after dry 24h at 140 DEG C, resulting sample is warming up to 800 DEG C of roastings in Muffle furnace with 4 DEG C/min
16h。
(2) platinum acid chloride solution for having configured 50mol/L is then added dropwise to Sn/Al2O3On carrier, stand after 12h, treat
The colourless hypsokinesis of upper liquid goes to impregnate raffinate, is then placed in 140 DEG C of drying 12h of baking oven.Sample after drying is placed in Muffle furnace with 4
DEG C/min be warming up to 800 DEG C roasting 16h.
(3) by 10mol/L KNO3The aqueous solution is dipped in Pt-Sn/Al2O3On, stand after 12h, 48h is dried in 140 DEG C.Dry
Sample after dry is placed in Muffle furnace and is warming up to 4 DEG C/min after 800 DEG C of roasting 12h, and taking-up is cooled to room temperature.
(4) by 15mol/L AlCl3The aqueous solution is dipped in K-Pt-Sn/Al2O3On,
Stand after 12h, 48h is dried in 140 DEG C, the sample after drying is placed in Muffle furnace and is warming up to 800 DEG C of roastings with 4 DEG C/min
After 12h, taking-up is cooled to room temperature.
(5) by 3mol/L H2SO4The aqueous solution is dipped in Cl-K-Pt-Sn/Al2O3On, stand after 12h, in 140 DEG C of drying
48h, the sample after drying is placed in Muffle furnace and is warming up to 4 DEG C/min after 800 DEG C of roasting 12h, and taking-up is cooled to room temperature.
(6) by S-Cl-K-Pt-Sn/Al2O3It is placed in tube furnace, the H containing 5ppm2Mixed gas handles 8h in 400 DEG C,
Heating rate is 4 DEG C/min, and mixture pressure is 2.5MPa, and air speed is 15000/h.Resulting sample is cooled to room temperature i.e.
To obtain catalyst.
The performance of the catalyst dehydrogenating propane is as shown in table 4.
The catalyst dehydrogenating propane reaction experiment result of table 4
| Reaction time (h) | Conversion of propane (%) | Olefine selective (%) | Olefin yields (%) |
| Initially | 58.2 | 93.3 | 54.3 |
| 4 | 57.8 | 91.9 | 52.1 |
| 8 | 56.6 | 88.3 | 50.9 |
| 12 | 55.9 | 86.8 | 49.1 |
| 16 | 54.4 | 86.3 | 47.8 |
| 20 | 52.1 | 85.9 | 46.7 |
| 30 | 50.8 | 83.8 | 44.6 |
The catalyst has preferable dehydrogenating propane performance, and preferable reactivity is still kept after reaction 30h.
Claims (9)
1. one kind is used for low-carbon alkanes producing light olefins catalyst, it is characterised in that the composition of catalyst is：
Supported on carriers has a carrier quality 0.01-5% activity component metal element, 0.01-10% assistant metal element,
0.01-10% alkali metal, 0.2-15% halogen and 0.01-3% element sulphur, surplus is carrier.
2. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that activearm parting
Category is the one or more in platinum, palladium, iridium, rhodium, osmium or rhenium.
3. as claimed in claim 2 a kind of be used for low-carbon alkanes producing light olefins catalyst, it is characterised in that active component is
Metal is platinum.
4. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that described auxiliary agent
Metal is one or more of elements in Si, Ge, Sn or Pb.
5. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that described alkali gold
Belong to for one or more of elements in Li, Na, K, Rb, Cs or Fr.
6. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that described halogen family
Element is F, Cl, Br, I or At halogen.
7. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that described sulphur member
Element is S.
8. it is as claimed in claim 1 a kind of for low-carbon alkanes producing light olefins catalyst, it is characterised in that described carrier
For ZSM-5 molecular sieve.
9. a kind of preparation method for low-carbon alkanes producing light olefins catalyst as described in claim any one of 1-8, its
It is characterised by comprising the following steps：
(1) carrier is warming up to 600-900 DEG C with 3-5 DEG C/min, is calcined 10-12h, obtains pretreated carrier；
(2) the soluble predecessor of auxiliary agent is configured to the aqueous solution that concentration is 0.01-10mol/L, then constituted by catalyst
Carrier is added in solution and impregnates stirred in water bath of the carrier after 8-10h, dipping at 80-100 DEG C, then at 120-140 DEG C
12-24h is dried, resulting sample is warming up to after 600-800 DEG C, roasting 10-12h with 2-4 DEG C/min, obtains loading auxiliary agent
The carrier of oxide；
(3) the 0.01-50mol/L aqueous solution is configured to the soluble predecessor of active component again, constitutes and impregnate by catalyst
On carrier obtained by step (2), stand and upper strata raffinate is removed after 12-15h, and after 120-140 DEG C of dry 10-12h,
600-800 DEG C of roasting 12-16h is warming up to 2-4 DEG C/min, the carrier of oxide containing active component and auxiliary agent oxide is made；
(4) soluble-salt of alkali metal is configured to the 0.01-10mol/L aqueous solution, is then added to by the composition of catalyst
In step (3) in obtained carrier, stand after 9-12h, 24-48h is dried in 120-140 DEG C, by resulting sample with 2-4
DEG C/min is warming up to 600-800 DEG C, after roasting 10-12h, taking-up is cooled to room temperature；
(5) soluble-salt of halogen element is configured to the 0.2-15mol/L aqueous solution, then step is added to by the composition of catalyst
Suddenly in (4) in obtained carrier, stand after 9-12h, 24-48h dried in 120-140 DEG C, by resulting sample with 2-4 DEG C/
Min is warming up to after 600-800 DEG C, roasting 10-12h, and taking-up is cooled to room temperature；
(6) soluble-salt of element sulphur is configured to the 0.01-3mol/L aqueous solution, then step is added to by the composition of catalyst
Suddenly in (5) in obtained carrier, stand after 9-12h, 24-48h dried in 120-140 DEG C, by resulting sample with 2-4 DEG C/
Min is warming up to after 600-800 DEG C, roasting 10-12h, and taking-up is cooled to room temperature；
(7) with the H containing 0.1-5ppm2Sample obtained by mixed gas reduction step (6), mixture pressure is 1-
2.5MPa, the temperature of processing is 200-400 DEG C, and the air speed of gas is 10000-15000/h, and heating rate is 2-4 DEG C/min, sample
Product are handled after 5-8h under this condition, are cooled to room temperature, that is, are obtained catalyst.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833903A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application |
| CN113198513A (en) * | 2021-05-18 | 2021-08-03 | 中南大学 | Catalyst for preparing olefin by dehydrogenating alkane, preparation method and dehydrogenation method thereof |
| CN113751052A (en) * | 2021-08-31 | 2021-12-07 | 厦门大学 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
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| CN1155451A (en) * | 1996-01-24 | 1997-07-30 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN105268459A (en) * | 2014-07-21 | 2016-01-27 | 中国石油化工股份有限公司 | Sulfur-containing low-carbon alkane dehydrogenation catalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1155451A (en) * | 1996-01-24 | 1997-07-30 | 中国科学院大连化学物理研究所 | Preparation of low carbon alkane dehydrogenating catalyst |
| CN105268459A (en) * | 2014-07-21 | 2016-01-27 | 中国石油化工股份有限公司 | Sulfur-containing low-carbon alkane dehydrogenation catalyst and preparation method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109833903A (en) * | 2017-11-29 | 2019-06-04 | 中国科学院大连化学物理研究所 | A kind of low-carbon alkanes anaerobic dehydrogenation alkene catalyst and its preparation and application |
| CN113198513A (en) * | 2021-05-18 | 2021-08-03 | 中南大学 | Catalyst for preparing olefin by dehydrogenating alkane, preparation method and dehydrogenation method thereof |
| CN113751052A (en) * | 2021-08-31 | 2021-12-07 | 厦门大学 | Catalyst for preparing propylene by propane dehydrogenation and preparation method and application thereof |
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