CN1069226C - Preparation of low carbon alkane dehydrogenating catalyst - Google Patents
Preparation of low carbon alkane dehydrogenating catalyst Download PDFInfo
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- CN1069226C CN1069226C CN96115049A CN96115049A CN1069226C CN 1069226 C CN1069226 C CN 1069226C CN 96115049 A CN96115049 A CN 96115049A CN 96115049 A CN96115049 A CN 96115049A CN 1069226 C CN1069226 C CN 1069226C
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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
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Abstract
The present invention relates to a preparation method of a carried metal catalyst for the dehydrogenation reaction of low-carbon alkane. The catalyst components of the IV group of metal elements, a platinum group of transition metal elements, alkali metal elements, halogen elements and sulfur elements are orderly and respectively dipped on Al2O3, SiO2, spinel or a molecular sieve carrier. In the preparation process, after being dipped and carried on carries, the IVA group of metal elements and the platinum group of metal elements need to be processed by water steam. The catalyst is used for the dehydrogenation reaction of C2 to C5 alkane, has the characteristics of high alkane conversion rate, high monoene selectivity and high thermal stability and is suitable for application in industrial production.
Description
The present invention relates to a kind of low-carbon alkanes (C
2～C
5) preparation method of dehydrogenation.
Dehydrating alkanes is an important catalysis industrial process, and its dehydrogenation product is an important industrial chemicals of making a lot of chemical products (as plastics, rubber, gasoline, washing agent etc.).As preparing isobutene through dehydrogenation of iso-butane, can synthesizing polyisobutylene, lucite, methyl tertiary butyl ether(MTBE) (MTBE) etc.Alkane dehydrogenating catalyst, its important class are that to include platinum group be main active component, add all kinds auxiliary agent, the high performance catalyst that utilizes advanced technology to make.As USP 4,353,815 is Pt-Re-Mn/Al
2O
3Catalyst is used for dehydrogenation of isobutane; USP4,420,649 is Pt-Ru-Re/Al
2O
3Catalyst is used for dehydrogenation of isobutane; Ep 98,622 is Pt-Sn-Cs/Al
2O
3Catalyst is used for dehydrogenation of isobutane; USP 4,914, and 075 is Pt-Sn-Cs/Al
2O
3Catalyst is used for dehydrogenating propane; EP 562,906 is Pt-Sn-K/Al
2O
3Catalyst, moving-burden bed reactor are used for dehydrogenation of isobutane (C
2～C
20).USP 4,506, and 032 is Pt-Sn-K-Cl/Al
2O
3Catalyst contains Sn alumina carrier H
2PtCl
6Aqueous solution dipping, KNO is soaked in drying, dechlorination, roasting then
3, dry, roasting, and in the time of 525 ℃, through water-bath certain density HCl solution is passed through catalyst with air, make catalyst contain a certain amount of Cl element after the roasting, the catalyst that makes is used for ethane and dehydrogenation of isobutane.USP 4,595, and 673 is Pt-Sn-K-Li-Cl/Al
2O
3Catalyst contains Sn alumina carrier H
2PtCl
6And LiNO
3Soak altogether, use KNO after drying, the roasting
3Solution impregnation is carried out drying and roasting again and is made, and this catalyst is used for dehydrogenation of long-chain alkane.
The purpose of this invention is to provide a kind of preparation method who is used for the dehydrogenating low-carbon alkane catalysts, the catalyst by this method is prepared has higher activity than known catalyst to above-mentioned reaction.
Catalyst provided by the invention is an active component with the platinum family transition metal, adds IV A family's metallic element and alkali metal as auxiliary agent.Also contain halogen and element sulphur simultaneously in the catalyst as modified component, the carrier of catalyst is SiO
2, molecular sieve, magnesium aluminate spinel or aluminium oxide.The weight content of each component is in the catalyst: platinum family transition metal: 0.01～5%; IV A family metallic element: 0.1～5%; Alkali metal: 0.1～10%; Halogens: 0.2～15%, element sulphur: 0.01～3%.
Above-mentioned platinum family transition metal as active component is one or more elements in platinum, palladium, iridium, rhodium, osmium or the rhenium, wherein is best with the metal platinum.Preferable platinum family transition metal weight content is 0.01～2.0%.Auxiliary agent IV A family metallic element is Ga, and one or more elements among Sn or the Pb are the best with the Sn element wherein, and preferable IV family metallic element weight content is 0.2～3%.Alkali metal is Li, Na, and K, Rs, Cs, one or more elements among the Fr are the best with Li or K wherein, the preferable weight content of alkali metal is 0.1～5%.Nonmetalloid modifier halogen in the catalyst is F, Cl, Br or I, wherein is best with Cl.
Preparation of catalysts method provided by the present invention is that the solubility soln using dipping technique as each component of catalyst is supported on the carrier, it is characterized in that dipping process press the order carry out:
1) adjuvant component that will contain IV A family element is impregnated on the carrier, and drying and roasting make the carrier that carries IV A family element.Its drying and roasting technology are routinely carried out;
2) be used as the solution impregnation 1 of the platinum group transition metal of active component again), through make the carrier that carries IV A family's element and platinum family transition elements in dry and roasting; Its drying and roasting technology are routinely carried out;
3) 2) on the carrier that makes, dipping contains the solution of alkali metal ion, make and supported alkali metal ion on the carrier, drying and roasting again, its dry and roasting process also routinely technology carry out;
4) with containing halogen family element solution, dipping 3) carrier that makes carries out drying and roasting more according to a conventional method;
5) use Na at last
2S or (NH
4)
2S sulfur compound solution impregnating carrier 4), make catalyst after drying.
Dipping solution in the above-mentioned preparation process, the available nitrate that contains each metal component, chloride; Halogen can be sour accordingly with it, but best halogen maceration extract is a hydrochloric acid.Drying was carried out 1～10 hour usually at 50～150 ℃, and roasting process carried out 1～10 hour under 400～800 ℃.
In Preparation of catalysts method of the present invention, it is characterized in that the carrier 1 that carrier impregnation auxiliary agent and active component make) and 2) after, for improving activity of such catalysts, also use water vapour and handle, the steam treatment time is 1～8 hour, and treatment temperature is 500～700 ℃.
Catalyst of the present invention before being used for the dehydrogenating low-carbon alkane reaction, needs to reduce with hydrogen, makes the platinum family transition elements be reduced into metallic state.Reduction temperature is 300～600 ℃, and 1～5 hour time, the catalyst after reduction promptly can be used for catalytic reaction.The condition of its catalytic reaction is:
Reaction temperature: 500～700 ℃, reaction pressure: normal pressure～1Mpa, liquid air speed: 0.1～10h
-1Below by embodiment technology of the present invention is given to illustrate further.
Example 1
Catalyst " A " consists of 0.375%Pt, 0.45%Sn, and 1.4%K, 1.2%Cl and 0.2%S are supported on γ-Al
2O
3On.The preparation method is as follows:
(1) 0.45%Sn/Al
2O
3Preparation
A certain amount of carrier places the dipping bottle, will prepare to be equivalent to 0.45%Sn content SnCl
2The maceration extract of hydrochloric acid (quite alumina carrier weight 2%) put into carrier fast, kept 4 hours, and constantly shake, make dipping evenly, incline then and flood surplus liquid, take out airing, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, bubbling air (SV=5000/ hour) in tube furnace then was in 550 ℃ of calcination process 4 hours; Then air is switched water bath with thermostatic control, use steam treatment 4 hours by 70 ℃.
(2) 0.375%Pt～0.45%Sn/Al
2O
3Preparation
With 0.45%Sn/Al
2O
3Place dipping bottle, will prepare and be equivalent to 0.375%Pt content H
2PtCl
6The maceration extract of hydrochloric acid (quite alumina carrier weight amount 2%) put into 0.45%Sn/Al fast
2O
3In, kept 4 hours, and constantly shake, make dipping evenly, incline then and flood surplus liquid, take out airing, respectively dried by the fire 4 hours at 60 ℃ and 120 ℃, bubbling air (SV=5000/ hour) in tube furnace then was in 500 ℃ of calcination process 4 hours; Then air is switched water bath with thermostatic control, use steam treatment 4 hours by 70 ℃.
(3) 0.375%Pt～0.45%Sn-1.4%K-1.2%Cl/Al
2O
3Preparation
The KNO that will be equivalent to 1.4K content
3Solution is dipped in Pt-Sn/Al
2O
3On after drying, 525 ℃ of roastings of blowing air are one hour in tube furnace, take out to be cooled to room temperature.Then, will contain Cl amount is that 1.2% hydrochloric acid solution is dipped in K-Pt-Sn/Al
2O
3On, after the drying, use air roasting one hour down for 525 ℃.
(4) wet type sulfuration
(NH is adopted in sulfuration
4)
2S makes vulcanizing agent, and the sulfuration amount is 0.2%, with (the NH after the metering
4)
2S solution is dipped on the catalyst, and room temperature dipping 24 hours inclines then and floods surplus liquid, takes out airing, respectively dries by the fire 4 hours at 60 ℃ and 120 ℃.
Catalyst " A " reactivity worth such as table 1
Table 1 normal butane dehydrogenation reaction performance reaction time (hr) n-butane conversion monoene selectivity monoene productive rate
(wt%) (wt%) (wt%) just 57.1 94.8 54.2 2 55.9 95.2 53.3 4 55.7 95.0 52.9 6 54.2 94.2 51.0 8 55.9 95.0 53.1 10 55.0 94.9 52.2
Reaction condition: 610 ℃ of LHSV=6h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Example 2
Catalyst " B " consists of 0.375%Pt, 0.45%Sn, and 1.4%Li, 1.2%Cl and 0.2%S are supported on γ-Al
2O
3On.The preparation method is with example 1, with LiNO
3Replace KNO
3
Reactivity worth such as table 2
(hr) n-butane conversion monoene selectivity monoene productive rate of anti-performance reaction time of table 2 normal butane dehydrogenation
(wt%) (wt%) (wt%) just 56.8 95.4 54.2 2 56.3 95.2 53.6 4 55.0 95.9 52.8 6 56.0 94.8 53.1 8 55.2 94.7 52.310 55.0 94.8 52.2
Reaction condition: 610 ℃ of LHSV=6h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Example 3
Catalyst " C " consists of 0.5%Pt, and 0.6%, 1.4%K, 1.2%Cl and 0.2%S are supported on γ-Al
2O
3On.The preparation method is with example 1, and Pt content is 0.5%, and Sn content is 0.6%.
Reactivity worth such as table 3
Table 3 dehydrogenation of isobutane reactivity worth reaction time (hr) iso-butane conversion ratio selective isobutene isobutene productive rate
(wt%) (wt%) (wt%) just 62.2 98.4 61.2 2 61.2 98.7 60.4 4 60.4 98.7 59.6 6 59.6 98.8 58.9 8 58.5 98.8 57.810 57.0 98.8 56.3
Reaction condition: 625 ℃ of LHSV=9h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Example 4
Catalyst " D " consists of 0.5%Pt, 0.6%Sn, and 0.7%Li, 0.7%K, 1.2%Cl and 0.2%S are supported on γ-Al
2O
3On.The preparation method is with example 1, and Pt content is 0.5%, and Sn content is 0.6%, with LiNO
3And KNO
3Soak altogether.
Reactivity worth and catalyst one way life test the results are shown in table 4 and table 5
Table 4 dehydrogenation of isobutane reactivity worth reaction time (hr) iso-butane conversion ratio selective isobutene isobutene productive rate
(wt%) (wt%) (wt%) just 59.6 98.4 58.9 2 59.1 98.7 58.3 4 58.5 98.7 57.7 6 59.6 98.8 57.4 8 57.4 98.8 56.710 54.1 98.8 53.2
Reaction condition: 625 ℃ of LHSV=9h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Table 5 catalyst is to (wt%) (wt%) (wt%) (wt%) 1 40.8 96.1 43.6 96.1 24 40.6 96.1 43.3 95.6 48 40.5 96.4 43.2 94.6 72 39.8 96.7 42.8 93.9 96 41.2 95.8 42.2 96.2120 40.8 95.7 41.5 96.1144 40.3 95.3 41.4 95.9168 40.9 94.6 41.6 95.8192 40.2 94.8 42.2 95.6216 40.1 94.3 41.9 95.4240 39.8 93.5 40.5 95.1264 39.1 91.7 40.4 95.1288------40.2 94.5 of butane dehydrogenation reaction test bearing reaction time butanes conversion butylene selective iso-butane conversion ratio selective isobutene (hr)
Reaction condition: 590 ℃ of P=0.05Mpa of reaction temperature (gauge pressure), LHSV=3.0 (1/h)
H
2/C
4=2.0
Comparative example 1
The main composition of catalyst E is identical with catalyst C, but does not soak HCl, and its normal butane dehydrogenation reaction performance is compared as follows:
Normal butane dehydrogenation reaction performance catalyst reaction time (hr) of table 6 catalyst C and E
First 2468 10 catalyst C conversion ratios (wt%), 63.63 56.93----51.95 50.94 49.82
Selectivity (wt%) 92.09 91.82----91.63 91.48 91.60 catalyst E conversion ratios (wt%) 52.26 45.78 43.45 44.5 43.85
Selectivity (wt%) 92.12 92.42 91.23 90.83 91.14
Reaction condition: 610 ℃ of LHSV=6h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Comparative example 2
The main composition of catalyst F is identical with catalyst D, but does not soak HCl, and its normal butane dehydrogenation reaction performance is compared as follows:
Normal butane dehydrogenation reaction performance catalyst reaction time (hr) of table 7 catalyst D and F
First 2468 10 catalyst D conversion ratios (wt%) 61.78 58.09 56.16 51.18 51.17 49.19
Selectivity (wt%) 92.31 91.46 91.32 91.81 90.50 91.49 catalyst F conversion ratios (wt%) 52.65 50.96 49.46 47.69 45.23
Selectivity (wt%) 94.80 94.00 96.20 94.83 95.65
Reaction condition: 610 ℃ of LHSV=6h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
Comparative example 3
The composition of catalyst G and preparation method are identical with catalyst D, and the composition of catalyst H is identical with catalyst D, but is making Sn/Al
2O
3After, high-temperature vapor dechlorination of no use.Normal butane dehydrogenation reaction performance is compared as follows:
Normal butane dehydrogenation reaction performance catalyst reaction time (HR) of table 8 catalyst G and H
First 2468 10 12 catalyst G conversion ratios (wt%) 63.34 60.15 57.79 55.28 51.85 46.99 44.56
Selectivity (wt%) 93.79 93.44 93.86 93.75 93.54 93.24 93.89 catalyst H conversion ratio (wt%) 62.43--54.03--47.79--35.77
Selectivity (wt%) 91.48--94.58--95.65--95.86
Reaction condition: 610 ℃ of LHSV=6h of reaction temperature
-1H
2/ C
4=1 (mol)
The reaction pressure normal pressure
By the explanation of above-mentioned sample result, adopt catalyst that the inventive method provides to low-carbon alkanes C
2～C
5Dehydrogenation reaction has active high, and selectivity is good, and good heat endurance is arranged, and is suitable for using in the suitability for industrialized production.
Claims (5)
1. preparation method who is used for dehydrogenating low-carbon alkane reaction supported metal catalyst is characterized in that in the catalyst that it is to press order to carry out that each component dipping supports on the carrier:
1) adjuvant component that will contain IV A family metallic element is impregnated on the carrier drying and roasting;
2) solution impregnation 1 of usefulness platinum group transition metal) gained carrier, drying and roasting again;
3) use the solution impregnation 2 of alkali metal containing element again) the gained carrier, drying and roasting;
4) then with the solution impregnation 3 that contains the halogen family element) gained carrier, drying and roasting again;
5) use Na at last
2S or (NH
4)
2S sulfur compound solution impregnating carrier 4), make catalyst after drying;
Wherein dry run was carried out 1～10 hour under 50～150 ℃, and roasting process carried out 1～10 hour under 400～800 ℃; After catalytic component IV A family's metallic element and platinum family transition metal dipping, drying and the roasting, also through steam treatment 1～8 hour, treatment temperature was 500～700 ℃; The carrier that catalyst uses is γ-Al
2O
3, SiO
2, molecular sieve or magnesium aluminate spinel.
2. according to the described preparation method of claim 1, it is characterized in that each dipping solution nitrate or chloride that contains each metal component.
3. according to the described preparation method of claim 1, it is characterized in that halogen makes maceration extract with halide.
4. according to the described preparation method of claim 3, it is characterized in that halide hydrochloric acid.
5. according to the described preparation method of claim 1, the carrier that it is characterized in that catalyst is γ-Al
2O
3
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115049A CN1069226C (en) | 1996-01-24 | 1996-01-24 | Preparation of low carbon alkane dehydrogenating catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115049A CN1069226C (en) | 1996-01-24 | 1996-01-24 | Preparation of low carbon alkane dehydrogenating catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1155451A CN1155451A (en) | 1997-07-30 |
| CN1069226C true CN1069226C (en) | 2001-08-08 |
Family
ID=5122350
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115049A Expired - Fee Related CN1069226C (en) | 1996-01-24 | 1996-01-24 | Preparation of low carbon alkane dehydrogenating catalyst |
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| Country | Link |
|---|---|
| CN (1) | CN1069226C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000593A (en) * | 2010-11-09 | 2011-04-06 | 北京化工大学 | Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof |
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| CN114588899A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | Catalyst and preparation and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506032A (en) * | 1983-03-22 | 1985-03-19 | Uop Inc. | Dehydrogenation catalyst composition |
| US4727216A (en) * | 1983-09-12 | 1988-02-23 | Chevron Research Company | Dehydrogenation of isobutane over a zeolitic catalyst |
| CN87101513A (en) * | 1987-03-13 | 1988-10-12 | 中国科学院大连化学物理研究所 | Dehydrogen of saturated hydrocarbon platinum, tin, lithium, sulfur catalyst |
| CN1031946A (en) * | 1987-07-31 | 1989-03-29 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof |
| US5128300A (en) * | 1989-06-30 | 1992-07-07 | Uop | Reforming catalyst with homogeneous metals dispersion |
-
1996
- 1996-01-24 CN CN96115049A patent/CN1069226C/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4506032A (en) * | 1983-03-22 | 1985-03-19 | Uop Inc. | Dehydrogenation catalyst composition |
| US4727216A (en) * | 1983-09-12 | 1988-02-23 | Chevron Research Company | Dehydrogenation of isobutane over a zeolitic catalyst |
| CN87101513A (en) * | 1987-03-13 | 1988-10-12 | 中国科学院大连化学物理研究所 | Dehydrogen of saturated hydrocarbon platinum, tin, lithium, sulfur catalyst |
| CN1031946A (en) * | 1987-07-31 | 1989-03-29 | 埃尼里瑟奇公司 | Dehydrogenation catalyst and preparation method thereof |
| US5128300A (en) * | 1989-06-30 | 1992-07-07 | Uop | Reforming catalyst with homogeneous metals dispersion |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102000593A (en) * | 2010-11-09 | 2011-04-06 | 北京化工大学 | Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof |
| CN102000593B (en) * | 2010-11-09 | 2013-06-05 | 北京化工大学 | Catalyst for preparation of isobutene by isobutene dehydrogenation as well as preparation process and dehydrogenation process thereof |
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| Publication number | Publication date |
|---|---|
| CN1155451A (en) | 1997-07-30 |
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