CN1597111A - Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof - Google Patents
Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof Download PDFInfo
- Publication number
- CN1597111A CN1597111A CN200410041604.7A CN200410041604A CN1597111A CN 1597111 A CN1597111 A CN 1597111A CN 200410041604 A CN200410041604 A CN 200410041604A CN 1597111 A CN1597111 A CN 1597111A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- metal
- indoles
- prepares
- ethyl aniline
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- MLPVBIWIRCKMJV-UHFFFAOYSA-N 2-ethylaniline Chemical compound CCC1=CC=CC=C1N MLPVBIWIRCKMJV-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 title claims description 13
- SIKJAQJRHWYJAI-UHFFFAOYSA-N Indole Chemical compound C1=CC=C2NC=CC2=C1 SIKJAQJRHWYJAI-UHFFFAOYSA-N 0.000 title abstract description 12
- PZOUSPYUWWUPPK-UHFFFAOYSA-N indole Natural products CC1=CC=CC2=C1C=CN2 PZOUSPYUWWUPPK-UHFFFAOYSA-N 0.000 title abstract description 6
- RKJUIXBNRJVNHR-UHFFFAOYSA-N indolenine Natural products C1=CC=C2CC=NC2=C1 RKJUIXBNRJVNHR-UHFFFAOYSA-N 0.000 title abstract description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 18
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 10
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 9
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 9
- 239000011701 zinc Substances 0.000 claims abstract description 9
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 7
- 239000002184 metal Substances 0.000 claims abstract description 7
- 150000002475 indoles Chemical class 0.000 claims description 16
- 238000006356 dehydrogenation reaction Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910052783 alkali metal Inorganic materials 0.000 claims description 8
- 150000001340 alkali metals Chemical class 0.000 claims description 8
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 8
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 8
- 239000002808 molecular sieve Substances 0.000 claims description 8
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 2
- -1 platinum metals Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007598 dipping method Methods 0.000 description 6
- 239000011949 solid catalyst Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 238000009834 vaporization Methods 0.000 description 4
- 230000008016 vaporization Effects 0.000 description 4
- 239000011261 inert gas Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000007363 ring formation reaction Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PXWYZLWEKCMTEZ-UHFFFAOYSA-N 1-ethyl-2-nitrobenzene Chemical compound CCC1=CC=CC=C1[N+]([O-])=O PXWYZLWEKCMTEZ-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SGDSMOHDZFWNFH-UHFFFAOYSA-N NC1=CC=CC=C1.C1=CC=C2NC=CC2=C1 Chemical class NC1=CC=CC=C1.C1=CC=C2NC=CC2=C1 SGDSMOHDZFWNFH-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- ZYIFLKPDFLWFAE-UHFFFAOYSA-N aniline;toluene Chemical compound CC1=CC=CC=C1.NC1=CC=CC=C1 ZYIFLKPDFLWFAE-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000006200 vaporizer Substances 0.000 description 1
Landscapes
- Indole Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a dehydrocyclization catalyst for preparing indole from o-ethylaniline and a preparation method thereof, wherein ZSM-5 is used as a carrier of the catalyst, and the catalyst at least contains one or more of copper, chromium, zinc, iron, nickel, palladium, platinum metals and oxides thereof. Under the action of the catalyst, o-ethylaniline and steam are dehydrocyclized and aromatized together to generate indole under the oxygen-free condition, and then the indole product with higher purity is obtained through rectification and separation.
Description
Technical field
The present invention relates to the Catalysts and its preparation method that a kind of o ethyl aniline catalytic dehydrogenation cyclisation prepares indoles.
Background technology
Indoles (II) is one of important organic intermediate, has purposes very widely.In its synthetic route, the method for preparing indoles by o ethyl aniline (I) has industrial value preferably, is the active relatively poor of dehydrocyclization catalyst but there is a serious problem in this method, causes this technology not see industrialization at home so far.
Former studies person has report for the research of the used dehydrocyclization catalyst of this technology more, but all weak point is arranged.Use SiO
2-Al
2O
3Be dehydrogenation (UK 2232152) that because needed catalytic amount is bigger, and catalyst life is shorter, therefore do not have industrial use value; Adopting supported palladium and active carbon is catalyst (Hung 179388), though active higher, the selling at exorbitant prices of noble metal has limited its application; Hung176149 is described, and o-nitroethylbenzene vaporization and hydrogen are reacted synthesis of indole in the presence of iron, chromium, zinc, nickel, cobalt simple substance catalyst, but that the shortcoming of this method is a product yield is too low, and catalyst life is lacked.Hung155310 is described, with o ethyl aniline vaporization back and steam together, is the catalyst reaction synthesis of indole with the pottery, and the shortcoming of this method is that product yield is not high; US 5332838 is described, adopts Cu/Al
2O
3-B
2O
3For catalyst can obtain catalytic result preferably, but, make B in course of reaction because reaction temperature is too high
2O
3Run off gradually, its catalytic activity can reduce gradually, and the B that runs off
2O
3Can condense upon the discharging opening inwall, cause reactor plugs.
Therefore, finding a suitable efficient dehydrocyclization catalyst and a corresponding technological conditions thereof, is that the method that adopts o ethyl aniline to prepare indoles realizes industrialized key.
Summary of the invention:
The object of the invention provides a kind of dehydrocyclization catalyst efficiently, is used for the technology that o ethyl aniline prepares indoles, makes reaction that higher conversion ratio and selectivity be arranged.
Another purpose of the object of the invention provides the preparation method that o ethyl aniline prepares the dehydrocyclization catalyst of indoles.
Purpose of the present invention can reach by following measure:
A kind of o ethyl aniline catalytic dehydrogenation cyclisation prepares the catalyst of indoles, it is characterized in that with the ZSM-5 molecular sieve being the loaded catalyst of carrier, wherein contains in copper, chromium, zinc, iron, nickel, palladium and platinum and the oxide thereof one or more at least; Also add in alkali metal and the alkaline-earth metal one or more in the catalyst; Alkaline-earth metal and alkali-metal load capacity mass percent are 0.1-8.0% in this catalyst, and the load capacity mass percent of other metal ions is 0.1-20.0%.
In the catalyst, copper, chromium, zinc, iron and nickel exist with metal simple-substance or two kinds of forms of its oxide, and palladium and platinum mainly exist with the metal simple-substance form.
Method for preparing catalyst provided by the invention:
In 50-100 ℃ temperature range, get the ZMS-5 molecular sieve, add in the metal salt solution of 10-20%, flood after 1-2 hour, filter and take out solid, oven dry made catalyst at 550-750 ℃ of roasting 2-3 hour, alkaline-earth metal and alkali-metal load capacity mass percent are 0.1-8.0% in this catalyst, and the load capacity mass percent of other metal ions is 0.1-20.0%.
In the metallic solution, wherein contain in copper, chromium, zinc, iron, nickel, palladium and platinum and the oxide thereof one or more at least; Also add in alkali metal and the alkaline-earth metal one or more in the catalyst.
This catalyst can be used for fixed bed and fluid bed, has stability preferably.During reaction, bed temperature is 520-780 ℃, and best bed temperature scope is 580-650 ℃.
The detailed process that o ethyl aniline prepares indoles is as follows: homemade o ethyl aniline and water are pressed 1: the 8-12 mixed in molar ratio pumps into vaporizer with measuring pump, 300-320 ℃ of vaporization down, with bed air speed 0.1-0.45h
-1Enter the fixed bed reactors that are filled with dehydrogenation, bed temperature is 520-780 ℃, along with steam is taken out of, after the cooling, takes out the buff solid in the water, and rectifying can get the sheet white crystals, finally obtains the compound (II) of 83-94% productive rate
Preparation of Catalyst of the present invention has been compared following advantage with the catalytic dehydrogenation cyclization with existing additive method:
1) selecting with the ZSM-5 molecular sieve is carrier, contains in copper, chromium, zinc, iron, nickel, palladium and platinum and the oxide thereof one or more at least and prepares catalyst, and catalyst activity and durability are all very high;
2) catalytic dehydrogenation cyclization process is at 620 ℃, and the bed air speed is 0.1h
-1, water is under 15: 1 the condition than the mol ratio of water and o ethyl aniline, the conversion ratio 90-100% of final o ethyl aniline, and selectivity is higher than 90%, and the productive rate of indoles reaches 83-94%.
Wherein the definition of conversion ratio and selectivity is as follows:
Conversion ratio=1-reaction back o ethyl aniline percentage (%)
The specific embodiment:
Embodiment 1:
Get the ZMS-5 molecular sieve of 500g, add 20% CuSO
4Among the solution 5L, behind the dipping 2h, filter and take out solid catalyst, oven dry joins among the 5%KCl solution 2L again, behind the dipping 0.5h, filters and takes out solid catalyst, and oven dry at 550 ℃ of roasting 3h, is directly used in the self-control tubular reactor.The mass ratio of each component is as follows in the catalyst: CuO-K
2O-ZSM-5,5: 3: 92
Embodiment 2:
Get the ZMS-5 molecular sieve of 100g, among the PdCl solution 200mL of adding 10%, behind the dipping 2h, filter and take out solid catalyst, oven dry, join again among the 5%KCl solution 500mL, behind the dipping 0.5h, filter and take out solid catalyst, oven dry, at 650 ℃ of roasting 3h, directly use the reduction back in the self-control tubular reactor.The mass ratio of each component is as follows in the catalyst: Pa-K
2O-ZSM-5,3: 3: 94
Embodiment 3:
Get the ZMS-5 molecular sieve of 100g, add 25% NiNO
3Among the solution 1L, behind the dipping 2h, filter and take out solid catalyst, dry, add 20% CuSO again
4Among the solution 5L, behind the dipping 2h, filter and take out solid catalyst, oven dry at 750 ℃ of roasting 3h, is directly used in the self-control tubular reactor.The mass ratio of each component is as follows in the catalyst: NiO-CuO-ZSM-5,4.5: 5: 90.5;
Embodiment 4:
In the bed air speed is 0.1h
-1, the mol ratio of water and o ethyl aniline is 15: 1 o'clock, and the mist of back o ethyl aniline of vaporization and steam is distinguished dehydrocyclization under the multiple catalyst action in the present invention in different temperatures, and reaction result sees Table 1.
Table 1
Product distribution (%)
Temperature
Catalyst conversion ratio (%) methylbenzene aminobenzene
(K) the aniline indoles other
Amine ethene
873 91.4 73.7 1.97 9.77 14.66 0
Fe
2O
3-ZSM-5 893 92.6 71.6 0.99 14.31 13.11 0
923 93.4 60.09 0.86 14.89 24.21 0
873 25.89 18.1 9.19 0 72.65 0
ZnO-K
2O-ZSM-5 893 77.11 5.99 5.87 8.12 78.38 0
923 96.67 2.82 3.26 1.25 92.67 0
873 100 29.53 0.88 1.0 61.25 7.33
NiO-CuO-ZSM-5
923 90.96 0 12.13 0 87.87 0
873 99.06 30.06 1.09 0 55.68 12.23
Cr
2O
3-BaO-ZSM-5?893 99.66 20.74 0.51 0 70.3 8.11
923 100 14.4 0 0 83.59 1.97
873 100 3.1 1.9 9.3 85.7 0
Pa-K
2O-ZSM-5 893 100 0.77 1.13 5.4 91.1 0
923 100 0 1.79 1.36 96.9 0
873 100 3.4 2.9 2.4 91.4 0
CuO-K
2O-ZSM-5 893 100 1.9 3.2 8.53 95.6 0
923 100 2.1 2.8 4.18 91.3 0
Embodiment 5:
In the bed air speed is 0.1h
-1, reaction temperature is 620 ℃, with CuO-K
2O-ZSM-5 is a catalyst, adopts different inert gases less to the reaction influence, the results are shown in Table 2.
Table 2
Inert gas and product distribution (%)
Inert gas conversion ratio (%)
Substrate mol ratio anilinomethyl aniline aminobenzene ethene indoles
N 2∶1 81.5 1.8 1.2 5.7 91.3
Ar 2∶1 82.6 0 1.6 3.4 95.0
H
2O 2∶1 84.5 3.1 1.9 5.2 89.8
Embodiment 6:
In the bed air speed is 0.1h
-1, reaction temperature is 620 ℃, with CuO-K
2O-ZSM-5 is a catalyst, and the mol ratio of investigating different water and o ethyl aniline is 15: 1 o'clock, and the influence to reaction the results are shown in Table 3.
Table 3
Water vapour: o ethyl aniline ratio (mol ratio) conversion ratio (%) selectivity (%)
O ethyl aniline 80 88
5∶1 94.7 89
10∶1 100 88
15∶1 100 90
20∶1 100 92
Embodiment 7:
Mol ratio at water and o ethyl aniline is 15: 1 o'clock, and reaction temperature is 620 ℃, with CuO-K
2O-ZSM-5 is a catalyst, investigates the influence of different bed air speeds to reaction, the results are shown in Table 4.
Table 4
Bed air speed (h
-1) conversion ratio (%) selectivity (%)
0.1 100 97.1
0.15 95.6 96.0
0.20 89.2 95.7
0.30 80.3 96.4
0.45 68.7 95.6
Claims (4)
1. an o ethyl aniline catalytic dehydrogenation cyclisation prepares the catalyst of indoles, it is characterized in that with the ZSM-5 molecular sieve being the loaded catalyst of carrier, wherein contains in copper, chromium, zinc, iron, nickel, palladium and platinum and the oxide thereof one or more at least; Also add in alkali metal and the alkaline-earth metal one or more in the catalyst; Alkaline-earth metal and alkali-metal load capacity mass percent are 0.1-8.0% in this catalyst, and the load capacity mass percent of other metal ions is 0.1-20.0%.
2. o ethyl aniline catalytic dehydrogenation cyclisation according to claim 1 prepares the catalyst of indoles, it is characterized in that in the catalyst, and copper, chromium, zinc, iron and nickel exist with metal simple-substance or two kinds of forms of its oxide, and palladium and platinum mainly exist with the metal simple-substance form.
3. one kind prepares the method that the described o ethyl aniline catalytic dehydrogenation of claim 1 cyclisation prepares the catalyst of indoles, it is characterized in that in 50-100 ℃ temperature range, get the ZMS-5 molecular sieve, add in the metal salt solution of 10-20%, flood after 1-2 hour, filter and take out solid, oven dry, made catalyst at 550-750 ℃ of roasting 2-3 hour, alkaline-earth metal and alkali-metal load capacity mass percent are 0.1-8.0% in this catalyst, and the load capacity mass percent of other metal ions is 0.1-20.0%.
4. o ethyl aniline catalytic dehydrogenation cyclisation according to claim 3 prepares the Preparation of catalysts method of indoles, it is characterized in that in the metallic solution, wherein contains in copper, chromium, zinc, iron, nickel, palladium and platinum and the oxide thereof one or more at least; Also add in alkali metal and the alkaline-earth metal one or more in the catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041604.7A CN1286563C (en) | 2004-08-04 | 2004-08-04 | Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200410041604.7A CN1286563C (en) | 2004-08-04 | 2004-08-04 | Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1597111A true CN1597111A (en) | 2005-03-23 |
| CN1286563C CN1286563C (en) | 2006-11-29 |
Family
ID=34665156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200410041604.7A Expired - Fee Related CN1286563C (en) | 2004-08-04 | 2004-08-04 | Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1286563C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316915A (en) * | 2015-06-23 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing indole through dehydrocyclizing o-ethylaniline |
| CN111530461A (en) * | 2020-05-28 | 2020-08-14 | 中国科学院兰州化学物理研究所 | Low-load high-dispersion single-active-site Cu catalyst and preparation method and application thereof |
-
2004
- 2004-08-04 CN CN200410041604.7A patent/CN1286563C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106316915A (en) * | 2015-06-23 | 2017-01-11 | 中国石油化工股份有限公司 | Method for preparing indole through dehydrocyclizing o-ethylaniline |
| CN106316915B (en) * | 2015-06-23 | 2018-11-13 | 中国石油化工股份有限公司 | A kind of method of o ethyl aniline dehydrocyclization indoles |
| CN111530461A (en) * | 2020-05-28 | 2020-08-14 | 中国科学院兰州化学物理研究所 | Low-load high-dispersion single-active-site Cu catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1286563C (en) | 2006-11-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107051566B (en) | Preparation method of nitrogen-doped carbon-coated cobalt catalyst and unsaturated compound catalytic transfer hydrogenation method based on catalyst | |
| CN101065344A (en) | Method for the production of menthol | |
| CN1323754C (en) | Catalyst for synthesizing dimethyl carbonate and its preparing process | |
| CN1680296A (en) | New process for the synthesis of (7-methoxy-1-naphthyl)acetonitrile and application in the synthesis of agomelatine | |
| CN113731465A (en) | Pd/N-CNTs catalyst, and preparation method and application thereof | |
| CN104971740A (en) | Catalyst for continuously preparing N-isopropyl-4-fluoroanilines, and preparation method and application of catalyst | |
| CN1416949A (en) | Metal oxide catalyst for synthesizing methyl carbonate by urea process and its prepn | |
| CN101033177A (en) | Method of synthesizing 2-ethoxy-phenol | |
| CN108586514B (en) | Synthesis method of diisopropylamine silane | |
| CN1597111A (en) | Catalyst for preparing indole by catalytic dehydrocyclization of o-ethylaniline and preparation method thereof | |
| CN1299990C (en) | Refining process of ammonia | |
| CN1939587A (en) | Metal carrier catalyst for producing synthetic gas by methane carbon dioxide reformation and its production | |
| CN1133493C (en) | Efficient catalyst for synthesizing ammonia and its preparing process | |
| CN1175089C (en) | Reforming catalyst containing molecular sieve | |
| CN1050152C (en) | Dehydrogenating catalyst | |
| CN1283358C (en) | Catalyst in use for preparing carbon fiber, preparation method and usage | |
| CN1535942A (en) | Preparation method of Ru-B load type catalyst | |
| CN1168534C (en) | Prepn of catalyst for tetramethylbenzene isomerization to prepare durene | |
| CN1795046A (en) | Hydrocarbon steam cracking catalyst, method for preparing the same and method for preparing light olefin by using the same | |
| CN1493661A (en) | Method of eliminating arsenic in acetylene containing hydrocarbon and dearsenic agent | |
| CN1137773C (en) | Solid super acid and its prepn. | |
| CN1605387A (en) | Quenched Ni skeleton catalyst for preparing 3-phenylpropyl aldehyde by cinnamaldehyde hydrogenization and its preparing process | |
| CN1412177A (en) | Catalytic synthesis of methyl phenyl oxalate and phenostal by using load metal oxide | |
| CN1958571A (en) | Method for preparing compound in category of cyanopyridine | |
| CN1724156A (en) | Copper catalyst for synthesizing organic silicon monomer and its preparation process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061129 Termination date: 20100804 |