CN1201861C - Catalyst for producing propene from propane by selective carbon dioxide oxidation - Google Patents
Catalyst for producing propene from propane by selective carbon dioxide oxidation Download PDFInfo
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- CN1201861C CN1201861C CNB031320384A CN03132038A CN1201861C CN 1201861 C CN1201861 C CN 1201861C CN B031320384 A CNB031320384 A CN B031320384A CN 03132038 A CN03132038 A CN 03132038A CN 1201861 C CN1201861 C CN 1201861C
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- catalyst
- nitrate
- propane
- potassium
- sio
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- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000001294 propane Substances 0.000 title claims abstract description 25
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 10
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 9
- 230000003647 oxidation Effects 0.000 title claims description 8
- 238000007254 oxidation reaction Methods 0.000 title claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 15
- 239000011651 chromium Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 9
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000011591 potassium Substances 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 17
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 10
- 239000011777 magnesium Substances 0.000 claims description 7
- 239000004323 potassium nitrate Substances 0.000 claims description 7
- 235000010333 potassium nitrate Nutrition 0.000 claims description 7
- 229910052788 barium Inorganic materials 0.000 claims description 6
- 239000011575 calcium Chemical group 0.000 claims description 6
- 229910052791 calcium Inorganic materials 0.000 claims description 6
- 229910052742 iron Chemical group 0.000 claims description 6
- 229910052746 lanthanum Inorganic materials 0.000 claims description 6
- 229910052749 magnesium Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical group [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 4
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical group [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- IWOUKMZUPDVPGQ-UHFFFAOYSA-N barium nitrate Chemical group [Ba+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O IWOUKMZUPDVPGQ-UHFFFAOYSA-N 0.000 claims description 4
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical group [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical group [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 4
- 238000007598 dipping method Methods 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical group [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical group [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 18
- 229910004298 SiO 2 Inorganic materials 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910018663 Mn O Inorganic materials 0.000 description 4
- 229910003176 Mn-O Inorganic materials 0.000 description 4
- 150000001336 alkenes Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 241000345998 Calamus manan Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910002846 Pt–Sn Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 235000012950 rattan cane Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a catalyst used for preparing propene by the process that propane is oxidized in a selective mode by carbon dioxide. The present invention adopts superfine silicon dioxide whose specific surface area is equal to 200 to 500m<2>/g as a carrier loaded with 5 % of chromium and 0.2 to 0.4% of potassium. When the catalyst of the present invention is adopted, propane reacts with CO2, the propane can be converted into propene in a high selectivity mode, the per pass conversion of the propane is equal to 30%, the selectivity of the propene can reach 90%, and the conversion temperature can be greatly lowered. The present invention also discloses a method for preparing the catalyst.
Description
One, technical field
The present invention relates to a kind of Catalysts and its preparation method of producing propylene with the carbon dioxide selectivity propane oxide.
Two, background technology
In natural gas, oil liquefied gas and refinery gas, there is a large amount of low-carbon alkanes,, is translated into important industrial chemicals such as alkene and will produces remarkable economic efficiency and social benefit along with the development of producing.For the manufacturing olefin by low-carbon alkane dehydrogenation process, twentieth century begins to realize suitability for industrialized production the thirties, develops again in the seventies and adopts Cr
2O
3/ Al
2O
3Or Pt-Sn/Al
2O
3Catalyst carries out propane, butane is produced propylene and the new process route of butylene.But prepare propylene by alkane such as propane direct dehydrogenation, be subjected to thermodynamics equilibrium limit, conversion of propane is not high, and needs high temperature, and the energy consumption of reaction is bigger.And by the method for air oxidation dehydrogenating propane, then because side reactions such as deep oxidation and oxygen molecule insertion still fail to obtain all gratifying result of its catalytic activity and propylene selectivity.Produce propylene with carbon dioxide as a kind of selective oxidation agent catalyzed conversion propane, can provide important raw material of industry propylene on the one hand, can eliminate the carbon dioxide that causes greenhouse effects again simultaneously, this is a catalytic reaction with industrial applications prospect.Her rattan stretches one (1, Japanization association will, 8 (1999) 553) and uses V
2O
5-Rh/SiO
2Catalyst shows at CO
2In the atmosphere dehydrogenating propane is had certain catalytic activity, but the selectivity of propylene is not ideal.The result of Takahara (2, Catal.Today, 45 (1998) 55) is 5wt%Cr
2O
3/ SiO
2Catalyst is at 550 ℃ CO
2In the atmosphere, propylene selectivity and yield bring up to 94.0% and 9.1% respectively by 90.4% and 6.5% in the Ar atmosphere.People (3, Ind.Eng.Chem.Res., 34 (1995) 474) such as Krylov O V adopt 1.5%K-5.5%Cr-17%Mn-O/SiO
2, at 830 ℃, 3600hr
-1And CO
2/ C
3H
8Under=1.5 the condition, the conversion ratio of propane is 96%, and the total recovery of alkene is 73%, but the directional selectivity of propylene is not high enough.In addition Xu Long child wait (4, CN 1181993A; CN1152566A) at 11%K-5%Cr-14%Mn-O/SiO
2On the catalyst, at 740 ℃, 0.6Mpa, 800hr
-1And CO
2/ C
3H
8Under=1 the condition, obtained the result of conversion of propane 84.2%, propylene selectivity 42.4% and ethylene selectivity 30.2%.
Three, summary of the invention
The purpose of this invention is to provide a kind of Catalysts and its preparation method that carbon dioxide selective oxidation propane is produced propylene that is used for.
Technical scheme of the present invention is as follows:
A kind ofly be used for the catalyst that carbon dioxide selective oxidation propane is produced propylene, it is to be 200～500m with specific area
2The superfine silicon dioxide of/g is 5% chromium and 0.2～0.4% potassium for the supported carrier mass ratio.
The loading of the above-mentioned preferred potassium of catalyst is 0.4%.
Potassium can be substituted by magnesium, calcium, barium, nickel, lanthanum or iron in the above-mentioned catalyst.
The loading of magnesium, calcium, barium, nickel, lanthanum or iron is 0.4% in the above-mentioned catalyst.
A kind of method for making of above-mentioned catalyst, it is made up of following steps:
Step 1, the chromic nitrate and the potassium nitrate of metering is water-soluble, wiring solution-forming, the adding specific area is 200～500m
2The superfine silicon dioxide dipping of/g, evaporate to dryness.
Step 2, with the roasting 4～10 hours under 650～800 ℃ of air atmospheres of the silica that is impregnated with chromic nitrate and potassium nitrate of step 1 gained, promptly get catalyst of the present invention.
Potassium nitrate can be substituted by magnesium nitrate, calcium nitrate, barium nitrate, nickel nitrate, lanthanum nitrate or ferric nitrate in the above-mentioned catalyst method for making.
Adopt catalyst of the present invention, propane and CO
2But react the propylene that is converted into of high selectivity, the propane conversion per pass is 30%, and the selectivity of propylene can reach 90%.And conversion temperature can reduce greatly.
Four, the specific embodiment
Embodiment one
With 18.24 gram chromic nitrate (Cr (NO
3)
39H
2O) and 0.49 gram potassium nitrate (KNO
3) add 50 milliliters of dissolvings of water, adding 50 gram specific areas is 200m
2The superfine silicon dioxide of/g dipping heats while stirring that it is dried to be evaporated to, and roasting 4 hours under 800 ℃ of air atmospheres then makes catalyst of the present invention and (consists of 5%Cr-0.4%K/SiO
2).Propane and CO
2Catalytic conversion reaction in continuous feed fixed-bed quartz reactor (6 millimeters of internal diameters), carry out, catalyst purged 0.5 hour with oxygen and nitrogen respectively successively at 650 ℃, switched to the reaction gas (ratio of amount of substance: CO then
2/ C
3H
8=1/3.6, down together) begin to react.Product is through online gas chromatographic analysis.The results are shown in table 1.
Table 1.C
3H
8And CO
2At the 5%Cr/SiO that contains different content co-catalyst K
2Reaction result on the catalyst
Conversion ratio (%) selectivity (%)
Catalyst
C
3H
8 C
3H
6 CH
4 C
2H
4+C
2H
6
5％Cr/SiO
2 27.0 85.0 12.4 2.6
5％Cr-0.1％K/SiO
2 24.8 80.0 15.3 4.7
5％Cr-0.2％K/SiO
2 22.3 100 - -
5％Cr-0.4％K/SiO
2 31.3 91.2 7.7 1.1
5％Cr-0.8％K/SiO
2 17.4 89.1 8.6 2.3
5％Cr-1.0％K/SiO
2 3.0 70.0 21.6 8.4
*GHSV=2800h
-1, atmospheric pressure, 650 ℃, 2 hours reaction results.
Embodiment two
The employing specific area is 500m
2The superfine silicon dioxide of/g, other step are with embodiment one, and sintering temperature is 650 ℃, roasting 10 hours, the catalyst that the catalytic effect of prepared catalyst of the present invention makes with embodiment one substantially.
Embodiment three
The employing specific area is 300m
2The ultra-fine SiO of/g
2Be carrier, adopt embodiment 1 described method,, make catalyst of the present invention, and be used for propane and CO with the alternative potassium nitrate of the nitrate of K, Mg, Ca, Ba, La, Ni, Fe etc.
2Catalytic conversion reaction, reaction result is listed in table 2.
Table 2.C
3H
8And CO
2Containing the 5%Cr/SiO of different co-catalysts
2Reaction result on the catalyst
Conversion ratio (%) selectivity (%)
Catalyst
C
3H
8 C
3H
6 CH
4 C
2H
4+C
2H
6
5％Cr/SiO
2 27.0 85.0 12.4 2.6
5％Cr-0.4％Mg/SiO
2 24.8 100 - -
5％Cr-0.4％K/SiO
2 31.3 91.2 7.7 1.1
5％Cr-0.4％Ca/SiO
2 19.8 100 - -
5％Cr-0.4％Ba/SiO
2 14.2 100 - -
5％Cr-1％Ni/SiO
2 16.2 100 - -
5％Cr-0.4％La/SiO
2 23.4 90.0 10.0 -
5％Cr-0.4％Fe/SiO
2 20.5 100 - -
*GHSV=2800h
-1, atmospheric pressure, 650 ℃, 2 hours reaction results.
Embodiment four,
Compare with the document result
The used catalyst of catalyst of the present invention and document is used for propane and CO
2The result of catalytic conversion reaction relatively be shown in table 3.
Table 3. catalyst of the present invention and document catalyst are used for propane and CO
2The catalytic conversion reaction result
Catalyst C
3H
8Conversion ratio (%) C
3H
6Selectivity (%) reaction temperature (℃)
aCr-Mg/SiO
2 24.8 100 650
aCr-K/SiO
2 31.3 91.2 650
b1V-Rh/SiO
2 42.4 43.4 650
b2Cr
2O
3/SiO
2 9.6 94.0 550
b3K-Cr-Mn-O/SiO
2 96.0 c73 830
b4K-Cr-Mn-O/SiO
2 84.2 42.4 740
(a) catalyst of the present invention, (b) document catalyst system therefor, (c) total olefin selectivity
This shows, adopt catalyst of the present invention, CO
2Can be with the propylene that is converted into of propane high selectivity.And catalyst of the present invention reduces the temperature of conversion reaction greatly.In view of CO
2Be one of pernicious gas that causes the atmosphere greenhouse effects, utilize it to come the selective oxidation low-carbon alkanes significant.
Claims (6)
1. one kind is used for the catalyst that carbon dioxide selective oxidation propane is produced propylene, it is characterized in that: it is to be 200～500m with specific area
2The superfine silicon dioxide of/g is 5% chromium and 0.2～0.4% potassium for the supported carrier mass ratio.
2. catalyst according to claim 1 is characterized in that: the loading of potassium is 0.4%.
3. catalyst according to claim 2 is characterized in that: potassium is substituted by magnesium, calcium, barium, nickel, lanthanum or iron.
4. catalyst according to claim 3 is characterized in that: the loading of magnesium, calcium, barium, nickel, lanthanum or iron is 0.4%.
5. the method for making of the described catalyst of claim 1 is characterized in that it is made up of following steps:
Step 1, the chromic nitrate and the potassium nitrate of metering is water-soluble, wiring solution-forming, the adding specific area is 200～500m
2The superfine silicon dioxide dipping of/g, the heating evaporate to dryness,
Step 2, with the roasting 4～10 hours under 650～800 ℃ of air atmospheres of the silica that is impregnated with chromic nitrate and potassium nitrate of step 1 gained, promptly get catalyst of the present invention.
6. the method for making of catalyst according to claim 5 is characterized in that: potassium nitrate is substituted by magnesium nitrate, calcium nitrate, barium nitrate, nickel nitrate, lanthanum nitrate or ferric nitrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031320384A CN1201861C (en) | 2003-07-15 | 2003-07-15 | Catalyst for producing propene from propane by selective carbon dioxide oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB031320384A CN1201861C (en) | 2003-07-15 | 2003-07-15 | Catalyst for producing propene from propane by selective carbon dioxide oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1472005A CN1472005A (en) | 2004-02-04 |
| CN1201861C true CN1201861C (en) | 2005-05-18 |
Family
ID=34153956
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB031320384A Expired - Fee Related CN1201861C (en) | 2003-07-15 | 2003-07-15 | Catalyst for producing propene from propane by selective carbon dioxide oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1201861C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1321098C (en) * | 2005-04-28 | 2007-06-13 | 复旦大学 | Method for preparing propylene through oxydehydrogenation of propane and carbon dioxide |
| CN100428993C (en) * | 2005-09-29 | 2008-10-29 | 北京化工大学 | Metal carrier catalyst for propylene by carbon dioxide propane oxide and its production |
| DE602009000800D1 (en) * | 2008-07-10 | 2011-04-14 | Rohm & Haas | Autothermal catalytic hybrid process for the conversion of alkanes to alkenes and catalysts therefor |
| CN112657499A (en) * | 2019-10-15 | 2021-04-16 | 中石化南京化工研究院有限公司 | Catalyst for oxidizing cyclohexane by carbon dioxide and preparation method and application thereof |
-
2003
- 2003-07-15 CN CNB031320384A patent/CN1201861C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1472005A (en) | 2004-02-04 |
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