CN1087654C - Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof - Google Patents
Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof Download PDFInfo
- Publication number
- CN1087654C CN1087654C CN96115387A CN96115387A CN1087654C CN 1087654 C CN1087654 C CN 1087654C CN 96115387 A CN96115387 A CN 96115387A CN 96115387 A CN96115387 A CN 96115387A CN 1087654 C CN1087654 C CN 1087654C
- Authority
- CN
- China
- Prior art keywords
- reaction
- catalyst
- low
- carbon
- carbon dioxide
- 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.)
- Expired - Fee Related
Links
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
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a process for preparing low-carbon olefine from low-carbon alkane, which is a reaction of low-carbon alkane with carbon dioxide to directly prepare low-carbon olefine. A supported or non-supported metal oxide catalyst containing the elements of Cr, Mn and K is adopted in the reaction. Under the catalytic action of the catalyst and in the reaction conditions of 300 to 900 DEG C of reaction temperature, 0.01 to 5.0MPa of reaction pressure and 100 to 10000/h of reaction space velocity, the low-carbon alkane can be converted into the low-carbon olefine with high conversion rate and high selectivity. The process can be used for converting ethane in dry catalytic cracking gas into ethene, and can also be used for converting a large amount of ethane contained in oil field gas into ethene. The reaction process has simple technological process and convenient operation, and thus, the reaction process is suitable for industrial application.
Description
The Cr-Mn-alkali metal System Catalyst that provides for this process is provided the process that the present invention relates to a kind of low-carbon alkanes and the direct producing light olefins of carbon dioxide reaction.
Raising along with living standards of the people, demand to ethene will grow with each passing day, update prediction at present, world wide is to ethene, the demand of propylene will be respectively rises to 2000 8700 ten thousand tons/year and 47,000,000 tons/year from 6,700 ten thousand tons/year and 3,600 ten thousand tons/year in 1994, especially the shared share of consumption of ethylene will increase to 17% by 13% in the world market of developing Asian country, on the other hand, along with petroleum resources with worsening shortages, cause ethene and the two alkene contradiction that supply falls short of demand are becoming increasingly acute, although utilize natural gas (or coal) resource to produce low-carbon alkene, has distant view, but difficulty is very big, and processing step is quite complicated, is difficult to industrial production in the short time, what especially generate is the mixture of various lower carbon number hydrocarbons, form complexity, separation difficulty, simultaneously, the carbon dioxide that by-product is a large amount of, cause the waste of a large amount of natural gases (coal) resource, and produce the serious environmental pollution, thereby the making ethylene from ethane oxidative dehydrogenation important function for of research is caused chemists' attention always.At present, the industrial production procedure of high-temperature water vapor cracking low-carbon alkanes and the corresponding commercial plant of all adopting produced low-carbon alkene, and high-temperature water vapor cracking low-carbon alkanes is produced the process of low-carbon alkene, cracking temperature is higher, and need a large amount of steam, the energy consumption of process is very big, and the product of cracking is simultaneously formed complicated, the isolation of purified difficulty.Thereby, research is both at home and abroad adopted oxygen to directly oxidize ethane system ethene (patent: EP261264 with it, EP407091, EP480594), and carry out its catalyst research and corresponding technical study, yet the ethane direct oxidation is a strong exothermal reaction, is difficult to its degree of oxidation of control, reaction generates great amount of carbon dioxide, and yield of ethene is very low.
The purpose of this invention is to provide a kind of course of reaction the new system catalyst that provides for this process is provided by the low-carbon alkanes producing light olefins.This process is used general fixed-bed process device, has characteristics simple to operate, stable, and is easy to suitability for industrialized production.Not only can reduce ethane significantly by this process and be converted into the ethylene reaction fuel factor, can make full use of the ethane highly selective and produce ethene, significantly improve the yield of low-carbon alkenes such as ethene, and can make full use of carbon resource by-product synthesis gas and hydrogen in the carbon dioxide, alleviate the environmental pollution that causes because of carbon dioxide.
Another object of the present invention is above-mentioned course of reaction to be used for the rare ethane of catalytic cracked dry gas produce ethene, rare ethene and the benzene that generates can be carried out alkylation reaction production ethylbenzene then.
Provided by the present inventionly produce the course of reaction of low-carbon alkene, it is characterized in that by low-carbon alkanes (C by low-carbon alkanes
2H
6～C
5H
12) make low-carbon alkene (C with the direct reaction of carbon dioxide
2H
4～C
5H
10), reaction is adopted and is contained the catalyst that active component is the Cr element.When this course of reaction was carried out in fixed-bed reactor, its reaction condition was:
Reaction temperature: 300～900 ℃,
Reaction pressure: 0.01～5.0Mpa,
Reaction velocity: 100～10000h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.05～200;
Optimum reaction condition is:
Reaction temperature: 600～850 ℃,
Reaction pressure: 0.04～1.0Mpa,
Reaction velocity: 500～5000h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.2～25.
Above-mentioned course of reaction is used for catalytic cracked dry gas or rare ethane of catalytic pyrolysis tail gas and carbon dioxide reaction process of producing ethylene, and its optimum reaction condition is:
Reaction temperature: 650～850 ℃,
Reaction pressure: 0.01～1.0Mpa,
Reaction velocity: 500～2500h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.5～10.
The Cr element catalyst that contains used in the course of reaction of the present invention is a chromium oxide.Also can add auxiliary agent Mn or/and alkali metal, forming Cr-Mn-alkali metal is the metal oxide catalyst of active component, the weight ratio of each component is (0～20) alkali metal in the catalyst: (0～25) Mn: (0.1～24) Cr, Mn or alkali metal are not zero simultaneously, and Cr, Mn or alkali metal are to exist with oxide form.In addition, above-mentioned activity of such catalysts component is supported on SiO
2, Al
2O
3, on one or more compounds are made in alkaline earth oxide or the molecular sieve the carrier, also can be supported on SiO
2, Al
2O
3, constitute supported catalyst on alkaline earth oxide and the molecular sieve.The weight ratio of each component is in the catalyst: (100) carrier: (0～20) alkali metal: (0～25) Mn: (0.1～24) Cr.Preferable components by weight is: (100) carrier: (2～15) alkali metal: (2～18) Mn: (4～16) Cr.
Above-mentioned alkali metal is Li, Na, K or Cs; Alkaline earth oxide is MgO, CaO or BaO; Molecular sieve is the Silicalite type, ZSM type or APO type molecular sieve, and metallic element is to exist with oxide form in the catalyst.
Preparation of catalysts process of the present invention is pressed step and is carried out:
One. non-supported catalyst:
1. with Cr
2O
3, Cr
2O
3With MnO
2And/or alkali metal oxide mixes by a certain percentage, or with said mixture and binding agent, clay for example, SiO
2Or Al
2O
3The even aftershaping of mechanical mixture, the content of binding agent can be 0～80% of catalyst weight;
2. the also available Cr that contains, the salt of Cr and Mn and/or alkali metal or alkali mixes by a certain percentage or with above-mentioned salt and the even aftershaping of binding agent mechanical mixture, the content of binding agent can be 0～80% of catalyst weight;
With the catalyst after 1 or 2 moulding in 300～800 ℃ of following calcination process 1～10 hour, can obtain catalyst of the present invention.
Two. supported catalyst:
1. with carrier SiO
2, Al
2O
3, alkaline earth oxide or molecular sieve, mechanical compression molding or add the binding agent moulding, or carrier mixed the back reshaping with the salt of part active component earlier.The binding agent addition is 0～40% of a carrier weight.
2. with containing active component Cr, Cr and Mn and/or alkali-metal solubility salt or aqueous slkali flood above-mentioned carrier, and active component and auxiliary element are supported on the carrier.
3. the carrier of dipping active component carried out calcination process 1～10 hour in 300～800 degree after drying, and catalyst gets product.
Course of reaction of the present invention also can be used for directly reacting with the ethane in a large amount of ethane contained in the casing-head gas or other source and carbon dioxide or with the carbon dioxide of chemical engineering industry discharging and produces low-carbon alkene and downstream product thereof.
Below by example content of the present invention is described in detail:
Embodiment 1 SiO
2Or Al
2O
3The preparation of supported catalyst A
With SiO
2Or Al
2O
3(500 gram) mechanical compression molding through 540 degree roastings 3 hours, vacuumizes dipping Cr (NO
3)
3Or Cr (NO
3)
3With Mn (NO
3)
2And/or KNO
3Mixed solution or other saline mixed solution of Cr-Mn-K, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst A, it is formed weight ratio and is: (100) carrier: (0-20) K: (0-20) Mn: (0.4-20) Cr.
The catalyst that is used to estimate catalytic perfomance sees Table 1 concrete the composition.
Embodiment 2 SiO
2, Al
2O
3Or the preparation of MgO supported catalyst B
With SiO
2, Al
2O
3Or MgO 500 gram and KMnO
4Or with MgO 500 grams and Mn (NO
3)
2After the mixing, add weigh 10% clay mechanical mixture by catalyst after, compression molding through 540 degree roastings 3 hours, vacuumizes dipping Mn (NO again
3)
2, Cr (NO
3)
3Or KNO
3Mixed solution or other saline mixed solution of Cr-Mn-K, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst B.It forms weight ratio: (100) carrier: (0-20) K: (1-20) Mn: (0.4-20) Cr.The catalyst that is used to estimate catalytic perfomance sees Table 1 concrete the composition.
The preparation of embodiment 3 phosphate aluminium molecular sieve supported catalyst C
With Silicalite-2 (or Silicalita-1, ZSM-5, ZSM-11, ZSM-12, ZSM-48) (SAPO-11) the mechanical compression molding of zeolite molecular sieve 500 grams is respectively through 410 for or SAPO-5, APO-11 for molecular sieve or APO-5,500,540 degree roastings vacuumized dipping Mn (NO after 2 hours
3)
2, Cr (NO
3)
3Or KNO
3Mixed solution or other saline mixed solution of Cr-Mn-K, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst C.It forms weight ratio: (100) carrier: (0-20) K: (0-25) Mn: (1-24) Cr.The catalyst that is used to estimate catalytic perfomance sees Table 2 concrete the composition.
The preparation of the molecular sieve supported type catalyst D of embodiment 4 high silicon (phosphorus aluminium)
With Silicalite-2 (or Silicalita-1, ZSM-5, ZSM-11, ZSM-12, ZSM-48) molecular sieve or APO-5 (or SAPO-5, APO-11, SAPO-11) zeolite molecular sieve 500 gram and KMnO
4And add and to weigh 20% stack by catalyst and tie native mechanical mixture aftershaping, respectively through 410,500,540 degree roastings vacuumize dipping Mn (NO after 2 hours again
3)
2, Cr (NO
3)
3Or KNO
3Mixed solution or other saline mixed solution of Cr-Mn-K, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst D.It forms weight ratio: (100) carrier and binding agent: (1-20) K: (1-25) Mn: (1-24) Cr.The catalyst that is used for the evaluate catalysts reactivity worth sees Table 2 concrete the composition.
The preparation of embodiment 5 non-supported Cr-Mn-K or Cs catalyst E
With a certain proportion of KMnO
4, Cr (NO
3)
3, CsNO
3After mixing with clay machinery, compression molding through 540 degree roastings 3 hours, promptly gets catalyst E
1With a certain proportion of KMnO
4, Cr (NO
3)
3, KNO
3Mix with clay machinery, compression molding after 3 hours, vacuumizes a certain amount of Mn (NO of dipping through 540 degree roastings again
3)
2, Cr (NO
3)
3, KNO
3Mixed solution or other saline mixed solution of Cr-Mn-K, 120 degree oven dry are 8 hours then, 540 degree roastings 10 hours, the catalyst of gained is called catalyst E
2, toward containing a certain proportion of KMnO
4, Cr (NO
3)
3In the mixed aqueous solution, add a certain amount of KOH aqueous solution, the precipitation of gained is washed for several times with deionized water, the clay moulding is added in oven dry then, promptly gets catalyst E in 3 hours through 540 degree roastings
3Its metal is formed weight ratio: (0.5-20) K or Cs: (2-25) Mn: (0.5-24) Cr, binder content are 40% of catalyst.The catalyst that is used to estimate catalytic perfomance sees Table 3 concrete the composition.
Embodiment 6～12 ethane and carbon dioxide reaction high selectivity system ethene experiment 1～7
On continuous flow fixed bed reactor, load 20 milliliters of above-mentioned made catalyst A, B, C, D or E respectively, at 0.05-4.0MPa, 600-800 ℃, 500-2500h
-1, C
2H
6/ CO
2Under the reaction condition of=0.5-100, carry out catalyst reaction performance evaluation experiment 1～7, its reaction result sees Table 1～3.
Embodiment 13 propane and carbon dioxide reaction system ethene, propylene experiment 8
Adopt the continuous flow fixed bed reactor identical with above-mentioned example 6 to reach under the reaction condition identical with above-mentioned example 6, carry out the propane of catalyst (20 milliliters of loading amounts) and the catalytic perfomance evaluation of carbon dioxide reaction, catalyst reaction the results are shown in Table 4.C wherein
3H
8Conversion ratio can reach 84.2%, C
3H
8The selectivity that is converted into propylene reaches 42.4%, C
3H
8Be converted into ethylene selectivity and reach 30.2%, simultaneously by-product carbon monoxide, hydrogen and a certain amount of water.
Ethane and carbon dioxide reaction high selectivity system ethene experiment 9～12 in embodiment 14～17 catalytic cracked dry gas.
Utilize the prepared catalyst of the reaction unit of embodiment 6 and embodiment 2～4, at 0.05～4.00MPa, 700～850 ℃, 500～2500h
-1, C
2H
6Under the reaction condition of=0.5-10, catalytic cracked dry gas and carbon dioxide reaction are produced ethene, its reaction result sees Table 5.
Can be used for ethane or propane and carbon dioxide are produced ethene or propylene as the direct highly selective of raw material by reaction provided by the invention of above-mentioned example and catalyst.At reaction pressure 0.05-5.0MPa, under reaction temperature 600-800 ℃ the condition, but ethane high conversion (the ethane conversion per pass is greater than 75%), high selectivity is converted into ethene (ethylene selectivity is greater than 86%).And this process and catalyst can be used for propane and carbon dioxide reaction, and the primary product of its reaction is propylene and ethene.A large amount of synthesis gas and hydrogen and a certain amount of water of by-product utilizes the synthesis gas of its generation can further produce downstream product such as methyl alcohol or dimethyl ether simultaneously.This course of reaction is simple to operate, is easy to industry and applies.
Table 1, and the ethylene reaction produced result of ethane and carbon dioxide reaction (catalyst A, B)
| Catalyst among the embodiment | Catalyst A | Catalyst B |
| Catalyst is formed (weight) | The surplus SiO of 3%K 3%K 20%Cr 1%K 8%Mn 8%Mn 2%Mn 6%Cr 6%Cr 7%Cr 2Surplus Al 2O 3Surplus SiO 2Surplus Al 2O 3 | The surplus SiO of 6%K 6%K 4%K 2%Mn 10%Mn 10%Mn 8%Mn 12%Cr 8%Cr 8%Cr 10%Cr 2The surplus Al of surplus MgO 2O 3Surplus MgO |
| Reaction condition: reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) ethane/carbon dioxide (molecule) ratio | 780 600 740 720 2.5 4.0 0.2 0.15 1000 1000 1000 1200 0.8 0.8 1.0 20.0 | 770 770 710 720 2.0 1.0 0.1 0.2 1200 1200 1400 1100 0.9 10.9 4.0 50.0 |
| Ethane conversion (%) ethane is converted into selectivity of ethylene (%) | 60.5 65.9 72.4 70.8 72.6 60.7 76.2 81.2 | 74.8 707.1 73.8 76.7 75.6 71.2 84.4 78.2 |
Table 2, and the ethylene reaction produced result of ethane and carbon dioxide reaction (catalyst C, D)
| Catalyst among the embodiment | Catalyst C | Catalyst D |
| Catalyst is formed (weight) | The surplus Si-1 of the 4%K 4%K 15%Cr 4%K 10%Mn 10%Mn 16%Mn surplus Si-2 of the surplus Si-1 of the surplus Si-2 of 2%Cr 2%Cr | The surplus ZSM-11 of the 11%K 11%K 9%K 6%K 14%Mn 14%Mn 16%Mn 4%Mn 5%Cr 5%Cr surplus SAPO-5 of the surplus ZSM-5 of the surplus Si-2 of 8%Cr 15%Cr |
| Reaction condition: reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) ethane/carbon dioxide (molecule) ratio | 770 770 680 720 1.5 1.5 0.15 0.15 1100 1100 1200 1000 1.0 1.0 10.0 2.0 | 750 750 760 740 0.4 0.4 1.0 0.5 1000 1100 1200 1800 0.9 0.9 1.0 1.0 |
| Ethane conversion (%) ethane is converted into selectivity of ethylene (%) | 68.7 66.8 72.4 60.8 72.4 69.2 80.5 68.6 | 81.7 72.1 65.5 70.2 84.4 75.2 73.0 78.5 |
Table 3, the ethylene reaction produced result of ethane and carbon dioxide reaction (catalyst E
1, E
2, E
3)
| Catalyst among the embodiment | Catalyst E 1 | Catalyst E 2 | Catalyst E 3 |
| Catalyst is formed (weight) (surplus is binding agent) | 8％K 15％K 8％Cr 6％K 10％Mn 10％Mn 10％Mn 10％Mn 2％Cr 5％Cr 5％Cr 15％Cr | 8％K 9％K 9％K 9％Mn 15％Mn 12％Mn 16％Mn 12％Cr 6％Cr 10％Cr 8％Cr 24％Cr | 12％K 12％K 12％K 12％Mn 12％Mn 12％Mn 8％Cr 8％Cr 8％Cr |
| Reaction condition: reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) ethane/carbon dioxide (molecule) ratio | 770 670 740 720 2.0 2.0 0.12 0.12 1800 1800 1800 1800 0.8 0.8 5.0 9.5 | 760 760 740 710 1.0 1.0 0.15 0.1 1600 1400 1200 1400 0.9 0.9 10.0 1.0 | 760 760 600 0.8 0.8 1.15 1400 1400 1000 1.0 1.0 5.0 |
| Ethane conversion (%) ethane is converted into selectivity of ethylene (%) | 88.7 76.6 80.8 78.6 60.2 62.3 66.0 68.4 | 88.1 87.2 86.2 78.2 70.8 68.9 78.2 74.9 | 91.3 87.6 72.8 88.3 88.6 65.6 |
Table 4, propane and carbon dioxide reaction system propylene and ethylene reaction result
| Catalyst among the embodiment | Catalyst A | Catalyst D | Catalyst E 2 |
| Catalyst is formed | The surplus SiO of 6%K 1%K 10%Mn 2%Mn 8%Cr 17%Cr 2Surplus Al 2O 3 | The surplus Si-2 of the 11%K 4%K 14%Mn 4%Mn surplus Si-2 of 5%Cr 18%Cr | 9%K 9%K 16%Mn 16%Mn 6%Cr 6%Cr is surplus to be that clay is surplus for clay |
| Reaction condition: reaction temperature (℃) reaction pressure (MPa) reaction velocity (h -1) propane/carbon dioxide (molecule) ratio | 760 720 2.5 0.5 1000 1200 1.0 1.0 | 740 700 0.6 0.1 800 1600 1.0 4.0 | 750 690 1.5 0.15 1200 1000 1.0 0.5 |
| Selectivity (%) propane that conversion of propane (%) propane is converted into propylene is converted into selectivity of ethylene (%) | 76.6 88.9 35.6 23.4 28.3 42.6 | 84.2 82.4 42.4 25.4 80.2 46.4 | 87.1 74.8 33.8 23.6 26.7 38.2 |
Ethane and carbon dioxide reaction the system third rare and ethylene reaction result in table 5. catalytic cracked dry gas
| Catalyst among the embodiment | Catalyst B | Catalyst C | Catalyst C | Catalyst D |
| Catalyst is formed | The surplus SiO of 10%K 12%Mn 6%Cr 2 | The surplus Si-2 of 4%K 2%Mn 8%Cr | The surplus Si-2 of 4%K 2%Mn 8%Cr | 8%K 16%Mn 10%Cr is surplus to be ZSM-5 |
| Reaction condition: reaction temperature (℃) reaction pressure (MPa) reaction velocity (h-1) ethane/carbon dioxide (molecule) forms than reaction gas | 760 2.5 1000 0.5 (1) | 740 0.6 800 1.0 (1) | 750 1.5 1200 1.0 (2) | 820 1.5 1500 2.0 (2) |
| Ethane conversion (%) ethane is converted into selectivity of ethylene (%) | 70.2 81.2 | 72.4 83.6 | 73.8 84.8 | 75.2％ 86.1％ |
(1) catalytic cracked dry gas: contain 10～20 ethane, 10～20 ethene,
(2) through with benzene alkylation after do not contain the catalytic cracked dry gas of ethene: contain 10～25 ethane.
Claims (9)
1. a catalyst that is used for by low-carbon alkanes and carbon dioxide reaction preparing low carbon olefin hydrocarbon is characterized in that this catalyst is is the Cr of active component with the Cr element
2O
3Catalyst.
2. by the described catalyst of claim 1, it is characterized in that adding Mn in the catalyst or/and alkali metal as auxiliary agent, each components by weight:
(0-20) alkali metal: (0-25) Mn: (0.1-24) Cr; Mn or alkali metal are not zero simultaneously, and Cr, Mn or alkali metal are to exist with oxide form.
3. by claim 1 or 2 described catalyst, it is characterized in that active component is supported on SiO
2, Al
2O
3, on one or more compounds are made in alkaline earth oxide or the molecular sieve the carrier, each components by weight is:
(100) carrier: (0-20) alkali metal: (0-25) Mn: (0.1-24) Cr.
4. by the described catalyst of claim 3, it is characterized in that the weight ratio of each component in the catalyst is: (100) carrier: (2-15) alkali metal: (2-18) Mn: (4-16) Cr.
5. according to the described catalyst of claim 3, it is characterized in that molecular sieve is the Silicalite type, ZSM type or APO type molecular sieve, alkaline earth oxide is MgO, CaO or BaO.
6. one kind is utilized the described catalyst of claim 1 by low-carbon alkanes reaction for preparing light olefins process, it is characterized in that C
2H
6-C
5H
12Low-carbon alkanes and carbon dioxide are under the above-mentioned catalyst action of Cr, and directly reaction makes C
2H
4～C
5H
10Low-carbon alkene.
7. by the described course of reaction of claim 6, it is characterized in that reaction condition is:
Reaction temperature: 300～900 ℃,
Reaction pressure: 0.01～5.0MPa,
Reaction velocity: 100～10000h
-1, reactant low-carbon alkanes/carbon dioxide molecule is than 0.05～200.
8. by claim 6 or 7 described courses of reaction, it is characterized in that reaction condition is:
Reaction temperature: 600～850 ℃,
Reaction pressure: 0.04～1.0Mpa,
Reaction velocity: 500～5000h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.2～25.
9. according to the described course of reaction of claim 6, it is characterized in that reactant is rare ethane and a carbon dioxide reaction system ethene in the catalytic cracked dry gas, reaction condition is:
Reaction temperature: 650～850 ℃,
Reaction pressure: 0.01～1.0Mpa,
Reaction velocity: 500～2500h
-1,
Low-carbon alkanes/carbon dioxide molecule ratio: 0.5～10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN96115387A CN1087654C (en) | 1995-08-30 | 1996-06-19 | Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN95111957 | 1995-08-30 | ||
| CN95111957.5 | 1995-08-30 | ||
| CN96115387A CN1087654C (en) | 1995-08-30 | 1996-06-19 | Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1181993A CN1181993A (en) | 1998-05-20 |
| CN1087654C true CN1087654C (en) | 2002-07-17 |
Family
ID=25743760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN96115387A Expired - Fee Related CN1087654C (en) | 1995-08-30 | 1996-06-19 | Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1087654C (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1091086C (en) * | 1998-12-28 | 2002-09-18 | 中国科学院金属研究所 | Microwave reinforced ethylene preparation process including methane oxidizing and coupling-ethane carbon dioxide oxidizing, dehydrogenating and coupling reactions |
| CN1318131C (en) * | 2004-07-07 | 2007-05-30 | 北京化工大学 | Catalyst foir preparing ethylene by using ethane as raw material oxidized by carbon dioxide, and its prepn. method |
| 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 |
| CN101116827B (en) * | 2006-07-31 | 2010-12-01 | 中国石油化工股份有限公司 | Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking and its uses |
| CN103086825B (en) * | 2011-10-28 | 2016-01-13 | 中国石油化工股份有限公司 | A kind of production method of low-carbon alkene and Ethylene vapor cracking system |
| CN103864556A (en) * | 2012-12-13 | 2014-06-18 | 中国科学院大连化学物理研究所 | Method for production of low carbon olefins from synthetic gas via low carbon alkanes |
| CN103073378B (en) * | 2013-01-28 | 2014-12-24 | 神华集团有限责任公司 | Low-temperature methanol washing and alkane dehydrogenation combination system and coupling system of low-temperature methanol washing and alkane dehydrogenation combination system and alkene separation system |
| CN104016822B (en) * | 2014-06-25 | 2015-11-04 | 厦门中科易工化学科技有限公司 | A kind of ethane prepares the method for ethene or ethylene dichloride |
| CN104785286B (en) * | 2015-04-23 | 2017-05-10 | 中国科学院大连化学物理研究所 | Light hydrocarbon and carbon dioxide conversion catalyst, as well as preparation method and application thereof |
| CN104857968A (en) * | 2015-04-23 | 2015-08-26 | 中国科学院大连化学物理研究所 | Low carbon hydrocarbon and CO2 conversion catalyst and application thereof |
| CN106964392B (en) * | 2016-01-13 | 2021-08-03 | 中国石油化工股份有限公司 | Propane oxidative dehydrogenation catalyst and application thereof |
| CN106563489B (en) * | 2016-10-28 | 2020-01-10 | 复旦大学 | Catalyst for preparing ethylene by ethane dehydrogenation under carbon dioxide atmosphere and preparation method thereof |
| CN115430457A (en) * | 2021-06-03 | 2022-12-06 | 中国科学院大连化学物理研究所 | Single-layer dispersed low-Cr-load propane dehydrogenation propylene preparation catalyst and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4041645A1 (en) * | 1990-12-22 | 1992-06-25 | Nuenchritz Chemie Gmbh | High yield prodn. of silylated prim. or sec. amine(s) - by solventless reaction of amine(s) with hexa:methyl:di:silazane in presence of specified amt. of water |
-
1996
- 1996-06-19 CN CN96115387A patent/CN1087654C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4041645A1 (en) * | 1990-12-22 | 1992-06-25 | Nuenchritz Chemie Gmbh | High yield prodn. of silylated prim. or sec. amine(s) - by solventless reaction of amine(s) with hexa:methyl:di:silazane in presence of specified amt. of water |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1181993A (en) | 1998-05-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN1040397C (en) | Iron manganese catalyst for preparation of low carbon olefines by synthetic gas and synthetic reaction | |
| CN1087654C (en) | Reaction process for preparing low-carbon olefine from low-carbon alkane and catalyst thereof | |
| JP4364126B2 (en) | Method for producing dimethyl ether from methanol | |
| CN101177374B (en) | Method for producing propylene by carbinol or dimethyl ether | |
| CN101116827B (en) | Catalyzer for preparing low carbon olefinic hydrocarbon through hydrocarbons catalytic oxidation cracking and its uses | |
| CN1045283C (en) | Making low carbon olefines by hydrogenation reaction of carbon dioxide and catalyst | |
| EP2796197B1 (en) | Method for preparing ethylene and propylene by using methyl alcohol and/or dimethyl ether, | |
| CN101417911A (en) | Method for preparing light olefins from methanol using hydrocarbons as part material | |
| CN101696145A (en) | Process for preparing low carbon olefine by adopting methanol or dimethyl ether | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN101381271A (en) | Method for preparing ethylene and propylene by means of copyrolysis | |
| CN100586910C (en) | Method for producing propylene by conversion of carbinol or dimethyl ether | |
| CN1087656C (en) | Catalyst for producing synthetic gas through the reaction between low-carbon alkane and carbon dioxide and its use | |
| CN101381272B (en) | Method for preparing ethylene and propylene by two-step method | |
| CN103664436A (en) | Method for directly transforming synthesis gas into low-carbon olefin | |
| CN101367699B (en) | Preparation of propylene | |
| CN101165020B (en) | Method for increasing yield of propylene | |
| CN100395314C (en) | Aromatization catalyst, preparation method, and application | |
| CN1915931A (en) | Method for producing propylene from methanol or dimethyl ether | |
| CN1152566A (en) | Process of preparing low carbon olefines from low carbon paraffins and used catalyst | |
| KR101173529B1 (en) | Process for producing lower olefins under negative pressure | |
| CN100368356C (en) | Method for producing propylene through catalytic cracking C4 olefin | |
| CN1915934A (en) | Method for producing propylene | |
| CN112742456A (en) | Dehydrogenation cracking catalyst, preparation method thereof and method for producing ethylene and propylene by using hydrocarbon four | |
| CN1010476B (en) | Methane conversion |
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 | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |