CN103772112A - Method used for production of isobutene via isomerization of n-butene skeleton - Google Patents
Method used for production of isobutene via isomerization of n-butene skeleton Download PDFInfo
- Publication number
- CN103772112A CN103772112A CN201210408295.7A CN201210408295A CN103772112A CN 103772112 A CN103772112 A CN 103772112A CN 201210408295 A CN201210408295 A CN 201210408295A CN 103772112 A CN103772112 A CN 103772112A
- Authority
- CN
- China
- Prior art keywords
- butene
- molecular sieve
- reaction
- catalyzer
- sodium potassium
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a method used for production of isobutene via isomerization of n-butene skeleton. According to the method, a sodium-potassium-hydrogen-type FER molecular sieve with a SiO2/Al2O3 molar ratio of 10 to 50 is taken as a catalyst; a raw material containing n-butene is subjected to skeleton isomerization at a reaction temperature of 300 to 600 DEG C, under a total pressure of 0 to 0.25MPa, and at a weight space velocity of 0.5 to 20/h so as to obtain isobutene. The sodium-potassium-hydrogen-type FER molecular sieve comprises, by weight, 0.1 to 0.5% of Na2O, and 4.0 to 6.3% of K2O. Advantages of the method are that: initial isobutene selectivity is high, and no obvious selective 'climbing stage' is observed.
Description
Technical field
The present invention relates to a kind of method of n-butene skeletal isomerization preparing isobutene.
Background technology
Along with the continuous growth of market to stop bracket gasoline demand, the demand of the methyl tertiary butyl ether as octane value toughener mixing (MTBE) is also increased thereupon.For example 8141.1 ten thousand tons of China's gasoline output in 2011, on average mix different substances together than the aggregate demand of 4.5%, MTBE and exceed 3,500,000 tons in MTBE.The high market requirement of MTBE will certainly pull the demand to raw material iso-butylene, and the iso-butylene that adopts traditional catalytic cracking and cracking of ethylene route to produce is difficult to meet the need of market.And on the other hand, the utilization ratio of the n-butene after MTBE by-product ether in carbon four is lower, often sneaks into civil liquefied gas and burn.
N-butene skeletal isomerization preparing isobutene technique can be converted into iso-butylene by the n-butene in carbon after ether four, and recirculation is as MTBE raw material.This technique have raw materials cost low and be easy to get, technique is simple and invest low feature.Both the low value-added n-butene in carbon four after the ether of refinery and petrochemical plant can be converted into the iso-butylene of high added value, solve again the low problem of utilization ratio of carbon four after ether.
The method of existing n-butene skeletal isomerization preparing isobutene, all adopts the technical scheme contacting under isomerisation conditions with catalyzer containing n-butene raw material, and catalyzer is the key of this technology.Find that at present for the catalyzer of n-butene skeletal isomerization preparing isobutene reaction be mainly FER type, TON type and AEL type molecular sieve, wherein more superior (the Houvika J. and Ponec V. of the catalytic activity of FER type molecular sieve, selectivity and stability, Catal. Rev.-Sci. Eng.
1997,
39 (4), 319).
For FER type molecular sieve catalyst, selectivity at reaction starting stage iso-butylene is lower, be accompanied by the generation of a large amount of side reactions and the formation of carbon distribution, due to the double influence of carbon distribution, there is significant selectivity (the M é riaudeau P. and Naccache C. that " climbs the phase ", Adv. Catal.
1999,
44, 505).As CN1068320A discloses a kind of FER molecular sieve catalyst and method that normal olefine isomery is become to isoolefine, on this kind of catalyzer, initial n-butene transformation efficiency is about 62%, selective isobutene less than 50%; And in the time reacting 40 hours, n-butene transformation efficiency drops to 48% left and right, selective isobutene is elevated to 85%.And for example US5,491,276 disclose a kind of FER type molecular sieve catalyst and method of n-butene skeletal isomerization preparing isobutene, and on this catalyzer, initial n-butene transformation efficiency is about 75%, and iso-butylene initial selectivity is only 28% left and right; In the time reacting 20 hours, n-butene transformation efficiency drops to 30%, and selective isobutene is elevated to more than 90%.For another example US6,323,384 disclose a kind of linear alpha-olefin tautomerizes to FER type molecular sieve catalyst and the method for isoolefine, and initial n-butene transformation efficiency is 50%, and selective isobutene is only 70%; In the time reacting 20 hours, n-butene transformation efficiency drops to 32% left and right, and selective isobutene rises to more than 90%.
The existing technical scheme take FER molecular sieve as catalyzer, exists starting stage selective isobutene low, the selectivity longer deficiency of " climbing the phase ".
Summary of the invention
For the initial low deficiency of selective isobutene in prior art, the invention provides a kind of method of n-butene skeletal isomerization preparing isobutene of highly selective.It is high that the method has initial selective isobutene, do not have the remarkable selectivity advantage such as " climb the phase ".
The method of a kind of n-butene skeletal isomerization preparing isobutene of the present invention is as follows: with SiO
2/ Al
2o
3mol ratio is that 10～50 FER molecular sieve is catalyzer, is 300～600 ℃ containing the raw material of n-butene in temperature of reaction, reaction stagnation pressure (absolute pressure) 0～0.25MPa, and weight space velocity is at 0.5～20h
-1condition under there is skeletal isomerization reaction and generate iso-butylene, the FER molecular sieve that wherein used is sodium potassium Hydrogen FER molecular sieve.
In the inventive method, by the weight percent meter of sodium potassium Hydrogen FER molecular sieve, Na
2o content is 0.1%～0.5%, K
2o content is 4.0%～6.3%.
Described in aforesaid method containing the raw material of n-butene from the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant after the by-product carbon four of carbon four or methanol-to-olefins device.Temperature of reaction preferable range is 350～450 ℃, preferably 0.13～0.25MPa of reaction pressure (absolute pressure), and weight space velocity preferable range is 1～10 h
-1.Press the weight percent meter of sodium potassium Hydrogen FER molecular sieve, Na
2o content is preferably 0.1～0.4%, K
2o content is 4.5%～6.3%.FER molecular screening is from ferrierite, ZSM-35, NU-23 or FU-9, preferably ferrierite or ZSM-35, more preferably ferrierite.Sodium potassium Hydrogen FER molecular sieve SiO used
2/ Al
2o
3mol ratio preferable range is 10～20.
In the present invention, sodium potassium Hydrogen FER molecular sieve is the exchange of sodium potassium type FER molecular sieve through ammonium ion part, and then roasting makes.Concrete preparation method comprises the steps: that sodium potassium type FER molecular sieve mixes with ammonium salt solution making beating, temperature be under 20～95 ℃ of conditions preferably under 20～60 ℃ of conditions, exchange 1～2 hour, exchange disposed slurry after filtration, the thorough drip washing of deionized water for filter cake, oven dry, roasting obtains sodium potassium Hydrogen FER molecular sieve.
In the preparation method of sodium potassium Hydrogen FER molecular sieve of the present invention, in ion-exchange slurries, the concentration of ammonium ion is 0.1～0.5mol/L.In ion-exchange slurries, molecular sieve powder is 1:10 to 1:30 with exchange liquid mass ratio.The ammonium salt using is one or more mixing in ammonium nitrate, ammonium sulfate, ammonium chloride, ammonium acetate, ammonium phosphate, wherein preferred ammonium nitrate and ammonium chloride.By changing the ion-exchange degree of inorganic ammonium salt concentration of aqueous solution control FER molecular sieve.
In the inventive method, the preparation process of sodium potassium Hydrogen FER molecular sieve is as follows: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, mineral acid and water fully mix, and by gained mixture forming, drying, roasting obtain final catalyzer.Wherein sodium potassium Hydrogen FER content accounts for 10～90% by weight percentage, and all the other are binding agent.Wherein said binding agent can be conventional binding agent in the catalyzer preparation of this area, as one or more mixtures in aluminum oxide, silicon-dioxide or clay.Preferred binding agent is aluminum oxide, as pseudo-boehmite.Extrusion aid is generally sesbania powder.Mineral acid is nitric acid, hydrochloric acid or sulfuric acid, for making molecular sieve and binding agent be convenient to moulding, and the preferred nitric acid of wherein said mineral acid.Described moulding can adopt extrusion process, pressed disc method, drip ball method or spin comminution granulation, wherein preferably extrusion process moulding.Catalyzer is dried 5～20 hours in 80～150 ℃ after moulding, is at 400～600 ℃ roasting 2～15 hours, preferably 450～600 ℃ of maturing temperatures.
The inventive method is keeping under the transformation efficiency of stationary phase and the condition of yield, improve significantly the selectivity of initial iso-butylene, solve the selective isobutene longer problem of " climbing the phase ", greatly shorten initial reaction transformation efficiency and optionally fluctuateed the time, reaction unit having been reached fast and carry out smooth running stationary phase.
Embodiment
Below by embodiment and comparative example, the present invention is further set forth.
Ferrerite molecular sieve raw material used in the following example and comparative example, is provided content meter by weight, Na by eastern Cao Da (Shanghai) trade Co., Ltd
2o content is 0.9%, K
2o content is 6.32%.The chemical reagent using, as indicated without special, is analytical reagent.It is SW-17 type aluminium hydrate powder that catalyzer is prepared binding agent used, and pore volume is 0.47-0.53 ml/g, is greater than 250 m than table
2/ g, mean pore size is 7.5-8.5 nm, by Zibo, safe photoinitiator chemical company limited provides.
Embodiment 1～3
The preparation of sodium potassium Hydrogen FER molecular sieve.
By the NH of the concentration of ferrerite molecular sieve and different ammonium ions
4cl aqueous solution is evenly pulled an oar, change ferrerite molecular sieve solid and exchange liquid mass ratio, under differing temps, stir 2 hours, filter, gained filter cake with 30 times to the deionized water cleaning down of ferrerite molecular sieve butt weight, through 110 ℃ of oven dry and 550 ℃ of roastings, obtain sodium potassium Hydrogen FER molecular sieve, be labeled as respectively NaKH-1, NaKH-2 and NaKH-3.The Na of the sodium potassium Hydrogen FER molecular sieve that by weight percentage, employing x-ray fluorescence spectrometry makes
2o and K
2o content.Preparation condition and the Na that records sodium potassium Hydrogen FER molecular sieve
2o and K
2o content is in table 1.
Table 1
| Title | NH 4 +Concentration (mol/L) | Sieve/liquor ratio * (g/g) | Exchange temperature ( oC） | Na 2O content | K 2O content |
| NaKH-1 | 0.01 | 1/30 | 60 | 0.38 | 6.23 |
| NaKH-2 | 0.02 | 1/20 | 40 | 0.23 | 5.68 |
| NaKH-3 | 0.05 | 1/10 | 25 | 0.18 | 4.74 |
* ferrerite molecular sieve solid and exchange liquid mass ratio
By NaKH-1, mediate and form dense thick paste body at CD4X1TS type polyfunctional catalyst forming machine with SW-17 aluminium hydrate powder, sesbania powder, nitric acid and deionized water (mass ratio is 42.5:7.5:1.5:1:50), adopt the stainless steel moulded board extrusion molding in 1.5 mm holes.Gained extrudate is prior under room temperature dry 24 hours, then dries 8 hours in 110 ℃, finally, in 550 ℃ of roastings 12 hours, obtains final catalyzer, and respective markers is C-1.Adopt identical forming method, NaKH-1 is replaced with respectively to NaKH-2 and NaKH-2, make final catalyzer C-2 and C-3.
Embodiment 4
Adopt the performance of n-butene skeletal isomerization reaction evaluating catalyzer.Before each evaluating catalyst, need be by first pre-treatment 2 hours in the High Purity Nitrogen atmosphere of 500 ℃ of catalyzer, then be cooled to temperature of reaction.Take carbon after ether four as raw material, raw material forms in table 1.Reaction product adopts Agilent 7890 type gas-chromatography on-line analyses.Reaction product adopts Agilent 7890 type gas-chromatography on-line analyses.
Table 1
| Component | Raw material composition (% by weight) |
| Carbon three | 0.12 |
| Trimethylmethane | 48.44 |
| Iso-butylene | 1.93 |
| 1-butylene | 14.41 |
| Cis-2-butene | 10.33 |
| Trans-2-butene | 15.15 |
| Normal butane | 9.52 |
| Carbon five | 0.09 |
Take C-1 as catalyzer, take carbon after ether four as raw material, at 450 ℃, weight space velocity is 1h
-1, stagnation pressure is under 0.5MPa condition, to carry out n-butene skeletal isomerization, reaction result is listed in table 2.
Table 2
| Reaction times (h) | N-butene transformation efficiency (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 52.1 | 77.9 | 40.6 |
| 1 | 48.9 | 86.8 | 42.4 |
| 3.5 | 47.9 | 94.3 | 45.1 |
| 10 | 45.0 | 93.1 | 41.9 |
| 20 | 43.5 | 90.9 | 39.6 |
Embodiment 5
Take C-2 as catalyzer, take carbon four after the ether described in embodiment 4 as raw material, at 420 ℃, weight space velocity is 4h
-1, stagnation pressure is under 0.15MPa condition, to carry out n-butene skeletal isomerization, reaction result is listed in table 3.
Table 3
| Reaction times (h) | N-butene transformation efficiency (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 60.5 | 56.2 | 34.0 |
| 3.5 | 55.2 | 70.2 | 38.8 |
| 10 | 49.7 | 78.5 | 39.0 |
| 20 | 45.6 | 88.6 | 40.4 |
Embodiment 6
Take C-3 as catalyzer, take carbon four after the ether described in embodiment 4 as raw material, at 350 ℃, weight space velocity is 10h
-1, stagnation pressure is under 0.25MPa condition, to carry out n-butene skeletal isomerization, reaction result is listed in table 4..
Table 4
| Reaction times (h) | N-butene transformation efficiency (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 75.2 | 40.8 | 30.7 |
| 5 | 63.4 | 51.6 | 32.7 |
| 10 | 58.4 | 64.8 | 37.8 |
| 20 | 51.3 | 75.8 | 38.9 |
Comparative example 1
With embodiment 1～3, just sodium potassium Hydrogen FER molecular sieve is replaced with to Hydrogen HFER, the preparation process of HFER molecular sieve is as follows: by the NH of the ferrerite molecular sieve of 200 g, 214 g
4cl and 4000 g deionized waters mix making beating, stir 2 hours at 75 ℃, filter, repeat above-mentioned exchange process at least 5 times, after exchange through filter, gained filter cake with 30 times to the thorough drip washing of deionized water of NaK-FER zeolite butt weight, through 110 ℃ of oven dry and 550 ℃ of roastings, obtain HFER.The SiO of the HFER that employing x-ray fluorescence spectrometry makes
2/ Al
2o
3mol ratio 16.5.Method moulding described in employing embodiment 1～3, the final catalyzer of making is labeled as C-4.
Take C-4 as catalyzer, take carbon four after the ether described in embodiment 4 as raw material, at 450 ℃, weight space velocity is 1h
-1, under the condition that stagnation pressure is 0.15MPa, carrying out n-butene skeletal isomerization, reaction result is listed in table 5.
Table 5
| Reaction times (h) | N-butene transformation efficiency (%) | Selective isobutene (%) | Iso-butylene productive rate (%) |
| 0.5 | 67.0 | 35.0 | 23.5 |
| 5 | 51.0 | 48.9 | 24.9 |
| 10 | 44.8 | 60.1 | 26.9 |
| 20 | 44.6 | 66.2 | 29.5 |
Claims (10)
1. a method for n-butene skeletal isomerization preparing isobutene, is characterized in that: with SiO
2/ Al
2o
3mol ratio is that 10～50 sodium potassium Hydrogen FER molecular sieve is catalyzer, is 300～600 ℃ containing the raw material of n-butene in temperature of reaction, and reaction stagnation pressure is 0～0.25MPa, and weight space velocity is 0.5～20h
-1condition under there is skeletal isomerization reaction and generate iso-butylene.
2. method according to claim 1, is characterized in that: the described raw material containing n-butene from the ether of the methyl tertiary butyl ether device of refinery or petrochemical plant after the by-product carbon four of carbon four or methanol-to-olefins device.
3. method according to claim 1, is characterized in that: temperature of reaction is 350～450 ℃, and reaction stagnation pressure is 0.13～0.25MPa, and weight space velocity is 1～10 h
-1.
4. method according to claim 1, is characterized in that: in sodium potassium Hydrogen FER molecular sieve, by weight percentage, Na
2o content is 0.1%～0.5%, K
2o content is 4.0%～6.3%.
5. method according to claim 4, is characterized in that: Na
2o content is 0.1～0.4%, K
2o content is 5.5%～6.3%.
6. method according to claim 1, is characterized in that: SiO in sodium potassium Hydrogen FER molecular sieve
2/ Al
2o
3mol ratio is 10～50.
7. method according to claim 1, is characterized in that: FER molecular screening is from ferrierite, ZSM-35, NU-23 or FU-9.
8. method according to claim 1, it is characterized in that: the preparation process of described catalyzer is as follows: sodium potassium Hydrogen FER zeolite powder, binding agent, extrusion aid, mineral acid and water fully mix, by gained mixture forming, drying, roasting obtain final catalyzer.
9. method according to claim 8, is characterized in that: described moulding can adopt extrusion process, pressed disc method, drip ball method or spin comminution granulation.
10. method according to claim 8, is characterized in that: catalyzer is dried 5～20 hours in 80～150 ℃ after moulding, is at 400～600 ℃ roasting 2～15 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408295.7A CN103772112B (en) | 2012-10-24 | 2012-10-24 | A kind of method of n-butene skeletal isomerization preparing isobutene |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210408295.7A CN103772112B (en) | 2012-10-24 | 2012-10-24 | A kind of method of n-butene skeletal isomerization preparing isobutene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103772112A true CN103772112A (en) | 2014-05-07 |
| CN103772112B CN103772112B (en) | 2016-04-13 |
Family
ID=50564945
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210408295.7A Active CN103772112B (en) | 2012-10-24 | 2012-10-24 | A kind of method of n-butene skeletal isomerization preparing isobutene |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103772112B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106675639A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for producing isobutene and high-octane petrol by taking n-butene as raw material |
| CN105712832B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A method of isobutene is produced for raw material with MTO by-products carbon four |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942027A (en) * | 1986-08-05 | 1990-07-17 | Shell Oil Company | Method for preparing ferrierite |
| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN101928011A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Method for preparing ZSM-35 molecular sieve |
| CN103043682A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Sodium-potassium-hydrogen type ferrierite and method for preparing same |
-
2012
- 2012-10-24 CN CN201210408295.7A patent/CN103772112B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4942027A (en) * | 1986-08-05 | 1990-07-17 | Shell Oil Company | Method for preparing ferrierite |
| US5510560A (en) * | 1993-08-30 | 1996-04-23 | Texaco Inc. | Skeletal isomerization of n-olefins to iso-olefins on binded ferrierite zeolites |
| CN101928011A (en) * | 2009-06-18 | 2010-12-29 | 中国石油化工股份有限公司 | Method for preparing ZSM-35 molecular sieve |
| CN103043682A (en) * | 2011-10-17 | 2013-04-17 | 中国石油化工股份有限公司 | Sodium-potassium-hydrogen type ferrierite and method for preparing same |
Non-Patent Citations (3)
| Title |
|---|
| ALEXANDER G.STEPANOV,ET AL.,: "In situ monitoring of n-butene conversion on H-ferrierite by 1H,2H,and 13C MAS NMR:kinetics of a double-bond-shift reaction,hydrogen exchange,and the 13C-label scrambling", 《JOURNAL OF CATALYSIS》 * |
| YASUHIRO SUZUKI ET AL.,: "Cooperative Effect of Sodium and Potassium Cations on Synthesis of Ferrierite", 《TOP CATAL》 * |
| 陈鸿博等: "镁碱沸石掺杂ZSM-23后对正丁烯骨架异构化选择性的影响", 《厦门大学学报（自然科学版）》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105712832B (en) * | 2014-12-04 | 2018-10-12 | 中国石油化工股份有限公司 | A method of isobutene is produced for raw material with MTO by-products carbon four |
| CN106675639A (en) * | 2015-11-09 | 2017-05-17 | 中国石油化工股份有限公司 | Method for producing isobutene and high-octane petrol by taking n-butene as raw material |
| CN106675639B (en) * | 2015-11-09 | 2018-04-10 | 中国石油化工股份有限公司 | A kind of method that isobutene and high-knock rating gasoline are produced using n-butene as raw material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103772112B (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102822124A (en) | Method for making a catalyst comprising a phosphorus modified zeolite to be used in a MTO process | |
| CN103561867B (en) | Manufacture the improved method being used for that methanol is changed into the zeolite based catalysts of alkene | |
| CN103638963B (en) | P-xylene fluid catalyst prepared by performing alkylation of methylbenzene methyl alcohol and preparation method thereof | |
| CN104043477A (en) | ZSM-5/MCM-48 composite molecular sieve, preparation method and application thereof | |
| CN102372291A (en) | Preparation method of SAPO-18 / SAPO-34 intergrowth molecular sieve | |
| CN104549452A (en) | Toluene and methanol alkylation catalyst and preparation method and application thereof | |
| CN103769207A (en) | Catalyst used for production of isobutene via isomerization of n-butene skeleton and combined production of propylene, and preparation method and applications thereof | |
| CN105000574A (en) | HZSM-5 molecular sieve with special appearance and preparation method and application thereof | |
| CN103769204A (en) | Catalyst used for production of isobutene via isomerization of n-butene skeleton, and preparation method and applications thereof | |
| CN104117384A (en) | Toluene methylation catalyst and method for producing p-xylene in presence of same | |
| CN101678338A (en) | Solid phosphoric acid with controlled porosity | |
| CN103043677B (en) | A kind of modified ferrierite and its preparation method and application | |
| CN103041848B (en) | Catalyst used for heterogeneously producing isoalkene by utilizing direct-chain olefin skeleton and preparation method thereof | |
| CN103043682B (en) | Sodium-potassium-hydrogen type ferrierite and method for preparing same | |
| CN103772112B (en) | A kind of method of n-butene skeletal isomerization preparing isobutene | |
| CN105268475B (en) | The method that n-butene skeletal isomerization prepares isobutene | |
| CN105712832B (en) | A method of isobutene is produced for raw material with MTO by-products carbon four | |
| CN102909061A (en) | EU-1/ZSM-5 composite molecular sieve, and catalyst for toluene disproportionation and transalkylation and application of catalyst | |
| CN103769208B (en) | A kind of SAPO-11 molecular sieve catalyst of P Modification and its preparation method and application | |
| CN100475337C (en) | Catalyst of naphtha catalytic pyrolysis preparing ethylene and propylene | |
| CN101301624B (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by chemical precipitation method | |
| CN104557397B (en) | Method for producing propylene from n-butene | |
| CN101301625B (en) | Al2O3-HZSM-5 compound solid acid catalyst prepared by mechanical mixed method | |
| CN104437596A (en) | Methanol to arene catalyst and preparation method thereof | |
| CN104557403B (en) | A kind of n-butene skeletal isomerization produces the start-up method of isobutene. |
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 |