CN101270022B - Method for improving selectivity of low carbon olefin hydrocarbon - Google Patents
Method for improving selectivity of low carbon olefin hydrocarbon Download PDFInfo
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- CN101270022B CN101270022B CN2008100432419A CN200810043241A CN101270022B CN 101270022 B CN101270022 B CN 101270022B CN 2008100432419 A CN2008100432419 A CN 2008100432419A CN 200810043241 A CN200810043241 A CN 200810043241A CN 101270022 B CN101270022 B CN 101270022B
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- light olefin
- oxygen
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- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 21
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 20
- 239000004215 Carbon black (E152) Substances 0.000 title description 2
- 229930195733 hydrocarbon Natural products 0.000 title description 2
- -1 carbon olefin hydrocarbon Chemical class 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 28
- 239000001257 hydrogen Substances 0.000 claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 48
- 150000001336 alkenes Chemical class 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002808 molecular sieve Substances 0.000 claims description 9
- 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 9
- 239000000463 material Substances 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002191 fatty alcohols Chemical class 0.000 claims description 3
- 125000004432 carbon atom Chemical group C* 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 10
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910021536 Zeolite Inorganic materials 0.000 abstract 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 abstract 1
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 16
- 150000001335 aliphatic alkanes Chemical class 0.000 description 12
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 10
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000001294 propane Substances 0.000 description 8
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 150000002431 hydrogen Chemical class 0.000 description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 5
- 238000006276 transfer reaction Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 239000003208 petroleum Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 235000009508 confectionery Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000010517 secondary reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- JGNPSJMNGPUQIW-UHFFFAOYSA-N [C].CC=C Chemical compound [C].CC=C JGNPSJMNGPUQIW-UHFFFAOYSA-N 0.000 description 1
- CBIIVSNVIRRJAS-UHFFFAOYSA-N [C].CCC Chemical compound [C].CCC CBIIVSNVIRRJAS-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000005243 fluidization Methods 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 238000006140 methanolysis reaction Methods 0.000 description 1
- CXHHBNMLPJOKQD-UHFFFAOYSA-M methyl carbonate Chemical compound COC([O-])=O CXHHBNMLPJOKQD-UHFFFAOYSA-M 0.000 description 1
- GRVDJDISBSALJP-UHFFFAOYSA-N methyloxidanyl Chemical group [O]C GRVDJDISBSALJP-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a method used for improving the selectivity of low-carbon olefins and mainly solves the problem of the low selectivity of the products when oxygen-containing compounds are used for preparing the low-carbon olefins. In the technical proposal, oxygen-containing compounds with the weight hourly space velocity of 1 to 50 h<-1> are used as raw materials; the average temperature of the reaction zone in a reactor is 300 to 600 DEG C; the oxygen-containing compounds and aluminosilicophosphate zeolite catalysts contact in the reaction zone; when the transfer index of hydrogen in the reaction is between 0.001 and 0.1, the selectivity of the low-carbon olefins is highest; thus the problem can be well solved. The method can be used for the industrial production of the low-carbon olefins.
Description
Technical field
The present invention relates to a kind of method that improves selectivity of light olefin.
Technical background
Low-carbon alkene comprises ethene and propylene, is two kinds of important basic chemical industry raw materials, and its demand is in continuous increase.Usually, ethene, propylene are to produce through petroleum path, but because limited supply of petroleum resources and higher price, the cost of being produced ethene, propylene by petroleum resources constantly increases.In recent years, people begin to greatly develop the technology that alternative materials transforms system ethene, propylene.Wherein, One type of important alternative materials that is used for low-carbon alkene production is an oxygenatedchemicals; For example alcohols (methyl alcohol, ethanol), ethers (dme, methyl ethyl ether), ester class (methylcarbonate, methyl-formiate) etc., these oxygenatedchemicalss can be transformed through coal, Sweet natural gas, biomass equal energy source.Some oxygenatedchemicals can reach fairly large production, like methyl alcohol, can be made by coal or Sweet natural gas, and technology is very ripe, can realize up to a million tonnes industrial scale.Because the popularity in oxygenatedchemicals source is added and is transformed the economy that generates low-carbon alkene technology, so by the technology of oxygen-containing compound conversion to produce olefine (OTO), particularly the technology by methanol conversion system alkene (MTO) receives increasing attention.
In the US4499327 patent silicoaluminophosphamolecular molecular sieves catalyst applications is studied in great detail in methanol conversion system olefin process, think that SAPO-34 is the first-selected catalyzer of MTO technology.The SAPO-34 catalyzer has very high selectivity of light olefin, and activity is also higher, and can make methanol conversion is the degree that was less than in reaction times of low-carbon alkene 10 seconds, more even reach in the reaction time range of riser tube.
Announced among the US6166282 that a kind of oxygenate conversion is the technology and the reactor drum of low-carbon alkene; Adopt fast fluidized bed reactor; Gas phase is after the lower Mi Xiangfanyingqu reaction of gas speed is accomplished; After rising to the fast subregion that internal diameter diminishes rapidly, adopt special gas-solid separation equipment initial gross separation to go out most entrained catalyst.Because reaction after product gas and catalyzer sharp separation have effectively prevented the generation of secondary reaction.Through analog calculation, to compare with traditional bubbling fluidization bed bioreactor, this fast fluidized bed reactor internal diameter and the required reserve of catalyzer all significantly reduce.
Announced among the CN1723262 that it is low-carbon alkene technology that the multiple riser reaction unit that has central catalyst return is used for oxygenate conversion; This covering device comprises a plurality of riser reactors, gas solid separation district, a plurality of offset components etc.; Each riser reactor has the port of injecting catalyst separately; Be pooled to the disengaging zone of setting, catalyzer and product gas are separated.
At oxygenatedchemicals in the conversion process of low-carbon alkene, can be because side reaction generates the selectivity that the generation of by product, the especially propane do not expect to obtain has directly reduced propylene.The inventor has proved that propane is mainly generated by propylene generation hydrogen transfer reactions; And ethane mainly to be side chain through reaction intermediate (being mainly aromatic hydrocarbons) break off forms; And the growing amount of ethane is lower and comparatively stable; The hydrogen transference ability of ethene almost nil (oil and gas chemical industry, 2006,35 (1): 5-9).Therefore, the direct factor that influences selectivity of light olefin is the secondary reaction of propylene, i.e. hydrogen transfer reactions generates propane.So, be in the reaction process of low-carbon alkene in oxygenate conversion, it is very important to the selectivity that improves low-carbon alkene effectively to control hydrogen transfer reactions.
Summary of the invention
Technical problem to be solved by this invention is the not high problem of selectivity of light olefin that exists in the prior art, and a kind of method of new raising selectivity of light olefin is provided.This method is used for the production of low-carbon alkene, has that the propane selectivity is low, selectivity of light olefin is higher, the advantage of low-carbon alkene production technique better economy.
For addressing the above problem, the technical scheme that the present invention adopts is following: a kind of method that improves selectivity of light olefin, this method comprise that the raw material weight hourly space velocity of oxygenatedchemicals is 1～50 hour
-1, when the reactor reaction zone medial temperature is 300～600 ℃, the raw material that comprises oxygenatedchemicals is contacted at said reaction zone with the silicoaluminophosphamolecular molecular sieve catalyzer, when the reactive hydrogen shift index was in 0.001～1.0, selectivity of light olefin was the highest.
In the technique scheme; Said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56, and preferred version is selected from least a among SAPO-18 or the SAPO-34; Said oxygen-containing compound material contains at least a in the ether of the Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon atom, 1～4 carbon atom, and preferred version is selected from least a in methyl alcohol, ethanol or the dme; Said reactor drum is selected from fixed bed, moving-bed, fluidized-bed or riser tube, and preferred version is selected from fluidized-bed; Said oxygen-containing compound material weight hourly space velocity preferable range is 2～35 hours
-1, more preferably scope is 6～25 hours
-1, reaction zone medial temperature preferable range is 350～550 ℃, and when more preferably scope was 400～500 ℃, the reactive hydrogen shift index preferable range of acquisition was 0.01～0.2, and more preferably scope is 0.07～0.15.
Weight hourly space velocity according to the invention is defined as the raw material inlet amount that comprises in unit time active ingredient (like the molecular sieve) content divided by the reaction zone inner catalyst.
Reactive hydrogen shift index according to the invention is the ratio of propane carbon back selectivity and propylene carbon back selectivity in the reaction product, and the reactive hydrogen shift index is in a preferable scope time, and selectivity of light olefin is the highest.
The all right non-imposed a certain proportion of thinner co-fed of interpolation in reactor feed; Thinner can be low-carbon alkanes (methane, ethane), CO, nitrogen, water vapour, C4 hydrocarbon, mononuclear aromatics etc.; Wherein, Preferred low-carbon alkanes, water vapour, most preferably scheme is a water vapour, the amount of thinner and the volume ratio of raw material are 0.1～10: regulate in 1 scope.
The inventor is through discovering; In oxygenate conversion is in the reaction process of low-carbon alkene, and the alkane by-product of generation is mainly methane, ethane, propane, C4 alkane (normal butane, Trimethylmethane) and C5+ alkane, and in the alkane of above-mentioned generation; Main alkane or the bigger alkane of growing amount are methane and propane; A methane part forms in active intermediate (like methoxyl group) forming process, and a part is that methanolysis forms, and is irrelevant with hydrogen transfer reactions.And propane mainly to be hydrogen transfer reactions through propylene form, it directly consumes the output of propylene.Other alkane mainly be that side chain through reaction intermediate (being mainly aromatic hydrocarbons) breaks off and forming like ethane, and the ethane growing amount is lower and more stable; The growing amount of C4 alkane only accounts for below 5% of the total growing amount of C4, and its amount is lower and little with the variation of processing parameter; Alkane growing amount more than the C5 than C4 alkane still less.Therefore, less and comparatively stable in view of the growing amount of ethane, C4 alkane, C5+ alkane, the reactive hydrogen shift index among the present invention is defined as the ratio of propane selectivity and propylene selectivity, and more simple and direct reaches the purpose of control selectivity of light olefin.Therefore, adopt method of the present invention, the reactive hydrogen shift index is controlled in the preferable scope, can improve the selectivity of low-carbon alkene to a great extent.
Adopt technical scheme of the present invention: said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Said oxygen-containing compound material contains at least a in the ether of the Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon atom, 1～4 carbon atom; Said reactor drum is fixed bed, moving-bed, fluidized-bed or riser tube, saidly comprises that the raw material weight hourly space velocity of oxygenatedchemicals is 1～50 hour
-1, when the reactor reaction zone medial temperature is 300～600 ℃, when the reactive hydrogen shift index was controlled in 0.001～1.0, selectivity of light olefin can reach 81.04% (weight), has obtained better technical effect.
Through embodiment the present invention is done further elaboration below, but be not limited only to present embodiment.
Embodiment
[embodiment 1～4]
In small-sized fast fluidized bed reaction device, the reaction zone medial temperature is 500 ℃, pure methanol feeding, and the methyl alcohol weight hourly space velocity is 25 hours
-1, catalyst type is seen table 1.Said fluidized bed reaction has catalyst regeneration and recycle unit.Keep the stability of catalyst flow control, the reactor outlet product adopts online gas chromatographic analysis, and experimental result is seen table 1.
Table 1
| Parameter | Catalyst type | The reactive hydrogen shift index | Low-carbon alkene carbon back selectivity, % (weight) |
| Embodiment 1 | SAPO-11 | 0.51 | 30.52 |
| Embodiment 2 | SAPO-18 | 0.05 | 77.01 |
| Embodiment 3 | SAPO-56 | 0.01 | 48.03 |
| Embodiment 4 | SAPO-34 | 0.07 | 79.24 |
[embodiment 5～7]
According to embodiment 4 described conditions, just change temperature of reactor, experimental result is seen table 2.
Table 2
| Parameter | Temperature of reaction, ℃ | The reactive hydrogen shift index | Low-carbon alkene carbon back selectivity, % (weight) |
| Embodiment 5 | 400 | 0.17 | 75.55 |
| Embodiment 6 | 450 | 0.15 | 80.27 |
| Embodiment 7 | 550 | 0.05 | 74.87 |
[embodiment 8～14]
According to embodiment 4 described conditions, just change type of feed and raw material weight hourly space velocity, experimental result is seen table 3.
Table 3
| Parameter | Type of feed | The raw material weight hourly space velocity, hour -1 | The reactive hydrogen shift index | Low-carbon alkene carbon back selectivity, % (weight) |
| Embodiment 8 | Dme | 15 | 0.068 | 78.28 |
| Embodiment 9 | Methyl alcohol: dme=5: 1 | 6 | 0.071 | 78.31 |
| Embodiment 10 | Methyl alcohol: ethanol=5: 1 | 35 | 0.061 | 77.68 |
| Embodiment 11 | Methyl alcohol: propyl carbinol=8: 1 | 6 | 0.081 | 78.56 |
| Embodiment 12 | Methyl alcohol: methyl ethyl ether=7: 1 | 6 | 0.076 | 78.05 |
| Embodiment 13 | Methyl alcohol: ethanol: DME=2: 1: 1 | 6 | 0.05 | 81.04 |
| Embodiment 14 | Methyl alcohol: Virahol=1: 1 | 6 | 0.982 | 80.28 |
[embodiment 15～17]
According to embodiment 4 described conditions, just change the reactor drum pattern, experimental result is seen table 4.
Table 4
| Parameter | The reactor drum pattern | The raw material weight hourly space velocity, hour -1 | The reactive hydrogen shift index | Low-carbon alkene carbon back selectivity, % (weight) |
| Embodiment 15 | Fixed bed | 1 | 0.058 | 78.59 |
| Embodiment 16 | Moving-bed | 2 | 0.051 | 78.98 |
| Embodiment 17 | Riser tube | 50 | 0.044 | 76.28 |
Obviously, adopt method of the present invention, can reach the selectivity that reduces low-carbon alkanes, improve the purpose of selectivity of light olefin, have bigger technical superiority, can be used in the industrial production of low-carbon alkene.
Claims (4)
1. method that improves selectivity of light olefin; This method comprise the raw material weight hourly space velocity of oxygenatedchemicals be 6～25 hours-1, when the reactor reaction zone medial temperature is 400～500 ℃; This raw material that comprises oxygenatedchemicals is contacted at said reaction zone with the silicoaluminophosphamolecular molecular sieve catalyzer; When the reactive hydrogen shift index was in 0.07～0.15, selectivity of light olefin was the highest.
2. according to the method for the said raising selectivity of light olefin of claim 1, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-5, SAPO-11, SAPO-17, SAPO-18, SAPO-34, SAPO-35, SAPO-44 or the SAPO-56; Said oxygen-containing compound material contains at least a in the ether of the Fatty Alcohol(C12-C14 and C12-C18) of 1～4 carbon atom, 1～4 carbon atom; Said reactor drum is fixed bed, moving-bed, fluidized-bed or riser tube.
3. according to the method for the said raising selectivity of light olefin of claim 2, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from least a among SAPO-18 or the SAPO-34; Said oxygen-containing compound material is selected from least a in methyl alcohol, ethanol or the dme; Said reactor drum is a fluidized-bed.
4. according to the method for the said raising selectivity of light olefin of claim 3, it is characterized in that said silicoaluminophosphamolecular molecular sieve is selected from SAPO-34; Said oxygen-containing compound material is selected from methyl alcohol.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439788A (en) * | 2015-12-10 | 2016-03-30 | 七台河宝泰隆煤化工股份有限公司 | Method for improving selectivity of olefins in methanol-to-olefin reaction process |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167654A (en) * | 1996-06-07 | 1997-12-17 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| CN101121529A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | A kind of rapid synthesis method of phosphorus silicon aluminum SAPO-34 molecular sieve |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1167654A (en) * | 1996-06-07 | 1997-12-17 | 中国科学院大连化学物理研究所 | Metal modified small-porosity P-Si-Al molecular sieve catalyst, its preparing process and use thereof |
| CN101121529A (en) * | 2006-08-08 | 2008-02-13 | 中国科学院大连化学物理研究所 | A kind of rapid synthesis method of phosphorus silicon aluminum SAPO-34 molecular sieve |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105439788A (en) * | 2015-12-10 | 2016-03-30 | 七台河宝泰隆煤化工股份有限公司 | Method for improving selectivity of olefins in methanol-to-olefin reaction process |
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