CN107866237B - Activation reduction method of low-carbon alkane dehydrogenation catalyst - Google Patents
Activation reduction method of low-carbon alkane dehydrogenation catalyst Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/135—Halogens; Compounds thereof with titanium, zirconium, hafnium, germanium, tin or lead
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
Abstract
The invention relates to the field of preparation of dehydrogenation catalysts, and discloses an activation reduction method of a low-carbon alkane dehydrogenation catalyst. The method comprises the following steps: the method comprises the steps of carrying out oxychlorination on an oxidation state low-carbon alkane dehydrogenation catalyst, then reducing the oxidation state low-carbon alkane dehydrogenation catalyst, and then carrying out vulcanization treatment by using a mixed gas of hydrogen and hydrogen sulfide, wherein the oxidation state low-carbon alkane dehydrogenation catalyst comprises an alumina carrier, 0.1-1 mass% of platinum, 0.1-1 mass% of tin, 0.5-2 mass% of alkali metal and 0.2-0.8 mass% of chlorine, the oxychlorination treatment is carried out under the condition that the carrier is taken as a reference, and the volume concentration of the hydrogen sulfide in a mixed gas of hydrogen and hydrogen sulfide used for the vulcanization treatment is 20-500 ppm. The dehydrogenation catalyst prepared by the activation reduction method has higher propane conversion rate and propylene selectivity and has better activity stability.
Description
Technical Field
The invention relates to the field of preparation of dehydrogenation catalysts, in particular to an activation reduction method of a low-carbon alkane dehydrogenation catalyst.
Background
With the increase of crude oil processing amount in China, a large amount of low-carbon alkanes such as ethane, propane, isobutane and the like can be produced in catalytic cracking and other technological processes of an oil refinery. How to effectively utilize the resources and convert the resources into the low-carbon olefin with high added value has important significance for improving the economic benefit of the oil refinery.
Propylene is an important basic organic chemical raw material and is widely applied to the production of various chemical products such as polypropylene, acetone, acrylonitrile, propylene oxide, acrylic acid and the like; isobutylene is the primary feedstock for the production of Methyl Tertiary Butyl Ether (MTBE); the butylene is mainly used in the fuel fields of synthesizing useful gasoline components and synthesizing MTBE and ETBE gasoline additives by alkylation, superposition, isomerization and dimerization processes, and is widely applied to the chemical field. Therefore, the dehydrogenation of the low-carbon alkane to prepare the olefin is a feasible process route for producing the corresponding olefin by using the low-carbon alkane.
The supported platinum-based catalyst is an important type of low-carbon alkane dehydrogenation catalyst, and usually takes alumina as a carrier, and is modified by adding other components to improve the activity and selectivity of the catalyst. Because the dehydrogenation reaction of the low-carbon alkane is limited by thermodynamic equilibrium, the reaction is carried out under the harsh conditions of high temperature and low pressure. Too high reaction temperature can aggravate cracking reaction and deep dehydrogenation, accelerate the carbon deposition rate of the catalyst and inactivate the catalyst. Therefore, the development of dehydrogenation catalysts with high activity, high selectivity and high stability is the key of the technology.
In order to improve the carbon deposit resistance of the catalyst and prolong the service life of the catalyst, besides the selection of the carrier, a proper activation reduction method is also one of the measures for improving the activity stability of the catalyst.
CN102380426A discloses that a dehydrogenation catalyst is firstly subjected to steam dechlorination, the molar ratio of hydrogen sulfide to hydrogen in mixed gas used in activation is 1 (2-30), and diluent gas is added.
CN102463148A discloses that dehydrogenation catalyst is impregnated with a solution containing a sulfurating agent, then is subjected to heat treatment in the presence of water vapor, and finally is subjected to reduction treatment with ammonia-containing hydrogen gas, and then is subjected to dehydrogenation reaction.
CN102909094A discloses that a dehydrogenation catalyst is subjected to steam dechlorination, then is reduced by hydrogen at 240-350 ℃, and then is heated to the dehydrogenation reaction temperature for reaction.
CN102909095A discloses a staged reduction method for dehydrogenation catalyst using low concentration hydrogen gas for high temperature and low temperature programming without sulfiding.
CN102909011A discloses that a dehydrogenation catalyst is dechlorinated by water vapor in the preparation process, and before use, the dehydrogenation catalyst is directly activated and sulfurized by using mixed gas containing hydrogen and hydrogen sulfide, wherein the hydrogen sulfide comes from a hydrogen sulfide generation reactor, and the molar ratio of the hydrogen sulfide to the hydrogen is 1 (2-30).
CN102909012A discloses that before use, a dehydrogenation catalyst is pre-reduced by mixed gas of nitrogen and hydrogen at a programmed temperature, then reduced at a constant temperature, and then passivated by mixed gas containing hydrogen, hydrogen sulfide and nitrogen, wherein the molar ratio of hydrogen sulfide to hydrogen to nitrogen is 1: 9: (0 to 30).
CN103041807A discloses that an alumina carrier is impregnated with platinum dehydrogenation active metal components, then the dechlorination treatment is carried out by water vapor, meanwhile, the catalyst is reduced by reducing gas containing hydrogen, and then the sulfuration is carried out, wherein the sulfuration gas is mixed gas containing hydrogen sulfide and diluent gas, and the molar ratio is 1 (0.5-20).
In the above activation reduction method of the dehydrogenation catalyst, it is generally necessary to perform dechlorination treatment with steam to reduce the chlorine content in the catalyst, and the concentration when sulfiding with hydrogen sulfide is high.
Disclosure of Invention
The invention aims to provide an activation reduction method of a low-carbon alkane dehydrogenation catalyst, and the dehydrogenation catalyst prepared by the method has high activity and selectivity and high stability.
The invention provides an activation reduction method of a low-carbon alkane dehydrogenation catalyst, which comprises the following steps: the method comprises the steps of carrying out oxychlorination on an oxidation state low-carbon alkane dehydrogenation catalyst, then reducing the oxidation state low-carbon alkane dehydrogenation catalyst, and then carrying out vulcanization treatment by using a mixed gas of hydrogen and hydrogen sulfide, wherein the oxidation state low-carbon alkane dehydrogenation catalyst comprises an alumina carrier, 0.1-1 mass% of platinum, 0.1-1 mass% of tin, 0.5-2 mass% of alkali metal and 0.2-0.8 mass% of chlorine, the oxychlorination treatment is carried out under the condition that the carrier is taken as a reference, and the volume concentration of the hydrogen sulfide in a mixed gas of hydrogen and hydrogen sulfide used for the vulcanization treatment is 20-500 ppm.
In the activation reduction method of the low-carbon alkane dehydrogenation catalyst, the catalyst is directly reduced and sulfurized without dechlorination, and low-concentration H is adopted in the sulfurization process2The hydrogen of S simplifies the treatment process, and can improve the activity stability of the catalyst while maintaining high dispersity of the dehydrogenation active component.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The activation reduction method of the low-carbon alkane dehydrogenation catalyst comprises the following steps: the method comprises the steps of carrying out oxychlorination on an oxidation state low-carbon alkane dehydrogenation catalyst, then reducing the oxidation state low-carbon alkane dehydrogenation catalyst, and then carrying out sulfurization treatment on the oxidation state low-carbon alkane dehydrogenation catalyst by using a mixed gas of hydrogen and hydrogen sulfide, wherein the oxidation state low-carbon alkane dehydrogenation catalyst comprises an alumina carrier, and 0.1-1 mass% of platinum, 0.1-1 mass% of tin, 0.5-2 mass% of alkali metal and 0.2-0.8 mass% of chlorine, which are calculated by taking the carrier as a reference, and the oxychlorination treatment is carried out under the condition of containing water, chlorine-containing gas compounds and oxygen. The activation reduction method does not need steam dechlorination, but performs oxychlorination on the low-carbon alkane dehydrogenation catalyst in an oxidation state, and then adopts hydrogen containing low-concentration hydrogen sulfide for vulcanization after reduction, so that the use amount of sulfur-containing toxic substances is reduced, and the hazard is reduced.
The volume concentration of hydrogen sulfide in the mixed gas of hydrogen and hydrogen sulfide is 20 to 500ppm, and may be, for example, 20ppm, 30ppm, 40ppm, 50ppm, 60ppm, 80ppm, 100ppm, 150ppm, 200ppm, 250ppm, 300ppm, 350ppm, 400ppm, 450ppm or 500ppm, or any value between any two of these ranges, and preferably 50 to 300 ppm.
In the method of the present invention, the chlorine content in the catalyst obtained after the activation reduction treatment is preferably 0.8 to 1.5% by mass based on the support, and may be, for example, 0.8%, 0.85%, 0.9%, 0.95%, 0.97%, 1%, 1.05%, 1.1%, 1.2%, 1.26%, 1.3%, 1.4%, or 1.5% or any value between any two of the ranges, and preferably 0.95 to 1.3%.
In the method of the present invention, the oxychlorination treatment is carried out so that the dehydrogenation active component platinum is well dispersed on the carrier. The oxychlorination treatment is preferably carried out in an atmosphere comprising water and chlorine-containing gaseous compounds. The chlorine-containing gas compound is preferably at least one of chlorine gas, hydrogen chloride, chloroform, tetrachloroethylene, dichloroethylene and carbon tetrachloride. Preferably, the oxychlorination treatment is performed in air containing water and chlorine-containing gas compounds, and the molar ratio of water to chlorine element contained in the chlorine-containing gas compounds may be 3:1 to 55:1, preferably 20 to 55:1, for example, can be any ratio between 5:1, 10:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1, and 55:1, and any two ratios.
In the method, the temperature of the oxychlorination treatment can be 400-600 ℃.
In the method, the temperature of the reduction can be 400-650 ℃, preferably 500-600 ℃, and more preferably 550-580 ℃.
In the method of the present invention, the reduction is preferably performed by using hydrogen or a mixture of hydrogen and an inert gas. In the mixed gas of hydrogen and the inert gas, the volume fraction of the inert gas may be 5 to 70%, for example, 5%, 10%, 20%, 30%, 40%, 50%, 60%, or 70%, and any value between any two ranges. The inert gas may be nitrogen, helium, neon, argon, or the like.
In the method of the present invention, the temperature of the vulcanization treatment may be 400 to 650 ℃, preferably 500 to 600 ℃.
In the method of the present invention, the mixed gas of hydrogen and hydrogen sulfide used in the sulfidation process may be a prepared mixed gas of hydrogen sulfide and hydrogen, or a mixed gas generated by the reaction of hydrogen and a precursor of hydrogen sulfide. When the mixed gas of hydrogen and hydrogen sulfide is a mixed gas generated by the reaction of hydrogen and a precursor of hydrogen sulfide, the precursor of hydrogen sulfide may be at least one of carbon disulfide, dimethyl disulfide and mercaptan.
In the method of the present invention, the alumina support is preferably theta-alumina. More preferably, the alumina carrier has a thickness of 50-130 m2Specific surface area of the polymer per gram and total pore volume of 0.5-1 mL/g.
In the process of the present invention, the alkali metal is preferably potassium.
In the method of the present invention, the light alkane dehydrogenation catalyst can be prepared by a conventional method. In one embodiment, the preparation process may comprise: platinum is introduced into an alumina carrier containing Sn through impregnation, the alumina carrier is dried at the temperature of 60-150 ℃, the drying time is preferably 1-20 hours, then the alumina carrier is roasted at the temperature of 400-600 ℃, the drying time is preferably 1-10 hours, then alkali metal is introduced through impregnation, and the drying time is preferably 1-20 hours at the temperature of 60-150 ℃.
In a preferred embodiment, the preparation of the light alkane dehydrogenation catalyst: the carrier is preferably theta-alumina, more preferably theta-alumina containing Sn, and the auxiliary Sn is introduced in the carrier forming process, so that the Sn component is uniformly distributed in the carrier, and the content of the Sn component is 0.1-1% of the mass of the carrier; introducing platinum into the Sn-containing alumina carrier by an impregnation method, wherein the content of the platinum is 0.1-1% of the mass of the carrier, adding a proper competitive adsorbent into an impregnation solution, controlling the impregnation condition to uniformly disperse the platinum on the carrier, drying the carrier at 60-150 ℃ for 1-20 hours, and roasting the carrier at 400-600 ℃ for 1-10 hours; then, alkali metal, preferably potassium, is impregnated, the content of the alkali metal is 0.5-2% of the mass of the carrier, and then the carrier is dried for 1-20 hours at the temperature of 60-150 ℃, and then the activation reduction is carried out according to the method of the invention.
In a preferred embodiment, the specific processes and conditions of the activation reduction process of the present invention are as follows:
(1) carrying out oxychlorination treatment on the dried dehydrogenation catalyst containing Pt, Sn and K for 1-10 hours at the temperature of 400-650 ℃ by using gas containing water, chlorine gas compounds and oxygen; the gas containing water, chlorine-containing gas compound and oxygen is preferably air containing water and chlorine-containing gas compound,
(2) reducing the catalyst after the oxychlorination treatment at 400-650 ℃ for 1-10 hours by using an inert gas containing hydrogen as a reducing gas;
(3) and introducing hydrogen containing hydrogen sulfide into the reduced catalyst at the temperature of 400-650 ℃, preferably 500-600 ℃ for sulfurization treatment, wherein the volume concentration of the hydrogen sulfide in the hydrogen is 20-500 ppm, and the sulfurization time is 0.5-4 hours.
In the method of the invention, the lower alkane may be C3-C5 alkane, preferably propane and/or butane.
The present invention is further illustrated by the following examples, but the present invention is not limited thereto.
Example 1
A spherical Sn-containing theta-alumina carrier (Sasol company, Germany) with Sn content of 0.3% of the carrier mass was immersed in an immersion liquid containing chloroplatinic acid and hydrochloric acid at 25 ℃ for 4 hours, wherein the immersion liquid contained 0.3 mass% of platinum and 1.5 mass% of chlorine (both relative to the dry alumina carrier, the same applies hereinafter) and the liquid/solid ratio was 1.8 mL/g. After impregnation, the solid was dried at 120 ℃ for 12 hours and calcined at 500 ℃ for 4 hours. The calcined solid was immersed in a potassium hydroxide solution containing 1 mass% of potassium (relative to the alumina support) at 25 ℃ for 4 hours, and the liquid/solid ratio was 1.4 mL/g. The impregnated solid was dried at 120 ℃ for 12 hours, and contained 0.3 mass% of platinum, 0.6 mass% of chlorine, and 1.0 mass% of potassium.
Activation reduction conditions: taking the above oxidation state catalyst inHeating to 500 deg.C at a rate of 5 deg.C/min in air, introducing a mixture of water vapor and tetrachloroethylene at a molar ratio of water to tetrachloroethylene of 20:1, and at a volume space velocity of 1000h-1And (4) carrying out oxychlorination treatment for 4h under the condition. Then heating to 550 ℃ at the speed of 5 ℃/min in the mixed gas of hydrogen and nitrogen, reducing for 2H, wherein the volume fraction of nitrogen in the mixed gas is 50%, and then introducing H2The hydrogen gas of S was subjected to sulfidation treatment for 2 hours, and the volume concentration of hydrogen sulfide in the hydrogen gas was 200ppm, to obtain a catalyst a having a platinum content of 0.3 mass%, a tin content of 0.3 mass%, a potassium content of 1 mass%, a chlorine content of 1.26 mass%, and a sulfur content of 0.08 mass%.
Example 2
A dehydrogenation catalyst was prepared in the same manner as in example 1.
Activation reduction conditions: taking an oxidation state catalyst, heating the oxidation state catalyst to 500 ℃ from room temperature at the speed of 10 ℃/min in the air, introducing a mixed gas of water vapor and hydrogen chloride, wherein the molar ratio of water to hydrogen chloride is 50:1, and the volume space velocity is 1000h-1And (4) carrying out oxychlorination treatment for 4h under the condition. Then heating to 550 ℃ at the speed of 5 ℃/min in pure hydrogen for reduction for 4H, and then introducing H2And (3) carrying out hydrogen vulcanization treatment for 3 hours, wherein the volume concentration of hydrogen sulfide in hydrogen is 50ppm, so as to prepare a catalyst B, wherein the platinum content, the tin content, the potassium content, the chlorine content and the sulfur content in the catalyst B are respectively 0.3 mass%, 1 mass%, 0.97 mass% and 0.06 mass%.
Example 3
A dehydrogenation catalyst was prepared in the same manner as in example 1.
Activation reduction conditions: taking an oxidation state catalyst, heating the oxidation state catalyst to 600 ℃ from room temperature at the speed of 10 ℃/min in the air, introducing a mixed gas of water vapor and carbon tetrachloride, wherein the molar ratio of water to carbon tetrachloride is 100:1, and the volume space velocity is 1000h-1Under the condition of (1), carrying out oxychlorination treatment for 6 h. Then cooling to 580 ℃, reducing in pure hydrogen for 2H at constant temperature, and then introducing H2Hydrogen sulfuration of S for 1h, the volume concentration of hydrogen sulfide in hydrogen being 300ppm, catalyst C was prepared, the platinum content in the catalyst was 0.3 mass%, the tin content was 0.3 mass%The content of potassium, chlorine and sulfur were 1% by mass, 1.05% by mass and 0.1% by mass, respectively.
Comparative example 1
A dehydrogenation catalyst was prepared in the same manner as in example 1.
Activation reduction conditions: heating in air from room temperature to 500 deg.C at a rate of 5 deg.C/min, introducing a mixture of water and air at a volume ratio of 1:30 and a volume space velocity of 1000h-1And washing chlorine for 4h at constant temperature. Then heating to 550 ℃ in a mixed gas of hydrogen and nitrogen at the speed of 5 ℃/min, reducing the nitrogen with the volume fraction of 50 percent at constant temperature for 2H, and then introducing H2And (2) carrying out hydrogen vulcanization on the S, wherein the volume concentration of hydrogen sulfide is 200ppm, carrying out constant-temperature vulcanization for 2 hours to obtain a catalyst D, and the catalyst D contains 0.3 mass% of platinum, 0.3 mass% of tin, 1 mass% of potassium, 0.15 mass% of chlorine and 0.1 mass% of sulfur.
Comparative example 2
A dehydrogenation catalyst was prepared in the same manner as in example 1.
Activation reduction conditions: heating from room temperature to 500 deg.C at a rate of 10 deg.C/min in air, introducing a mixed gas of water and hydrogen chloride at a water/hydrogen chloride molar ratio of 50:1 and a volume space velocity of 1000h-1And carrying out constant-temperature oxychlorination treatment for 4 hours. Then, the temperature was raised to 550 ℃ at a rate of 5 ℃/min in pure hydrogen, and the catalyst E was reduced at a constant temperature for 4 hours without being vulcanized, and the catalyst E was obtained, wherein the content of platinum, tin, potassium and chlorine in the catalyst was 0.3, 1 and 1.02 mass%, respectively.
Comparative example 3
A dehydrogenation catalyst was prepared in the same manner as in example 1.
Activation reduction conditions: heating from room temperature to 500 deg.C at a rate of 10 deg.C/min in air, introducing a mixed gas of water and hydrogen chloride at a water/hydrogen chloride molar ratio of 80:1 and a volume space velocity of 1000h-1And carrying out constant-temperature oxychlorination treatment for 4 hours. Then heating to 550 ℃ at the speed of 5 ℃/min in pure hydrogen, reducing for 4H at constant temperature, and then introducing H2S hydrogen sulfide, volume concentration of hydrogen sulfide is 50ppm, constantWarm vulcanization is carried out for 3 hours to obtain a catalyst F, wherein the content of platinum, tin, potassium, chlorine and sulfur in the catalyst F is 0.3 mass%, 1 mass%, 0.72 mass% and 0.06 mass%, respectively.
Test example
In a quartz tube reactor of a micro-reactor, 3 ml of catalyst (prepared by the above examples and comparative examples, respectively) was charged, and a mixed gas of hydrogen and propane was used as a raw material, and the feed mass space velocity of propane was 3.5h at 620 ℃, 0.21MPa (absolute pressure) and propane-1Hydrogen/propane molar ratio 0.5: 1 for 50 hours, and samples were taken every 1 hour for chromatography. The propane conversion and propylene selectivity were calculated and the results are shown in table 1.
TABLE 1
As shown in Table 1, the dehydrogenation catalyst prepared by the activation reduction method of the present invention has higher propane conversion rate and propylene selectivity and better activity stability than the comparative catalyst D, E, F, the propane conversion rate is reduced by only 1.3 percent at most after 50 hours of reaction, the propylene selectivity is kept stable, the carbon deposit amount of the catalyst is lower, and the catalyst has excellent reaction performance.
Claims (9)
1. A method for activating and reducing a low-carbon alkane dehydrogenation catalyst comprises the following steps: carrying out oxychlorination treatment on the low-carbon alkane dehydrogenation catalyst in an oxidation state, wherein the oxychlorination treatment is carried out in air containing water and chlorine-containing gas compounds, and the molar ratio of the water to chlorine contained in the chlorine-containing gas compounds is 3: 1-55: 1, reducing with hydrogen or a mixed gas of hydrogen and an inert gas, and vulcanizing with the mixed gas of hydrogen and hydrogen sulfide, wherein the volume concentration of hydrogen sulfide in the mixed gas of hydrogen and hydrogen sulfide used in the vulcanizing treatment is 20-500 ppm, the oxidized low-carbon alkane dehydrogenation catalyst comprises an alumina carrier, and 0.1-1 mass% of platinum, 0.1-1 mass% of tin, 0.5-2 mass% of alkali metal and 0.2-0.8 mass% of chlorine, and the chlorine content in the catalyst obtained after the activating reduction treatment is 0.85-1.5 mass% based on the carrier.
2. The method according to claim 1, wherein the oxychlorination treatment temperature is 400-600 ℃.
3. The method of claim 1, wherein the chlorine-containing gas compound is at least one of chlorine gas, hydrogen chloride, chloroform, tetrachloroethylene, dichloroethylene, and carbon tetrachloride.
4. The method according to claim 1, wherein the temperature of the reduction is 400 to 650 ℃, and the volume fraction of the inert gas in the mixed gas of hydrogen and the inert gas is 5 to 70%.
5. The method according to claim 1, wherein the temperature of the vulcanization treatment is 400 to 650 ℃.
6. The method according to claim 1 or 5, wherein the mixed gas of hydrogen and hydrogen sulfide is prepared mixed gas of hydrogen sulfide and hydrogen or mixed gas generated by reaction of hydrogen and a precursor of hydrogen sulfide;
when the mixed gas of hydrogen and hydrogen sulfide is the mixed gas generated by the reaction of hydrogen and hydrogen sulfide precursors, the hydrogen sulfide precursors are at least one of carbon disulfide, dimethyl disulfide and mercaptan.
7. The method of claim 1, wherein the alumina support is theta alumina.
8. The method of claim 1, wherein the alkali metal is potassium.
9. The method of claim 1, wherein the lower alkane is C3~C5Of (a) an alkane.
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