CN109879711A - Method for preparing methane by hydrothermal method of fatty acid - Google Patents
Method for preparing methane by hydrothermal method of fatty acid Download PDFInfo
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- CN109879711A CN109879711A CN201910185198.8A CN201910185198A CN109879711A CN 109879711 A CN109879711 A CN 109879711A CN 201910185198 A CN201910185198 A CN 201910185198A CN 109879711 A CN109879711 A CN 109879711A
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- fatty acid
- methane
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- reaction kettle
- reaction
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 239000000194 fatty acid Substances 0.000 title claims abstract description 37
- 235000014113 dietary fatty acids Nutrition 0.000 title claims abstract description 35
- 229930195729 fatty acid Natural products 0.000 title claims abstract description 35
- 150000004665 fatty acids Chemical class 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 title claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 10
- 238000006073 displacement reaction Methods 0.000 claims abstract description 9
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000002904 solvent Substances 0.000 claims abstract description 3
- 238000010792 warming Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 31
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 7
- 239000001569 carbon dioxide Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 3
- 229910021536 Zeolite Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 2
- -1 graphite Alkene Chemical class 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052743 krypton Inorganic materials 0.000 claims description 2
- DNNSSWSSYDEUBZ-UHFFFAOYSA-N krypton atom Chemical compound [Kr] DNNSSWSSYDEUBZ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910052704 radon Inorganic materials 0.000 claims description 2
- SYUHGPGVQRZVTB-UHFFFAOYSA-N radon atom Chemical compound [Rn] SYUHGPGVQRZVTB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000007790 solid phase Substances 0.000 claims description 2
- 229910052724 xenon Inorganic materials 0.000 claims description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000010457 zeolite Substances 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 229910052757 nitrogen Inorganic materials 0.000 claims 1
- 239000002699 waste material Substances 0.000 abstract description 14
- 239000004519 grease Substances 0.000 abstract description 9
- 230000001681 protective effect Effects 0.000 abstract description 3
- 239000012298 atmosphere Substances 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 150000001721 carbon Chemical group 0.000 description 5
- 239000003245 coal Substances 0.000 description 4
- 239000008162 cooking oil Substances 0.000 description 4
- 238000001802 infusion Methods 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 235000019198 oils Nutrition 0.000 description 4
- 235000021355 Stearic acid Nutrition 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000000975 co-precipitation Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 239000008246 gaseous mixture Substances 0.000 description 3
- 238000007327 hydrogenolysis reaction Methods 0.000 description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 3
- 239000008117 stearic acid Substances 0.000 description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001410 inorganic ion Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002048 multi walled nanotube Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 235000015112 vegetable and seed oil Nutrition 0.000 description 2
- 239000008158 vegetable oil Substances 0.000 description 2
- OYHQOLUKZRVURQ-NTGFUMLPSA-N (9Z,12Z)-9,10,12,13-tetratritiooctadeca-9,12-dienoic acid Chemical compound C(CCCCCCC\C(=C(/C\C(=C(/CCCCC)\[3H])\[3H])\[3H])\[3H])(=O)O OYHQOLUKZRVURQ-NTGFUMLPSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical group 0.000 description 1
- 239000010775 animal oil Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000000508 aqueous-phase reforming Methods 0.000 description 1
- 238000005815 base catalysis Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 125000001664 diethylamino group Chemical group [H]C([H])([H])C([H])([H])N(*)C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000005446 dissolved organic matter Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses the methods that fatty acid hydro-thermal method prepares methane, using fatty acid as raw material, it takes water as a solvent, under the conditions of 200~400 DEG C of temperature, catalysis reaction is prepared into methane, specifically includes the following steps: fatty acid, water and catalyst are added in reaction kettle by (1), then the air being passed through in gas displacement reaction kettle；(2) then the reaction kettle in step (1) is heated, is warming up to 200~400 DEG C, and be stirred to react 0.5~15h at such a temperature, the mixed gas rich in methane is prepared.This method simple process, it is environmentally protective, while because there are also a large amount of fatty acid in waste grease, so the present invention also provides a new thinking for the resource utilization of waste grease.
Description
Technical field
The present invention relates to waste grease resource utilizations to recycle field, and in particular to fatty acid hydro-thermal method prepares methane
Method.
Background technique
Methane (CH4) be a kind of high-quality, cleaning, efficient green energy resource, it is main by coal gasification be prepared rich in CO,
CO2And H2Gaseous mixture, gaseous mixture then methanation and be made.Coal is fossil fuel, non-renewable, and in coal gasification course
Certain sulfur-containing oxide can be generated, is polluted the environment.Compared with fossil fuel, it can be greatly reduced using methane
SO2、NOXWith the discharge of the pollutants such as heavy metal, the no pollution to environment can be realized.Therefore, the coal substitution of super quality and competitive price is developed
Raw material and its efficient, science switch technology are to realize biology CH4The antecedent basis of large-scale development, simultaneously for protecting ecology
Environment realizes that the sustainable development of human society has very important reality and far-reaching significance.
Fatty acid refers to the aliphatic hydrocarbon chain that the length of a carboxyl is contained in one end, mainly for the manufacture of daily cosmetics,
Detergent, commercial fatty hydrochlorate, coating, paint, rubber, soap etc., are widely present in nature, such as various animal tallows,
Vegetable oil, microalgae oil and various small molecule fatty acid etc..After the uses such as various animal and vegetable oils are pan-fried through high temperature, fry, it can generate and contain
There is the abandoned oil of a large amount of organic acids.Such as inappropriate processing, pollutes the environment, flow back into food and drink and food processing if being illegally used
Industry can endanger health.
Therefore, if the fatty acid in waste grease can be used to produce methane, this will be a kind of good industrial development think of
Road.But so far still without the research achievement for producing methane this respect using fatty acid or waste grease.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the invention is that providing fatty acid hydro-thermal method prepares methane
Method, this method simple process is environmentally protective, provides a new thinking for the resource utilization of waste grease.
The technical scheme of the present invention is realized as follows:
The method that fatty acid hydro-thermal method prepares methane takes water as a solvent using fatty acid as raw material, in 200~400 DEG C of temperature
Under the conditions of degree, catalysis reaction is prepared into methane.Specifically includes the following steps:
(1) fatty acid, water and catalyst are added in reaction kettle, then the air being passed through in gas displacement reaction kettle；
(2) then the reaction kettle in step (1) is heated, is warming up to 200~400 DEG C, and stir at such a temperature
0.5~15h is reacted, the mixed gas rich in methane is prepared.
Further, the mass ratio of fatty acid and water is 1:0.1~50 in the step (1)；Fatty acid and catalyst
Mass ratio is 5~100:1.
Further, the fatty acid is C2~C28Fatty acid.
Further, the active component of the catalyst is one or more of Ru, Rh, Ni, Co, Fe, and catalyst carries
Body is active carbon, mesoporous carbon, carbon nanotube, graphene, SiO2、ZrO2、TiO2、CeO2、Al2O3、γ-Al2O3, in MgO and zeolite
Any one or or several complex carriers being composed.
The catalyst is commercial catalysts or the catalyst being prepared using coprecipitation or infusion process.
Wherein catalyst carrier is SiO2, ZrO2、Al2O3、γ-Al2O3, MgO catalyst using coprecipitation prepare, altogether
The specific implementation method of the precipitation method: the molten of the mass ratio of certain stoicheiometry active component cation and carrier cation is first prepared
Then liquid is added suitable precipitating reagent and obtains forming uniform precipitating, be filtered, washed, dried, restore calcination after be catalyzed
Agent.
Wherein catalyst carrier is active carbon (AC), the catalyst of mesoporous carbon (MC), multi-walled carbon nanotube (MWCNTs) is adopted
It is prepared with infusion process, the specific implementation method of infusion process: first preparing certain density solution, quantitative carrier is then added and carries out
Incipient impregnation obtains catalyst after ultrasound, standing, dry, reduction calcination.Pass through coprecipitation and infusion process preparation catalysis
The catalyst activity component good dispersion degree that agent process is simple, obtains.
Further, the gas in step (1) is nitrogen (N2), carbon dioxide (CO2), helium (He), neon (Ne), argon
One or more of gas (Ar), Krypton (Kr), xenon (Xe), radon gas (Rn).
Further, 0.5~10h is stirred to react in step (2) at 300~400 DEG C, stirring rate is 10~1000rpm.
Under the reaction temperature, reaction dissolvent water is in subcritical or supercriticality, has much advantageous to reaction
Property: (1) ability of dissolved organic matter and gas is stronger, and the solubility of the substances such as fatty acid, hydrogen is higher, it is easier to react；
(2) contain a large amount of inorganic ions in waste grease, when being applied to waste grease, which can reduce the molten of inorganic matter
Xie Du, weaken inorganic ion influences caused by reaction；(3) high temperature liquid water itself has the function of acid catalysis and base catalysis
Can, accelerate reaction rate.Stirring appropriate can weaken mass transfer and limit during the reaction simultaneously, accelerate reaction rate.
Further, the mixed gas being prepared in step (2) includes methane, carbon dioxide, hydrogen, bivinyl and C2
~C5Alkane, wherein main component is methane.
Further, further include step (3), after step (2) reaction kettle is cooling, collects mixed gas and solid phase in kettle and urge
Then agent is passed through H in tube furnace or Muffle furnace furnace2、N2Or calcination regenerated catalyst in inert gas.Solid catalyst warp
It may be reused after regeneration.
Methane production approach of the invention mainly has: hydrogenolysis and methanation reaction.
1) hydrogenolysis
Wherein: n is carbon atom number, and RN~1Middle carbon atom number ratio RnIn carbon atom number few one, RN~2In
Carbon atom number ratio RnIn carbon atom number few two, so reaction successively carries out, and constantly chain length is made to shorten, while producing first
Alkane.
2) methanation reaction
Following reaction occurs simultaneously for fatty acid during hydrogenolysis:Wherein CO is easily
Anti- raw react generates CO with water2And H2.CO and CO2The reaction equation that methanation reaction generates methane occurs are as follows:
CO+3H2——→H2O+CH4
CO2+4H2——→2H2O+CH4
Hydrogen needed for the above reaction is reacted by the aqueous phase reforming that fatty acid, alkane occur and CO steam conversion reaction is raw
At.
Compared with prior art, the invention has the following beneficial effects:
1, present invention process is simple, environmentally protective, and a new think of can be provided for the resource utilization of waste grease
Road.
2, the content for the methane that the present invention is prepared and yield are higher, can reduce energy loss, supplement China
Natural gas resource.
Specific embodiment
Invention is further described in detail With reference to embodiment.
The molar yield of methane=generation methane mole/addition fatty acid mole in following embodiment mixed gas
Amount * 100%.
Embodiment 1
10g stearic acid, 1g Ru/C catalyst, 160gH are added in the intermittent high-temperature high-pressure reaction kettle of 250mL2O, and it is close
Envelope, uses N2Air in displacement kettle controls N three times2For atmosphere in 0.1MPa, being kept stirring rate is 300rpm, is heated to
380 DEG C of reaction 5h.After reaction, reaction product is cooled to room temperature, collects the mixed gas in reaction kettle.Gained mixed gas
Each component volume fraction is shown in Table 1, wherein CH4Volume fraction be 36.80%, molar yield 288.42%.
The volume fraction of mixed gas each component in 1 embodiment 1 of table
Embodiment 2
10g stearic acid, 4gNi/ZrO are added in the intermittent high-temperature high-pressure reaction kettle of 250mL2Catalyst, 200gH2O, and
Sealing, three times with the air in Ar displacement kettle, for control Ar atmosphere in 0.1MPa, being kept stirring rate is 800rpm, heat temperature raising
To 370 DEG C of reaction 8h.After reaction, reaction product is cooled to room temperature, collects the mixed gas in reaction kettle.Gained gaseous mixture
Body each component volume fraction is shown in Table 2, wherein CH4Volume fraction be 54.98%, molar yield 341.14%.
The volume fraction of mixed gas each component in 2 embodiment 2 of table
| Product | Ratio (%) | Product | Ratio (%) |
| CH4 | 54.98 | C5H12 | 0.38 |
| C2H6 | 0.76 | 1,3Butadiene | 0.49 |
| C3H8 | 0.17 | CO2 | 14.89 |
| C4H10isobutane | 0.97 | H2 | 5.37 |
| C4H10N~butane | 0.17 | Ar | 19.88 |
Embodiment 3
10g oleic acid, 2g Rh/C catalyst, 120gH are added in the intermittent high-temperature high-pressure reaction kettle of 250mL2O, and it is close
Envelope, uses N2Air in displacement kettle controls N three times2For atmosphere in 0.1MPa, being kept stirring rate is 600rpm, is heated to
400 DEG C of reaction 5h.After reaction, reaction product is cooled to room temperature, collects the mixed gas in reaction kettle.Gained mixed gas
Middle CH4Volume fraction be 6.19%, molar yield 108.07%.
Embodiment 4
10g linoleic acid, 3gNi/ZrO are added in the intermittent high-temperature high-pressure reaction kettle of 250mL2Catalyst, 160gH2O, and
Sealing, three times with the air in He displacement kettle, for control He atmosphere in 0.1MPa, being kept stirring rate is 500rpm, heat temperature raising
To 350 DEG C of reaction 10h.After reaction, reaction product is cooled to room temperature, collects the mixed gas in reaction kettle.Gained mixing
CH in gas4Volume fraction be 38.23%, molar yield 161.76%.
Embodiment 5
15g stearic acid, 1g Ru/C catalyst, 120gH are added in the intermittent high-temperature high-pressure reaction kettle of 250mL2O, and it is close
Envelope, uses N2Air in displacement kettle controls N three times2For atmosphere in 0.1MPa, being kept stirring rate is 1000rpm, is heated to
380 DEG C of reaction 4h.After reaction, reaction product is cooled to room temperature, collects the mixed gas in reaction kettle.Gained mixed gas
Middle CH4Volume fraction be 56.13%, molar yield 203.18%.
Embodiment 6
10g waste cooking oil is added in the intermittent high-temperature high-pressure reaction kettle of 250mL, and (waste cooking oil is eaten collected from University Of Chongqing
Hall oil separator removes part of impurity by pretreatment), 1g Ru/ZrO2Catalyst, 180g H2O, and seal, use N2Displacement
Air in kettle three times, controls N2For atmosphere in 0.1MPa, being kept stirring rate is 500rpm.It is heated to 360 DEG C of reaction 9h.
After reaction, reaction product is cooled to room temperature, collects gas in kettle.CH in gained mixed gas4Volume fraction be
44.17%, molar yield 377.59%.
Embodiment 7
10g waste cooking oil is added in the intermittent high-temperature high-pressure reaction kettle of 250mL, and (waste cooking oil is eaten collected from University Of Chongqing
Hall oil separator removes part of impurity by pretreatment), 1g Rh/Al2O3Catalyst, 120g H2O, and seal, it is set with Ne
Change air in kettle three times, for control Ne atmosphere in 0.1MPa, being kept stirring rate is 700rpm.It is heated to 300 DEG C of reactions
15h.After reaction, reaction product is cooled to room temperature, collects gas in kettle.CH in gained mixed gas4Volume fraction be
28.72%, molar yield 124.03%.
From embodiment 6 and embodiment 7 as can be seen that present invention can apply to waste greases to prepare methane resourceization using neck
Domain.
Finally, it should be noted that the above embodiment of the present invention is only example to illustrate the invention, and it is not
It is the restriction to embodiment of the present invention.For those of ordinary skill in the art, on the basis of the above description also
Other various forms of variations and variation can be made.Here all embodiments can not be exhaustive.It is all to belong to this
The technical solution changes and variations that derived from of invention are still in the scope of protection of the present invention.
Claims (9)
1. the method that fatty acid hydro-thermal method prepares methane, which is characterized in that using fatty acid as raw material, take water as a solvent, 200~
Under the conditions of 400 DEG C of temperature, catalysis reaction is prepared into methane.
2. the method that fatty acid hydro-thermal method according to claim 1 prepares methane, which is characterized in that specifically include following step
It is rapid:
(1) fatty acid, water and catalyst are added in reaction kettle, then the air being passed through in gas displacement reaction kettle；
(2) then the reaction kettle in step (1) is heated, is warming up to 200~400 DEG C, and be stirred to react at such a temperature
The mixed gas rich in methane is prepared in 0.5~15h.
3. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that fatty in step (1)
The mass ratio of acid and water is 1:0.1~50；The mass ratio of fatty acid and catalyst is 5~100:1.
4. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that the fatty acid is C2
~C28Fatty acid.
5. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that the work of the catalyst
Property group be divided into one or more of Ru, Rh, Ni, Co, Fe, catalyst carrier is active carbon, mesoporous carbon, carbon nanotube, graphite
Alkene, SiO2、ZrO2、TiO2、CeO2、Al2O3、γ-Al2O3, the compound load that is composed of any one or a few in MgO and zeolite
Body.
6. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that the gas in step (1)
Body is one or more of nitrogen, carbon dioxide, helium, neon, argon gas, Krypton, xenon, radon gas.
7. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that 300 in step (2)
~400 DEG C are stirred to react 0.5~10h, and stirring rate is 10~1000rpm.
8. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that preparation in step (2)
Obtained mixed gas includes methane, carbon dioxide, hydrogen, bivinyl and C2~C5Alkane, wherein main component is methane.
9. the method that fatty acid hydro-thermal method according to claim 2 prepares methane, which is characterized in that it further include step (3),
After step (2) reaction kettle is cooling, mixed gas and solid-phase catalyst in kettle are collected, is then led in tube furnace or Muffle furnace furnace
Enter H2、N2Or calcination regenerated catalyst in inert gas.
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