CN108421547B - Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof - Google Patents
Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof Download PDFInfo
- Publication number
- CN108421547B CN108421547B CN201810088867.5A CN201810088867A CN108421547B CN 108421547 B CN108421547 B CN 108421547B CN 201810088867 A CN201810088867 A CN 201810088867A CN 108421547 B CN108421547 B CN 108421547B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tartaric acid
- carbon dioxide
- oil
- hydrogenation
- 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.)
- Active
Links
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 41
- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000011975 tartaric acid Substances 0.000 claims abstract description 16
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 12
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 12
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 11
- 239000012018 catalyst precursor Substances 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 14
- 229960001367 tartaric acid Drugs 0.000 claims description 14
- 238000011068 loading method Methods 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 238000005470 impregnation Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 229960001270 d- tartaric acid Drugs 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000006116 polymerization reaction Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000011521 glass Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Inorganic materials [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000013535 sea water Substances 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- -1 ethylene, propylene Chemical group 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 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
- 230000008569 process Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
- C10G2/50—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon dioxide with hydrogen
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
-
- 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
- Y02P30/00—Technologies relating to oil refining and petrochemical industry
- Y02P30/40—Ethylene production
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a catalyst for preparing oil by carbon dioxide hydrogenation, a preparation method and application thereof, wherein the catalyst is Fe (NO)3)3•9H2O, tartaric acid and water as raw materials for preparing catalyst precursor, Pd and K as cocatalyst, Fe (NO)3)3•9H2The mass ratio of O, tartaric acid and water is 1: 0.4-0.5: 0.35-0.40. By adopting the technology, the invention provides the catalyst for preparing the oil by hydrogenating the carbon dioxide, and the preparation method is limited, the preparation method is simple, the operation links are few, and the obtained catalyst has high activity and C at the temperature lower than 250 DEG C5+ Hydrocarbon selectivity, greater C synthesis2‑C4Olefin, C2‑C4The oil yield can be further improved by subsequent polymerization of the olefins.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a carbon dioxide hydrogenation oil preparation catalyst for preparing oil by carbon dioxide hydrogenation, and a preparation method and application thereof.
Background
Carbon dioxide (CO) with green house effect2) Hydrogenated into organic substances such as methane, methanol, oil, etc., and then used as fuel, and is regarded as CO2Zero emission renewable energy production route and CO capture from seawater as proposed by Hardy et al2And obtaining H2And then they are synthesized into a route for liquid fuels [ u.s. Patent 7420004, B2, 2008.]Can simultaneously solve CO2And H2The technical route can promote CO on the basis of utilizing vast area of ocean to develop solar energy, wind energy, tidal energy and the like as energy sources for electrolyzing seawater2The large-scale industrialization of hydrogenation to prepare liquid fuel is a technical progress which is beneficial to synchronously solving the greenhouse effect and the stable supply of renewable energy sources. Therefore, highly active CO is developed2Hydrogenation catalysts have urgent practical requirements.
By CO under the action of catalyst2The hydrogenation can synthesize a wide variety of organic substances, and can be used as fuel such as methane, methanol, formic acid, dimethyl ether, oil and mixed alcohol [ chem. Soc. Rev. 40 (2011) 3703-2Util, 5 (2014) 66-81, physical and chemical reports 30 (2014) 2177-.]Wherein CO is2The oil obtained by hydrogenation can be further processed into gasoline and diesel oil from petroleumThe liquid fuel with the same property can be directly used for the existing vehicles; moreover, liquid fuels represented by gasoline and diesel oil are main fuels in the transportation industry, the existing consumption market capacity is very large, for example, the apparent consumption of finished oil in China in 2015 reaches 2.76 hundred million tons, so that CO2The hydrogenation oil production technology is not only easy to be accepted by the market, but also has huge consumption requirements.
For CO2The development of hydroprocessing oil catalysts has made great progress in recent years, such as Wei et al [ nat. Commun. 8, 15174 doi: 10.1038/ncomms15174 (2017).]Reported as Na-Fe3O4Catalyst of/HZSM-5, CO2Conversion 22%, CO selectivity 20.1%, in total hydrocarbons, CH4Selectivity 4%, C2-C4Hydrocarbon selectivity 16.6%, C5+ hydrocarbons 79.4% (reaction conditions: H)2/CO23, 320 ℃, 3 MPa, 4L/(h.g-cat), Gao, etc. [ nat. chem.DOI: 10.1038/NCHEM.2794]In is reported2O3Catalyst of/HZSM-5, CO2Conversion was 13.1%, CO selectivity was 44.8%, and the remaining product was hydrocarbons, CH among total hydrocarbons4Selectivity 1%, C2-C4Hydrocarbon selectivity 20.4%, C5+ 78.6% of hydrocarbon (reaction conditions: H)2/CO2/N2= 73/24/3, 340 ℃, 3.0 MPa, 9L/(h · g-cat)). The catalysts developed by these works in CO2All hydrogenation reactions showed high oil (C)5+ hydrocarbon) selectivity, but the reaction temperature required to fully exploit the reactivity of the molecular sieve component (HZSM-5) in the catalyst is higher than 300 ℃.
Due to CO2The hydro-oil production reaction is exothermic and thermodynamically at low temperature higher CO can be achieved2The conversion rate and the low-temperature reaction are beneficial to reducing the manufacturing cost of reaction equipment and improving the safety of operators. Therefore, to increase CO2The comprehensive benefit of the hydrogenation oil-making process is to develop a catalyst with high activity at low temperature.
Disclosure of Invention
For CO2The invention provides a method for recyclingThe catalyst for preparing oil by carbon dioxide hydrogenation, which has simple method and few operation links, and the preparation method and the application thereof. The catalyst has high activity at the temperature lower than 250 ℃, and can synthesize more C2-C4The oil yield can be further improved by subsequent polymerization of the olefins.
The catalyst for preparing oil by hydrogenating carbon dioxide is characterized by using Fe (NO)3)3•9H2O, tartaric acid and water as raw materials for preparing catalyst precursor, Pd and K as cocatalyst, Fe (NO)3)3•9H2The mass ratio of O, tartaric acid and water is 1: 0.4-0.5: 0.35-0.40.
The catalyst for preparing the oil by hydrogenating the carbon dioxide is characterized by Fe (NO)3)3•9H2The mass ratio of O, tartaric acid and water is 1: 0.46: 0.38.
the catalyst for preparing oil by carbon dioxide hydrogenation is characterized in that tartaric acid comprises D-tartaric acid, L-tartaric acid or a mixture of D-tartaric acid and L-tartaric acid in any ratio.
The preparation method of the catalyst for preparing the oil by hydrogenating the carbon dioxide is characterized by comprising the following steps of:
1) dissolving tartaric acid in water to form tartaric acid solution, and adding Fe (NO)3)3•9H2Pouring O into tartaric acid solution, and stirring until the O is completely dissolved to obtain mixed solution; the mixed solution is put into an air blast oven with the temperature of 80-120 ℃ to be dried overnight to obtain solid, the obtained solid is put into a muffle furnace to be roasted for 9-48 hours at the temperature of 300-450 ℃ to obtain Fe2O3Particles;
2) fe obtained in step 1) by an isovolumetric impregnation method2O3Pd and K are loaded on the particles, and the particles are dried in an air blast oven at the temperature of 80-120 ℃ overnight and then are roasted in a muffle furnace at the temperature of 300-450 ℃ for 6-12 hours to prepare the catalyst for preparing the oil by hydrogenating the carbon dioxide.
The preparation method of the catalyst for preparing the oil by hydrogenating the carbon dioxide is characterized in that Fe2O3The loading amount of Pd is 1 to 5wt%, preferably 1.5 to 4 wt%, based on the mass.
The preparation method of the catalyst for preparing the oil by hydrogenating the carbon dioxide is characterized in that Fe2O3The loading amount of K is 1 to 6 weight percent, preferably
1.5wt % - 5wt %。
The application of the catalyst for preparing oil by hydrogenating carbon dioxide in preparing oil by hydrogenating carbon dioxide is disclosed.
By adopting the technology, compared with the prior art, the invention has the following beneficial effects:
by adopting the technology, the invention provides the catalyst for preparing the oil by hydrogenating the carbon dioxide, and the preparation method is limited, the preparation method is simple, the operation links are few, and the obtained catalyst has high activity and C at the temperature lower than 250 DEG C5+ Hydrocarbon selectivity, greater C synthesis2-C4Olefin, C2-C4The oil yield can be further improved by subsequent polymerization of the olefins.
Detailed Description
It should be noted that those skilled in the art can implement various modifications of the embodiments without departing from the technical principle of the present invention, and these modifications should be considered as within the scope of the present invention.
Example 1:
1) firstly, 18.576 g of L-tartaric acid is weighed and put into a glass beaker, 15 g of water is added into the glass beaker, the mixture is stirred and dissolved to obtain L-tartaric acid solution, and then 40 g of Fe (NO) is weighed3)3•9H2Pouring O into the L-tartaric acid solution, and stirring until the O is completely dissolved to obtain a mixed solution; then placing the beaker containing the mixed solution into an air blast oven at 90 ℃ for drying overnight to obtain a solid, placing the obtained solid into a muffle furnace for roasting at 350 ℃ for 9 hours to obtain Fe2O3Particles;
2) the materials are fed according to the proportion, namely relative to Fe2O3The mass, Pd and K loading amounts were 4 wt% and 4 wt%, respectively, Pd (NO) was weighed3)2Solution and KNO3Preparing a mixed solution, and loading Pd and K to Fe by adopting an isometric impregnation method2O3The particles were dried overnight in an air-blown oven at 90 c and then calcined in a muffle furnace at 400 c for 6 hours to produce catalyst 1.
3) The application of the catalyst comprises the following steps: 1 g of the catalyst 1 was charged into a fixed bed reactor, and after reduction at 300 ℃ for 6 hours with 3L/(h.g-cat) of CO at normal pressure, 6L/(h.g-cat) of H at 235 ℃ and 1.6MPa2/CO2The molar ratio of the two gases) =3, and the reaction results are shown in table 1.
Example 2:
1) firstly, 18.576 g of L-tartaric acid is weighed and put into a glass beaker, 15 g of water is added into the glass beaker, the mixture is stirred and dissolved, and then 40 g of Fe (NO) is weighed3)3•9H2O, pouring the mixture into the reactor, and stirring and dissolving the mixture; then placing the beaker filled with the liquid into an air blast oven with the temperature of 80 ℃ for drying overnight, and then placing the obtained solid into a muffle furnace for roasting for 9 hours at the temperature of 350 ℃ to obtain Fe2O3Particles;
2) according to the relative ratio to Fe2O3The mass, Pd and K loading amounts were 2.5 wt% and 2 wt%, respectively, Pd (NO) was weighed3)2Solution and KNO3Preparing solution, and loading Pd and K to Fe by adopting an equal-volume impregnation method2O3Drying the particles in an air blast oven at 80 ℃ overnight and roasting the particles in a muffle furnace at 350 ℃ for 10 hours to obtain a catalyst 2;
3) the application of the catalyst comprises the following steps: 1 g of the catalyst 2 was charged into a fixed bed reactor, reduced at 300 ℃ for 6 hours with 3L/(h.g-cat) of CO at normal pressure, and then reduced at 235 ℃ for 6L/(h.g-cat) of H at 1.6MPa2/CO2Reaction time was 24 hours under the condition of =3, and the reaction results are shown in table 1.
Example 3:
1) firstly, 18.576 g of D-tartaric acid is weighed and put into a glass beaker, 15 g of water is added into the glass beaker, the mixture is stirred and dissolved, and then 40 g of Fe (NO) is weighed3)3•9H2O, pouring the mixture into the reactor, and stirring and dissolving the mixture; then placing the beaker filled with the liquid into an air blast oven at 110 ℃ for drying overnight, placing the obtained solid into a muffle furnace for roasting at 450 ℃ for 9 hours to obtain Fe2O3Particles;
2) according to the relative ratio to Fe2O3The mass, Pd and K loading amounts were 1.5 wt% and 2 wt%, respectively, Pd (NO) was weighed3)2Solution and KNO3Preparing solution, and loading Pd and K to Fe by adopting an equal-volume impregnation method2O3Drying the particles in an air blast oven at 100 ℃ overnight and roasting the particles in a muffle furnace at 300 ℃ for 12 hours to obtain a catalyst 3;
3) the application of the catalyst comprises the following steps: 1 g of the catalyst 3 was charged into a fixed bed reactor, reduced at 300 ℃ for 6 hours with 3L/(h.g-cat) of CO at normal pressure, and then reduced at 235 ℃ for 6L/(h.g-cat) of H at 1.6MPa2/CO2Reaction time was 24 hours under the condition of =3, and the reaction results are shown in table 1.
Example 4:
1) firstly, 9.288 g of D-tartaric acid and 9.288 g of L-tartaric acid are respectively weighed and put into a glass beaker, 15 g of water is added into the glass beaker, the mixture is stirred and dissolved, and then 40 g of Fe (NO) is weighed and taken3)3•9H2O, pouring the mixture into the reactor, and stirring and dissolving the mixture; then placing the beaker filled with the liquid into an air blast oven with the temperature of 120 ℃ for drying overnight, and then placing the obtained solid into a muffle furnace for roasting for 18 hours at the temperature of 300 ℃ to obtain Fe2O3Particles;
2) according to the relative ratio to Fe2O3The mass, Pd and K loading amounts were 2 wt% and 4 wt%, respectively, Pd (NO) was weighed3)2Solution and KNO3Preparing solution, and loading Pd and K to Fe by adopting an equal-volume impregnation method2O3Drying the particles in an air blast oven at 110 ℃ overnight and roasting the particles in a muffle furnace at 450 ℃ for 6 hours to obtain a catalyst 4;
3) the application of the catalyst comprises the following steps: 1 g of catalyst 4 was charged into a fixed bed reactor, reduced at 300 ℃ for 6 hours with 3L/(h.g-cat) of CO at normal pressure, and then reduced at 235 ℃ for 6L/(h.g-cat) of H at 1.6MPa2/CO2Reaction time was 24 hours under the condition of =3, and the reaction results are shown in table 1.
Example 5:
1) firstly, 18.576 g of L-tartaric acid is weighed and put into a glass beaker, 15 g of water is added into the glass beaker, the mixture is stirred and dissolved, and then 40 g of Fe (NO) is weighed3)3•9H2O, pouring the mixture into the reactor, and stirring and dissolving the mixture; then placing the beaker filled with the liquid into an air blast oven with the temperature of 100 ℃ for drying overnight, and then placing the obtained solid into a muffle furnace for roasting at the temperature of 350 ℃ for 48 hours to obtain Fe2O3Particles;
2) according to the relative ratio to Fe2O3The mass, Pd and K loading amounts were 2 wt% and 2 wt%, respectively, Pd (NO) was weighed3)2Solution and KNO3Preparing solution, and loading Pd and K to Fe by adopting an equal-volume impregnation method2O3Drying the granules in an air blast oven at 120 ℃ overnight and roasting the granules in a muffle furnace at 350 ℃ for 6 hours to obtain a catalyst 5;
3) the application of the catalyst comprises the following steps: 1 g of the catalyst 5 was charged into a fixed bed reactor, and after reduction at 300 ℃ for 6 hours with 3L/(h.g-cat) of CO at normal pressure, 6L/(h.g-cat) of H at 235 ℃ and 1.6MPa2/CO2Reaction time was 24 hours under the condition of =3, and the reaction results are shown in table 1.
Catalyst reaction Performance in the example of Table 1
a：C5+ hydrocarbon: the following hydrocarbon molecules having carbon number 5 in the molecule are collectively referred to as "C5".
b: alkene/alkane ratio (C)2-C4）：C2-C4The ratio of the sum of the olefins (ethylene, propylene and butylene) to the sum of the alkanes (ethane, propane and butane) in the hydrocarbon.
According to the data in Table 1, the catalyst prepared by the technology disclosed in the patent has high CO at 235 ℃ reaction temperature2Conversion, C5+ Hydrocarbon Selectivity higher than 41% with higher C production2-C4Olefins, which can further increase the oil yield by subsequent polymerization reactions.
Claims (5)
1. Catalyst for preparing oil by carbon dioxide hydrogenation in preparation of oil by carbon dioxide hydrogenationCharacterized by having a high CO content at a reaction temperature of 235 DEG C2Conversion and C5+ hydrocarbon selectivity with Fe (NO) over said catalyst3)3•9H2O, tartaric acid and water as raw materials for preparing catalyst precursor, Pd and K as cocatalyst, Fe (NO)3)3•9H2The mass ratio of O, tartaric acid and water is 1: 0.4-0.5: 0.35-0.40, wherein the tartaric acid is selected from D-tartaric acid, L-tartaric acid or mixture of D-tartaric acid and L-tartaric acid in any ratio.
2. The use of the catalyst for oil production by hydrogenation of carbon dioxide according to claim 1, wherein the catalyst is Fe (NO)3)3•9H2The mass ratio of O, tartaric acid and water is 1: 0.46: 0.38.
3. the application of the carbon dioxide hydrogenation oil-making catalyst according to claim 1 in the carbon dioxide hydrogenation oil-making, characterized in that the preparation method of the catalyst comprises the following steps:
1) dissolving tartaric acid in water to form tartaric acid solution, and adding Fe (NO)3)3•9H2Pouring O into tartaric acid solution, and stirring until the O is completely dissolved to obtain mixed solution; putting the mixed solution into an air blast oven at the temperature of 80-120 ℃ for drying overnight to obtain solid, putting the obtained solid into a muffle furnace for roasting at the temperature of 300-450 ℃ for 9-48 hours to obtain Fe2O3Particles;
2) fe obtained in step 1) by an isovolumetric impregnation method2O3Pd and K are loaded on the particles, and the particles are dried in an air blast oven at the temperature of 80-120 ℃ overnight and then are roasted in a muffle furnace at the temperature of 300-450 ℃ for 6-12 hours to prepare the catalyst for preparing the oil by hydrogenating the carbon dioxide.
4. The use of the catalyst for oil production by hydrogenation of carbon dioxide according to claim 3, wherein Fe is used2O3The load amount of Pd is 1-5 wt% by mass.
5. The use of the catalyst for oil production by hydrogenation of carbon dioxide according to claim 3, wherein Fe is used2O3The loading amount of K is 1.5-5 wt% by mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810088867.5A CN108421547B (en) | 2018-01-30 | 2018-01-30 | Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810088867.5A CN108421547B (en) | 2018-01-30 | 2018-01-30 | Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108421547A CN108421547A (en) | 2018-08-21 |
| CN108421547B true CN108421547B (en) | 2020-12-01 |
Family
ID=63156156
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810088867.5A Active CN108421547B (en) | 2018-01-30 | 2018-01-30 | Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108421547B (en) |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309967A (en) * | 2011-06-10 | 2012-01-11 | 浙江工业大学 | Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106031871B (en) * | 2015-03-17 | 2018-10-19 | 中国科学院大连化学物理研究所 | A kind of CO2Hydrogenation takes ferrum-based catalyst and its preparation and the application of low-carbon alkene |
| CN107572597A (en) * | 2017-09-19 | 2018-01-12 | 浙江工业大学 | A kind of γ Fe2O3The preparation method of nano material |
-
2018
- 2018-01-30 CN CN201810088867.5A patent/CN108421547B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102309967A (en) * | 2011-06-10 | 2012-01-11 | 浙江工业大学 | Catalyst for hydrocarbon synthesis by CO2 catalytic hydrogenation and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| Role of alkali metal in a highly active Pd/alkali/Fe2O3 catalyst for water gas shift reaction;Ryo Watanabe et al.;《Applied Catalysis A: General》;20130316;第457卷;第1-11页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108421547A (en) | 2018-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102452878B (en) | Method for preparing low-carbon olefin by synthetic gas one-step technology | |
| CN102441383B (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN105728020B (en) | A kind of hud typed iron-carbonide catalyst preparation method | |
| CN105623702B (en) | A kind of method that aviation kerosine cycloalkane and aromatised fraction are synthesized using wood chip | |
| CN114939433A (en) | Composite catalyst for directly preparing light aromatic hydrocarbon by carbon dioxide hydrogenation, preparation and application thereof | |
| CN101940958A (en) | Method for preparing low-carbon olefine catalyst by loading iron-based synthetic gas | |
| CN103664436B (en) | The method of low-carbon alkene is converted into by synthetic gas | |
| CN107913729B (en) | Composite catalyst and preparation method thereof | |
| CN102441400B (en) | Preparation method of catalyst in process of producing light olefins by high-activity load type iron-based synthesis gas | |
| CN102773106A (en) | Catalyst for preparing low carbon olefin by synthetic gas as well as preparation method and application of catalyst | |
| CN105562026B (en) | Ferrum-based catalyst of sulfur-bearing and its preparation method and application | |
| CN101279281B (en) | High stability molecular sieve catalyst for preparing propylene transformed from methanol and preparation thereof | |
| CN108421547B (en) | Catalyst for preparing oil by carbon dioxide hydrogenation and preparation method and application thereof | |
| CN109304216B (en) | Catalyst for producing low-carbon olefin by synthesis gas one-step method | |
| CN107617446B (en) | Catalyst for preparing gasoline fraction hydrocarbon by directly converting synthesis gas and preparation and application thereof | |
| CN104178204B (en) | A kind of preparation method rich in isoparaffin gasoline | |
| CN109647492B (en) | Catalyst for directly producing low-carbon olefin by synthesis gas | |
| CN109305871B (en) | Method for producing low-carbon olefin by synthesis gas one-step method | |
| CN109304215B (en) | Catalyst for preparing low-carbon olefin by synthesis gas one-step method | |
| CN102372549A (en) | Method for preparing ethylbenzene and styrene by side-chain alkylation reaction of toluene with methanol | |
| CN109305870B (en) | Method for preparing low-carbon olefin by synthesis gas one-step method | |
| CN102389832A (en) | Catalyst for preparing C5 and C6 alkanes by hydrogenating high-activity sorbierite water phase, and preparation method of catalyst | |
| CN109651031B (en) | Method for directly producing low-carbon olefin by using synthesis gas | |
| CN114471744B (en) | Pretreatment method of iron-based catalyst and application thereof | |
| CN111909727B (en) | Green synthesis method for preparing saturated hydrocarbon fuel from isoprene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240409 Address after: Room 802, Building C, Qingwang Science and Technology Park, Baohe Economic Development Zone, Hefei City, Anhui Province, 230041 Patentee after: Hefei xingzhicheng Information Technology Co.,Ltd. Country or region after: China Address before: 310014 Zhejiang University of Technology, 18, Chao Wang Road, Xiacheng District, Hangzhou, Zhejiang Patentee before: JIANG University OF TECHNOLOGY Country or region before: China |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20240425 Address after: 115002 No.11-19 Tianti South Street, Zhanqian District, Yingkou City, Liaoning Province (No. 13) Patentee after: Liaoning Zhongcarbon New Energy Technology Co.,Ltd. Country or region after: China Address before: Room 802, Building C, Qingwang Science and Technology Park, Baohe Economic Development Zone, Hefei City, Anhui Province, 230041 Patentee before: Hefei xingzhicheng Information Technology Co.,Ltd. Country or region before: China |