CN110721686B - Catalytic cracking catalyst using peat carbon as carrier - Google Patents
Catalytic cracking catalyst using peat carbon as carrier Download PDFInfo
- Publication number
- CN110721686B CN110721686B CN201910922220.2A CN201910922220A CN110721686B CN 110721686 B CN110721686 B CN 110721686B CN 201910922220 A CN201910922220 A CN 201910922220A CN 110721686 B CN110721686 B CN 110721686B
- Authority
- CN
- China
- Prior art keywords
- peat
- carbon
- catalytic cracking
- peat carbon
- cracking catalyst
- 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
- 239000003415 peat Substances 0.000 title claims abstract description 165
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 111
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 49
- 230000004913 activation Effects 0.000 claims abstract description 89
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000012298 atmosphere Substances 0.000 claims abstract description 36
- 239000007833 carbon precursor Substances 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910021642 ultra pure water Inorganic materials 0.000 claims abstract description 18
- 239000012498 ultrapure water Substances 0.000 claims abstract description 18
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 238000005470 impregnation Methods 0.000 claims abstract description 6
- 230000003213 activating effect Effects 0.000 claims abstract 2
- 239000012300 argon atmosphere Substances 0.000 claims description 47
- 239000007789 gas Substances 0.000 claims description 32
- 239000002131 composite material Substances 0.000 claims description 31
- 229910052759 nickel Inorganic materials 0.000 claims description 21
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 65
- 239000013543 active substance Substances 0.000 abstract description 26
- 238000011068 loading method Methods 0.000 abstract description 13
- 239000011148 porous material Substances 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 56
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000000243 solution Substances 0.000 description 20
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 16
- 230000000694 effects Effects 0.000 description 10
- 229910002092 carbon dioxide Inorganic materials 0.000 description 8
- 239000001569 carbon dioxide Substances 0.000 description 8
- 238000005259 measurement Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- 229910018098 Ni-Si Inorganic materials 0.000 description 3
- 229910018529 Ni—Si Inorganic materials 0.000 description 3
- 229910002803 Si-O-Fe Inorganic materials 0.000 description 3
- 229910004298 SiO 2 Inorganic materials 0.000 description 3
- 229910002802 Si–O–Fe Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- 230000006978 adaptation Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 229910001151 AlNi Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004811 liquid chromatography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 238000009270 solid waste treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Images
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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/60—
-
- B01J35/61—
-
- 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
- B01J37/08—Heat treatment
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
Abstract
The invention discloses a catalytic cracking catalyst taking peat carbon as a carrier. The catalytic cracking catalyst is prepared by the following steps: (1) Pyrolyzing the dried peat in an inert atmosphere to obtain a peat carbon precursor; (2) Heating the peat carbon precursor in an inert atmosphere, introducing ultrapure water for high-temperature water vapor activation, and converting the inert atmosphere into CO 2 Atmosphere, maintaining temperature using CO 2 Activating the peat carbon precursor, and then adding CO 2 Converting the atmosphere into inert atmosphere and naturally cooling to room temperature to obtain peat carbon; (3) And (3) carrying out loading on peat carbon by using a wet impregnation method, and then drying and calcining to obtain the catalytic cracking catalyst. The invention utilizes high-temperature water vapor activation and CO 2 The activation method combines two physical activation methods to activate the peat carbon precursor under the synergistic effect, so that the specific surface area and the pore structure of carbon are increased, the loading capacity of active substances is improved, and the contact area of a catalyst and a reactant in the reaction is increased.
Description
Technical Field
The invention relates to the technical field of solid waste treatment, in particular to a catalytic cracking catalyst taking peat carbon as a carrier.
Background
The biomass energy is renewable carbonaceous energy, and the thermal conversion is an effective utilization mode of the biomass energy. Tar is a byproduct in the biomass pyrolysis and gasification processes, has complex components, most of which are benzene derivatives and polycyclic aromatic hydrocarbons, wherein heavy components are easy to coke and difficult to utilize, and are harmful to human health and environment when entering the environment. Therefore, how to convert the tar heavy component into clean gas is a key scientific problem, wherein the conversion of the heavy component into the clean gas through cracking or reforming under the action of the catalyst is a well-known effective treatment mode. The research of catalytic conversion of heavy components by using the carbon-based material prepared by taking the solid waste as the precursor as the catalyst or the catalyst carrier has the advantages of high-quality catalytic performance, low cost, substance reproducibility and the like.
Peat is a byproduct in the coal production process, and the source of peat is wide, but the peat is rarely reported as a catalyst carrier in the prior art.
Disclosure of Invention
The invention provides a catalytic cracking catalyst with peat carbon as a carrier, which takes peat carbon as a catalyst carrier and utilizes a wet impregnation method to carry out catalytic cracking on an active substance FeCl 3 Or Ni (NO) 3 ) 2 Uniformly loaded on the surface of a carrier, aims to solve the problems that active components of a catalyst are easy to run off in the reaction and the stability of the catalyst is poor by utilizing the existence of Si-O-Fe, ni-Si and Al-Ni-Si bonds, and has better loading effect by utilizing high-temperature water vapor activation and CO to increase the specific surface area of carbon 2 Activation two physical activation methods are combined to perform synergistic action to activate the peat carbon precursor.
The invention aims to provide a catalytic cracking catalyst taking peat carbon as a carrier, which is prepared by the following steps:
(1) Pyrolyzing the dried peat at 700-900 ℃ in an inert atmosphere to obtain a peat carbon precursor;
(2) Heating the peat carbon precursor obtained in the step (1) to 700-900 ℃ in inert atmosphere, introducing ultrapure water for high-temperature water vapor activation, and converting the inert atmosphere into CO after water vapor activation 2 Atmosphere, maintaining temperature using CO 2 Activation of peat carbon precursor, CO 2 After activation, CO is added 2 Converting the atmosphere into inert atmosphere and naturally cooling to room temperature to obtain peat carbon;
(3) FeCl on peat carbon by wet impregnation 3 Or Ni (NO) 3 ) 2 The composite catalyst is dried and then calcined to obtain the catalytic cracking catalyst taking peat carbon as a carrier, wherein the load amount of Fe or Ni in the catalytic cracking catalyst is 5-15%.
The main components of the peat carbon precursor obtained by pyrolyzing peat are C and high-temperature-resistant oxide SiO 2 、Al 2 O 3 And the coal slime carbon is subjected to high-temperature water vapor activation and CO 2 After activation, the carbon surface has rich pore structure and surface chemical functional groups, which accords with the characteristics of catalytic cracking catalyst carrier, C and SiO in peat carbon 2 The structure provides extremely favorable conditions for the catalyst carrier, and simultaneously, the existence of Si-O-Fe, ni-Si and Al-Ni-Si bonds ensures that the catalytic performance and the stability of the catalytic cracking catalyst taking peat carbon as the carrier are better.
Preferably, the high temperature water vapor activation in the step (2) is carried out, the injection amount of ultrapure water is 0.2mL/min, the high temperature water vapor activation time in the step (2) is 30-40min, and the CO is added 2 Under a gas atmosphere, CO 2 The activation time is 30-40min.
Preferably, the wet impregnation method of step (3) performs FeCl on peat carbon 3 Or Ni (NO) 3 ) 2 The load comprises the following specific steps: taking FeCl 3 Or Ni (NO) 3 ) 2 Dissolving in water to obtain FeCl 3 Or Ni (NO) 3 ) 2 Solution, weighing the peat carbon obtained in the step (2) and dissolving the peat carbon in the solutionFeCl 3 Or Ni (NO) 3 ) 2 Stirring in the solution, wherein the mass ratio of Fe or Ni to peat is 0.05.
Preferably, the calcination step in step (3) is to calcine the dried composite catalyst at 700-900 ℃ for 1-2 h under argon atmosphere.
The invention also provides the application of the catalytic cracking catalyst taking peat carbon as a carrier in the preparation of clean gas.
Preferably, the application of the peat carbon-based supported catalytic cracking catalyst in the preparation of clean gas comprises the following steps: and (2) placing the catalytic cracking catalyst with the peat carbon base as the carrier into a reaction vessel, heating to 800 ℃ under the argon atmosphere, simultaneously introducing phenol and ultrapure water, and catalyzing the phenol and the water by the catalytic cracking catalyst with the peat carbon base as the carrier under the drive of the argon to obtain clean gas.
Preferably, the ratio of the flow rate of phenol to the flow rate of ultrapure water is 1.
Preferably, the cleaning gas comprises carbon monoxide, hydrogen, methane and the like.
Compared with the prior art, the invention has the beneficial effects that:
(1) The raw material peat provided by the invention has wide sources and low price.
(2) The invention utilizes high-temperature water vapor activation and CO 2 The two physical activation methods are combined to activate the peat carbon precursor under the synergistic effect, so that the specific surface area and the pore structure of carbon are increased, the loading capacity of active substances is improved, and the contact area of a catalyst and a reactant in the reaction is increased.
(3) The catalytic activity and stability of the catalyst are improved by the existence of Si-O-Fe, ni-Si and Al-Ni-Si bonds in the catalytic cracking catalyst taking peat carbon as a carrier, the catalytic activity of the catalyst is strong, and the conversion rate of phenol is up to 95.3%.
Drawings
FIG. 1 is an SEM photograph of a peat carbon-based supported catalytic cracking catalyst prepared in example 1;
FIG. 2 is an XRD pattern of a peat carbon-based supported catalytic cracking catalyst prepared in example 1;
FIG. 3 is an SEM photograph of a peat carbon-based supported catalytic cracking catalyst prepared in example 2;
fig. 4 is an XRD pattern of the peat carbon-based supported catalytic cracking catalyst prepared in example 2.
Detailed Description
The following examples are further illustrative of the present invention and are not intended to be limiting thereof. The equipment and reagents used in the present invention are, unless otherwise specified, conventional commercial products in the art.
Example 1
The peat carbon-based catalytic cracking catalyst loaded with active substance iron is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to an activation temperature of 800 ℃ in an argon atmosphere, introducing 0.2mL/min of ultrapure water after reaching the activation temperature, maintaining the activation temperature to perform water vapor activation for 40min, and converting the argon atmosphere into CO after the water vapor activation is completed 2 Maintaining the activation temperature in a gas atmosphere for 40min of carbon dioxide activation 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) Taking 4.8g FeCl 3 ·6H 2 Dissolving O in 500mL of water to obtain FeCl 3 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in FeCl 3 Stirring the solution for 3 hours at the rotating speed of 700rmp to obtain a composite catalyst, placing the obtained composite catalyst in a drying box at 105 ℃ for drying for 24 hours, and calcining the dried composite catalyst at 800 ℃ for 2 hours in an argon atmosphere to obtain peat carbon-based loaded active substance ironThe catalytic cracking catalyst of (3), wherein the loading amount of iron is 10%.
The obtained peat carbon-based catalytic cracking catalyst loaded with an active substance iron is characterized, as shown in fig. 1, the surface of the obtained catalyst is in a polymerized nano particle form, and surface particles are uniformly distributed. As shown in FIG. 2, the main structures of the catalyst are C and SiO 2 With the presence of small amounts of FeC and FeSiO 3 And (5) structure. FeC and FeSiO 3 The existence of the structure not only ensures the catalytic activity of the catalyst, but also enhances the stability of the catalyst.
In order to test the catalytic activity of the obtained catalyst, 0.5g of peat carbon-based catalytic cracking catalyst loaded with an active substance iron is placed in a vertical tubular furnace reaction device, the temperature is raised to 800 ℃ under the argon atmosphere, phenol is introduced at the speed of 0.1mL/min after the temperature reaches 800 ℃, ultrapure water is introduced at the speed of 0.3mL/min, phenol and ultrapure water are simultaneously introduced into the vertical tubular furnace reaction device, phenol and water are catalyzed by the peat carbon-based catalytic cracking catalyst loaded with the active substance iron under the drive of argon to obtain clean gases such as methane, carbon monoxide, hydrogen and the like, unreacted phenol is collected by a gas-liquid separator, and the generated gas is collected by an air bag. The liquid was checked by liquid chromatography and the gas was checked by gas chromatography, and the conversion of phenol was calculated to be 92.7% from the results of the check.
Example 2
The peat carbon-based catalytic cracking catalyst loaded with active substance nickel is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to an activation temperature of 800 ℃ in an argon atmosphere, introducing 0.2mL/min of ultrapure water after the activation temperature is reached, maintaining the activation temperature, performing water vapor activation for 40min, and converting the argon atmosphere into CO after the water vapor activation is completed 2 Maintaining the activation temperature in a gas atmosphere for 40min of carbon dioxide activation 2 After the activation is completed, the mixture isCO 2 The gas atmosphere is converted to argon atmosphere and naturally cooled to room temperature, activated peat carbon is obtained and stored in a drying vessel, and the activated peat carbon is placed in a drying oven at 105 ℃ for drying for 24 hours, so that peat carbon is obtained for standby;
(3) Take 4.9g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 500mL water to obtain Ni (NO) 3 ) 2 Solution, weighing 10g of peat carbon obtained in step (2) and dissolving in Ni (NO) 3 ) 2 Stirring the solution for 3 hours at the rotation speed of 700rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at the temperature of 105 ℃ for 24 hours, and calcining the dried composite catalyst at the temperature of 800 ℃ for 2 hours in an argon atmosphere to obtain the peat carbon-based catalytic cracking catalyst loaded with an active substance nickel, wherein the loading capacity of the nickel is 10%.
The obtained peat carbon-based catalytic cracking catalyst loaded with the active substance nickel is characterized, as shown in fig. 3, the active substance in the obtained catalyst is uniformly dispersed on the surface of a peat carbon carrier, and the size of the active substance is in a nanometer level. FIG. 4 shows the XRD pattern of the synthesized catalyst, and as shown, the main structures of the catalyst are C and SiO 2 The simple substance nickel, niSi and a small amount of AlNi exist simultaneously 2 A Si substance. Further illustrates that the active component Ni is better to be mixed with SiO in the peat carrier 2 And Al 2 O 3 And the combination ensures the good activity and stability of the active substance nickel in the catalytic reaction process.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 95.3% based on the measurement results.
Comparative example 1
(1) Drying peat in a drying box at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain peat carbon precursor;
(2) Placing the peat carbon precursor obtained in the step (1) in a vertical tubular furnace, heating to an activation temperature of 800 ℃ in an argon atmosphere, introducing ultrapure water of 0.2mL/min after reaching the activation temperature, maintaining the activation temperature, performing water vapor activation for 40min, after the water vapor activation is completed, naturally cooling to room temperature in the argon atmosphere to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and placing the activated peat carbon in a drying oven of 105 ℃ for drying for 24h to obtain peat carbon for later use;
(3) Taking 4.9g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 500mL water to obtain Ni (NO) 3 ) 2 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in Ni (NO) 3 ) 2 Stirring the solution for 3 hours at the rotating speed of 700rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at the temperature of 105 ℃ for 24 hours, and calcining the dried composite catalyst at the temperature of 800 ℃ for 2 hours in an argon atmosphere to obtain the peat carbon-based catalytic cracking catalyst loaded with an active substance nickel, wherein the loading capacity of the nickel is 10%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was found to be 88.4% based on the measurement results.
Comparative example 2
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 800 ℃ in the argon atmosphere, and converting the argon atmosphere into CO after the activation temperature is reached 2 Maintaining the activation temperature in a gas atmosphere for 40min of carbon dioxide activation 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) Taking 4.9g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 500mL water to obtain Ni (NO) 3 ) 2 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in Ni (NO) 3 ) 2 Stirring the solution for 3h at the rotation speed of 700rmp to obtain a composite catalyst, placing the obtained composite catalyst in a drying box at 105 ℃ for drying for 24h, and drying the dried composite catalyst in an argon atmosphereCalcining for 2 hours at 800 ℃ to obtain the peat carbon-based catalytic cracking catalyst loaded with the active substance nickel, wherein the loading capacity of the nickel is 10%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 90.1% based on the measurement results.
Example 3
The peat carbon-based catalytic cracking catalyst loaded with active substance nickel is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 900 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 700 ℃ under the argon atmosphere, introducing 0.2mL/min of ultrapure water after reaching the activation temperature, maintaining the activation temperature for water vapor activation for 40min, and converting the argon atmosphere into CO after the water vapor activation is finished 2 Maintaining the activation temperature in a gas atmosphere for 30min of carbon dioxide activation 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) 2.45g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 500mL of water to obtain Ni (NO) 3 ) 2 Solution, weighing 10g of peat carbon obtained in step (2) and dissolving in Ni (NO) 3 ) 2 Stirring the solution for 3 hours at the rotating speed of 600rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at the temperature of 105 ℃ for 24 hours, and calcining the dried composite catalyst at the temperature of 800 ℃ for 1 hour in an argon atmosphere to obtain the peat carbon-based catalytic cracking catalyst loaded with an active substance nickel, wherein the loading capacity of the nickel is 5%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 93.9% based on the measurement results.
Example 4
The peat carbon-based catalytic cracking catalyst loaded with active substance nickel is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 700 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 700 ℃ in the argon atmosphere, introducing 0.2mL/min of ultrapure water after the activation temperature is reached, maintaining the activation temperature for water vapor activation for 30min, and converting the argon atmosphere into CO after the water vapor activation is finished 2 Maintaining the activation temperature in a gas atmosphere, performing carbon dioxide activation for 40min 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) Take 7.35g of Ni (NO) 3 ) 2 ·6H 2 Dissolving O in 500mL water to obtain Ni (NO) 3 ) 2 Solution, weighing 10g of peat carbon obtained in step (2) and dissolving in Ni (NO) 3 ) 2 Stirring the solution for 3 hours at the rotating speed of 800rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at the temperature of 105 ℃ for 24 hours, and calcining the dried composite catalyst at the temperature of 700 ℃ for 2 hours in an argon atmosphere to obtain the peat carbon-based catalyst loaded with the active substance nickel, wherein the loading capacity of the nickel is 15%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 93.4% based on the measurement results.
Example 5
The peat carbon-based catalytic cracking catalyst loaded with active substance iron is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 900 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 900 ℃ in an argon atmosphere, and reaching the activation temperatureThen, ultrapure water of 0.2mL/min is introduced, the activation temperature is maintained for water vapor activation for 30min, and after the water vapor activation is finished, the argon atmosphere is converted into CO 2 Maintaining the activation temperature in a gas atmosphere for 30min of carbon dioxide activation 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) Taking 7.2g FeCl 3 ·6H 2 Dissolving O in 500mL of water to obtain FeCl 3 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in FeCl 3 Stirring the solution for 3 hours at the rotating speed of 700rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at 105 ℃ for 24 hours, and calcining the dried composite catalyst at 900 ℃ for 2 hours in an argon atmosphere to obtain the peat carbon-based catalyst loaded with an active substance iron, wherein the iron loading is 15%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 91.3% based on the measurement results.
Example 6
The peat carbon-based catalytic cracking catalyst loaded with active substance iron is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 700 ℃ in the argon atmosphere, introducing 0.2mL/min of ultrapure water after the activation temperature is reached, maintaining the activation temperature for water vapor activation for 30min, and converting the argon atmosphere into CO after the water vapor activation is finished 2 Maintaining the activation temperature in a gas atmosphere for 40min of carbon dioxide activation 2 After activation, CO is added 2 The gas atmosphere is changed into argon atmosphere and is naturally cooled to room temperature, activated peat carbon is obtained and is stored in a drying dish, and the activated peat carbon is placed in a drying oven at 105 DEG CDrying the sludge in the box for 24 hours to obtain peat carbon for later use;
(3) 2.4g of FeCl was taken 3 ·6H 2 Dissolving O in 500mL of water to obtain FeCl 3 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in FeCl 3 Stirring the solution for 3 hours at the rotating speed of 600rmp to obtain a composite catalyst, drying the obtained composite catalyst in a drying box at 105 ℃ for 24 hours, and calcining the dried composite catalyst at 800 ℃ for 2 hours in an argon atmosphere to obtain the peat carbon-based catalyst loaded with an active substance iron, wherein the iron loading is 5%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 90.5% based on the measurement results.
Example 7
The peat carbon-based catalytic cracking catalyst loaded with active substance iron is prepared by the following steps:
(1) Drying peat in a drying oven at 105 ℃ for 24 hours, and pyrolyzing the dried peat at 800 ℃ for 2 hours under the argon atmosphere to obtain a peat carbon precursor;
(2) Putting the peat carbon precursor obtained in the step (1) into a vertical tubular furnace, heating to the activation temperature of 700 ℃ under the argon atmosphere, introducing 0.2mL/min of ultrapure water after reaching the activation temperature, maintaining the activation temperature to perform water vapor activation for 40min, and converting the argon atmosphere into CO after the water vapor activation is finished 2 Maintaining the activation temperature in a gas atmosphere for 30min of carbon dioxide activation 2 After activation, CO is added 2 Converting the gas atmosphere into argon atmosphere, naturally cooling to room temperature to obtain activated peat carbon, storing the activated peat carbon in a drying vessel, and drying the activated peat carbon in a drying oven at 105 ℃ for 24 hours to obtain peat carbon for later use;
(3) 2.4g of FeCl was taken 3 ·6H 2 Dissolving O in 500mL of water to obtain FeCl 3 Solution, weighing 10g of peat carbon obtained in the step (2) and dissolving in FeCl 3 Stirring the solution for 3h at the rotation speed of 600rmp to obtain a composite catalyst, placing the obtained composite catalyst in a drying box at 105 ℃ for drying for 24h, and drying the dried composite catalyst in an argon atmosphereCalcining at 800 ℃ for 1h to obtain the peat carbon-based catalyst loaded with the active substance iron, wherein the iron loading is 5%.
The catalyst activity was measured in the same manner as in example 1, and the conversion of phenol was calculated to be 90.5% based on the measurement results.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (7)
1. A catalytic cracking catalyst with peat carbon as a carrier is characterized by being prepared by the following steps:
(1) Pyrolyzing the dried peat at 700-900 ℃ in an inert atmosphere to obtain a peat carbon precursor;
(2) Heating the peat carbon precursor obtained in the step (1) to 700-900 ℃ in inert atmosphere, introducing ultrapure water for high-temperature water vapor activation, and converting the inert atmosphere into CO after water vapor activation 2 Atmosphere, maintaining temperature using CO 2 Activating peat carbon precursor to CO 2 After activation, CO is added 2 Converting the atmosphere into inert atmosphere and naturally cooling to room temperature to obtain peat carbon, wherein the activation time of water vapor is 30-40min under high-temperature water vapor in CO 2 Under a gas atmosphere, CO 2 The activation time is 30-40min;
(3) FeCl on peat carbon by wet impregnation 3 Or Ni (NO) 3 ) 2 The composite catalyst is dried and then calcined to obtain the catalytic cracking catalyst taking peat carbon as a carrier, wherein the load capacity of Fe or Ni in the catalytic cracking catalyst is 5-15%.
2. The peat carbon based supported catalytic cracking catalyst according to claim 1,characterized in that the wet impregnation method in the step (3) is used for FeCl on peat carbon 3 Or Ni (NO) 3 ) 2 The specific steps of the load of (2) are as follows: taking FeCl 3 ·6H 2 O or Ni (NO) 3 ) 2 ·6H 2 Dissolving O in water to obtain FeCl 3 Or Ni (NO) 3 ) 2 Solution, namely weighing the peat carbon obtained in the step (2) and dissolving the peat carbon in FeCl 3 Or Ni (NO) 3 ) 2 Stirring in the solution, wherein the mass ratio of Fe or Ni to peat is 0.05.
3. The peat carbon based catalytic cracking catalyst as claimed in claim 1, wherein the calcination step (3) is to calcine the dried composite catalyst at 700-900 ℃ for 1-2 h under argon atmosphere.
4. Use of the peat carbon based supported catalytic cracking catalyst according to claim 1 for the preparation of clean gas.
5. The use of peat carbon based supported catalytic cracking catalyst according to claim 4 for the preparation of clean gas, characterized in that it comprises the following steps: placing the catalytic cracking catalyst with peat carbon based as a carrier in a reaction vessel, heating to 800 ℃ in an argon atmosphere, simultaneously introducing phenol and ultrapure water, and catalyzing the phenol and water with the catalytic cracking catalyst with peat carbon based as a carrier under the drive of argon to obtain clean gas.
6. The use of peat carbon based supported catalytic cracking catalyst according to claim 5 in the preparation of clean gas, wherein the ratio of the flow rate of phenol to the flow rate of ultrapure water is 1.
7. The use of peat carbon based supported catalytic cracking catalyst according to claim 5 in the preparation of clean gas comprising carbon monoxide, hydrogen and methane.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910922220.2A CN110721686B (en) | 2019-09-27 | 2019-09-27 | Catalytic cracking catalyst using peat carbon as carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910922220.2A CN110721686B (en) | 2019-09-27 | 2019-09-27 | Catalytic cracking catalyst using peat carbon as carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110721686A CN110721686A (en) | 2020-01-24 |
| CN110721686B true CN110721686B (en) | 2022-10-14 |
Family
ID=69218452
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910922220.2A Active CN110721686B (en) | 2019-09-27 | 2019-09-27 | Catalytic cracking catalyst using peat carbon as carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110721686B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111592903B (en) * | 2020-04-29 | 2021-10-19 | 中国科学院广州能源研究所 | Method for removing tar by using municipal sludge |
| CN111592904B (en) * | 2020-04-29 | 2021-07-02 | 中国科学院广州能源研究所 | Method for removing tar by using solid waste carbon-based bimetallic material |
| CN113522322A (en) * | 2021-07-06 | 2021-10-22 | 中国科学院广州能源研究所 | Preparation method and application of high-activity catalyst for methane carbon dioxide reforming hydrogen production |
| CN115709091A (en) * | 2022-11-18 | 2023-02-24 | 太原理工大学 | Preparation method and application of coal slime-based nonmetal hybrid porous catalyst |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628234A (en) * | 2008-07-18 | 2010-01-20 | 赢创德固赛有限责任公司 | Method for producing improved catalyst |
| CN102333848A (en) * | 2009-02-23 | 2012-01-25 | 塔夫茨大学 | Converting biomass to gaseous fuel hydrocarbons |
| CN103265028A (en) * | 2013-06-04 | 2013-08-28 | 山东省科学院能源研究所 | Preparation method of high-adsorptive selectivity activated carbon for separating CO2 and CH4 |
| CN103339093A (en) * | 2011-01-24 | 2013-10-02 | 巴斯夫欧洲公司 | Hydrogenation catalyst comprising nickel on carbon |
| CN109529847A (en) * | 2018-11-21 | 2019-03-29 | 江汉大学 | A kind of method and application preparing carbon base catalyst using waste residue of Chinese herbs |
-
2019
- 2019-09-27 CN CN201910922220.2A patent/CN110721686B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101628234A (en) * | 2008-07-18 | 2010-01-20 | 赢创德固赛有限责任公司 | Method for producing improved catalyst |
| CN102333848A (en) * | 2009-02-23 | 2012-01-25 | 塔夫茨大学 | Converting biomass to gaseous fuel hydrocarbons |
| CN103339093A (en) * | 2011-01-24 | 2013-10-02 | 巴斯夫欧洲公司 | Hydrogenation catalyst comprising nickel on carbon |
| CN103265028A (en) * | 2013-06-04 | 2013-08-28 | 山东省科学院能源研究所 | Preparation method of high-adsorptive selectivity activated carbon for separating CO2 and CH4 |
| CN109529847A (en) * | 2018-11-21 | 2019-03-29 | 江汉大学 | A kind of method and application preparing carbon base catalyst using waste residue of Chinese herbs |
Non-Patent Citations (3)
| Title |
|---|
| Control of pore development during CO2 and steam activation of olive stones;S. Román et al.,;《FUEL PROCESSING TECHNOLOGY》;20071220;第715-720页 * |
| Synthesis of calcium materials in biochar matrix as a highly stable catalyst for biodiesel production;Shuxiao Wang et al.，;《Renewable Energy》;20180614;第41-49页 * |
| 活性炭负载镍催化剂的制备及催化甲苯水蒸气重整研究;刘雪景;《中国优秀博硕士学位论文全文数据库(硕士) 工程科技Ⅰ辑》;20170215;第B014-1419页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110721686A (en) | 2020-01-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110721686B (en) | Catalytic cracking catalyst using peat carbon as carrier | |
| CN109759064B (en) | Co @ C/biomass catalyst and preparation method and application thereof | |
| CN109794245B (en) | Honeycomb iron-based hydrogenation catalyst (Fe)3O4@ C)/C and preparation method and application thereof | |
| CN109794246B (en) | Integrated honeycomb Ni @ C/C catalyst and preparation method and application thereof | |
| Zhu et al. | Metal modified hexaaluminates for syngas generation and CO2 utilization via chemical looping | |
| CN111250092B (en) | Preparation method and application of biomass honeycomb-shaped semicoke-loaded nickel-iron nanoparticle catalyst | |
| CN114522688B (en) | Porous carbon supported bimetallic catalyst and preparation and application thereof | |
| CN112536037A (en) | Preparation method of biomass charcoal-loaded nickel-copper nano alloy catalyst and application of catalyst in catalytic cracking of tar | |
| CN109746016A (en) | Metallicity nickel oxide/azotized carbon nano piece catalysis material and preparation method and application | |
| Zhao et al. | Sulphur as medium: directly converting pitch into porous carbon | |
| CN113457657A (en) | Carbon-based methanol hydrogen production catalyst and preparation method and application thereof | |
| Zhang et al. | Catalytic performance of CH4–CO2 reforming over metal free nitrogen-doped biomass carbon catalysts: Effect of different preparation methods | |
| CN105013519A (en) | Catalyst for ammonia decomposition and application of catalyst | |
| Habimana et al. | Effect of Cu promoter on Ni-based SBA-15 catalysts for partial oxidation of methane to syngas | |
| CN104984769A (en) | Synthesis-gas carbon-based catalyst preparation method by reforming methane and carbon dioxide | |
| Liu et al. | Catalytic pyrolysis of tar model compound with various bio-char catalysts to recycle char from biomass pyrolysis | |
| CN110721690A (en) | Ni-Fe bimetal multifunctional catalyst for biological oil steam reforming hydrogen production | |
| Dong et al. | Re-promoted Ni-Mn bifunctional catalysts prepared by microwave heating for partial methanation coupling with water gas shift under low H2/CO conditions | |
| CN107952442B (en) | A kind of biomass and the catalyst of preparing methane from coal and its preparation method and application | |
| CN107233888A (en) | Biomass prepares gas combustion multifunction catalyst and preparation method | |
| CN114452998B (en) | Preparation method and application of multiwall carbon nanotube and graphitized carbon nitride composite material | |
| CN112007687B (en) | Catalyst modification method for improving yield of biomass catalytic pyrolysis hydrocarbons | |
| Nurhadi | Modification of Coal Char-loaded TiO2 by Sulfonation and Alkylsilylation to Enhance Catalytic Activity in Styrene Oxidation with Hydrogen Peroxide as Oxidant | |
| CN104475111B (en) | A kind of catalyst of coal and reaction of carbon monoxide methane and preparation method thereof | |
| Li et al. | Preparation of a Ni/LaAlO3 catalyst and its application in catalytic pyrolysis of soybean straw for syngas production |
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 |