CN111411000A - Noble metal FCC catalyst regeneration flue gas combustion improver and preparation method thereof - Google Patents
Noble metal FCC catalyst regeneration flue gas combustion improver and preparation method thereof Download PDFInfo
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- CN111411000A CN111411000A CN202010240091.1A CN202010240091A CN111411000A CN 111411000 A CN111411000 A CN 111411000A CN 202010240091 A CN202010240091 A CN 202010240091A CN 111411000 A CN111411000 A CN 111411000A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
- C10L3/003—Additives for gaseous fuels
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L2230/00—Function and purpose of a components of a fuel or the composition as a whole
- C10L2230/22—Function and purpose of a components of a fuel or the composition as a whole for improving fuel economy or fuel efficiency
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Abstract
The invention discloses a noble metal FCC catalyst regeneration flue gas combustion improver and a preparation method thereof, and relates to the technical field of carbon monoxide combustion improvers in the process of petroleum refining catalytic cracking (FCC). The preparation method comprises the following steps: firstly, loading an active component on a carrier to obtain a front combustion improver; then, dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution, and introducing fatty acid molecules into the framework pore canal/gap of the carrier through dipping; after drying, roasting is carried out in a nitrogen atmosphere to cover active points in the pore channels/gaps of the carrier framework. In the fatty acid absolute ethyl alcohol solution, the weight of a fatty acid solute is 0.10-10.00% of the weight of an absolute ethyl alcohol solvent. The noble metal FCC catalyst regeneration flue gas combustion improver prepared by the preparation method has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity in the FCC catalyst regeneration process.
Description
Technical Field
The invention relates to the field of catalyst regeneration flue gas and carbon monoxide combustion improvers in a catalytic cracking (FCC) process in petroleum refining, in particular to a noble metal FCC catalyst regeneration flue gas combustion improver and a preparation method thereof.
Background
In the catalytic cracking (FCC) process, a carbon deposited catalyst can generate a large amount of carbon monoxide through carbon burning regeneration, part of the carbon monoxide rises from a dense phase layer to a dilute phase layer to be reacted with oxygen for post combustion, and a large amount of heat is released, so that the temperature rise of the dilute phase layer is too high, and the catalyst is damaged or even a regeneration device is damaged; or part of the carbon monoxide is discharged along with the flue gas without being converted, thereby polluting the environment. The main means for solving the problems is to add a proper amount of carbon monoxide combustion improver to further catalyze and convert most of carbon monoxide into carbon dioxide in a regenerated dense phase layer.
The noble metal FCC catalyst regeneration flue gas combustion improver in the prior art is basically alumina composite inorganic oxide loaded by noble metal platinum (Pt) or palladium (Pd). The conversion rate of the combustion improver to carbon monoxide in the flue gas is high and low, and mainly depends on the content of active noble metal particles, the composition of a carrier and the abrasion strength of the carrier; after the content of active noble metal particles and the composition of the carrier are optimized and determined, the durability of the overall activity of the combustion improver is greatly influenced by the abrasion strength of the carrier: the wear strength is high, the consumption of the combustion improver is small, the durability of the overall activity of the combustion improver is high, the wear strength is low, the consumption of the combustion improver is large, and the durability of the overall activity of the combustion improver is low. It should be noted that the durability of the overall activity of the actual combustion improver mainly depends on the overall storage amount of the combustion improver and the content of active noble metal particles; the fine particles (powder) of the combustion improver, which are formed by abrasion, enter a dust removal system along with the flue gas, so that the whole storage (loss) of the combustion improver is reduced, and the whole activity durability of the combustion improver is reduced; the reduction in the content of active noble metal particles also reduces the overall activity durability of the combustion improver.
The microstructure of the alumina composite inorganic oxide carrier has a large number of pore channels and gaps. A large amount of water vapor (existing in a catalytic cracking process) exists in the regenerated flue gas of the FCC catalyst, and high-temperature (more than 500 ℃) water molecules can enter a pore channel or a gap of a carrier framework of the combustion improver to act with an active point (acid point) on a pore channel wall or a gap wall to destroy the framework structure of the carrier (alumina composite inorganic oxide), so that the wear strength of the carrier is reduced, the pulverization degree of the carrier is increased, the loss of the combustion improver is increased, and the carbon monoxide conversion efficiency of the combustion improver in a dense phase layer is reduced; meanwhile, the dedusting load of the regenerated flue gas of the FCC catalyst is increased, and the dedusting effect of the discharged flue gas is seriously influenced. In addition, the existence of high-temperature water vapor also easily promotes the active noble metal particles on the surface of the combustion improver carrier to agglomerate, reduces the content of the active noble metal particles and reduces the conversion rate of the combustion improver to carbon monoxide in the flue gas. Therefore, the existence of high-temperature steam not only has important influence on the loss of the noble metal FCC catalyst regeneration flue gas combustion improver, but also has important influence on the content of active noble metal ions, thereby seriously restricting the durability of the overall activity of the combustion improver. In the real production process, in order to maintain the durability of the overall activity of the combustion improver, fresh combustion improver needs to be supplemented regularly, which also causes the increase of the operation cost of the catalytic cracking unit. Therefore, the high-temperature steam resistance, namely high hydrothermal stability plays an important and non-negligible role in the carbon monoxide conversion rate and the durability of the overall activity of the noble metal FCC catalyst regeneration flue gas combustion improver.
Disclosure of Invention
The technical problems to be solved by the invention are as follows: in the prior art, the high-temperature steam in the regenerated flue gas of the FCC catalyst damages the carrier skeleton of the carbon monoxide combustion improver and promotes the agglomeration of active noble metal particles on the surface of the carrier, so that the overall activity durability of the combustion improver and the conversion rate of carbon monoxide in the flue gas are reduced.
In order to solve the above technical problems, an object of the present invention is to provide a method for preparing a noble metal FCC catalyst regeneration flue gas combustion improver, wherein the noble metal FCC catalyst regeneration flue gas combustion improver prepared by the method has high hydrothermal stability, high carbon monoxide conversion rate and high durable combustion-supporting activity in the FCC catalyst regeneration process.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing a noble metal FCC catalyst regeneration flue gas combustion improver comprises the steps of firstly loading an active component on a carrier to obtain a front combustion improver; then, dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution, and introducing fatty acid molecules into a skeleton pore canal/gap of the carrier through dipping; after drying, roasting is carried out in a nitrogen atmosphere to cover active points in the pore channels/gaps of the carrier framework.
The beneficial technical effects directly brought by the technical scheme are as follows:
the invention is a main improvement point, the prior combustion improver is dipped by fatty acid absolute ethyl alcohol solution, which aims to introduce a proper amount of fatty acid molecules into pore channels or gaps of a combustion improver carrier framework, carbonize the fatty acid molecules into hydrophobic spheres (layers) under the oxygen-free atmosphere at high temperature (500-650 ℃), cover active points (acid points) in the pore channels or the gaps, relieve or prevent the action of water molecules and the active points (acid points), maintain the abrasion strength of the carrier, reduce the pulverization degree of the carrier, reduce the loss of the combustion improver and maintain the lasting integral activity of the combustion improver.
In a preferred embodiment of the present invention, the weight of the solute of the fatty acid in the above-mentioned fatty acid absolute ethyl alcohol solution is 0.10 to 10.00% of the weight of the absolute ethyl alcohol solvent, and the above-mentioned fatty acid is C with an impurity content of less than 0.50 wt%6～C18A fatty acid.
In another preferable embodiment of the invention, the pre-combustion improver is immersed in the fatty acid absolute ethyl alcohol solution for 2 to3 hours, dried in a drying oven at a temperature of 50 to 90 ℃ for 2 to3 hours, and calcined in a muffle furnace at a temperature of 500 to 650 ℃ for 2 to3 hours in a nitrogen atmosphere.
Further, the active component is platinum, the carrier is a composite of alumina and other inorganic oxides, the active component accounts for 0.01-0.05 wt% of the carrier, and the alumina accounts for more than 70 wt% of the carrier.
Further, the other inorganic oxide mentioned above is a mixture of silicon oxide, rare earth metal oxide and transition metal oxide.
Further, the rare earth metal oxide is cerium oxide or/and lanthanum oxide.
Further, the transition metal oxide is one or more of titanium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum and tungsten.
Further, the preparation method of the front combustion improver comprises the following steps:
preparing a carrier, mixing the raw materials required by the preparation of the carrier, uniformly stirring the mixture into slurry, and drying the slurry to prepare a spherical object; roasting the spherical object in a muffle furnace at a certain temperature, and cooling to room temperature to obtain a carrier;
and (2) dipping the carrier in chloroplatinic acid solution at room temperature for 2-3 hours, setting the drying temperature in a drying oven to be 80-120 ℃ and the drying time to be 2-3 hours, transferring the carrier into a muffle furnace at the temperature of 500-650 ℃ and the roasting time to be 3-5 hours, and cooling to room temperature to obtain the front combustion improver.
Further, in the preparation process of the carrier, the carrier is uniformly stirred into slurry, then the slurry is prepared into a spherical object with the granularity of 30-150 mu m through a spray drying system, and the spherical object is roasted in a muffle furnace at the temperature of 500-650 ℃ for 3-5 hours.
The invention also aims to provide a noble metal FCC catalyst regeneration flue gas combustion improver which is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial technical effects:
according to the preparation method, the front combustion improver is subjected to dipping treatment by a fatty acid absolute ethyl alcohol solution, and after drying and oxygen-free roasting treatment, part of fatty acid molecules are carbonized and anchored on the surface of the combustion improver to form a carbon island, so that the agglomeration of active noble metal particles playing a key role in carbon monoxide conversion (combustion supporting) can be effectively prevented, and the carbon monoxide conversion activity of the combustion improver is maintained.
The noble metal FCC catalyst regeneration flue gas combustion improver prepared by the preparation method has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity in the FCC catalyst regeneration process, and the beneficial effects are shown in the embodiment.
Compared with the prior art, the noble metal FCC catalyst regeneration flue gas combustion improver supplements little fresh combustion improver at regular time in the using process, thereby saving the running cost of the device and being capable of being popularized and applied.
Detailed Description
The invention provides a noble metal FCC catalyst regeneration flue gas combustion improver and a preparation method thereof, and in order to make the advantages and technical scheme of the invention clearer and clearer, the invention is described in detail by combining specific embodiments.
(1) Firstly, the main raw materials selected by the invention are explained as follows:
the precursor of active component platinum (Pt) is chloroplatinic acid, a carrier is soaked in a chloroplatinic acid solution with a proper concentration, and platinum is loaded on the carrier after drying and roasting to obtain a front combustion improver, wherein the active component platinum accounts for 0.01-0.05 wt% of the carrier;
the carrier is a compound of alumina and other inorganic oxides, wherein the alumina (Al2O3) component accounts for more than or equal to 70 wt% of the carrier, and the other inorganic oxide components accounts for less than or equal to 30 wt% of the carrier.
The precursor of the alumina component in the carrier is Al2O3Content (wt.)>97wt％、Na2Content of O<0.1 wt% and specific surface area not less than 150m2A pore volume of 0.20 to 0.50ml/g, a bulk density of 0.90 to 0.95g/cm3And active alumina powder with the ignition loss of less than 10 wt% and the granularity of less than 20 microns at 900 ℃.
The other inorganic oxide component in the carrier is silicon oxide (SiO)2) One or more of rare earth metal oxide and transition metal oxide.
Silica (SiO) in carrier2) The precursor of (A) is SiO2The content is more than or equal to 30wt percent and Na2O content of not more than 0.03 wt%, pH (25 ℃) of 2 to 4, specific gravity (25 ℃) of 1.19 to 1.21g/cm3And the viscosity (25 ℃) is less than or equal to 6 mpa.s.
The rare earth metal oxide in the carrier is cerium oxide or a mixture of lanthanum oxide and cerium oxide, and the precursor of the carrier is soluble inorganic salt with the corresponding content of more than or equal to 99.5 wt%.
The transition metal oxide in the carrier is one or a mixture of several oxides of titanium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, tungsten and the like, and the precursor of the transition metal oxide is soluble inorganic salt with the corresponding content of more than or equal to 99.5 wt%.
The weight of the fatty acid absolute ethyl alcohol solution is 0.10-10.00% of the weight of the absolute ethyl alcohol solvent, and the fatty acid is carbon six to carbon eighteen fatty acid with the impurity content of less than 0.50 wt%.
(2) The detection method of the related indexes comprises the following steps:
the water absorption of the sample was measured according to HG/T3927-2007 standard.
The abrasion index of the sample was measured according to ASTM D5757-00 (straight tube method); the greater the abrasion index, the lower the corresponding abrasion strength, and the more susceptible the sample to chalking.
The present invention will be described in detail with reference to specific examples.
Example 1:
the method specifically comprises the following steps:
first, a front combustion improver is prepared.
Mixing the aqueous solution of alumina precursor, silica precursor and other inorganic metal oxide precursor in certain proportion, stirring to form slurry, spray drying to obtain spherical material with particle size of 50-60 microns, roasting at 550 deg.c in muffle furnace for 3 hr, and cooling to room temperature to obtain carrier comprising Al2O3(74.62wt％)、SiO2(15.40wt％)、CeO2(6.08wt％)、Fe2O3(3.93wt％)；
And (2) soaking the carrier in chloroplatinic acid solution at room temperature for 2 hours, setting the drying temperature in a drying oven to be 85 ℃ and the drying time to be 2 hours, transferring the carrier into a muffle furnace at the setting temperature of 550 ℃ and the roasting time to be 3 hours, and cooling to room temperature to obtain the front combustion improver, wherein the load of Pt is 0.05 wt% of the carrier.
And secondly, treating the front combustion improver by using a fatty acid absolute ethyl alcohol solution.
And (3) dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution for 2 hours, drying the front combustion improver in a drying oven at the temperature of 60 ℃ for 2 hours, roasting the front combustion improver in a muffle furnace at the temperature of 550 ℃ for 2 hours in a nitrogen atmosphere, and cooling the front combustion improver to room temperature to obtain the target sample.
In this example, 2.00 wt% of an absolute ethanol solution of fatty acid (the weight ratio of fatty acid C-hexa to fatty acid C-octadecanoic is 1:1) was used.
Comparative example 1:
the front combustion improver described above in example 1 was used as a comparative sample.
The products obtained in the above example 1 and comparative example 1 are subjected to high-temperature hydrothermal treatment, specifically:
carrying out hydrothermal treatment on a sample by using a laboratory fixed bed hydrothermal treatment device: the ratio of the volume of deionized water entering the reactor per hour to the volume of a sample in the constant-temperature section of the reactor is 10 at the normal pressure and the temperature of 550 ℃, and the ratio of the volume of nitrogen entering the reactor per minute to the volume of the sample in the constant-temperature section of the reactor is 1000.
The method for testing the carbon monoxide conversion rate of a sample by using a laboratory fixed bed micro-reverse evaluation device is specifically divided into two technical processes:
the first process is as follows: the ratio of the volume of raw material gas entering the reactor at normal pressure and 550 ℃ per minute to the volume of a sample in a constant-temperature section of the reactor is 1000, and the raw material gas is mixed gas of nitrogen, oxygen and carbon monoxide (high-purity nitrogen is diluent gas, the molar content of oxygen is 30000ppm, and the molar content of carbon monoxide is 3000 ppm); a testo350 flue gas detector detects the composition of tail gas of gas at the outlet of a reactor after the gas passes through a condenser; the conversion rate of carbon monoxide is: (3000-X)/3000, wherein X is the concentration (ppm) of carbon monoxide in the tail gas.
And a second process: adding deionized water into the reactor, wherein the ratio of the volume of the deionized water entering the reactor per hour to the volume of the sample in the constant-temperature section of the reactor is 10, and other conditions and processes are the same.
The test results for the product of example 1 and the product of comparative example 1 are as follows:
⑴ the water absorption of comparative example 1 and example 1 was 31.43% and 7.21%, respectively.
⑵ the wear indices of comparative example 1 and example 1 were 1.81 and 1.19, respectively.
⑶, the abrasion index of comparative example 1 and example 1 was 8.07 and 1.66, respectively, after 5 hours of hydrothermal treatment.
⑷ procedure one, the carbon monoxide conversion was greater than 99.90% for both comparative example 1 and example 1 after 5 hours of reaction.
⑸ Process two, after 5 hours of reaction, the carbon monoxide conversion of comparative example 1 decreased from greater than 99.71% to 84.90%, and the carbon monoxide conversion of example 1 decreased from greater than 99.58% to 96.61%.
According to the detection result (1), the water absorption of the sample is reduced by 77.06% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (2), the abrasion index of the sample is reduced by 34.25% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (3), the abrasion index of the sample which is not treated by the fatty acid absolute ethyl alcohol solution is increased by 345.86% after the high-temperature hydrothermal treatment, while the abrasion index of the sample which is treated by the fatty acid absolute ethyl alcohol solution is only increased by 39.49%; as can be seen from the test results (4) and (5), the data of the microreflected evaluations of the first process and the second process show that, under the same high-temperature water vapor environment, the activity (carbon monoxide conversion rate) of the sample without the fatty acid absolute ethyl alcohol solution decreases by 14.85% in the 5-hour test process, while the activity (carbon monoxide conversion rate) of the sample treated with the fatty acid absolute ethyl alcohol solution decreases by only 2.98% in the 5-hour test process.
The comparison result shows that: compared with a corresponding sample (a front combustion improver) which is not treated by the fatty acid absolute ethyl alcohol solution, the target sample provided by the embodiment 1 of the invention has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity.
Example 2:
the method specifically comprises the following steps:
first, a front combustion improver is prepared.
Mixing the aqueous solution of alumina precursor, silica precursor and other inorganic metal oxide precursor in certain proportion, stirring to form slurry, spray drying to obtain spherical material with particle size of 50-60 microns, roasting at 550 deg.c in muffle furnace for 3 hr, and cooling to room temperature to obtain carrier comprising Al2O3(80.23wt％)、SiO2(13.51wt％)、CeO2(4.47wt％)、CuO(1.79wt％)；
And (2) soaking the carrier in chloroplatinic acid solution at room temperature for 2 hours, setting the drying temperature in a drying oven to be 85 ℃ and the drying time to be 2 hours, transferring the carrier into a muffle furnace at the setting temperature of 550 ℃ and the roasting time to be 3 hours, and cooling to room temperature to obtain the front combustion improver, wherein the load of Pt is 0.04 wt% of the carrier.
And secondly, treating the front combustion improver by using a fatty acid absolute ethyl alcohol solution.
And (3) dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution for 2 hours, drying the front combustion improver in a drying oven at the temperature of 60 ℃ for 2 hours, roasting the front combustion improver in a muffle furnace at the temperature of 550 ℃ for 2 hours in a nitrogen atmosphere, and cooling the front combustion improver to room temperature to obtain the target sample.
In this example, 2.00 wt% of an absolute ethanol solution of fatty acid (the weight ratio of fatty acid C-hexa to fatty acid C-octadecanoic is 1:1) was used.
Comparative example 2:
the front combustion improver described above in example 2 was used as a comparative sample.
The products obtained in the above example 2 and comparative example 2 were examined and evaluated in the same manner as in the above example 1 and comparative example 1.
The detection and evaluation results of the product of example 2 and the product of comparative example 2 are as follows:
⑴ the water absorption of comparative example 2 and example 2 was 35.30% and 8.21%, respectively.
⑵ the wear indices of comparative example 2 and example 2 were 1.89 and 1.33, respectively.
⑶, the abrasion index of sample comparative example 2 and sample example 2 was 8.95 and 1.92, respectively, after 5 hours of hydrothermal treatment.
⑷ procedure one, after 5 hours of reaction, the carbon monoxide conversion was greater than 99.50% for both sample comparative example 2 and sample example 2.
⑸ Process two, after 5 hours of reaction, the CO conversion of sample comparative example 2 decreased from 99.43% to 82.45% and the CO conversion of sample example 2 decreased from 99.12% to 95.29%.
According to the detection result (1), after the sample is treated by the fatty acid absolute ethyl alcohol solution, the water absorption is reduced by 76.74%; according to the detection result (2), the abrasion index of the sample is reduced by 29.63% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (3), after the high-temperature hydrothermal treatment, the abrasion index of the sample which is not treated by the fatty acid absolute ethyl alcohol solution is increased by 373.54%, while the abrasion index of the sample which is treated by the fatty acid absolute ethyl alcohol solution is only increased by 44.36%; as can be seen from the test results (4) and (5), the microreflected evaluation data of the first process and the second process show that, under the same high-temperature water vapor environment, the activity (carbon monoxide conversion rate) of the sample without the fatty acid absolute ethyl alcohol solution is reduced by 17.08% in the 5-hour test process, while the activity (carbon monoxide conversion rate) of the sample treated with the fatty acid absolute ethyl alcohol solution is reduced by only 3.86% in the 5-hour test process.
The comparison result shows that: compared with a corresponding sample (a front combustion improver) which is not treated by the fatty acid absolute ethyl alcohol solution, the target sample provided by the embodiment 2 of the invention has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity.
Example 3:
the method specifically comprises the following steps:
first, a front combustion improver is prepared.
Mixing the aqueous solution of alumina precursor, silica precursor and other inorganic metal oxide precursor in certain proportion, stirring to form slurry, spray drying to obtain spherical material with particle size of 50-60 microns, roasting at 550 deg.c in muffle furnace for 3 hr, cooling to room temperature to obtain carrier comprising Al2O3(75.28wt％)、SiO2(16.36wt％)、CeO2(5.71wt％)、CuO(2.64wt％)；
And (2) impregnating the carrier with chloroplatinic acid solution at room temperature for 2 hours, setting the drying temperature in a drying oven to be 85 ℃ and the drying time to be 2 hours, transferring the carrier into a muffle furnace at the setting temperature of 550 ℃ and the roasting time to be 3 hours, and cooling to room temperature to obtain the front combustion improver, wherein the load of Pt is 0.03 wt% of the carrier.
And secondly, treating the front combustion improver by using a fatty acid absolute ethyl alcohol solution.
And (3) dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution for 2 hours, drying the front combustion improver in a drying oven at the temperature of 60 ℃ for 2 hours, roasting the front combustion improver in a muffle furnace at the temperature of 550 ℃ for 2 hours in a nitrogen atmosphere, and cooling the front combustion improver to room temperature to obtain the target sample.
In this example, 2.00 wt% of an absolute ethanol solution of fatty acid (the weight ratio of fatty acid C-hexa to fatty acid C-octadecanoic is 1:1) was used.
Comparative example 3:
the front combustion improver described above in example 3 was used as a comparative sample.
The products obtained in the above example 3 and comparative example 3 were examined and evaluated in the same manner as in the above example 1 and comparative example 1.
The detection results of the products (samples) of example 3 and comparative example 3 are as follows:
(1) the water absorption rates of comparative example 3 and example 3 were 30.16% and 7.04%, respectively.
(2) The wear indices of comparative example 3 and example 3 were 1.73 and 1.01, respectively.
(3) The abrasion index of comparative example 3 and example 3 after 5 hours of hydrothermal treatment was 7.86 and 1.55, respectively.
(4) Procedure one, after 5 hours of reaction, the carbon monoxide conversion was greater than 99.00% for both comparative example 3 and example 3.
(5) Process two, after 5 hours of reaction, the carbon monoxide conversion of comparative example 3 dropped from 99.32% to 79.28%; the carbon monoxide conversion of example 3 decreased from greater than 99.07% to 93.19%.
According to the detection result (1), after the sample is treated by the fatty acid absolute ethyl alcohol solution, the water absorption is reduced by 76.66%; according to the detection result (2), the abrasion index of the sample is reduced by 41.62% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (3), after the high-temperature hydrothermal treatment, the abrasion index of the sample which is not treated by the fatty acid absolute ethyl alcohol solution is increased by 354.33%, while the abrasion index of the sample which is treated by the fatty acid absolute ethyl alcohol solution is only increased by 53.47%; as can be seen from the test results (4) and (5), the data of the microreflected evaluations of the first process and the second process show that, under the same high-temperature water vapor environment, the activity (carbon monoxide conversion) of the sample without the fatty acid absolute ethyl alcohol solution is reduced by 20.18% in the 5-hour test process, while the activity (carbon monoxide conversion) of the sample treated with the fatty acid absolute ethyl alcohol solution is reduced by only 5.94% in the 5-hour test process.
The comparison result shows that: compared with a corresponding sample (a front combustion improver) which is not treated by the fatty acid absolute ethyl alcohol solution, the target sample provided by the embodiment 3 of the invention has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity.
Example 4:
the method specifically comprises the following steps:
first, a front combustion improver is prepared.
Mixing the aqueous solution of alumina precursor, silica precursor and other inorganic metal oxide precursor in certain proportion, stirring to form slurry, spray drying to obtain spherical material with particle size of 50-60 microns, roasting at 550 deg.c in muffle furnace for 3 hr, and cooling to room temperature to obtain carrier comprising Al2O3(71.39wt％)、SiO2(18.54wt％)、CeO2(5.23wt％)、CuO(4.72wt％)；
And (2) impregnating the carrier with chloroplatinic acid solution at room temperature for 2 hours, setting the drying temperature in a drying oven to be 85 ℃ and the drying time to be 2 hours, transferring the carrier into a muffle furnace at the setting temperature of 550 ℃ and the roasting time to be 3 hours, and cooling to room temperature to obtain the front combustion improver, wherein the load of Pt is 0.02 wt% of the carrier.
And secondly, treating the front combustion improver by using a fatty acid absolute ethyl alcohol solution.
Soaking the front combustion improver in a fatty acid absolute ethyl alcohol solution for 2 hours, drying the front combustion improver in a drying oven at the temperature of 60 ℃ for 2 hours, roasting the front combustion improver in a muffle furnace at the temperature of 550 ℃ for 2 hours in a nitrogen atmosphere, and then cooling the front combustion improver to room temperature to obtain the target sample.
In this example, 2.00 wt% of an absolute ethanol solution of fatty acid (the weight ratio of fatty acid C-hexa to fatty acid C-octadecanoic is 1:1) was used.
Comparative example 4:
the front combustion improver described above in example 4 was used as a comparative sample.
The products obtained in example 4 and comparative example 4 were examined and evaluated in the same manner as in example 1 and comparative example 1.
The results of the tests on the products (samples) of example 4 and comparative example 4 are:
(1) the water absorption of comparative example 4 and example 4 was 27.36% and 6.78%, respectively.
(2) The wear indices of comparative example 4 and example 4 were 1.57 and 0.96, respectively.
(3) The abrasion index of comparative example 4 and example 4 after 5 hours of hydrothermal treatment was 6.83 and 1.49, respectively.
(4) Procedure one, after 5 hours of reaction, the carbon monoxide conversion was greater than 98.00% for both comparative example 4 and example 4.
(5) Process two, after 5 hours of reaction, the carbon monoxide conversion of comparative example 4 decreased from 98.10% to 72.85%; the carbon monoxide conversion of example 4 dropped from 97.44% to 92.62%.
According to the detection result (1), after the sample is treated by the fatty acid absolute ethyl alcohol solution, the water absorption is reduced by 75.22%; according to the detection result (2), the abrasion index of the sample is reduced by 38.85% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (3), after the high-temperature hydrothermal treatment, the abrasion index of the sample which is not treated by the fatty acid absolute ethyl alcohol solution is increased by 335.03%, while the abrasion index of the sample which is treated by the fatty acid absolute ethyl alcohol solution is only increased by 55.21%; as can be seen from the test results (4) and (5), the data of the microreflected evaluations of the first process and the second process show that, under the same high-temperature water vapor environment, the activity (carbon monoxide conversion) of the sample without the fatty acid absolute ethyl alcohol solution decreases by 25.74% in the 5-hour test process, while the activity (carbon monoxide conversion) of the sample treated with the fatty acid absolute ethyl alcohol solution decreases by only 4.95% in the 5-hour test process.
The comparison result shows that: compared with a corresponding sample (a front combustion improver) which is not treated by the fatty acid absolute ethyl alcohol solution, the target sample provided by the embodiment 4 of the invention has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity.
Example 5:
the method specifically comprises the following steps:
first, a front combustion improver is prepared.
Mixing the aqueous solutions of alumina precursor, silica precursor and other inorganic metal oxide precursors in certain proportionStirring to obtain slurry, spray drying to obtain spherical material with particle size of 50-60 μm, calcining at 550 deg.C in muffle furnace for 3 hr, cooling to room temperature to obtain carrier containing Al2O3(70.46wt％)、SiO2(11.52wt％)、CeO2(5.30wt％)、La2O3(2.69wt％)、CuO(5.57wt％)、Fe2O3(4.41wt％)；
And (2) impregnating the carrier with chloroplatinic acid solution at room temperature for 2 hours, setting the drying temperature in a drying oven to be 85 ℃ and the drying time to be 2 hours, transferring the carrier into a muffle furnace at the setting temperature of 550 ℃ and the roasting time to be 3 hours, and cooling to room temperature to obtain the front combustion improver, wherein the load of Pt is 0.01 wt% of the carrier.
And secondly, treating the front combustion improver by using a fatty acid absolute ethyl alcohol solution.
Soaking the front combustion improver in a fatty acid absolute ethyl alcohol solution for 2 hours, drying the front combustion improver in a drying oven at the temperature of 60 ℃ for 2 hours, roasting the front combustion improver in a muffle furnace at the temperature of 550 ℃ for 2 hours in a nitrogen atmosphere, and then cooling the front combustion improver to room temperature to obtain the target sample.
In this example, 2.00 wt% of an absolute ethanol solution of fatty acid (the weight ratio of fatty acid C-hexa to fatty acid C-octadecanoic is 1:1) was used.
Comparative example 5:
the front combustion improver described above in example 5 was used as a comparative sample.
The products obtained in the above example 5 and comparative example 5 were examined and evaluated in the same manner as in the above example 1 and comparative example 1.
The results of the tests on the products (samples) of example 5 and comparative example 5 are:
(1) the water absorption rates of comparative example 5 and example 5 were 32.23% and 7.81%, respectively.
(2) The wear indices of comparative example 5 and example 5 were 1.97 and 1.49, respectively.
(3) The abrasion index of comparative example 5 and example 5 after 5 hours of hydrothermal treatment was 9.24 and 2.07, respectively.
(4) Procedure one, after 5 hours of reaction, the carbon monoxide conversion was greater than 97.00% for both comparative example 5 and example 5.
(5) Process two, after 5 hours of reaction, the carbon monoxide conversion of comparative example 5 decreased from 96.76% to 69.80%; the carbon monoxide conversion of example 5 dropped from 96.11% to 90.34%.
According to the detection result (1), after the sample is treated by the fatty acid absolute ethyl alcohol solution, the water absorption is reduced by 75.77%; according to the detection result (2), the abrasion index of the sample is reduced by 24.37% after the sample is treated by the fatty acid absolute ethyl alcohol solution; according to the detection result (3), the abrasion index of the sample which is not treated by the fatty acid absolute ethyl alcohol solution is increased by 369.04% after the high-temperature hydrothermal treatment, while the abrasion index of the sample which is treated by the fatty acid absolute ethyl alcohol solution is only increased by 38.93%; as can be seen from the test results (4) and (5), the microreflected evaluation data of the first process and the second process show that, under the same high-temperature water vapor environment, the activity (carbon monoxide conversion rate) of the sample without the fatty acid absolute ethyl alcohol solution is reduced by 27.86% in the test process of 5 hours, while the activity (carbon monoxide conversion rate) of the sample treated with the fatty acid absolute ethyl alcohol solution is reduced by only 6.00% in the test process of 5 hours.
The comparison result shows that: compared with a corresponding sample (a front combustion improver) which is not treated by the fatty acid absolute ethyl alcohol solution, the target sample provided by the embodiment 5 of the invention has high hydrothermal stability, high carbon monoxide conversion rate and high lasting combustion-supporting activity.
The impregnation of the pre-oxidizer with the remaining, unrecited, anhydrous alcohol solution of fatty acids is clearly achieved under the guidance of examples 1-5 above.
The parts which are not described in the invention can be realized by taking the prior art as reference.
It should be noted that: any equivalents or obvious modifications thereof which may occur to persons skilled in the art and which are given the benefit of this description are deemed to be within the scope of the invention.
Claims (10)
1. A preparation method of a noble metal FCC catalyst regeneration flue gas combustion improver is characterized by comprising the following steps: firstly, loading an active component on a carrier to obtain a front combustion improver; then, dipping the front combustion improver by using a fatty acid absolute ethyl alcohol solution, and introducing fatty acid molecules into a skeleton pore canal/gap of the carrier through dipping; after drying, roasting is carried out in a nitrogen atmosphere to cover active points in the pore channels/gaps of the carrier framework.
2. The preparation method of the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 1, is characterized in that: in the fatty acid absolute ethyl alcohol solution, the weight of a fatty acid solute is 0.10-10.00% of the weight of an absolute ethyl alcohol solvent, and the fatty acid is C with the impurity content of less than 0.50 wt%6～C18A fatty acid.
3. The preparation method of the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 1, is characterized in that: dipping the front combustion improver in a fatty acid absolute ethyl alcohol solution for 2-3 hours, drying the front combustion improver in a drying oven at 50-90 ℃ for 2-3 hours, and roasting the front combustion improver in a muffle furnace at 500-650 ℃ for 2-3 hours in a nitrogen atmosphere.
4. The method for preparing the flue gas combustion improver for the regeneration of the noble metal FCC catalyst, according to claim 2 or 3, is characterized in that: the active component is platinum, the carrier is a compound of alumina and other inorganic oxides, the active component accounts for 0.01-0.05 wt% of the carrier, and the alumina accounts for more than 70 wt% of the carrier.
5. The method for preparing the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 4, is characterized in that: the other inorganic oxide is a mixture of silicon oxide, rare earth metal oxide and transition metal oxide.
6. The method for preparing the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 5, is characterized in that: the rare earth metal oxide is cerium oxide or/and lanthanum oxide.
7. The method for preparing the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 5, is characterized in that: the transition metal oxide is one or more of titanium, manganese, iron, cobalt, nickel, copper, zinc, zirconium, molybdenum and tungsten.
8. The method for preparing the combustion improver of the regenerated flue gas of the noble metal FCC catalyst as claimed in claim 5, wherein the preparation step of the front combustion improver comprises:
preparing a carrier, mixing the raw materials required by the preparation of the carrier, uniformly stirring the mixture into slurry, and drying the slurry to prepare a spherical object; roasting the spherical object in a muffle furnace at a certain temperature, and cooling to room temperature to obtain a carrier;
impregnating the carrier with a chloroplatinic acid solution at room temperature for 2-3 hours, setting the drying temperature in a drying oven to be 80-120 ℃ and the drying time to be 2-3 hours, transferring the carrier into a muffle furnace at the temperature of 500-650 ℃ and the roasting time to be 3-5 hours, and cooling to room temperature to obtain the front combustion improver.
9. The method for preparing the flue gas combustion improver regenerated by the noble metal FCC catalyst, according to claim 8, is characterized in that: in the preparation process of the carrier, the mixture is uniformly stirred into slurry, then the slurry is prepared into a spherical object with the granularity of 30-150 mu m through a spray drying system, and the spherical object is roasted in a muffle furnace at the temperature of 500-650 ℃ for 3-5 hours.
10. A noble metal FCC catalyst regeneration flue gas combustion improver is characterized in that: the catalyst is prepared by the preparation method of the noble metal FCC catalyst regeneration flue gas combustion improver according to any one of claims 1 to 3.
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