CN113198522A - Monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof - Google Patents
Monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/44—Noble metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J29/7876—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/76—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by condensation of hydrocarbons with partial elimination of hydrogen
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- 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
- C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/10—Feedstock materials
- C10G2300/1081—Alkanes
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/30—Aromatics
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention belongs to the field of catalysts and preparation thereof, and relates to an integral catalyst for preparing aromatic hydrocarbon from low-carbon alkane and a preparation method thereof. The catalyst takes organic acid treated cordierite honeycomb ceramic as a substrate, and a coating layer is a low silica-alumina ratio molecular sieve, an active component Ga element, an active auxiliary agent and a small amount of binder; the mass of the dry basis of the coating layer is 5-15% of that of cordierite, wherein the active component accounts for 0.2-3.0% of the mass of the dry basis of the coating layer, and the modification auxiliary agent accounts for 0.05-0.5%. The catalyst of the invention has excellent aromatization performance of low-carbon alkane, simple preparation process and better industrial application prospect.
Description
Technical Field
The invention belongs to the field of catalysts and preparation thereof, relates to an integral catalyst and a preparation method thereof, and particularly relates to an integral catalyst for preparing aromatic hydrocarbon from low-carbon alkane and a preparation method thereof.
Background
Benzene, toluene and xylene (BTX for short) have been widely used as important basic organic chemical raw materials in the preparation of various chemical products. The vigorous development of aromatic hydrocarbon production conforms to the development trend of traditional oil refining enterprises from fuel type to chemical type. In recent years, due to the rapid development of downstream industries, the demand for BTX in china has increased year by year, and although the production of aromatic hydrocarbons has been vigorously promoted, a large portion of the supply gaps still depend on import supplementation. With the increasing demand for light aromatic hydrocarbons and the extensive development and application of shale gas, the condensate contains a large amount of ethane and propane, so that the aromatization technology for catalyzing the conversion of light alkanes into BTX, especially propane, draws wide attention in both academic and industrial production fields.
Currently, aromatization processes that have been developed for use with C3 to C4 hydrocarbons include: a Cyclar process, an M2-forming process, an Aroforming process and the like. The modified ZSM-5 molecular sieve used in the above processes is used as an aromatization catalyst. Although this process is already industrialized, there are still a number of problems: quick carbon deposition inactivation, low aromatic hydrocarbon yield and more dry gas byproducts. The development of high performance aromatization catalysts is therefore the key core to solving the above problems. As is well known, a ZSM-5 molecular sieve is a base material with better performance in the current light hydrocarbon aromatization catalyst system; a plurality of research institutions at home and abroad widely and deeply research the aromatization catalyst of the ZSM-5 system and obtain better research results. CN1093431C, CN1268429C, CN101209947B, CN101588866B provide aromatization catalyst based on ZSM-5 molecular sieve as carrier; four patents of CN102895992B, CN106395851B, CN107915236B and CN108285151B provide a preparation method of an aromatization catalyst, which adopts a catalyst system with L zeolite as a carrier and Pt as an active component. However, the traditional extrusion molding process for preparing the aromatization catalyst is adopted in the above patents, the production process is complex, the utilization rate of raw materials is low, the pressure drop of a bed layer is high, and the mass transfer efficiency is low.
Disclosure of Invention
The invention provides an integral catalyst for preparing aromatic hydrocarbon from low-carbon alkane, aiming at the defects of low raw material utilization rate, high bed pressure drop, low mass transfer efficiency and the like of the traditional strip-shaped and spherical catalysts. Compared with granular catalyst, the monolithic catalyst has the advantages of small bed pressure drop, high heat and mass transfer efficiency, high mechanical strength, small back mixing, small amplification effect of the reactor, simple and convenient catalyst loading and unloading, and the like.
It is another object of the present invention to provide a method for preparing the above catalyst. The preparation method is low in cost, and the prepared catalyst can improve the reaction activity and the selectivity of BTX products, and has a good industrial application prospect.
In order to achieve the above purpose, the specific technical scheme of the invention is as follows:
a monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane comprises the following components: organic acid treated cordierite honeycomb ceramic is used as a substrate, and a coating layer is a low silica-alumina ratio molecular sieve, a main active component Ga element, an active additive and a small amount of binder.
As a better embodiment in the application, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane is characterized in that the dry mass (oxide) of the coating layer is 5-15% of the mass of cordierite.
In the coating layer, the active component accounts for 0.2-3.0% of the total mass of the coating layer, the modification auxiliary agent accounts for 0.05-0.5%, the dry mass of the binder calculated by the mass of the oxide accounts for 5-15% of the dry mass of the coating layer, the balance is the low-silica-alumina ratio molecular sieve, and the sum of the total mass percentage is 100%.
As a better implementation mode in the application, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane described above has the cordierite ceramic honeycomb mesh number of 200-400 meshes, the open pore ratio of 65-75% and the bulk density of 0.5-0.6.
As a preferred embodiment of the present application, the monolithic catalyst for preparing aromatic hydrocarbons from low-carbon alkanes is described above, wherein the organic acid solution is any one of acetic acid, citric acid and oxalic acid, and the acid mass concentration is 10% to 20%.
As a preferred embodiment of the present application, the method for producing an organic acid-treated cordierite honeycomb ceramic comprises the steps of: treating for 1-4 h at the temperature of 60-100 ℃, then washing with deionized water for multiple times, and drying at 150 ℃ for later use.
As a preferred embodiment in the present application, the monolithic catalyst for preparing aromatics from light alkanes is described above, wherein the low silica alumina ratio molecular sieve is any one or two of ZSM-5 and MCM-22 molecular sieves, and SiO thereof2/Al2O3The molar ratio is less than 100.
As a preferred embodiment in the present application, the monolithic catalyst for preparing aromatic hydrocarbons from low-carbon alkanes is described above, wherein the source of the Ga element as an active component is gallium nitrate; the modifier is one or two of Pt, Cr and Zn, and the sources of the modifier are chloroplatinic acid, chromium nitrate and zinc nitrate.
As a preferred embodiment in the present application, the monolithic catalyst for producing aromatic hydrocarbons from light alkanes is described above, wherein the small amount of binder is alumina sol or silica sol.
As a better embodiment in the application, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane described above is prepared by the following steps:
1) mixing weighed molecular sieve, gallium nitrate, active assistant and binder with organic acid-treated cordierite honeycomb ceramic, adding a certain amount of deionized water to form a suspension, carrying out ball milling in a ball mill for 0.5-2 h, and taking out;
2) soaking cordierite honeycomb ceramic in the suspension, performing ultrasonic treatment for 1h, then standing for soaking for 2-8 h, and performing ultrasonic treatment for 1 h; then drying in a vacuum drying oven at 120 ℃;
3) calcining the sample obtained in the step 2) at 500-600 ℃ for 3-6 h to obtain the required catalyst.
As a better implementation mode in the application, the ultrasonic treatment temperature is 40-80 ℃, and the ultrasonic frequency is 28KHz or 40 KHz.
As a better embodiment in the application, the water content in the suspension is preferably completely immersed into cordierite, the particle size of the suspension in ball milling is less than 30 microns, and the ball milling time is 0.5-2.0 h.
Compared with the prior art, the positive effects of the invention are as follows:
compared with granular catalyst, the monolithic catalyst has the advantages of small bed pressure drop, high heat and mass transfer efficiency, high mechanical strength, small back mixing, small amplification effect of the reactor, simple and convenient catalyst loading and unloading, and the like.
The catalyst prepared by the invention has low cost, can improve the reaction activity and the selectivity of BTX products, and has good industrial application prospect.
Detailed Description
A monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane comprises the following components: taking organic acid treated cordierite honeycomb ceramic as a substrate, and taking a coating layer of a low silica-alumina ratio molecular sieve, a main active component Ga element, an active additive and a small amount of binder; the dry basis weight (oxide) of the coating layer is 5-15% of the weight of cordierite. The active component in the coating layer accounts for 0.2-3.0% of the total mass of the coating layer, the modification auxiliary agent accounts for 0.05-0.5%, the dry basis mass of the binder calculated by the mass of the oxide accounts for 5-15% of the dry basis mass of the coating layer, the balance is the low-silicon-aluminum ratio molecular sieve, and the sum of the total mass percentage is 100%.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane has cordierite ceramic honeycombs with meshes of 200-400 meshes, an open porosity of 65-75% and a bulk density of 0.5-0.6.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane is characterized in that the organic acid solution is any one of acetic acid, citric acid and oxalic acid, and the acid mass concentration is 10-20%.
Preferably, the method for preparing the cordierite honeycomb ceramic treated by the organic acid comprises the following steps: treating for 1-4 h at the temperature of 60-100 ℃, then washing with deionized water for multiple times, and drying at 150 ℃ for later use.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane is described above, wherein the low silica alumina ratio molecular sieve is any one or two of ZSM-5 and MCM-22 molecular sieves, and SiO is2/Al2O3The molar ratio is less than 100.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane is described above, wherein the source of the element Ga as the active component is gallium nitrate; the modifier is one or two of Pt, Cr and Zn, and the sources of the modifier are chloroplatinic acid, chromium nitrate and zinc nitrate.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane is characterized in that a small amount of binder is aluminum sol or silica sol, and the dry basis mass (oxide) of the binder accounts for 5-15% of the dry basis mass of the coating layer.
Preferably, the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane described above is prepared by the following steps:
1) mixing the weighed molecular sieve, gallium nitrate, active assistant and binder with organic acid-treated cordierite honeycomb ceramic, adding a certain amount of deionized water to form a suspension, carrying out ball milling in a ball mill for 0.5-2 h, and taking out.
2) Soaking cordierite honeycomb ceramic in the suspension, performing ultrasonic treatment for 1h, then standing for soaking for 2-8 h, and performing ultrasonic treatment for 1 h; then dried in a vacuum drying oven at 120 ℃.
3) Calcining the sample obtained in the step 2) at 500-600 ℃ for 3-6 h to obtain the required catalyst.
Preferably, the preparation method of the monolithic catalyst for preparing the aromatic hydrocarbon from the low-carbon alkane is characterized by comprising the following steps: the ultrasonic treatment temperature is 40-80 ℃, and the ultrasonic frequency is 28KHz or 40 KHz.
Preferably, the preparation method of the monolithic catalyst for preparing the aromatic hydrocarbon from the low-carbon alkane is characterized by comprising the following steps: the amount of water in the suspension is preferably that the cordierite is completely immersed, the particle size of the suspension in ball milling is less than 30 microns, and the ball milling time is 0.5-2.0 h.
The foregoing summary of the invention is described in further detail below with reference to specific embodiments.
It should not be understood that the scope of the above-described subject matter of the present invention is limited to the following examples. Various substitutions and alterations can be made without departing from the technical idea of the invention as described above, according to the common technical knowledge and conventional means in the field, and the scope of the invention is covered.
The following percentages, unless otherwise specified, represent the mass percentages of (oxides) based on the total mass of the coating layer on a dry basis.
Example 1:
a preparation method of an integral catalyst for preparing aromatic hydrocarbon from low-carbon alkane comprises the following steps:
(1) cordierite honeycomb ceramic treatment:
200-mesh cordierite honeycomb ceramic with the aperture ratio of 65%; the cordierite is soaked in an acetic acid solution with the mass percentage of 15% at the temperature of 60 ℃ for 3 hours, then washed with deionized water for multiple times (5 times), and dried at the temperature of 150 ℃ (the surface moisture is removed) for later use.
(2) Preparing a catalyst:
1) mixing weighed ZMS-5 molecular sieve (silicon-aluminum molar ratio is 40), gallium nitrate, chloroplatinic acid and silica sol with the mass fraction of 25%, adding a certain amount of deionized water to form suspension, carrying out ball milling in a ball mill for 1h, and taking out the suspension, wherein the average particle size of particles is about 30 microns;
2) soaking cordierite honeycomb ceramic in the suspension, treating for 1h under the ultrasonic condition of 60 ℃ and 28KHz, standing, soaking for 3h, and drying in a vacuum drying oven at 120 ℃;
3) calcining the sample obtained in the step 2) at 500 ℃ for 4h to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: the dry mass of the coating layer is 5 percent, wherein the Ga content is 1.0 percent, the Pt content is 0.2 percent, and the adhesive SiO is2The content is 10 percent, and the balance is ZSM-5 molecular sieve.
Example 2:
(1) cordierite honeycomb ceramic treatment:
300-mesh cordierite honeycomb ceramic with the aperture ratio of 70%; oxalic acid solution with the mass content of 15% is adopted to treat cordierite for 1.5h at the temperature of 100 ℃, and then deionized water is used for washing for multiple times and then the cordierite is dried for standby at the temperature of 150 ℃.
(2) Preparing a catalyst:
1) mixing weighed ZMS-5 molecular sieve (the silicon-aluminum ratio is 50), gallium nitrate, chromium nitrate and 15% aluminum sol by mass, adding a certain amount of deionized water to form a suspension, carrying out ball milling in a ball mill for 0.5h, and taking out the suspension, wherein the average particle size of particles is about 25 microns;
2) soaking cordierite honeycomb ceramic in the suspension, treating for 1h under 40 ℃ and 40KHz ultrasonic conditions, standing, soaking for 6h, and drying in a vacuum drying oven at 120 ℃;
3) calcining the sample obtained in the step 2) at 550 ℃ for 3h to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: the dry mass of the coating layer is 9 percent, wherein the Ga content is 0.8 percent, the Cr content is 0.5 percent, and the adhesive Al2O3The content is 8 percent, and the balance is ZSM-5 molecular sieve.
Example 3:
(1) cordierite honeycomb ceramic treatment:
400-mesh cordierite honeycomb ceramic with the opening rate of 75%; the cordierite is treated by citric acid solution with the mass content of 20% at the temperature of 80 ℃ for 2h, and then is washed by deionized water for multiple times and dried at the temperature of 150 ℃ for later use.
(2) Preparing a catalyst:
1) mixing weighed ZMS-5 molecular sieve (silicon-aluminum ratio is 30), gallium nitrate, zinc nitrate, chloroplatinic acid and silica sol with the mass fraction of 25%, adding a certain amount of deionized water to form suspension, and taking out after ball milling for 1.0h in a ball mill, wherein the average particle size of particles is about 20 microns;
2) soaking cordierite honeycomb ceramic in the suspension, performing ultrasonic treatment at 80 ℃ and 40KHz for 1h, standing, soaking for 8h, and drying in a vacuum drying oven at 120 ℃;
3) calcining the sample obtained in the step 2) at 500 ℃ for 6h to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: the content of cordierite is 88 percent, and the dry basis weight of the coating layer is 12 percent; wherein the Ga content is 1.2 percent, the Zn content is 0.15 percent, the Pt content is 0.15 percent, and the adhesive Al2O3The content is 6 percent, and the rest is ZSM-5 molecular sieve.
Example 4:
(1) cordierite honeycomb ceramic treatment:
300-mesh cordierite honeycomb ceramic with the aperture ratio of 70%; the cordierite is treated by a citric acid solution with the mass content of 10% at the temperature of 90 ℃ for 4h, then washed by deionized water for multiple times and dried at the temperature of 150 ℃ for later use.
(2) Preparing a catalyst:
1) mixing the weighed MCM-22 molecular sieve (the silica-alumina ratio is 25), gallium nitrate, chromium nitrate, chloroplatinic acid and 15% silica sol by mass, adding a certain amount of deionized water to form a suspension, carrying out ball milling in a ball mill for 1.5h, and taking out the suspension, wherein the average particle size of particles is about 22 microns;
2) soaking cordierite in the suspension, treating for 1h under ultrasonic condition of 40 deg.C and 28KHz, standing for soaking for 7h, and drying in vacuum drying oven at 120 deg.C;
3) calcining the sample obtained in the step 2) at 600 ℃ for 3h to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: the content of cordierite is 92%, and the dry basis weight of the coating layer is 8%; wherein the Ga content is 1.5 percent, the Cr content is 0.2 percent, the Pt content is 0.1 percent, and the adhesive SiO2The balance of MCM-22 molecular sieve with the content of 8 percent.
Example 5:
(1) cordierite honeycomb ceramic treatment:
400-mesh cordierite honeycomb ceramic with the opening rate of 75%; oxalic acid solution with the mass content of 20% is adopted to treat cordierite for 3 hours at the temperature of 80 ℃, and then deionized water is used for washing for multiple times and then the cordierite is dried for standby at the temperature of 150 ℃.
(2) Preparing a catalyst:
1) mixing weighed ZSM-5 molecular sieve (the silica-alumina ratio is 80), gallium nitrate, chromium nitrate, zinc nitrate and silica sol with the mass fraction of 25%, adding a certain amount of deionized water to form suspension, carrying out ball milling in a ball mill for 2.0h, and taking out the suspension, wherein the average particle size of the particles is about 28 microns;
2) soaking cordierite in the suspension, treating for 1h under ultrasonic condition of 28KHz at 60 deg.C, standing for 5h, and drying at 120 deg.C in vacuum drying oven;
3) calcining the sample obtained in the step 2) at 500 ℃ for 5 hours to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: the dry basis weight of the coating layer is 10 percent, wherein the Ga content is 2.0 percent, the Cr content is 0.1 percent, the Zn content is 0.1 percent, and the adhesive SiO2The content is 12 percent, and the rest is ZSM-5 molecular sieve.
Comparative example 1:
the conventional catalyst preparation was carried out according to the coating content of example 2, with the following preparation steps:
1) and extruding and molding the weighed ZMS-5 molecular sieve (the silicon-aluminum ratio is 50) and 15 mass percent of aluminum sol in a proper amount of deionized water, and calcining for 4 hours at 500 ℃.
2) Weighing and dissolving the weighed gallium nitrate and chromium nitrate in deionized water, soaking the sample obtained in the step 1) in the solution in an equal volume for 6 hours, standing in a drying oven, and finally calcining at 500 ℃ for 4 hours to obtain the required catalyst.
The catalyst comprises the following components in percentage by weight: ga 0.8%, Cr 0.5%, and Al as binder2O3The content is 8 percent, and the balance is ZSM-5 molecular sieve.
Comparative example 2:
the catalyst preparation was carried out as in example 5, except that 20% by weight ofInorganic acid HNO3Treating cordierite, wherein the final catalyst comprises the following components in percentage by weight: the dry basis weight of the coating layer is 10 percent, wherein the Ga content is 2.0 percent, the Cr content is 0.1 percent, the Zn content is 0.1 percent, and the adhesive SiO2The content is 12%.
7 samples in total of examples 1 to 5 and comparative examples 1 to 2 were subjected to evaluation of propane aromatization performance in a fixed bed microreactor. Activity evaluation conditions: normal pressure, propane mass space velocity 0.45h-1，N2/C3H8The reaction temperature is 2.0 and 540-590 ℃. Regeneration conditions are as follows: the temperature is 550 ℃, N is obtained after 24 hours of reaction2-O2(5%) the mixed gas is burnt to regenerate.
The initial activity after 2 hours of reaction of examples 1 to 5 and comparative examples 1 to 2 is shown in Table 1. The initial activity and after 20 evaluation-regeneration cycles of example 5 and comparative example 2, the aromatization performance is shown in table 2.
TABLE 1 initial Activity of examples and comparative example 1
Table 2 comparison of regeneration performance of example 5 and comparative example 2
As can be seen from tables 1 and 2, the monolithic catalyst prepared by the invention has good propane aromatization activity and regeneration stability while maintaining high strength, and particularly, the BTX selectivity is obviously improved compared with the traditional process, and the industrial application potential is large.
The above examples are only preferred embodiments of the patent, but the scope of protection of the patent is not limited thereto. It should be noted that, for those skilled in the art, without departing from the principle of this patent, several improvements and modifications can be made according to the patent solution and its patent idea, and these improvements and modifications should also be regarded as the protection scope of this patent.
Claims (10)
1. The monolithic catalyst for preparing the aromatic hydrocarbon from the low-carbon alkane is characterized by comprising the following components: taking organic acid treated cordierite honeycomb ceramic as a substrate, and taking a coating layer of a low silica-alumina ratio molecular sieve, an active component Ga element, an active auxiliary agent and a small amount of binder; the dry mass of the coating layer is 5-15% of the mass of cordierite.
2. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, which is characterized in that: the active component in the coating layer accounts for 0.2-3.0% of the dry mass of the coating layer, the active additive accounts for 0.05-0.5% of the dry mass of the coating layer, the dry mass of the binder calculated by the mass of the oxide accounts for 5-15% of the dry mass of the coating layer, and the balance is the low-silica-alumina ratio molecular sieve, and the sum of the total mass percentage is 100%.
3. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, which is characterized in that: the cordierite ceramic honeycomb has a mesh number of 200-400 meshes, an open porosity of 65-75% and a bulk density of 0.5-0.6.
4. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, wherein the cordierite honeycomb ceramic treated by organic acid is prepared by treating organic acid solution at 60-100 ℃ for 1-4 h, washing with deionized water for multiple times, and drying at 150 ℃ for later use; the organic acid solution is any one of acetic acid, citric acid and oxalic acid, and the acid mass concentration is 10-20%.
5. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, which is characterized in that: the low silica-alumina ratio molecular sieve is any one of ZSM-5 and MCM-22 molecular sievesOr a mixture of the two, SiO2/Al2O3The molar ratio is less than 100.
6. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, which is characterized in that: the source of the active component Ga element is gallium nitrate; the active auxiliary agent is any one or two of Pt, Cr and Zn, and the sources of the active auxiliary agent are chloroplatinic acid, chromium nitrate and zinc nitrate.
7. The monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane according to claim 1, which is characterized in that: the binder is aluminum sol or silica sol.
8. A preparation method of the monolithic catalyst for preparing aromatic hydrocarbon from lower alkane according to any one of claims 1 to 6, which is characterized by comprising the following steps:
1) soaking cordierite honeycomb ceramics by using an organic acid solution for 1-4 hours at the temperature of 60-100 ℃, then washing by using deionized water for multiple times and drying at 150 ℃ for later use; mixing the weighed molecular sieve, gallium nitrate, active auxiliary agent and binder, adding a certain amount of deionized water to form suspension, and taking out after ball milling in a ball mill.
2) Soaking cordierite honeycomb ceramic subjected to mechanical acid treatment in the suspension prepared in the step 1), performing ultrasonic treatment for 1 hour, standing and soaking for 2-8 hours, and then drying in a vacuum drying oven at 120 ℃;
3) calcining the sample obtained in the step 2) at 500-600 ℃ for 3-6 h to obtain the required catalyst.
9. The preparation method of the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane, according to claim 7, is characterized in that: the ultrasonic treatment temperature is 40-80 ℃, and the ultrasonic frequency is 28KHz or 40 KHz.
10. The preparation method of the monolithic catalyst for preparing aromatic hydrocarbon from low-carbon alkane, according to claim 7, is characterized in that: the amount of water in the suspension is preferably that the cordierite is completely immersed, the particle size of the suspension in ball milling is less than 30 microns, and the ball milling time is 0.5-2.0 h.
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