CN112657540A - Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof - Google Patents
Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof Download PDFInfo
- Publication number
- CN112657540A CN112657540A CN201910976988.8A CN201910976988A CN112657540A CN 112657540 A CN112657540 A CN 112657540A CN 201910976988 A CN201910976988 A CN 201910976988A CN 112657540 A CN112657540 A CN 112657540A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- toluene disproportionation
- transalkylation
- molecular sieve
- hours
- 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.)
- Pending
Links
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to a toluene disproportionation and transalkylation catalyst, a preparation method and application thereof. The toluene disproportionation and transalkylation catalyst comprises: porous carrier, molecular sieve containing mesopores, and at least one metal component selected from IB, VIB, VIIB and VIII family metals. In the catalyst of the present invention, at least 70% by weight of the metal component is distributed on the outer surface of the molecular sieve. The catalyst can obviously enhance the hydrogenation selectivity of aromatic hydrocarbon, is beneficial to improving the quality of benzene and reducing the loss of monocyclic aromatic hydrocarbon, and mainly solves the problems of narrow application raw material range, low indene series substance tolerance, low hydrogenation selectivity of polycyclic aromatic hydrocarbon and high loss rate of monocyclic aromatic hydrocarbon of the toluene disproportionation and transalkylation catalyst in the prior art.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a toluene disproportionation and transalkylation catalyst, and a preparation method and application thereof.
Background
Benzene, toluene and xylene are important basic organic raw materials in petrochemical industry and are mainly obtained by catalytic reforming of naphtha. However, due to the thermodynamic limitation of the reaction, the total amount of aromatic hydrocarbons generated by catalytic reforming and the distribution structure of products cannot meet the market demand, and the yield of benzene and xylene with high added value is low. In order to meet the market demand and improve the economic benefit, the aromatics complex mainly increases the yield of the xylene by toluene disproportionation and taking toluene and C9A, C10A and more than ten carbon heavy aromatics (C10+ A) as raw materials for toluene disproportionation and transalkylation reactions. The heavy naphtha raw material is aggravated due to the large-scale of an aromatic hydrocarbon combination device and the construction of a megaton large ethylene device, and heavy aromatic hydrocarbons are more and more by-produced. Because the condensed ring compounds in the heavy aromatics are easy to aggravate the carbon deposition deactivation of the catalyst, the heavy aromatics (C10+ A) with carbon ten or more can only be partially utilized at present, and therefore, the traditional disproportionation and transalkylation processes have strict limitations on the content of C10+ A in the reaction raw materials.
In order to improve the yield and heavy aromatic hydrocarbon processing capacity of monocyclic aromatic hydrocarbon, accelerate the aromatic hydrocarbon dealkylation reaction of C9+ A and improve the conversion rate of C9+ A, hydrogenation metal components such as platinum, rhenium, molybdenum, nickel and the like are required to be introduced to a molecular sieve catalyst for modification, and the carbon deposition rate is slowed down by hydrogenation of a saturated carbon deposition precursor, so that the stability of the catalyst is improved. However, the stronger hydrogenation function can lead to the improvement of the selectivity of non-aromatic hydrocarbon, increase the hydrogen consumption of reaction and release strong heat, and the C6-C7 non-aromatic hydrocarbon generated by the hydrogenation of benzene and toluene is difficult to be completely separated from the benzene product by a rectification method, thus leading to the reduction of the quality of the benzene product. In order to improve the overall performance of the supported catalyst, the hydrogenation performance of the active metal is generally adjusted by optimizing reaction process conditions (such as reducing hydrogen partial pressure and increasing reaction temperature) and methods of pre-carbon deposition of the catalyst, metal vulcanization, adding a second metal auxiliary agent (lead and tin) and the like, so that the side reaction of aromatic hydrogenation is kinetically or thermodynamically inhibited. CN1259930A discloses a multi-layer molecular sieve catalytic process for heavy aromatics treatment. The benzene product with the purity higher than 99.85 percent can be obtained by adopting the process, but the dealkylation and light conversion performance of the heavy aromatics is lower, and the conversion capability of the heavy aromatics is poorer. Especially on the second layer catalyst which takes ZSM-5 as the main active component, the catalyst is easy to be quickly deactivated because of heavier raw materials. CN105272803A discloses a method for disproportionation and transalkylation of toluene and heavy aromatics, which divides the reactions of the disproportionation and transalkylation of toluene and heavy aromatics into different zones by distinguishing the reaction characteristics of different reactions, wherein the first layer of catalyst is used for selective dealkylation of heavy aromatics and partial hydrocracking and lightening of naphthalene series, the second layer of catalyst is used for disproportionation and transalkylation of methylbenzene to maximize the production of dimethylbenzene and benzene, and the third layer of catalyst is used for selective cracking of non-aromatic hydrocarbons with boiling points close to that of benzene in the hydrogenation side reaction to generate light hydrocarbon components, thereby improving the quality of benzene products. The process can integrate the advantages of catalysts of all layers, improve the conversion rate of heavy aromatics and co-produce qualified benzene products. However, due to the formation of indanes and tetralin compounds which are hydrogenation products generated after the raw materials pass through the first layer of catalyst, unsaturated hydrocarbons generated by cracking of cycloalkanes formed by excessive hydrogenation in the subsequent hydrocracking process for preparing monocyclic aromatic hydrocarbons easily cause the coverage of catalyst active sites on the second layer and the reduction of mass transfer efficiency and activity caused by pore channel blockage caused by coke and coke precursors. How to avoid the coverage of active sites on active component molecular sieves in the catalyst and the formation of macromolecular coke and coke precursors in the pore channels is an important way for improving the activity stability of the catalyst. Patent US6623626 describes a catalyst system for ring opening of naphthenes, mainly consisting of two layers, the upper layer being a Pt/Pd catalyst, aiming at isomerizing six-membered ring hydrocarbons into five-membered ring hydrocarbons, and the lower layer being a catalyst containing Ir, to achieve ring opening of five-membered ring hydrocarbons. The catalyst system is mainly used for improving the cetane number of diesel oil fraction, and the acid function is weak. CN103120954A discloses a catalyst for preparing monocyclic aromatic hydrocarbon from polycyclic aromatic hydrocarbon. The catalyst can convert polycyclic aromatic hydrocarbon into benzene, toluene, xylene, C9 aromatic hydrocarbon and partial monocyclic C10 aromatic hydrocarbon, and the conversion rate is over 30 percent.
Disclosure of Invention
The invention aims to solve the technical problems of narrow raw material range, poor tolerance of polycyclic aromatic hydrocarbon, low hydrogenation selectivity and low yield of monocyclic aromatic hydrocarbon in the existing toluene disproportionation and transalkylation technology, and provides a novel toluene disproportionation and transalkylation catalyst with a selective hydrogenation function.
One of the purposes of the invention is to provide a catalyst for toluene disproportionation and transalkylation, which comprises the following components,
a) a porous support;
b) a molecular sieve containing mesopores;
c) at least one metal component selected from group IB, VIB, VIIB, VIII metals;
the content of the metal component is 0.005-10%, preferably 0.2-8% by weight based on the total weight of the porous carrier, the molecular sieve and the metal component; the content of the molecular sieve is 10-90%, and preferably 20-80%; the balance of the carrier content.
In the molecular sieve containing mesopores, the proportion of the mesopores is preferably 2-90%, and more preferably 10-50%; the proportion of the micropores is preferably 10-98%, more preferably 50-90%.
The molecular sieve is preferably at least one of ZSM-5, ZSM-11, ZSM-22, EU-1, MCM-22, ITQ-13, Beta, FER, FAU and MOR molecular sieves.
The porous carrier is preferably at least one of alumina, silica and porous activated carbon.
The IB group metal comprises at least one of Cu, Ag and Au, preferably Cu and Au;
the VIB group metal comprises at least one of W, Cr and Mo, preferably at least one of Cr and Mo;
the VIIB metal comprises at least one of Tc, Mn and Re, preferably at least one of Mn and Re;
the group VIII metal comprises at least one of Ru, Ni, Co, Pt, Pd, Ir and Os, and preferably at least one of Ni, Co, Pt and Pd.
In the metal component, at least 70 wt% of the metal component is distributed on the outer surface of the molecular sieve, preferably 75-95 wt%.
According to the technical scheme, the selective hydrogenation activity of the condensed ring compound is improved through the synergistic effect of mixed metals.
The second purpose of the invention is to provide a preparation method of the toluene disproportionation and transalkylation catalyst, which comprises the following steps:
1) contacting components containing the molecular sieve and a template organic matter to obtain a modified molecular sieve;
2) contacting the modified molecular sieve with a metal source solution;
3) then mixing with the carrier, molding, roasting and reducing to obtain the catalyst.
Wherein the organic template agent is at least one selected from quaternary ammonium compounds, quaternary phosphorus compounds and organic amines.
The quaternary ammonium compound is tetraalkylammonium halide or tetraalkylammonium hydroxide, preferably one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrapropylammonium hydroxide and tetraethylammonium hydroxide;
the quaternary phosphorus compound is tetraalkyl phosphorus halide or tetraalkyl phosphorus hydroxide, preferably one or more of tetramethyl phosphorus bromide, tetraethyl phosphorus bromide, tetrapropyl phosphorus bromide and tetrabutyl phosphorus bromide;
the organic amine is selected from one or more of ethylamine, propylamine and isomers thereof, isopropylamine, butylamine and isomers thereof, pentylamine and isomers thereof, hexylamine-1 and isomers thereof, hexamethylenediamine and isomers thereof, octylamine and isomers thereof, and octylamine and isomers thereof.
The organic template is preferably a solution of the organic template, including an aqueous solution, an ethanol solution and other solvents.
The concentration of the solution of the template organic matter is preferably 0.001-0.5 mol/L, and more preferably 0.002-0.3 mol/L.
The metal source is a compound of the metal, and preferably a solution of the metal compound, a metal compound solution including an aqueous solution, an ethanol solution and other solvents is used.
The metal source of the group IB metal preferably comprises at least one of Cu, Ag, Au metal compounds; particularly preferably at least one of Cu and Au, such as anhydrous copper chloride and the like;
the metal source of the group VIB metal preferably comprises at least one of W, Cr, Mo metal compounds; particularly preferably at least one of Cr and Mo, such as ammonium molybdate and the like;
the metal source of the group VIIB metal preferably includes at least one of Tc, Mn, Re metal compounds; specifically, at least one of Mn and Re, such as ammonium perrhenate, is preferably included;
the VIII group metal preferably comprises at least one of Ru, Ni, Co, Pt, Pd, Ir, Os and Au metal compound; specifically, it preferably includes at least one of Ni, Co, Pt and Pd, such as nickel nitrate hexahydrate, cobalt nitrate heptahydrate, palladium chloride, chloroplatinic acid, etc.
In the step 1), preferably, the contact temperature is 15-150 ℃, the contact time is 5-300 minutes, and the solid-to-liquid ratio is (1:50) - (1: 2); the weight ratio of the organic template to the molecular sieve is 0.1-30 wt%;
more preferably, the contact temperature is 20-120 ℃, the contact time is 30-240 minutes, the solid-to-liquid ratio is (1:20) - (1:2), and the organic matter of the template accounts for 0.1-25 wt% of the weight of the molecular sieve.
In the step 2), preferably, the contact time is 1-100 hours;
more preferably, the contact time is 0.5 to 48 hours.
In the step 3), the technological conditions for roasting can be reasonably selected by a person skilled in the art, and creative labor is not required. Preferably, the roasting temperature is 350-600 ℃, and preferably 400-550 ℃; the roasting time is 2-10 hours, preferably 2-8 hours. The firing temperature is, for example, but not limited to, 350 to 600 ℃, and further non-limiting examples thereof are 400 ℃, 450 ℃, 500 ℃, 550 ℃. The baking time is, for example, but not limited to, 2 to 10 hours, and further non-limiting examples of the baking time are 4 hours, 5 hours, 6 hours, 8 hours, and the like.
The process conditions for the reduction can be chosen reasonably by the person skilled in the art and without any inventive effort. The reduction conditions are as follows: the reduction temperature is 300-600 ℃, the reduction time is 1-6 hours, the reduction pressure is 0-20 MPa, preferably, the reduction temperature is 350-500 ℃, the reduction time is 2-5 hours, and the reduction pressure is 1-5 MPa.
The preparation method of the invention can also comprise the steps of drying (drying) and the like before the step 1) of contacting, after the step 2) of contacting and after the step 3) of forming. The steps of drying, forming, roasting, reducing and the like all adopt the processes and equipment which are common in the field.
The drying can adopt the conditions common in the field, and is preferably dried for 1-100 h at the temperature of 60-300 ℃.
The forming can be carried out by adopting a method and equipment for extruding, rolling ball or oil column forming and the like which are common in the field, and concretely comprises the steps of fully mixing the obtained catalyst with sesbania powder, nitric acid and other auxiliaries, kneading and extruding.
Specifically, the preparation method of the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function comprises the following steps:
(a) drying the molecular sieve at 60-300 ℃ for 1-100 h, wherein the molecular sieve can be at least one of molecular sieves consisting of hydrogen type molecular sieves, ammonium type molecular sieves and sodium type molecular sieves, and preferably the hydrogen type molecular sieves or the ammonium type molecular sieves. When the sodium type molecular sieve is used, it can be converted into a hydrogen type molecular sieve or an ammonium type molecular sieve by means commonly used in the art, such as acid treatment or ammonium exchange;
(b) adding the dried molecular sieve into a template organic matter solution with a certain concentration according to a certain solid-to-liquid ratio, stirring for a certain time at a certain temperature, filtering, and directly drying to obtain molecular sieve powder;
(c) dissolving one or more metal elements or metal salt compounds selected from IB, VIB, VIIB and VIII group metals in deionized water to obtain a uniform aqueous solution;
(d) adding the uniform aqueous solution obtained in the step (2) into the molecular sieve powder obtained in the step (1) by adopting an impregnation method, an incipient wetness impregnation method, pulping, spraying and other metal loading modes, standing for a period of time, and drying to obtain a modified molecular sieve;
(e) and (4) uniformly kneading the modified molecular sieve obtained in the step (3) with a porous carrier, a certain amount of dilute nitric acid and sesbania powder, extruding, forming, drying, roasting and reducing to obtain the heavy aromatic hydrocarbon hydrocracking catalyst.
In the invention: in the step (1), quaternary ammonium salt (or alkali) cations or quaternary phosphonium salt (or alkali) cations or organic amine molecules can be preferentially adsorbed at the pore openings of the molecular sieve, so that the pore openings are blocked, metal components are prevented from entering the inner pore passages of the molecular sieve in the subsequent treatment process, and the metal components are ensured to be enriched on the outer surface of the molecular sieve in the step (2). By calculating the using amount and characteristics of the organic matter in the template during preparation, at least 70 wt% of the metal components of the catalyst of the invention can be estimated to be distributed on the outer surface of the molecular sieve, preferably 75-95 wt%. In the process of converting the polycyclic aromatic hydrocarbon, raw material molecules firstly have a pre-hydrogenation effect on a carrier, part of heavy aromatic hydrocarbon in the raw material is selectively hydrogenated into monocyclic aromatic hydrocarbon and indene series substances, when unreacted heavy aromatic hydrocarbon molecules and the indene series substances formed after the pre-hydrogenation are diffused to the outer surface of the active component molecular sieve, the bimolecular reaction of the polycyclic aromatic hydrocarbon caused by acid catalysis is inhibited on the outer surface of the molecular sieve due to the enriched metal hydrogenation function, the formation of heavier components, coke precursors and coke is reduced, and the service life of the catalyst is prolonged. After hydrogenation is carried out on the outer surface of the molecular sieve, the polycyclic aromatic hydrocarbon can be directly subjected to acid catalytic cracking reaction after being diffused into the pore channels of the molecular sieve, and the yield of the monocyclic aromatic hydrocarbon is improved through shape-selective catalysis. The hydrogenation function in the pore canal of the molecular sieve is reduced, which is beneficial to reducing the possibility that monocyclic aromatic hydrocarbon is continuously hydrogenated to form non-aromatic before benzene, thereby improving the purity of the benzene product.
The third purpose of the invention is to provide the toluene disproportionation and transalkylation catalyst prepared by the preparation method of the toluene disproportionation and transalkylation catalyst.
The fourth purpose of the invention is to provide the application of the catalyst for toluene disproportionation and transalkylation in toluene disproportionation and transalkylation.
The catalyst is applied to the toluene disproportionation and transalkylation reaction of raw materials containing a small amount of naphthalene and indene compounds, and the pressure is 3.0-5.0 MPa, the temperature is 350-425 ℃, and the weight space velocity is 2.5-5.0 h-1Toluene containing a small amount of naphthalene-based substances and indene-based substances under the condition that the hydrogen-hydrocarbon molar ratio is 2: 1-10: 1, and C9Aromatic hydrocarbons and C10The simultaneous action of aromatic hydrocarbon on metal active site outside pore canal and inside and outside acid site of molecular sieve pore canal in carrier and active component can convert the material molecule into benzene, toluene, xylene and C9Aromatic hydrocarbons and partially monocyclic C10The conversion rate of aromatic hydrocarbon is high, the service life is long, the quality of benzene is improved, the loss of monocyclic aromatic hydrocarbon is reduced, and a good technical effect is achieved.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the embodiments of the present invention are commercially available.
The composition of the catalyst was analyzed by ICP (inductively coupled plasma) and XRF (X-ray fluorescence) methods. The ICP test conditions were: the Varian 700-ES series XPS instrument. XRF test conditions were: rigaku ZSX 100e model XRF instrument.
The composition of the reaction raw materials and the product is determined by gas chromatography. The chromatography model is Agilent7890A, and comprises FID detector with hydrogen ion flame, FFAP capillary chromatographic column for separation, programmed temperature raising to initial temperature of 90 deg.C, holding for 15min, raising temperature to 220 deg.C at a rate of 15 deg.C/min, and holding for 45 min.
Reaction conditions are as follows: the pressure is 3.0MPa, the temperature is 375 ℃, and the weight space velocity is 4.0h-1And under the condition that the hydrogen-hydrocarbon molar ratio is 3:1, reacting raw materials: mixed aromatics feed containing small amounts of naphthalene/indane (see tables 3 and 4 for specific compositions).
In the invention, the mesoporous is N of a sample measured by a Quantachrome specific surface and aperture analyzer at the low temperature of-196 DEG C2Adsorption-desorption isotherms. The specific surface area of the sample is calculated by a BET (Brunauer-Emmett-Teller) equation; the distribution of pore diameters (PSD) is calculated by a Barrett-Joyner-Halenda (BJH) model; the total pore volume was calculated using the amount of adsorption of the sample at a partial pressure of 0.99. The micropore volume and the external surface area are calculated by a t-plot method.
Calculation of the data of the main results of the examples and comparative examples:
[ example 1 ]
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 50, a mesopore proportion of 25% and a micropore proportion of 75%4 +Drying a-ZSM-5 molecular sieve at 180 ℃ for 10 hours to obtain solid powder 1; 100g of the obtained powder was added to 300ml of a 0.2mol/L tetraethylammonium bromide solution, stirred at 50 ℃ for 4 hours, filtered and directly dried at 150 ℃ for 4 hours to obtain solid powder 2.
(2) 3.9g of nickel nitrate hexahydrate is dissolved in 50g of deionized water to prepare a uniform aqueous solution, the uniform aqueous solution is soaked in the solid powder 2 by adopting an incipient wetness soaking method, and after being dried for 24 hours in shade (namely contact time), the solid powder 3 is obtained by drying for 24 hours at 150 ℃.
(3) And (3) kneading uniformly the solid powder 3g obtained in the step (2), the carrier alumina 57.1g, a certain amount of dilute nitric acid and sesbania powder, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 3 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the catalyst composition is shown in Table 1, and the catalytic performance is shown in Table 3.
Comparative example 1
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 50, a mesopore proportion of 25% and a micropore proportion of 75%4 +Drying the-ZSM-5 molecular sieve at 180 ℃ for 10h to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 57.1g of binder alumina and a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 3.9g of nickel nitrate hexahydrate in the kneading process, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 3 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 3.
[ example 2 ]
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 30, a mesoporous proportion of 15% and a microporous proportion of 85%4 +Drying the MOR molecular sieve at 180 ℃ for 10h to obtain solid powder 1; adding 100g of the obtained powder into 400ml of 0.022mol/L tetrapropylammonium hydroxide solution, stirring for 10min at 60 ℃, filtering, and directly drying for 4h at 150 ℃ to obtain solid powder 2.
(2) Dissolving 2.09g of anhydrous copper chloride in 50g of deionized water to prepare a uniform aqueous solution, soaking the solution in the solid powder 2 by adopting an incipient wetness soaking method, drying the solution in the shade for 0.5h, and drying the solution at 150 ℃ for 24h to obtain solid powder 3.
(3) And (3) uniformly kneading about 100g of the solid powder obtained in the step (2), 100g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 400 ℃ for 3 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the catalyst composition is shown in Table 1, and the catalytic performance is shown in Table 3.
Comparative example 2
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 30, a mesoporous proportion of 15% and a microporous proportion of 85%4 +Drying the MOR molecular sieve at 180 ℃ for 10h to obtain solid powder 1;
(2) and (2) uniformly kneading 100g of the solid powder 1 obtained in the step (1), 100g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 2.09g of anhydrous copper chloride in the kneading process, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 400 ℃ for 3 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in a table 1, and the catalytic performance is shown in a table 3.
[ example 3 ]
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 100, a mesopore proportion of 10% and a micropore proportion of 90%4 +Drying the MOR molecular sieve at 180 ℃ for 10h to obtain solid powder 1; adding 100g of the obtained powder into 5000ml of 0.024mol/L tetraethylammonium hydroxide solution, stirring at 145 ℃ for 30min, filtering, and directly drying at 150 ℃ for 4h to obtain solid powder 2.
(2) Dissolving 81.6g of ammonium molybdate in 50g of deionized water to prepare a uniform aqueous solution, soaking the solution in the solid powder 2 by adopting an incipient wetness impregnation method, drying the solution in the shade for 1h, and drying the solution at 150 ℃ for 24h to obtain solid powder 3.
(3) And (3) uniformly kneading about 100g of the solid powder obtained in the step (2), 400g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 5 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the catalyst composition is shown in Table 1, and the catalytic performance is shown in Table 3.
Comparative example 3
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 100, a mesopore proportion of 10% and a micropore proportion of 90%4 +Drying the-MOR molecular sieve at 180 ℃ for 10h to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 400g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 81.6g of ammonium molybdate in the kneading process, extruding and molding, drying at 120 ℃ for 4 hours, roasting at 600 ℃ for 5 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 3.
[ example 4 ]
(1) Mixing SiO2/Al2O3H with a molecular ratio of 30, a mesopore proportion of 5% and a micropore proportion of 95%+Drying the-beta molecular sieve at 180 ℃ for 10h to obtain solid powder 1; 100g of the obtained powder is added into 200ml of 0.0022mol/L tetraethyl phosphonium bromide solution, stirred for 3h at 30 ℃, filtered and directly dried for 4h at 150 ℃ to obtain solid powder 2.
(2) 5.4g of ammonium perrhenate is dissolved in 50g of deionized water to prepare a uniform aqueous solution, the solution is soaked in the solid powder 2 by an incipient wetness soaking method, and the solid powder 3 is obtained after drying in shade for 2h and drying at 150 ℃ for 24 h.
(3) And (3) uniformly kneading about 100g of the solid powder obtained in the step (2), 25g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 6 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the catalyst composition is shown in Table 1, and the catalytic performance is shown in Table 4.
Comparative example 4
(1) Mixing SiO2/Al2O3The molecular ratio is 30, the proportion of mesopores is 5 percent, and the microporesIn a proportion of 95% of H+Drying the-beta molecular sieve at 180 ℃ for 10h to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 25g of binder alumina, a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 5.4g of ammonium perrhenate during the kneading, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 6 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
[ example 5 ]
(1) Mixing SiO2/Al2O3Na having a molecular ratio of 200, a mesopore proportion of 30% and a micropore proportion of 70%+Drying a-ZSM-5 molecular sieve at 180 ℃ for 10 hours to obtain solid powder 1; 100g of the obtained powder was added to 500ml of 0.0019mol/L tetraethylammonium bromide solution, stirred at 20 ℃ for 1h, filtered and directly dried at 150 ℃ for 4h to obtain solid powder 2.
(2) Dissolving 34.05g of cobalt nitrate heptahydrate in 50g of deionized water to prepare a uniform aqueous solution, soaking the uniform aqueous solution in the solid powder 2 by adopting an incipient wetness impregnation method, drying the solution in shade for 96 hours, and drying the solution at 150 ℃ for 24 hours to obtain solid powder 3.
(3) And (3) uniformly kneading about 100g of the solid powder obtained in the step (2), 43g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 8 hours, performing ammonium exchange, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
Comparative example 5
(1) Mixing SiO2/Al2O3Na having a molecular ratio of 200, a mesopore proportion of 30% and a micropore proportion of 70%+-ZSM-5 was dried at 180 ℃ for 10h to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 43g of binder alumina and a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 34.05g of cobalt nitrate heptahydrate in the kneading process, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 550 ℃ for 8 hours, performing ammonium exchange and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
[ example 6 ]
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 25, a mesopore proportion of 22% and a micropore proportion of 78%4 +Drying a-ZSM-11 molecular sieve at 180 ℃ for 10 hours to obtain solid powder 1; 100g of the obtained powder was added to 2000ml of 0.034mol/L tetraethylammonium hydroxide solution, stirred at 120 ℃ for 6 hours, filtered and directly dried at 150 ℃ for 4 hours to obtain solid powder 2.
(2) 0.273g of palladium chloride is dissolved in 50g of deionized water to prepare a uniform aqueous solution, the solution is soaked in the solid powder 2 by adopting an incipient wetness soaking method, and after being dried for 48 hours, the solution is dried for 24 hours at 150 ℃ to obtain solid powder 3.
(3) And (3) kneading about 100g of the solid powder obtained in the step (2), 11g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder uniformly, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 8 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
Comparative example 6
(1) Mixing SiO2/Al2O3NH with a molecular ratio of 25, a mesopore proportion of 22% and a micropore proportion of 78%4 +Drying the-ZSM-11 molecular sieve at 180 ℃ for 10h to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 11g of binder alumina, a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 0.273g of palladium chloride in the kneading process, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 500 ℃ for 8 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
[ example 7 ]
(1) Mixing SiO2/Al2O3H with a molecular ratio of 60, a mesoporous proportion of 15% and a microporous proportion of 85%+Drying the FER molecular sieve at 180 ℃ for 10h to obtain solid powder 1; 100g of the obtained powder was added to 1000ml of a 0.0148mol/L tetrabutylphosphonium bromide solution, stirred at 100 ℃ for 2 hours, filtered, and then directly dried at 150 ℃ for 4 hours to obtain a solid powder 2.
(2) Dissolving 0.141g of chloroplatinic acid in 50g of deionized water to prepare a uniform aqueous solution, soaking the solution in the solid powder 2 by adopting an incipient wetness impregnation method, drying the solution for 24 hours in shade, and drying the solution for 24 hours at 150 ℃ to obtain solid powder 3.
(3) And (3) kneading about 100g of the solid powder obtained in the step (2), 566.7g of carrier alumina, a certain amount of dilute nitric acid and sesbania powder uniformly, extruding into strips, drying at 120 ℃ for 4 hours, roasting at 450 ℃ for 2 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the composition of the catalyst is shown in Table 1, and the catalytic performance is shown in Table 4.
Comparative example 7
(1) Mixing SiO2/Al2O3H with a molecular ratio of 60, a mesoporous proportion of 15% and a microporous proportion of 85%+FER was dried at 180 ℃ for 10 hours to obtain solid powder 1.
(2) Uniformly kneading 100g of the solid powder 1 obtained in the step 1, 566.7g of binder alumina, a certain amount of dilute nitric acid and sesbania powder, adding an aqueous solution prepared from 0.141g of chloroplatinic acid in the kneading process, extruding and forming, drying at 120 ℃ for 4 hours, roasting at 450 ℃ for 2 hours, and reducing at 400 ℃ and under the pressure of 3MPa for 4 hours to obtain the toluene disproportionation and transalkylation catalyst with the selective hydrogenation function, wherein the catalyst composition is shown in Table 1, and the catalytic performance is shown in Table 4.
TABLE 1 catalyst Components
TABLE 2 treatment conditions for the various catalyst components
TABLE 3-Performance results of catalysts for toluene disproportionation and transalkylation reactions catalyzed by the examples and comparative examples 1-3
TABLE 4-Performance results of catalysts for toluene disproportionation and transalkylation reactions catalyzed by the examples and comparative examples 4-7
By comparison, it can be seen from tables 3 and 4 that the catalysts prepared in the examples show higher overall conversion, indicating that the catalytic activity of the examples is higher than that of the comparative examples. The examples have higher benzene purity and lower non-aromatic content than the comparative examples, indicating that the examples have better hydrogenation metal site-acid site synergy. Thus, the examples have a higher catalytic advantage than the comparative examples at the same metal loading and the same molecular sieve content.
Claims (14)
1. A toluene disproportionation and transalkylation catalyst, which comprises the following components,
a) a porous support;
b) a molecular sieve containing mesopores;
c) at least one metal component selected from group IB, VIB, VIIB, VIII metals;
the content of the metal component is 0.005-10%, preferably 0.2-8% by weight based on the total weight of the porous carrier, the molecular sieve and the metal component; the content of the molecular sieve is 10-90%, and preferably 20-80%; the balance of the carrier content.
2. The toluene disproportionation and transalkylation catalyst of claim 1 wherein:
in the molecular sieve containing mesopores, the proportion of the mesopores is 2-90%, preferably 10-50%; the proportion of the micropores is 10-98%, preferably 50-90%.
3. The toluene disproportionation and transalkylation catalyst of claim 1 wherein:
the molecular sieve is at least one of ZSM-5, ZSM-11, ZSM-22, EU-1, MCM-22, ITQ-13, Beta, FER, FAU and MOR molecular sieves.
4. The toluene disproportionation and transalkylation catalyst of claim 1 wherein:
the porous carrier is at least one of alumina, silicon oxide and porous activated carbon.
5. The toluene disproportionation and transalkylation catalyst of claim 1 wherein:
the IB group metal comprises at least one of Cu, Ag and Au; and/or the presence of a gas in the gas,
the VIB group metal comprises at least one of W, Cr and Mo; and/or the presence of a gas in the gas,
the VIIB metal comprises at least one of Tc, Mn and Re; and/or the presence of a gas in the gas,
the VIII group metal comprises at least one of Ru, Ni, Co, Pt, Pd, Ir and Os.
6. The toluene disproportionation and transalkylation catalyst according to any one of claims 1-5, wherein:
in the metal component, at least 70 wt% of the metal component is distributed on the outer surface of the molecular sieve, preferably 75-95 wt%.
7. A method for preparing the catalyst for toluene disproportionation and transalkylation according to any one of claims 1-6, comprising the steps of:
1) contacting components containing the molecular sieve and a template organic matter to obtain a modified molecular sieve;
2) contacting the modified molecular sieve with a metal source solution;
3) then mixing with the carrier, molding, roasting and reducing to obtain the catalyst.
8. The method for preparing a catalyst for toluene disproportionation and transalkylation as claimed in claim 7, wherein:
the organic template agent is at least one selected from quaternary ammonium compounds, quaternary phosphorus compounds and organic amines.
9. The method for preparing a catalyst for toluene disproportionation and transalkylation as claimed in claim 8, wherein:
the quaternary ammonium compound is tetraalkylammonium halide or tetraalkylammonium hydroxide, preferably one or more of tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrapropylammonium hydroxide and tetraethylammonium hydroxide; and/or the presence of a gas in the gas,
the quaternary phosphorus compound is tetraalkyl phosphorus halide or tetraalkyl phosphorus hydroxide, preferably one or more of tetramethyl phosphorus bromide, tetraethyl phosphorus bromide, tetrapropyl phosphorus bromide and tetrabutyl phosphorus bromide; and/or the presence of a gas in the gas,
the organic amine is selected from one or more of ethylamine, propylamine and isomers thereof, isopropylamine, butylamine and isomers thereof, pentylamine and isomers thereof, hexylamine-1 and isomers thereof, hexamethylenediamine and isomers thereof, octylamine and isomers thereof, and octylamine and isomers thereof.
10. The method for preparing a catalyst for toluene disproportionation and transalkylation as claimed in claim 7, wherein:
in the step 1), the contact temperature is 15-150 ℃, the contact time is 5-300 minutes, the solid-to-liquid ratio is (1:50) - (1:2), and the weight ratio of the organic template to the molecular sieve is 0.1-30 wt%;
preferably, the contact temperature is 20-120 ℃, the contact time is 30-240 minutes, the solid-liquid ratio is (1:20) - (1:2), and the weight ratio of the organic template to the molecular sieve is preferably 0.1-25 wt%.
11. The method for preparing a catalyst for toluene disproportionation and transalkylation as claimed in claim 7, wherein:
in the step 2), the contact time is 1-100 hours, preferably 0.5-48 hours.
12. The method for preparing a catalyst for toluene disproportionation and transalkylation as claimed in claim 7, wherein:
in the step 3), the roasting temperature is 350-600 ℃, and the roasting time is 2-10 hours; and/or the presence of a gas in the gas,
the reduction temperature is 300-600 ℃, the reduction time is 1-6 hours, and the reduction pressure is 0-20 MPa.
13. A toluene disproportionation and transalkylation catalyst prepared by the method of any one of claims 7 to 12.
14. Use of the toluene disproportionation and transalkylation catalyst of any one of claims 1 to 6 or claim 13 in toluene disproportionation and transalkylation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910976988.8A CN112657540A (en) | 2019-10-15 | 2019-10-15 | Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910976988.8A CN112657540A (en) | 2019-10-15 | 2019-10-15 | Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112657540A true CN112657540A (en) | 2021-04-16 |
Family
ID=75399804
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910976988.8A Pending CN112657540A (en) | 2019-10-15 | 2019-10-15 | Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112657540A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532306A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Composite catalyst for transalkylation and preparation method and application thereof |
| CN116216734A (en) * | 2023-01-10 | 2023-06-06 | 昆明理工大学 | P-ZSM-5 molecular sieve and preparation method and application thereof |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1164440A (en) * | 1996-02-09 | 1997-11-12 | 法国石油公司 | Use of composite catalyst for dismutation and/or transalkylation of alkylaromatic hydrocarbons |
| CN1182376A (en) * | 1995-04-27 | 1998-05-20 | 恩格尔哈德公司 | Method of abating Nox and preparation of catalytic material therefor |
| US6040490A (en) * | 1995-03-06 | 2000-03-21 | Toray Industries, Inc. | Process for producing aromatic compounds by dealkylation, transalkylation, or disproportionation |
| CN103120947A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon |
| CN103120952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Disproportionation and alkyl transfer catalyst and preparation method thereof |
| CN105709856A (en) * | 2016-04-15 | 2016-06-29 | 中国石油大学(华东) | Method for preparing catalyst used for modulating distribution of metal on molecular sieve |
| CN106582801A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Toluene disproportionation and transalkylation catalyst and starting method thereof |
| CN108499597A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and transalkylation and preparation method thereof |
| CN109794284A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院大连化学物理研究所 | A kind of molecular screen material, preparation method and the application of surface enrichment metal |
-
2019
- 2019-10-15 CN CN201910976988.8A patent/CN112657540A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6040490A (en) * | 1995-03-06 | 2000-03-21 | Toray Industries, Inc. | Process for producing aromatic compounds by dealkylation, transalkylation, or disproportionation |
| CN1182376A (en) * | 1995-04-27 | 1998-05-20 | 恩格尔哈德公司 | Method of abating Nox and preparation of catalytic material therefor |
| CN1164440A (en) * | 1996-02-09 | 1997-11-12 | 法国石油公司 | Use of composite catalyst for dismutation and/or transalkylation of alkylaromatic hydrocarbons |
| CN103120947A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Catalyst for preparing mononuclear aromatics by using polycyclic aromatic hydrocarbon |
| CN103120952A (en) * | 2011-11-18 | 2013-05-29 | 中国石油化工股份有限公司 | Disproportionation and alkyl transfer catalyst and preparation method thereof |
| CN106582801A (en) * | 2015-10-19 | 2017-04-26 | 中国石油化工股份有限公司 | Toluene disproportionation and transalkylation catalyst and starting method thereof |
| CN105709856A (en) * | 2016-04-15 | 2016-06-29 | 中国石油大学(华东) | Method for preparing catalyst used for modulating distribution of metal on molecular sieve |
| CN108499597A (en) * | 2017-02-23 | 2018-09-07 | 中国石油化工股份有限公司 | Catalyst for toluene disproportionation and transalkylation and preparation method thereof |
| CN109794284A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院大连化学物理研究所 | A kind of molecular screen material, preparation method and the application of surface enrichment metal |
Non-Patent Citations (2)
| Title |
|---|
| 朱海波: "硬软模板法合成介孔沸石及其催化性能的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, no. 7, 15 July 2010 (2010-07-15), pages 146 * |
| 朱海波: "硬软模板法合成介孔沸石及其催化性能的研究", 《中国博士学位论文全文数据库 工程科技Ⅰ辑》, vol. 1, no. 7, pages 146 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115532306A (en) * | 2021-06-30 | 2022-12-30 | 中国石油化工股份有限公司 | Composite catalyst for transalkylation and preparation method and application thereof |
| CN115532306B (en) * | 2021-06-30 | 2024-01-30 | 中国石油化工股份有限公司 | Composite catalyst for alkyl transfer and preparation method and application thereof |
| CN116216734A (en) * | 2023-01-10 | 2023-06-06 | 昆明理工大学 | P-ZSM-5 molecular sieve and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI478768B (en) | Catalysts and methods for the production of light aromatics and light alkanes from hydrocarbon feedstocks | |
| CN101348733B (en) | Method for producing light arene and light alkane from hydrocarbon raw material | |
| CN101596462B (en) | Hydroisomerizaion catalyst and preparation method thereof | |
| CN111517906B (en) | Hydrocarbon conversion process using metal carbide nanomaterial catalyst | |
| EP3356035A1 (en) | Process for producing aromatics from a heavy hydrocarbon feed | |
| CN101428235B (en) | Regeneration method of molecular sieve catalysts | |
| CN112657540A (en) | Toluene disproportionation and transalkylation catalyst, and preparation method and application thereof | |
| CN101347742A (en) | Catalyst for preparing light aromatics and light paraffins using hydrocarbons as raw materials | |
| CN113881457A (en) | Method for treating distillate oil rich in aromatic hydrocarbon | |
| CN107398294B (en) | Preparation method and application of modified binder-free ZSM-11 molecular sieve catalyst | |
| CN110498725B (en) | Solid acid catalyzed alkylation method | |
| CN111097485A (en) | Catalyst for catalyzing diesel oil hydrogenation conversion, preparation method and application thereof | |
| CN104549456A (en) | Heavy aromatic lightening catalyst and preparation method thereof | |
| CN106669805A (en) | Low-carbon alkane isomerization catalyst and preparation method thereof | |
| CN111097484A (en) | Hydrocracking catalyst for producing high-quality lubricating oil base oil and preparation method and application thereof | |
| CN111097487A (en) | Catalyst for catalyzing diesel oil hydrogenation modification and preparation method and application thereof | |
| KR20210045351A (en) | Method for converting heavy reformate to BTX on metal-impregnated ZSM-5 and mesoporous mordenite zeolite composite catalyst | |
| CN110465327B (en) | High-activity heavy aromatic light catalyst and preparation method thereof | |
| CN112657539B (en) | Selective hydrocracking catalyst for polycyclic aromatic hydrocarbon and preparation method and application thereof | |
| CN113042097B (en) | Molecular sieve catalyst, preparation method and application thereof | |
| JP2013221016A (en) | Metal-containing zeolite catalyst, and method for producing unsaturated hydrocarbons using the catalyst | |
| CN107345154A (en) | A kind of method for hydrogen cracking of poor ignition quality fuel | |
| CN107754846B (en) | The reformate olefin-reducing catalyst for aromatic hydrocarbons of long-term operation | |
| CN116060122B (en) | Hydrocracking catalyst and preparation method and application thereof | |
| CN115212919B (en) | Catalyst containing ZSM-5/MOR eutectic zeolite and preparation method and application thereof |
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 |