CN111170817B - High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol - Google Patents

High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol Download PDF

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CN111170817B
CN111170817B CN202010055409.9A CN202010055409A CN111170817B CN 111170817 B CN111170817 B CN 111170817B CN 202010055409 A CN202010055409 A CN 202010055409A CN 111170817 B CN111170817 B CN 111170817B
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carbon olefin
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CN111170817A (en
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李忠
付廷俊
邵娟
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Taiyuan University of Technology
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    • 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
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    • 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
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • 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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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • C07C2529/072—Iron group metals or copper
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    • 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 provides a catalytic reaction process for preparing aromatic hydrocarbon from methanol with high stability and high selectivity, which comprises the steps of tabletting and crushing a special low-carbon olefin catalyst prepared from methanol and a special low-carbon olefin aromatization catalyst respectively, and screening particles of 80-100 meshes according to the proportion that the low-carbon olefin catalyst prepared from methanol is: the low-carbon olefin aromatization catalyst is filled in a fixed bed reactor in an upper and lower sectional manner respectively according to the mass ratio of 1: 1-1: 8, and then methanol aromatization reaction is carried out under certain reaction conditions. The process has the advantages of simple filling process of the catalyst, easy operation, high catalytic stability of the whole catalyst bed layer and high selectivity of aromatic hydrocarbon in the reaction process, wherein the service life of the catalyst is 8-10 times of that of the traditional one-step method, and the BTX selectivity can be improved by 20%.

Description

High-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol
Technical Field
The invention relates to a fixed bed reaction process for preparing aromatic hydrocarbon from methanol with high stability and high selectivity, a catalyst thereof and a preparation technology of the catalyst.
Background
Aromatic hydrocarbons, including benzene, toluene and xylene (BTX), are important chemical basic materials, widely used for synthetic fibers, synthetic resins and various fine chemicals; with the development of the chemical industry, the demand for aromatic hydrocarbons in the market is very vigorous at present. The main source of the aromatic hydrocarbon is a petroleum-based production process, and only a small part of the aromatic hydrocarbon is coal tar from coal chemical industry, so that the aromatic hydrocarbon production has great dependence on petroleum. However, petroleum resources are in short supply and coal resources are rich in China, and coal-based synthetic methanol is used as a mature coal chemical technology, so that the methanol production capacity far exceeds the actual demand.
Based on the fact that the aromatic hydrocarbon is prepared by methanol conversion, the dependence of aromatic hydrocarbon production on petroleum raw materials can be reduced, a practical and feasible technical path can be found for the methanol with surplus domestic capacity, and deep conversion, cleanness and efficient utilization of coal resources are realized. At present, the technology for preparing aromatic hydrocarbon from methanol with independent intellectual property rights in China mainly comprises a fluidized bed methanol-to-aromatic hydrocarbon preparation technology of the Qinghua university, a two-section fixed bed methanol-to-aromatic hydrocarbon preparation technology of Shanxi coal chemical institute and the like, and the process for preparing aromatic hydrocarbon by direct aromatization of methanol is urgently needed to be developed and applied.
Chinese patent CN101823929A discloses a system and process for preparing aromatic hydrocarbons by converting methanol or dimethyl ether, which improves the yield and selectivity of aromatic hydrocarbons by separating and recycling the products of the aromatization process of methanol or dimethyl ether. Compared with the technology for preparing aromatic hydrocarbon by fluidized bed methanol of the Qinghua university, the technology for preparing aromatic hydrocarbon by fixed bed methanol has better operation and lower cost.
Chinese patent CN1880288A proposes a two-stage fixed bed reaction process, in which methanol is catalytically converted into a product mainly comprising aromatic hydrocarbon through a first stage reaction, and the product is cooled and separated to obtain a gas phase product of low carbon hydrocarbon and a liquid phase product C 5+ Hydrocarbons, of which the liquid phase product C 5+ The hydrocarbons are extracted and separated to obtain aromatic hydrocarbons and non-aromatic hydrocarbons. The gas phase product low carbon hydrocarbon enters a second stage reactor to obtain a second stage reaction product, and finally the second stage liquid phase product and the first stage liquid phase product C are subjected to gas-liquid separation 5+ The hydrocarbons are mixed. The process needs two stages of reactors, the investment of reaction equipment is large, the requirements on devices and the process are high, intermediate products need to be separated for many times, and the process is complicated. The aromatization catalyst is used in both reactors, and its catalytic stability is poor and not mentioned in the patent.
Chinese patent CN104496743A proposes a method for preparing aromatic hydrocarbons by methanol conversion in a fixed bed reactor, in the same fixed bed reactor, the lower layer is a low-carbon olefin aromatization catalyst, and the upper layer is a catalyst for preparing low-carbon olefins by methanol conversion, thereby forming a catalyst combination unit, and a plurality of (3-7) catalyst combination units are arranged in the fixed bed reactor. Raw material methanol, circulating LPG and water vapor are mixed and then enter the fixed bed reactor from the top of the fixed bed reactor, and react in the first catalyst combination unit to generate a mixture of water and aromatic hydrocarbon. Methanol enters the fixed bed reactor from a material inlet positioned on the side wall of the reactor, and forms a reaction raw material of the next catalyst combination unit together with a reaction product from the previous catalyst combination unit. In the multiple catalyst combination units related in the patent, the catalyst filling operation process is complex, and the total catalyst filling bed layer is too high; the circulating LPG needs to be separated by a subsequent separation system and then recycled, so that the requirements on equipment and the process are high; the macromolecular aromatic hydrocarbon product generated by the previous catalyst combination unit can generate further cracking reaction and poison the next catalyst combination unit, so that the carbon deposition of the next catalyst combination unit is easily inactivated, the improvement of the catalytic stability and the aromatic hydrocarbon selectivity is not facilitated, and the related catalytic stability is not mentioned.
From the above analysis of the prior art, the technology for preparing aromatic hydrocarbon by methanol has been advanced to some extent in recent years, but the technology still has the problems of poor catalyst stability and low aromatic hydrocarbon selectivity.
Disclosure of Invention
The invention aims to provide a fixed bed reaction process for preparing aromatic hydrocarbon from methanol, a catalyst thereof and a preparation technology of the catalyst, wherein the fixed bed reaction process is easy to operate and easy to realize industrialization and has high stability and high selectivity.
The invention provides a reaction process for carrying out upper and lower segment sectional filling on two catalysts, namely a low-carbon olefin catalyst prepared from methanol and a low-carbon olefin aromatization catalyst, in a fixed bed reactor.
The technical scheme of the invention is as follows:
(1) synthesis of special catalyst for preparing low-carbon olefin from methanol
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), and then adding into deionized water with certain mass, wherein the TEOS is SiO 2 Meter (1 mol TEOS corresponds to 1 mol SiO) 2 ) Aging in a water bath kettle at 60-90 ℃ for 12-48 h, and then dropwise adding NaOH solution and Al (NO) 3 ) 3 Solution, the final molar composition of each starting material being: 1 SiO 2 : 0.05~0.40 TPAOH: 0.005~0.001 Al 2 O 3 : 0.004~0.250 NaOH: 5~500 H 2 And O. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 1-5 days at 140-180 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 4-12 hours at 450-600 ℃. Then using NH 4 And carrying out ion exchange on the Cl solution, and grinding and roasting to obtain the H-type molecular sieve. In a preferred embodiment of the present invention, in the special methanol-to-low carbon olefin catalyst product prepared by the above method, SiO is present 2 /Al 2 O 3 The ratio is 200-1000, the high silicon-aluminum ratio, and the particle size is about 70-500 nm.
(2) Synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropyl ammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, aging in a water bath kettle for a period of time, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. Aging, crystallizing, centrifuging, grinding, calcining, ion exchanging, calcining again to obtain H-type molecular sieve, regulatingAl(NO 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 25-100, and the particle size is about 100-600 nm. Then, 1-5 wt% of dehydrogenation metal Zn, Ga or Ni species are loaded on the low-silica-alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst so as to improve dehydrogenation performance and aromatization performance. The aging condition is stirring in a water bath kettle at 60-90 ℃ for 12-48 h, the crystallization condition is crystallization at 140-180 ℃ for 1-5 days, the obtained product is filtered, washed, dried, ground to powder state and roasted at 450-600 ℃ for 4-12 h. In a preferred embodiment of the present invention, the SiO in the special low-carbene hydrocarbon aromatization catalyst prepared by the above method 2 /Al 2 O 3 The ratio is 25 to 100, and the particle size is about 100 to 600 nm.
(3) Methanol aromatization reaction process
The special olefin catalyst and the special aromatic hydrocarbon catalyst are respectively tableted and crushed, then the particles with the particle size of 80-100 meshes are screened, and the upper and lower segmental filling is respectively carried out in a fixed bed reactor according to the proportion of 1: 1-1: 8, namely the upper layer is filled with the special methanol-to-low carbon olefin catalyst, and the lower layer is filled with the special low carbon olefin aromatization catalyst.
The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 350-450 ℃, the pressure is 0.1-2.0 MPa, and N is 2 The flow rate is 10-80 mL.min -1 The mass airspeed is 1-6 h -1 . Cooling and separating the reaction product by a condenser (-1 ℃), storing the liquid-phase product in a liquid storage tank, layering the liquid-phase product, analyzing the distribution of the hydrocarbon product in the liquid-phase product by adopting an Shimadzu chromatograph with the model of GC-2014C, wherein the upper layer is the liquid hydrocarbon product; the gas phase products were collected with an air bag and analyzed on a Zhongkehuifen gas phase chromatograph model GC-7820 for the products of gas phase lower hydrocarbons.
Compared with the existing methanol aromatization process, the invention has the following advantages and outstanding effects:
(1) the invention provides a new evaluation mode capable of simultaneously improving the reaction stability and the aromatic hydrocarbon selectivity of preparing aromatic hydrocarbon from methanol, the filling process is simple, the operation is easy, and the industrialization can be realized;
(2) the service life of the catalyst can be effectively prolonged by adjusting the loading mass ratio of the methanol-to-olefin catalyst and the low-carbon olefin aromatization catalyst which are loaded in an upper section and a lower section, which is due to the fact that the low-carbon olefin molecules generated in the upper section after the section loading are smaller, the carbon deposition possibility of the lower section aromatization catalyst bed layer is smaller, secondary reactions of macromolecular aromatic hydrocarbon products are reduced due to the fact that the macromolecular aromatic hydrocarbon products pass through the lower section of the shorter aromatization catalyst bed layer, the stability of the whole catalyst bed layer is improved, and the service life of the catalyst is 8-10 times that of the catalyst in the traditional one-step method;
(3) the coupling of the reaction for preparing the low-carbon olefin from the methanol and the aromatization two-stage reaction of the low-carbon olefin can effectively improve the yield of liquid hydrocarbon and the selectivity of aromatic hydrocarbon, which is attributed to the fact that the low-carbon olefin is generated by the catalyst for preparing the low-carbon olefin from the methanol at the upper stage in a high selectivity mode, the low-carbon olefin is further reacted in the aromatization catalyst bed layer at the lower stage, the aromatic hydrocarbon is generated in a high selectivity mode, and most importantly, compared with the traditional one-step method, the BTX selectivity can be improved by 20%.
Drawings
FIG. 1 is a TEM schematic diagram of a methanol-to-low carbon olefin catalyst (a) and a low carbon olefin aromatization catalyst (b) according to example 1 of the present invention, wherein the particle sizes are 120 nm and 150 nm, respectively, and the particle size of the catalyst is finely controlled by adjusting the water-to-silicon ratio and the alkalinity of the prepared feed liquid.
FIG. 2 shows NH of the catalyst for preparing low carbon olefin from methanol and the aromatization catalyst of low carbon olefin according to example 1 of the present invention 3 And (4) TPD result, the methanol to low carbon olefin catalyst is a molecular sieve with high silica-alumina ratio, and the low carbon olefin aromatization catalyst is a molecular sieve with low silica-alumina ratio, so the acidity of the methanol to low carbon olefin catalyst is obviously lower than that of the low carbon olefin aromatization catalyst.
Detailed Description
The following further details embodiments of the present invention by way of specific embodiments:
example 1
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
Adding template agent tetrapropyl ammonium hydroxide (TPAOH) solution into silicon sourceAdding tetraethyl orthosilicate (TEOS) into deionized water with certain mass, wherein the TEOS is SiO 2 Meter (1 mol TEOS for 1 mol SiO 2 ) Aging in 80 deg.C water bath for 24 hr, and dropwise adding NaOH solution and Al (NO) 3 ) 3 Solution, the final molar composition of each starting material being: 1 SiO 2 : 0.25 TPAOH: 0.0023 Al 2 O 3 : 0.1 NaOH: 8.3 H 2 And O. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 1 day at 170 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 6 hours at 550 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 435 and high silicon-aluminum ratio and the particle size of about 120 nm is used as a special catalyst for preparing low-carbon olefin from methanol;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By controlling Al (NO) 3 ) 3 The drop adding amount is used for preparing the molecular sieve with low silicon-aluminum ratio and SiO 2 /Al 2 O 3 The ratio is 60, the particle size is about 150 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.25 TPAOH: 0.0167 Al 2 O 3 : 0.1 NaOH: 8.3 H 2 And O. Then, 2 wt% of dehydrogenation metal Zn species is loaded on the low silica-alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the mixture is stirred for 24 hours in a water bath kettle at the temperature of 80 ℃, the crystallization condition is that the mixture is crystallized for 1 day at the temperature of 170 ℃, and the obtained product is filtered, washed and dried, ground to a powder state and roasted for 6 hours at the temperature of 550 ℃.
The morphology of the prepared molecular sieve is characterized by TEM. The TEM analysis results show that the dedicated methanol to lower olefin catalyst and the dedicated lower carbene aromatization catalyst prepared in example 1 have particle sizes of about 120 nm and 150 nm, respectively, and the results are shown in fig. 1.
Prepared molecular sieve NH for acid performance 3 -TPD. Analytical example 1The acid performances of the prepared special low-carbon olefin catalyst prepared from methanol and the special low-carbon olefin aromatization catalyst are known, the acid performance of the special low-carbon olefin catalyst prepared from methanol is weaker than that of the special low-carbon olefin aromatization catalyst, the obtained acid performance results are shown in a figure 2, and the acid amount results are shown in a table 1.
(3) Methanol aromatization reaction process
The special low-carbon olefin catalyst prepared from methanol and the special low-carbon olefin aromatization catalyst are respectively tableted and crushed, then particles of 100 meshes are screened, and methanol aromatization reaction evaluation is carried out in a fixed bed reactor, the prepared special low-carbon olefin catalyst prepared from methanol and the special low-carbon olefin aromatization catalyst are respectively filled in the fixed bed reactor from top to bottom according to the ratio of 1:1, namely the special low-carbon olefin catalyst prepared from methanol is filled in the upper layer, and the special low-carbon olefin aromatization catalyst is filled in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 430 ℃, the pressure is 0.1 MPa, N 2 Flow rate 35 mL.min -1 The mass space velocity is 2 h -1 . Cooling and separating the reaction product by a condenser (-1 ℃) and a gas-liquid separator, storing the liquid-phase product in a liquid storage tank, layering the liquid-phase product, analyzing the hydrocarbon product distribution in the liquid-phase product by adopting an Shimadzu chromatograph with the model of GC-2014C, and analyzing the methanol conversion rate by adopting a Zhongkehuifen gas-phase chromatograph with the model of GC-7820, wherein the upper layer is a liquid hydrocarbon product and the lower layer is an unreacted mixture of methanol and water; the gas phase products were collected with an air bag and analyzed on a Zhongkehuifen gas phase chromatograph model GC-7820 for the products of gas phase lower hydrocarbons. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 2
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.4 TPAOH: 0.00125 Al 2 O 3 : 0.004 NaOH: 5 H 2 O, adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TE)OS), adding a certain mass of deionized water, aging in a water bath kettle at 90 ℃ for 16 h, and then dropwise adding NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 5 days at 140 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 12 hours at 450 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 800 and the particle size of about 100 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By controlling Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 A ratio of 25, a particle size of about 250 nm, a final molar composition of each starting material: 1 SiO 2 : 0.3 TPAOH: 0.04 Al 2 O 3 : 0.12 NaOH: 50 H 2 And O. Then, 5 wt% of dehydrogenated metal Ga species is loaded on the low silica alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst so as to improve the dehydrogenation performance and aromatization performance, the aging condition is that the dehydrogenation metal Ga species is stirred for 16 hours in a water bath kettle at 90 ℃, the crystallization condition is that the dehydrogenation metal Ga species is crystallized for 5 days at 140 ℃, the obtained product is filtered, washed and dried, and then is ground into powder and roasted for 12 hours at 450 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol to low-carbon olefin catalyst and the dedicated low-carbon olefin aromatization catalyst prepared as described above were loaded in the fixed bed reactor in a ratio of 1: 4 from top to bottom, i.e., the dedicated methanol to low-carbon olefin catalyst was loaded in the upper layer and the dedicated low-carbon olefin aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 400 ℃, the pressure is 0.5 MPa, N 2 Flow rate of 70 ml.min -1 Mass space velocity of2 h -1 . The reaction product was cooled and separated by a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 3
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.1 TPAOH: 0.005 Al 2 O 3 : 0.02 NaOH: 500 H 2 O, adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding into deionized water with certain mass, aging in a water bath kettle at 60 ℃ for 48 hours, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 3 days at 160 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 4 hours at 600 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 200 and high silicon-aluminum ratio and the particle size of about 400 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 A ratio of 25, a particle size of about 250 nm, a final molar composition of each starting material: 1 SiO 2 : 0.3 TPAOH: 0.04 Al 2 O 3 : 0.12 NaOH: 50 H 2 And O. Then loading 1 wt% of dehydrogenation metal Ni species on the low silica-alumina ratio molecular sieve as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, wherein the aging condition is stirring for 16 hours in a water bath kettle at 90 ℃, the crystallization condition is crystallization for 3 days at 160 ℃, and the obtained product is filtered, washed and driedAfter that, the mixture was ground to a powder and calcined at 600 ℃ for 4 hours, and the results of the acid amount are shown in Table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1: 2, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 450 ℃, the pressure is 1.0 MPa, N 2 Flow rate of 10 mL. min -1 The mass space velocity is 3 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 4
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.1 TPAOH: 0.001 Al 2 O 3 : 0.01 NaOH: 500 H 2 O, adding a template agent tetrapropyl ammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding into deionized water with certain mass, aging in a 70 ℃ water bath kettle for 36 h, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 1 day at 180 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 10 hours at 480 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 1000 and high silicon-aluminum ratio and the particle size of about 500 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding template agent tetrapropyl ammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), and then adding a certain amount of template agent tetrapropyl ammonium hydroxide (TPAOH)Adding NaOH solution and Al (NO) dropwise into deionized water 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 100, the particle size is about 450 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.15 TPAOH: 0.01 Al 2 O 3 : 0.012 NaOH: 400 H 2 And O. Then, 1.5 wt% of dehydrogenation metal Zn species is loaded on the low silica-alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the mixture is stirred for 36 hours in a water bath kettle at 70 ℃, the crystallization condition is that the mixture is crystallized for 1 day at 180 ℃, the obtained product is filtered, washed and dried, and then ground to be in a powder state, and the powder state is roasted for 12 hours at 450 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1:8, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 450 ℃, the pressure is 2.0 MPa, N 2 Flow rate 50 mL.min -1 The mass space velocity is 6 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 5
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.1 TPAOH: 0.0023 Al 2 O 3 : 0.01 NaOH: 500 H 2 O, adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding into deionized water with certain mass, and putting into a water bath kettle at 90 DEG CAging for 12 h, then dropwise adding NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 5 days at 140 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 6 hours at 580 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 435 and high silicon-aluminum ratio and the particle size of about 500 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 60, the particle size is about 450 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.15 TPAOH: 0.0167 Al 2 O 3 : 0.006 NaOH: 200 H 2 And O. Then, 5 wt% of dehydrogenation metal Ni species is loaded on the low silica alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the mixture is stirred for 42 hours in a water bath kettle at the temperature of 60 ℃, the crystallization condition is that the mixture is crystallized for 3 days at the temperature of 150 ℃, the obtained product is filtered, washed and dried, and then is ground into powder to be roasted for 12 hours at the temperature of 470 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1:8, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 430 ℃, the pressure is 0.1 MPa, N 2 Flow rate of 60 mL.min -1 The mass space velocity is 1 h -1 . The reaction is carried out by using a condenser (-1 ℃) and a gas-liquid separatorCooling and separating the product, and analyzing the product by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 6
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.2 TPAOH: 0.005 Al 2 O 3 : 0.25 NaOH: 10 H 2 O, adding a template agent tetrapropyl ammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding into deionized water with certain mass, aging in a water bath kettle at 90 ℃ for 48 h, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 1 day at 180 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 6 hours at 580 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 200 and high silicon-aluminum ratio and the particle size of about 150 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The drop adding amount is used for preparing the molecular sieve with low silicon-aluminum ratio and SiO 2 /Al 2 O 3 The ratio is 100, the particle size is about 250 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.05 TPAOH: 0.01 Al 2 O 3 : 0.25 NaOH: 5 H 2 And O. Then, 1 wt% of dehydrogenation metal Ga species is loaded on the low silica alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the dehydrogenation metal Ga species is stirred for 38 hours in a water bath kettle at the temperature of 80 ℃, the crystallization condition is that the dehydrogenation metal Ga species is crystallized for 3.5 days at the temperature of 150 ℃, the obtained product is filtered, washed and dried, and is ground to be in a powder state and roasted for 12 hours at the temperature of 560 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene aromatization catalyst prepared above were loaded in a fixed bed reactor in a ratio of 1: 6 from top to bottom, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 350 ℃, the pressure is 0.1 MPa, N 2 Flow rate of 10 mL.min -1 Mass space velocity of 4 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 7
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.08 TPAOH: 0.00167 Al 2 O 3 : 0.004 NaOH: 50 H 2 O, adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding a certain mass of deionized water, aging in a water bath kettle at 60 ℃ for 12 hours, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 5 days at 180 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 12 hours at 600 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 600 and high silicon-aluminum ratio and the particle size of about 150 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 40, the particle size is about 100 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.3 TPAOH: 0.025 Al 2 O 3 : 0.25 NaOH: 5 H 2 And O. Then loading 1 wt% of dehydrogenation metal Zn species on the low silica-alumina ratio molecular sieve as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, wherein the aging condition is 80 ℃ Stirring in water bath for 38 h under crystallization condition of 150 deg.C for 3.5 days, filtering, washing, drying, grinding to powder, and calcining at 600 deg.C for 8 h, wherein the acid content is shown in Table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1:1, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 350 ℃, the pressure is 2.0 MPa, and N is 2 Flow rate of 40 mL.min -1 The mass space velocity is 6 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 8
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.4 TPAOH: 0.001 Al 2 O 3 : 0.25 NaOH: 10 H 2 O, adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding into deionized water with certain mass, aging in a water bath kettle at 60 ℃ for 48 hours, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 4 days at 170 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 12 hours at 480 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the high silicon-aluminum ratio of 1000 and the particle size of about 70 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in a table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 25, the particle size is about 600 nm, and the final molar composition of each raw material is: 1 SiO 2 : 0.05 TPAOH: 0.04 Al 2 O 3 : 0.004 NaOH: 500 H 2 And O. Then 2 wt% of dehydrogenated metal Ga species are loaded on the molecular sieve with low silica-alumina ratio to be used as a low-carbon olefin aromatization catalyst to improve the dehydrogenation performance and the aromatization performance, the aging condition is that the materials are stirred for 36 hours in a water bath kettle at 70 ℃, the crystallization condition is that the materials are crystallized for 2 days at 180 ℃, the obtained product is filtered, washed and dried, and then is ground into powder to be roasted for 12 hours at 480 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1: 6, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 450 ℃, the pressure is 2.0 MPa, N 2 Flow rate of 80 mL.min -1 Mass space velocity of 2 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. On the upper partThe catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention are shown in table 2, below.
Example 9
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.1 TPAOH: 0.0025 Al 2 O 3 : 0.006 NaOH: 100 H 2 Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding a certain mass of deionized water, aging in a 70 ℃ water bath kettle for 18 hours, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 3 days at 160 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 8 hours at 500 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the high silicon-aluminum ratio of 400 and the grain diameter of about 500 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in a table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 40, the particle size is about 600 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.05 TPAOH: 0.025 Al 2 O 3 : 0.004 NaOH: 450 H 2 And O. Then, 2 wt% of dehydrogenation metal Ni species is loaded on the low silica alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the mixture is stirred for 18 hours in a water bath kettle at 70 ℃, the crystallization condition is that the mixture is crystallized for 3 days at 160 ℃, the obtained product is filtered, washed and dried, and then is ground into powder and roasted for 10 hours at 500 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene aromatization catalyst prepared above were loaded in a fixed bed reactor in a ratio of 1: 2 from top to bottom, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 400 ℃, the pressure is 1.0 MPa, N 2 Flow rate 80 mL.min -1 The mass space velocity is 6 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Example 10
(1) Synthesis of special catalyst for preparing low-carbon olefin from methanol
The final molar composition of each raw material in example 1 was adjusted to be: 1 SiO 2 : 0.4 TPAOH: 0.0025 Al 2 O 3 : 0.25 NaOH: 8 H 2 Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding a certain mass of deionized water, aging in a water bath kettle at 80 ℃ for 20 hours, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. And finally, transferring the uniformly stirred feed liquid into a crystallization kettle, crystallizing for 1 day at 180 ℃, filtering, washing and drying the obtained product, grinding the product until the powder is roasted for 5 hours at 600 ℃. Preparation of SiO 2 /Al 2 O 3 The molecular sieve with the ratio of 400 and high silicon-aluminum ratio and the particle size of about 70 nm is used as a special catalyst for preparing low-carbon olefin from methanol, and the acid amount result is shown in table 1;
(2) synthesis of specialized low-carbene hydrocarbon aromatization catalysts
Adding a template agent tetrapropylammonium hydroxide (TPAOH) solution into silicon source Tetraethoxysilane (TEOS), then adding deionized water with certain mass, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 And (3) solution. By regulating Al (NO) 3 ) 3 The dropping amount is used for preparing the molecular sieve with low silicon-aluminum ratio, SiO thereof 2 /Al 2 O 3 The ratio is 40, the particle size is about 70 nm, and the final molar composition of each raw material is as follows: 1 SiO 2 : 0.4 TPAOH: 0.025 Al 2 O 3 : 0.25 NaOH: 5 H 2 And O. Then, 2.5 wt% of dehydrogenation metal Zn species is loaded on the low silica-alumina ratio molecular sieve to be used as a low-carbene hydrocarbon aromatization catalyst to improve the dehydrogenation performance and aromatization performance, the aging condition is that the mixture is stirred for 50 hours in a water bath kettle at 70 ℃, the crystallization condition is that the mixture is crystallized for 2.5 days at 170 ℃, the obtained product is filtered, washed and dried, and then is ground to be in a powder state and is roasted for 8 hours at 500 ℃, and the acid amount result is shown in table 1.
(3) Methanol aromatization reaction process
The reaction evaluation conditions of example 1 were adjusted, and the dedicated methanol-to-low carbon olefin catalyst and the dedicated low carbene hydrocarbon aromatization catalyst prepared as described above were loaded in a fixed bed reactor in a ratio of 1:1, respectively, i.e., the dedicated methanol-to-low carbon olefin catalyst was loaded in the upper layer and the dedicated low carbene hydrocarbon aromatization catalyst was loaded in the lower layer. The reaction conditions for preparing the aromatic hydrocarbon from the methanol are as follows: the reaction temperature is 400 ℃, the pressure is 0.1 MPa, N 2 Flow rate 50 mL.min -1 Mass space velocity of 1 h -1 . The reaction product was cooled and separated using a condenser (-1 ℃) and a gas-liquid separator, and the product was analyzed by a gas chromatograph. The catalyst reaction life and aromatics selectivity results for the integrated catalytic reaction process of the invention under the above reaction conditions are shown in table 2.
Comparative example 1
The aromatization catalyst of the low-carbon olefin synthesized in the example 1 was evaluated by using the conventional fixed bed reaction evaluation process for producing aromatics from methanol, and the reaction evaluation conditions were the same as those of the example 1. The catalytic stability of the reaction for preparing aromatic hydrocarbon from methanol under the reaction condition is obviously lower than that of the example 1, and the specific catalytic performance is shown in table 3.
Comparative example 2
The aromatization catalyst of the low-carbon olefin synthesized in the example 3 was evaluated by using the conventional fixed bed reaction evaluation process for producing aromatics from methanol, and the reaction evaluation conditions were the same as those of the example 3. The catalytic stability of the reaction for preparing aromatic hydrocarbon from methanol under the reaction condition is obviously lower than that of the example 3, and the specific catalytic performance is shown in the table 3.
Comparative example 3
The aromatization catalyst of the low-carbon olefin synthesized in the example 7 was evaluated by using the conventional fixed bed reaction evaluation process for producing aromatics from methanol, and the reaction evaluation conditions were the same as those of the example 7. The catalytic stability of the reaction for preparing aromatic hydrocarbon from methanol under the reaction condition is obviously lower than that of the example 7, and the specific catalytic performance is shown in table 3.
Comparative example 4
The aromatization catalyst of the low-carbene hydrocarbon synthesized in the example 9 is evaluated by adopting a traditional fixed bed reaction evaluation process for preparing aromatic hydrocarbon from methanol, and the reaction evaluation conditions are consistent with those of the example 9. The catalytic stability of the reaction for preparing aromatic hydrocarbon from methanol under the reaction condition is obviously lower than that of the example 9, and the specific catalytic performance is shown in table 3.
TABLE 1 catalytic stability and aromatics selectivity results for methanol to aromatics reactions as referred to in examples 1-10
Figure DEST_PATH_IMAGE001
TABLE 2 catalytic stability and aromatics selectivity results for methanol to aromatics reactions related to examples 1-10
Figure 467495DEST_PATH_IMAGE002
TABLE 3 catalytic stability and aromatics selectivity results for methanol to aromatics reactions related to comparative examples 1-5
Figure DEST_PATH_IMAGE003
From the catalytic performance results of the above examples 1,3,7,9 and the comparative examples 1 to 4, it can be seen that the catalytic stability obtained by the fixed bed reaction evaluation process of the present invention is much higher than that of the conventional methanol-to-aromatics reaction, the low carbon olefin molecules generated in the upper section after the sectional loading are smaller, the carbon deposition probability in the lower aromatization catalyst bed is smaller, the secondary reaction of the macromolecular aromatic hydrocarbon product is reduced because the macromolecular aromatic hydrocarbon product passes through the shorter aromatization catalyst bed in the lower section, and the stability of the whole catalyst bed is favorably improved, and the life obtained by the fixed bed reaction evaluation process of the present invention is 8 to 10 times of the conventional one-step conversion life.

Claims (9)

1. A catalytic reaction process for preparing aromatic hydrocarbon from methanol with high stability and high selectivity is characterized in that a special catalyst for preparing low-carbon olefin from methanol and a special catalyst for aromatizing low-carbon olefin are respectively tableted and crushed, and then particles of 80-100 meshes are screened, wherein the catalytic reaction process comprises the following steps: respectively filling the low-carbon olefin aromatization catalyst in a mass ratio of 1: 1-1: 8 in a fixed bed reactor in an up-and-down sectional manner, and then carrying out N-phase hydrogenation at a reaction temperature of 350-450 ℃, a pressure of 0.1-2.0 MPa 2 The flow rate is 10-80 mL.min -1 The mass space velocity of the methanol is 1-6 h -1 Carrying out methanol aromatization reaction under the process condition of (1);
the synthesis method of the special catalyst for preparing the low-carbon olefin from the methanol comprises the following steps: adding a certain mass of template agent TPAOH into a silicon source TEOS solution, adding a certain mass of deionized water, aging for a period of time in a water bath, and then dropwise adding a NaOH solution and Al (NO) 3 ) 3 The molar composition of each component in the mixed material is as follows: 0.05-0.40 TPAOH to 0.005-0.001 Al to 1 TEOS 2 O 3 : 0.004~0.250 NaOH: 5~500 H 2 O, then uniformly stirring the mixed material, transferring the mixed material into a crystallization kettle for crystallization, drying, grinding and roasting, performing ion exchange, and performing secondary grinding and roasting to obtain the special methanol-to-low carbon olefin catalyst;
the synthesis method of the special low-carbene hydrocarbon aromatization catalyst comprises the following steps: adding TPAOH with certain mass into TEOS solution, aging in a water bath for a period of time, and then dropwise adding NaOH solution and Al (NO) 3 ) 3 Solution by regulating Al (NO) 3 ) 3 Drop dosage controlSiO in catalyst 2 /Al 2 O 3 The molar composition of each component in the mixed material is as follows: 0.05-0.40 TPAOH to 0.01-0.04 Al to 1 TEOS 2 O 3 : 0.004~0.250 NaOH: 5~500 H 2 And O, then uniformly stirring the mixed material, transferring the mixed material into a crystallization kettle for crystallization, drying, grinding and roasting, performing ion exchange, and performing secondary grinding and roasting to obtain a special low-carbene hydrocarbon aromatization catalyst intermediate, and then loading 1-5 wt% of dehydrogenation metal Zn, Ga or Ni species on the surface of the special low-carbene hydrocarbon aromatization catalyst intermediate to obtain the special low-carbene hydrocarbon aromatization catalyst.
2. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol as claimed in claim 1, wherein in the synthesis method of the special catalyst for preparing low-carbon olefin from methanol, the aging is carried out in a water bath kettle at 60-90 ℃ for 12-48 h.
3. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbons from methanol according to claim 1, wherein in the synthesis method of the special catalyst for preparing low-carbon olefins from methanol, crystallization is performed at 140-180 ℃ for 1-5 days.
4. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol according to claim 1, wherein in the synthesis method of the special catalyst for preparing low-carbon olefin from methanol, the roasting condition is roasting at 450-600 ℃ for 4-12 h.
5. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbon from methanol according to claim 1, wherein SiO in the special catalyst for preparing low-carbon olefin from methanol is 2 /Al 2 O 3 The ratio is 200-1000, and the particle size of the catalyst is 70-500 nm.
6. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbons from methanol according to claim 1, wherein in the synthesis method of the special low-carbene hydrocarbon aromatization catalyst, the aging is carried out in a water bath kettle at 60-90 ℃ for 12-48 h.
7. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbons from methanol according to claim 1, wherein in the synthesis method of the special low-carbene aromatization catalyst, crystallization is performed for 1-5 days at 140-180 ℃.
8. The high-stability and high-selectivity catalytic reaction process for preparing aromatic hydrocarbons from methanol according to claim 1, wherein in the synthesis method of the special low-carbene aromatization catalyst, the roasting condition is that the roasting is carried out for 4-12 hours at 450-600 ℃.
9. The high stability and high selectivity catalytic methanol-to-aromatics reaction process of claim 1, wherein the SiO in the dedicated low-carbene aromatization catalyst 2 /Al 2 O 3 The ratio is 25-100, and the particle size is 100-600 nm.
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