CN109701598B - Catalyst for preparing aromatic hydrocarbon from methanol and application thereof - Google Patents
Catalyst for preparing aromatic hydrocarbon from methanol and application thereof Download PDFInfo
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Abstract
The invention relates to a catalyst for preparing aromatic hydrocarbon from methanol, which mainly solves the problem of low aromatization activity of the catalyst in the prior art. The invention adopts a methanol-to-aromatics catalyst, which comprises the following components in parts by weight: a) 0.5-10 parts of phosphorus element or its oxide; b) 1-15 parts of at least one element selected from group IIB of the periodic table or an oxide thereof; c)0.001 to 1 part of an alkaline earth metal element or an oxide thereof; d) 0.1-10 parts of copper element or its oxide; e) the technical scheme of 50-90 parts of the silicon-aluminum molecular sieve well solves the problem and can be used for industrial production of preparing aromatic hydrocarbon from methanol.
Description
Technical Field
The invention relates to an aromatization catalyst and application thereof, in particular to an aromatization catalyst for preparing aromatic hydrocarbon from methanol and application thereof.
Background
As a basic organic chemical raw material, more than 85 percent of aromatic hydrocarbons in China are produced by a petroleum route. On one hand, the shortage of petroleum and natural gas resources in China leads to the increasing production cost of aromatic hydrocarbon; on the other hand, the coal resources in China are relatively rich, and the production capacity of a large amount of coal-based methanol is finding ways. Therefore, the method for preparing aromatic hydrocarbon from methanol is a very promising technical route.
Chinese patent CN1880288A introduces a process and a catalyst for preparing aromatic hydrocarbon by methanol conversion, wherein the process takes small-grain ZSM-5 zeolite as a carrier, adopts a method of mixing with a binder (pseudo-boehmite, gamma-alumina or diatomite) and then carrying out extrusion forming, and finally loads active components of gallium and lanthanum to prepare the catalyst, wherein the catalyst is prepared under the conditions that the operation pressure is 0.1-5.0 MPa, the operation temperature is 300-460 ℃, and the airspeed of a raw material liquid is 0.1-6.0 h-1Under the condition, the reaction product is cooled and separated, the liquid phase selectivity is more than 33 percent, and the yield of the aromatic hydrocarbon in the liquid phase is more than 60 percent.
Chinese patent CN104174430B discloses a catalyst for converting alcohol ether into p-xylene and C2-C3 olefin and a preparation method thereof. The catalyst comprises a ZSM-5 molecular sieve, metal loaded on the ZSM-5 molecular sieve and a composite oxide layer wrapped outside the ZSM-5 molecular sieve and the metal, wherein the composite oxide layer consists of silicon oxide, iron oxide and magnesium oxide, and the metal is one or more of silver, zinc, manganese, molybdenum, gallium, nickel, platinum and copper. The catalyst of the invention can convert the catalyst containing water and a certain amount of higher alcohol,The methanol or dimethyl ether raw material of acid, ester, ketone or C3-C15 hydrocarbon impurities is at 0.1-3MPa, 450-520 ℃ and space velocity of 0.2-30h-1Under the condition of (3), the yield of the aromatic hydrocarbon reaches 69-80%.
Chinese patent CN103747869A reports a catalyst for the preparation of aromatic hydrocarbons and its use. Wherein the catalyst is a composition of a zeolite comprising the metals lanthanum and gallium and a lanthanum-modified binder.
Chinese patent CN103372456A reports a molecular sieve catalyst and its preparation and application. The catalyst mainly comprises a Zn, Ag, Ga and La modified HZSM-5 molecular sieve and a binder accounting for 5-50% of the total mass of the catalyst, wherein SiO in the molecular sieve2With Al2O3The molar ratio of (A) to (B) is 10 to 1000. By controlling the silica-alumina ratio of the molecular sieve, the conditions of part treatment and the like, the service life of the ZSM-5 molecular sieve catalyst on the fixed bed reactor is prolonged, and the activity of the catalyst and the selectivity of the reaction for preparing the aromatic hydrocarbon from the methanol are improved. The invention has the advantages of normal pressure, 400 ℃ and methanol airspeed of 3.0h-1Under the condition, the yield of the aromatic hydrocarbon in the product is about 60-80%. However, the reaction raw material is not 100% methanol, but 10% water.
Chinese patent CN101780417B discloses a catalyst for preparing paraxylene and low-carbon olefin by methanol conversion, a preparation method and application thereof. The catalyst provided by the invention is obtained by modifying the surface acidity and the pore structure of a zeolite molecular sieve modified by transition metal and rare earth metal by a siloxane compound. At the reaction temperature of 450 ℃, the mass space velocity of methanol is 2h-1Under the reaction conditions of (3), the yield of the aromatic hydrocarbon is about 50 percent.
US20100234658 reports a multimetallic supported zeolitic molecular sieve type aromatization catalyst. The catalyst consists of metal La, at least one metal selected from Mo, Ce and Cs, a molecular sieve and a binder. When methanol is used as raw material, the temperature is 450 ℃, the normal pressure and the weight space velocity are 9h-1Under the reaction conditions of (1), the yield of the aromatic hydrocarbon in the product reaches up to 43.0 percent, and the yield of BTX is 31.5 percent (weight of carbon base).
Chinese patent CN102294262B discloses a silicoaluminophosphate molecular sieve catalyst, a preparation method and application thereof. When the product diene is used in the reaction process of preparing olefin from methanol, the yield of the product diene is more than 82%.
At present, compared with the reaction for preparing olefin from methanol, the yield of aromatic hydrocarbon in the reaction for preparing aromatic hydrocarbon from methanol is low, and the aromatization activity of the catalyst is not high.
Disclosure of Invention
The invention aims to solve the technical problem of low aromatization activity of the existing methanol-to-aromatics catalyst and provides a novel aromatization catalyst. The catalyst has the advantage of high aromatization activity when used for preparing aromatic hydrocarbon by methanol aromatization.
In order to solve the technical problems, the technical scheme adopted by the invention is as follows: the catalyst for preparing the aromatic hydrocarbon from the methanol comprises the following components in parts by weight:
a) 0.5-10 parts of phosphorus element or its oxide;
b) 1-15 parts of at least one element selected from group IIB of the periodic table or an oxide thereof;
c)0.001 to 1 part of an alkaline earth metal element or an oxide thereof;
d) 0.1-10 parts of copper element or its oxide;
e) 50-90 parts of silicon-aluminum molecular sieve.
In the above technical solution, preferably, the content of the phosphorus element or the oxide thereof is 1 to 10 parts by weight.
In the technical scheme, the preferable group IIB element in the periodic table is ZnO and/or CdO, and the preferable element or the oxide thereof accounts for 3-15 parts by weight.
In the above technical solution, preferably, the content of the alkaline earth metal element or the oxide thereof is 0.01 to 0.5 parts by weight.
In the above technical solution, preferably, the content of the alkaline earth metal element or the oxide thereof is 0.1 to 0.5 parts by weight.
In the above technical scheme, preferably, the content of the copper element or the oxide thereof is 0.5 to 8 parts by weight.
In the above technical scheme, preferably, the content of the copper element or the oxide thereof is 4 to 7 parts by weight.
In the technical scheme, the silicon-aluminum molecular sieve containing ten-membered ring channels is selected from the silicon-aluminum molecular sieves, preferably at least one of ZSM-5, ZSM-11 and EU-1, and more preferably at least one of ZSM-5 and ZSM-11.
In the above technical scheme, preferably, the content of the silicon-aluminum molecular sieve is 60 to 90 parts by weight.
In the above technical scheme, preferably, the catalyst further comprises 0.01-1 part by weight of a halogen element.
In the above technical scheme, preferably, the catalyst further comprises 0.01 to 0.5 parts by weight of a halogen element.
In the above technical scheme, preferably, the catalyst further comprises 0.02 to 0.1 part by weight of a halogen element.
In the above embodiment, the halogen element is preferably selected from Cl and/or Br.
The preparation method of the catalyst can adopt the methods of dipping, chemical adsorption, chemical deposition, ion exchange, physical mixing and the like, and the catalyst is molded by the methods of extruding, rolling balls, tabletting, spray drying and the like.
The preparation method of the catalyst sequentially comprises the following steps: 1) dissolving acid, salt or oxide corresponding to elements in the IIB group of the periodic table, copper elements, alkaline earth metal elements and halogen in water to prepare solution I; 2) dissolving an acid or a salt corresponding to the phosphorus element in water to prepare a solution II; 3) and (3) sequentially dipping the silicon-aluminum molecular sieve with the solutions I and II or mixing the solutions I and II and then dipping the mixture with the silicon-aluminum molecular sieve to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol.
In the preparation method, after the silicon-aluminum molecular sieve is dipped in the solution I, the solution II or the mixed solution of the solution I and the solution II, the silicon-aluminum molecular sieve is dried for 8 to 24 hours at the temperature of 80 to 160 ℃, and is roasted for 2 to 10 hours at the temperature of 500 to 700 ℃ to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol.
The catalyst has better strength after being added with a proper amount of binder. The binder is selected from one or more of silica sol, aluminum sol and pseudo-boehmite.
The invention also provides a method for preparing aromatic hydrocarbon from methanol, which takes methanol as a raw material and obtains a material flow rich in aromatic hydrocarbon by the contact reaction of the methanol and the catalyst.
In the technical scheme, the reaction temperature is 350-500 ℃, and/or the reaction pressure is 0.001-1.0 MPa, and/or the mass space velocity of methanol is 0.1-5.0 h-1。
In the technical scheme, the preferable reaction temperature is 400-500 ℃, and the more preferable reaction temperature is 430-500 ℃.
In the above technical scheme, the preferable reaction pressure is 0.001 to 0.5MPa, and the more preferable reaction pressure is 0.001 to 0.2 MPa.
In the technical scheme, the preferable mass space velocity is 0.1-3.0 h-1More preferably, the space velocity is 0.5 to 2.0h-1。
The phosphorus element, the group IIB element selected from the periodic table of elements, the alkaline earth metal element and the copper element are modified on the silicon-aluminum molecular sieve with ten-membered ring together, and the aromatization activity of the catalyst for preparing the aromatic hydrocarbon from the methanol can be effectively improved through the interaction among the components. Moreover, the synergistic effect among the components is obvious, and the catalyst has good aromatization performance only when phosphorus element, elements selected from the group IIB of the periodic table of elements, alkaline earth metal elements and copper element exist. When active component halogen is added, the aromatization activity of the catalyst is obviously improved, and the yield of aromatic hydrocarbon can be improved by more than 5%. At the reaction temperature of 480 ℃, the reaction pressure of 0.01MPa and the methanol weight space velocity of 1h-1Under the condition, the catalyst is used for the reaction of preparing the aromatic hydrocarbon from the methanol, the yield of the product aromatic hydrocarbon is over 75 percent, and unexpected technical effects are achieved.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 0.006 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 120 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-1.
The catalyst was evaluated on a methanol to aromatics plant. The feeding is pure methanol, the reaction temperature is 480 ℃, the reaction pressure is 0.01MPa, and the weight space velocity of the methanol is 1h-1。
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 2 ]
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 120 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-2.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 3 ]
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 0.56 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 120 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (3) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-3.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 4 ]
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 2.8 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 120 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (3) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-4.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 5 ]
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 5.6 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 119 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-5.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 6 ]
40 g of zinc nitrate hexahydrate, 0.42 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 123 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-6.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 7 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-7.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 8 ]
40 g of zinc nitrate hexahydrate, 29 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 113 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-8.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 9 ]
40 g of zinc nitrate hexahydrate, 42 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 108 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-9.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 10 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate, 0.05 g of concentrated hydrochloric acid and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatic catalyst, namely MTA-10.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 11 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate, 0.1 g of concentrated hydrochloric acid and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-11.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 12 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate, 0.5 g of concentrated hydrochloric acid and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-12.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 13 ]
40 grams of zinc nitrate hexahydrate, 16.8 grams of copper nitrate trihydrate, 0.056 grams of calcium bicarbonate, 0.08 grams of ammonium bromide and 210 grams of water are mixed and stirred uniformly to obtain solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-13.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 14 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate, 1.4 g of concentrated hydrochloric acid and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-14.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 15 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate, 2.9 g of concentrated hydrochloric acid and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-15.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 16 ]
40 g of zinc nitrate hexahydrate, 12.6 g of copper nitrate trihydrate, 2.8 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 13.6 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (3) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-16.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 17 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-11 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-17.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ example 18 ]
40 g of zinc nitrate hexahydrate, 16.8 g of copper nitrate trihydrate, 0.056 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type EU-1 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (3) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the methanol-to-aromatics catalyst, namely MTA-18.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
[ examples 19 to 22 ]
The aromatization performance of the catalyst was evaluated under different reaction conditions using MTA-3 as the catalyst and methanol as the feedstock, and the results are shown in Table 2.
Comparative example 1
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 120 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol, wherein the catalyst is DBL-1.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
Comparative example 2
40 g of zinc nitrate hexahydrate, 0.006 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 123 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol, wherein the catalyst is DBL-2.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
Comparative example 3
40 g of zinc nitrate hexahydrate, 8.4 g of copper nitrate trihydrate, 11.2 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 118 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol, wherein the catalyst is DBL-3.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
Comparative example 4
40 g of zinc nitrate hexahydrate, 63 g of copper nitrate trihydrate, 0.006 g of calcium bicarbonate and 210 g of water are mixed and stirred uniformly to obtain a solution I. Adding 102 g of hydrogen type ZSM-5 molecular sieve into the solution I, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the modified molecular sieve. 11.3 g of diammonium hydrogen phosphate and 90 g of water are mixed and stirred uniformly to obtain a solution II. And (2) forming the modified molecular sieve, adding the formed modified molecular sieve into the solution II, uniformly mixing, heating to evaporate redundant water, and roasting at 550 ℃ for 4 hours to obtain the catalyst for preparing the aromatic hydrocarbon from the methanol, wherein the catalyst is DBL-4.
The catalyst was evaluated as in example 1.
The composition of the catalyst and the evaluation results are shown in Table 1.
TABLE 1
TABLE 2
| Reaction temperature/. degree.C | Reaction pressure/MPa | Reaction space velocity/h-1 | Aromatic hydrocarbon yield/% |
| 350 | 1 | 0.1 | 63 |
| 400 | 0.5 | 0.5 | 66 |
| 450 | 0.05 | 2 | 67 |
| 500 | 0.001 | 5 | 64 |
Claims (6)
1. The catalyst for preparing the aromatic hydrocarbon from the methanol comprises the following components in parts by weight:
a) 5-10 parts of phosphorus element or its oxide;
b) 8-15 parts of zinc element or its oxide;
c) 0.1-0.5 part of calcium element or an oxide thereof;
d) 2-8 parts of copper element or its oxide;
e) 60-90 parts of hydrogen type ZSM-5 molecular sieve.
2. The catalyst for preparing the aromatic hydrocarbon from the methanol comprises the following components in parts by weight:
a) 5-10 parts of phosphorus element or its oxide;
b) 8-15 parts of zinc element or its oxide;
c) 0.1-0.5 part of calcium element or an oxide thereof;
d) 2-8 parts of copper element or its oxide;
e) 60-90 parts of hydrogen type ZSM-5 molecular sieve; and 0.01 to 1 part of a halogen element.
3. The methanol-to-aromatics catalyst of claim 2, further comprising 0.01-0.5 parts by weight of a halogen element.
4. The catalyst for preparing aromatic hydrocarbon from methanol as claimed in claim 3, wherein the catalyst for preparing aromatic hydrocarbon from methanol further comprises 0.02-0.1 part by weight of halogen element.
5. A method for preparing aromatic hydrocarbon from methanol is characterized in that methanol is used as a raw material, and the methanol is in contact reaction with the catalyst of any one of claims 1-4 to obtain a material flow rich in aromatic hydrocarbon.
6. The method for preparing aromatic hydrocarbon from methanol according to claim 5, wherein the reaction temperature is 350-500 ℃, and/or the reaction pressure is 0.001-1.0 MPa, and/or the mass space velocity of methanol is 0.1-5.0 h-1。
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