Method and device for producing aromatic hydrocarbon from oxygen-containing raw material

Abstract

The invention discloses a method and a device for producing aromatic hydrocarbon from an oxygen-containing raw material. The method comprises the following steps: introducing the oxygen-containing raw material into an olefin production unit; enabling the product of the olefin production unit to pass through an adsorption dehydration unit; feeding a product of the adsorption dehydration unit into a dry gas removal unit to remove dry gas; a product of the dry gas removal unit is fed into an aromatic hydrocarbon production unit; a product of an aromatic hydrocarbon production unit passes through a quenching unit and an aromatic hydrocarbon separation unit in sequence, two streams of materials are separated, one stream is a non-aromatic hydrocarbon material flow, and the other stream is an aromatic hydrocarbon material flow; the non-aromatic hydrocarbon material flow of the aromatic hydrocarbon separation unit is divided into at least two parts, one part is returned to the olefin production unit, and the other part is returned to the dry gas removal unit. The novel device formed by several units is used for producing the aromatic hydrocarbon from the oxygen-containing raw material, and has the advantages of strong adaptability to the oxygen-containing raw material, high aromatic hydrocarbon yield, good long-period stability and low energy consumption.

Description

Technical Field

[0001] The invention relates to the technical field of organic chemical industry, and in particular to a method and device for producing aromatic hydrocarbons using oxygen-containing raw materials. Background Art

[0002] Aromatics, especially BTX (benzene, toluene and xylene), are important organic chemical raw materials. As basic chemical products, their downstream products have been widely used in many industries such as clothing, construction, automobiles, electronics, food, and pharmaceuticals, and their use fields are almost everywhere in human life. In recent years, with the continuous development of related chemical industries, the global demand for aromatics has continued to grow.

[0003] At present, there are two main sources of aromatics in industry. One is extracted from catalytic reforming gasoline, and the other is extracted from pyrolysis gasoline as the main raw material. The common point of the two is that they are both petrochemical routes. The main problem facing this route is that its competitiveness is deeply affected by oil price fluctuations. Under the current background of low-carbon, green, safe and environmentally friendly development, the production of aromatics with low-value oxygen-containing raw materials is an important technical development direction for the future. China's oil resources are relatively scarce, but coal and biomass resources are relatively abundant. In recent years, the production cost of oxygen-containing compounds such as coal-based methanol, dimethyl ether and ethanol has been greatly reduced, and the production of bio-based products such as cellulose and lignin has gradually matured. At the same time, some oxygen-containing low-value chemicals need to find the next way out, which provides a cheap source of raw materials for the production of downstream aromatic products. Therefore, the process of converting low-value oxygen-containing raw materials into aromatics on catalysts is of great significance for the development of low-carbon and green aromatic production processes and the extension of the coal and biomass chemical industry chain.

[0004] CN103464061A discloses a fluidized bed device for preparing aromatic hydrocarbons from alkanes and a preparation method thereof. The device includes a gas inlet, a gas outlet, a gas distributor and a catalyst recovery system, and also includes a distribution plate, a heating pipe, an external overflow pipe, a catalyst inlet and a deactivated catalyst outlet, wherein: the distribution plate is placed horizontally in the device, the heating pipe is arranged below and above the distribution plate, and the heating pipe inlet and outlet are connected to the inner wall of the device, the lower opening of the external overflow pipe is connected to the bottom catalyst bed layer, the upper part of the external overflow pipe is parallel to the longitudinal direction of the device, the lower part of the catalyst inlet is connected to the left side wall of the device, and the upper part extends upward from the left side wall of the device, the upper part of the deactivated catalyst is connected to the right side wall of the device, and the lower part extends downward from the right side wall of the device. The preparation method includes: adding a catalyst while passing a gas; energizing or passing a medium into the heating pipe; passing a raw gas; separating a gas product and a catalyst; recovering the catalyst; obtaining a gas product; regenerating the catalyst; and cycling the above process.

[0005] CN108017486A discloses a method for converting raw materials containing oxygen-containing compounds into aromatic hydrocarbons, wherein the raw materials containing oxygen-containing compounds enter a catalytic conversion reaction system to obtain a reaction product rich in aromatic hydrocarbons; the reaction product rich in aromatic hydrocarbons is passed through a cooling and separation system to obtain a water phase product and an oil phase product and is discharged from the system, wherein non-aromatic hydrocarbons with a carbon content of more than 5 are returned to the catalytic conversion reaction system containing the raw materials containing oxygen-containing compounds, and at least a portion of the obtained carbon three and carbon four hydrocarbons enter a light hydrocarbon aromatization reaction system; and the light hydrocarbon aromatization reaction product is returned to the cooling and separation system to produce aromatic hydrocarbons.

[0006] CN109395674A discloses a reactor and method for directly preparing p-xylene from alcohol / ether / C3-C5 hydrocarbons. The reactor includes a fluidized bed with two feed ports at different heights, an inlet for organic matter with large molecular weight at the bottom, an inlet for materials containing alcohol / ether / C2-C5 hydrocarbons at the top, and a regeneration catalyst return port lower than the inlet for materials containing alcohol / ether / C2-C5 hydrocarbons, and a deactivated catalyst extraction port higher than the inlet for materials containing alcohol / ether / C2-C5 hydrocarbons. Organic matter with large molecular weight and materials containing alcohol / ether / C3-C5 hydrocarbons are introduced from the two inlets respectively. At a certain temperature, the free-flowing catalyst contacts and reacts with the organic matter with large molecular weight, and a thin carbon layer is coated on the catalyst surface. The acidity of the catalyst surface decreases, but there is still enough activity to crack methanol and directly generate p-xylene. When the catalyst is deactivated and regenerated, it is introduced into the fluidized bed again, and preferentially contacts with organic matter with large molecular weight.

[0007] Therefore, it is necessary to invent a new process to solve the problems of poor adaptability of oxygen-containing raw materials, low yield of aromatic products, long-term stability and high energy consumption due to the presence of a large amount of water. Summary of the invention

[0008] The key technical problems to be solved by the present invention are the poor adaptability of the process conditions in the prior art to oxygen-containing raw materials, the low yield of aromatic products, and the long-term stability and high energy consumption caused by the large amount of water. A method and device for producing aromatics from oxygen-containing raw materials are provided. The method and device for producing aromatics from oxygen-containing raw materials have the advantages of strong adaptability to oxygen-containing raw materials, high yield of aromatics, good long-term stability and low energy consumption.

[0009] In order to achieve the above object, the first aspect of the present invention provides a method for producing aromatic hydrocarbons from oxygen-containing feedstocks, the method comprising:

[0010] Step A: passing an oxygen-containing feedstock into an olefin production unit to generate a product mainly containing carbon-containing compounds, hydrogen and water;

[0011] Step B: subjecting the product of the olefin production unit to an adsorption dehydration unit to obtain a product mainly containing carbon compounds and hydrogen;

[0012] Step C: sending the product of the adsorption dehydration unit to a dry gas removal unit to remove dry gas, thereby obtaining a product mainly containing carbon compounds;

[0013] Step D: sending the product of the dry gas removal unit to the aromatics production unit to obtain a product mainly containing aromatics and non-aromatics;

[0014] Step E: the product of the aromatics production unit is successively passed through a quenching unit and an aromatics separation unit to separate two streams of materials, one of which is a non-aromatics stream and the other is an aromatics stream, wherein the aromatics stream is the final product;

[0015] Step F: dividing the non-aromatic hydrocarbon stream of the aromatic hydrocarbon separation unit into at least two parts, one of which is returned to the olefin production unit, and the other is returned to the dry gas removal unit.

[0016] The second aspect of the present invention provides an apparatus for producing aromatics from oxygen-containing feedstocks, the apparatus comprising: an olefin production unit; an adsorption dehydration unit; a dry gas removal unit; an aromatics production unit; a quenching unit and an aromatics separation unit, which are connected in series in sequence along the flow direction of the logistics, wherein the aromatics separation unit comprises an aromatics logistics outlet and at least two non-aromatics logistics outlets, wherein one non-aromatics logistics outlet is connected to the olefin production unit, and one non-aromatics logistics outlet is connected to the dry gas removal unit.

[0017] Compared with the prior art, the present invention has the advantages of:

[0018] The method for producing aromatics from oxygen-containing raw materials of the present invention comprises the following steps: the oxygen-containing raw materials are sequentially introduced into an olefin production unit, an adsorption dehydration unit, a dry gas removal unit, an aromatics production unit, a quenching unit and an aromatics separation unit; finally, the non-aromatic hydrocarbon flow of the aromatics separation unit is divided into at least two parts, one part is returned to the olefin production unit, and the other part is returned to the dry gas removal unit; the method of the present invention can improve the adaptability of oxygen-containing raw materials, maximize the conversion of raw materials, reduce the influence of water on the catalyst of the aromatics production unit, better maintain the long-term stability of the device, and maximize the efficiency of producing aromatics.

[0019] The device for producing aromatics from oxygen-containing raw materials of the present invention is a new device formed by utilizing several units. The device is used for producing aromatics from oxygen-containing raw materials and has the advantages of strong adaptability to oxygen-containing raw materials, high aromatics yield, good long-term stability and low energy consumption. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 The schematic diagram of the device for producing aromatic hydrocarbons from oxygen-containing raw materials according to the present invention.

[0021] Description of Reference Numerals

[0022] ① is the olefin production unit; ② is the adsorption dehydration unit; ③ is the dry gas removal unit; ④ is the aromatics production unit; ⑤ is the quenching unit, and ⑥ is the aromatics separation unit. DETAILED DESCRIPTION

[0023] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0024] The first aspect of the present invention provides a method for producing aromatic hydrocarbons from an oxygen-containing feedstock, the method comprising:

[0025] Step A: passing an oxygen-containing feedstock into an olefin production unit to generate a product mainly containing carbon-containing compounds, hydrogen and water;

[0026] Step B: subjecting the product of the olefin production unit to an adsorption dehydration unit to obtain a product mainly containing carbon compounds and hydrogen;

[0027] Step C: sending the product of the adsorption dehydration unit to a dry gas removal unit to remove dry gas, thereby obtaining a product mainly containing carbon compounds;

[0028] Step D: sending the product of the dry gas removal unit to the aromatics production unit to obtain a product mainly containing aromatics and non-aromatics;

[0029] Step E: the product of the aromatics production unit is successively passed through a quenching unit and an aromatics separation unit to separate two streams of materials, one of which is a non-aromatics stream and the other is an aromatics stream, wherein the aromatics stream is the final product;

[0030] Step F: dividing the non-aromatic hydrocarbon stream of the aromatic hydrocarbon separation unit into at least two parts, one of which is returned to the olefin production unit, and the other is returned to the dry gas removal unit.

[0031] In the present invention, an artificial split can be arranged at the top of the aromatic separation unit to achieve the separation of the non-aromatic hydrocarbon flow of the aromatic separation unit into at least two parts.

[0032] The method for producing aromatics from oxygen-containing raw materials of the present invention comprises the following steps: the oxygen-containing raw materials are sequentially introduced into an olefin production unit, an adsorption dehydration unit, a dry gas removal unit, an aromatics production unit, a quenching unit and an aromatics separation unit; finally, the non-aromatic hydrocarbon flow of the aromatics separation unit is divided into at least two parts, one part is returned to the olefin production unit, and the other part is returned to the dry gas removal unit; the method of the present invention can improve the adaptability of oxygen-containing raw materials, maximize the conversion of raw materials, reduce the influence of water on the catalyst of the aromatics production unit, better maintain the long-term stability of the device, and maximize the efficiency of producing aromatics.

[0033] According to a preferred embodiment of the present invention, in step F, the non-aromatic hydrocarbon stream returned to the olefin production unit accounts for 10-85% of all non-aromatic hydrocarbon streams, preferably 16-80%, for example, 16%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 68%, 70%, 75%, 80%, in terms of weight percentage; in the embodiment of the present invention, 64% is used as an example to illustrate the advantages of the present invention, but the scope of the present invention is not limited thereto; by adopting the aforementioned preferred embodiment, the efficiency of producing aromatics can be further maximized.

[0034] According to a preferred embodiment of the present invention, in step A, the catalyst used in the olefin production unit can be a commonly used olefin production catalyst, for example, a commercial alcohol dehydration catalyst, such as molecular sieves, alumina, etc., or a catalyst composition of the required active components can be synthesized as needed. The present invention has no special requirements for this and is not described in detail herein.

[0035] According to a preferred embodiment of the present invention, in step D, the catalyst used in the aromatics production unit can be a catalyst commonly used in the art, such as a commercial aromatization catalyst, or can be synthesized as needed. According to a preferred embodiment of the present invention, in step D, the catalyst used in the aromatics production unit contains, by mass percentage, 0.05-2% of auxiliary phosphorus (for example, 0.05%, 0.1%, 0.15%, 0.2%, 0.4%, 0.6%, 0.8%, 1%, 1.5%, 2%, 0.2% is used as an exemplary illustration of the advantages of the present invention in the embodiment, but the present invention is not limited to this scope), 1-20% aromatization active component and 50-95% (for example, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95%, 62% is used as an exemplary illustration in the embodiment, but it is not limited to the scope of the present invention) of a zeolite molecular sieve with a ten-membered ring channel. By adopting the above-mentioned preferred embodiment, the selectivity of aromatics can be improved.

[0036] In the present invention, there is no special requirement for the aromatization active component, and commonly used active components can be used in the present invention. For the present invention, the aromatization active component preferably contains platinum, lanthanum, zinc, gallium, copper and cerium.

[0037] In the present invention, the zeolite molecular sieve with a ten-membered ring channel may be a commonly used zeolite molecular sieve with a ten-membered ring channel, such as one or more of ZSM-22, ZSM-23, ZSM-5, EU-1, and NU-87.

[0038] In the present invention, as long as the purpose of the present invention can be achieved, there is no particular limitation on the oxygen-containing raw material. According to a preferred embodiment of the present invention, the oxygen-containing raw material is one or more of alcohol, ether, oxygen-containing polymer, cellulose and lignin.

[0039] According to a preferred embodiment of the present invention, preferably, the oxygen-containing raw material contains 80-99 weight % of organic oxygen-containing compounds (for example, 80%, 85%, 90%, 95%, 99%, 95% is used as an example to illustrate the advantages of the present invention in the embodiment, but the present invention is not limited to this range) and 1-20 weight % of water (1%, 5%, 10%, 15%, 20%, 5% is used as an example to illustrate the advantages of the present invention in the embodiment, but the present invention is not limited to this range); preferably, it is 90-98 weight % of organic oxygen-containing compounds and 2-10 weight % of water.

[0040] According to a preferred embodiment of the present invention, more preferably, the organic oxygenate includes 40-60 wt % of methanol (for example, 40%, 45%, 50%, 55%, 60%, and 45% is used as an example to illustrate the advantages of the present invention in the embodiment, but the present invention is not limited to this range) and 40-60 wt % (for example, 40%, 45%, 50%, 55%, 60%, and 50% is used as an example to illustrate the advantages of the present invention in the embodiment, but the present invention is not limited to this range) of ethanol and / or propanol.

[0041] According to a preferred embodiment of the present invention, the water content in the raw material is greater than 0.2 wt%. By adopting the above-mentioned preferred embodiment, the efficiency of producing aromatics can be further maximized.

[0042] According to a preferred embodiment of the present invention, the inlet feedstock of the aromatics production unit comes from the product of the dry gas removal unit, and the water content of the inlet feedstock is less than 1000ppm, preferably less than 600ppm. By adopting the above-mentioned preferred embodiment, the influence of water on the catalyst of the aromatics production unit can be further reduced, and the long-term stability of the device can be better maintained.

[0043] According to a preferred embodiment of the present invention, the product in step A contains 30-97% carbon-containing compounds by total mass, preferably, the rest is hydrogen and water, and the specific results vary depending on process conditions, etc. By adopting the above-mentioned preferred embodiment, the efficiency of producing aromatics can be further maximized.

[0044] According to a preferred embodiment of the present invention, the product in step D contains 1-20% ethylene, 2-50% C3-C7 light hydrocarbons, 45-85% aromatic hydrocarbons, preferably, the rest is inorganic gas, etc., based on the total mass of carbon-containing compounds, and the results vary depending on the process conditions, etc. By adopting the above-mentioned preferred embodiment, the efficiency of producing aromatic hydrocarbons can be further maximized.

[0045] According to a preferred embodiment of the present invention, the operating conditions of the olefin production unit include: a reaction temperature of 240-630°C, preferably 270-550°C (for example, 270°C, 280°C, 300°C, 320°C, 340°C, 360°C, 370°C, 380°C, 400°C, 420°C, 440°C, 460°C, 470°C, 480°C, 500°C, 520°C, 540°C, 550°C, the present invention uses 450°C as an example to illustrate the advantages of the present invention, but the present invention is not limited to this range); a pressure of 0.05-3.2MPa (for example, 0.05, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 3, etc., the present invention uses 0.3 as an example to illustrate the advantages of the present invention, but the present invention is not limited to this). By adopting the above-mentioned preferred embodiment, the adaptability to oxygen-containing feedstocks can be further improved, and the maximization of feedstock conversion can be achieved according to the changes in the feedstocks.

[0046] In the present invention, the catalyst used in the olefin production unit can be a commonly used olefin production catalyst. For the present invention, the dehydration catalyst preferably contains 50-90% by weight (for example, 50%, 60%, 70%, 80%, 90%, and 70% in the embodiment of the present invention is used as an example to illustrate the advantages of the present invention, but the present invention is not limited to this range) of an eight-membered ring or a ten-membered ring molecular sieve and 10-50% by weight (for example, 10%, 20%, 30%, 40%, 50%, and 30% in the embodiment of the present invention is used as an example to illustrate the advantages of the present invention, but the present invention is not limited to this range) of alumina.

[0047] According to a preferred embodiment of the present invention, the ten-membered ring molecular sieve is selected from ZSM-5 molecular sieve.

[0048] According to a preferred embodiment of the present invention, the operating conditions of the aromatics production unit include: a reaction temperature of 450-680°C, preferably 480-650°C (for example, 480°C, 500°C, 520°C, 540°C, 550°C, 570°C, 580°C, 600°C, 620°C, 640°C, 650°C, the present invention uses 550°C as an example to illustrate the advantages of the present invention, but the present invention is not limited to this range); a pressure of 0.1-2.8MPa (for example, 0.1, 0.5, 1.0, 1.5, 2.0, 2.5, 2.8, etc., the present invention uses 0.4 as an example to illustrate the advantages of the present invention, but the present invention is not limited thereto). By adopting the above-mentioned preferred embodiment, the maximization of the aromatics yield is further achieved.

[0049] According to a preferred embodiment of the present invention, the operating conditions of the adsorption dehydration unit include: adsorption temperature of 10-150°C, preferably 20-125°C, more preferably 40-70°C, and particularly preferably 60-65°C; adsorption pressure of 0.1-2.8MPa, preferably 0.15-2.5MPa, further preferably 0.4-0.7MPa, and particularly preferably 0.5-0.55MPa. By adopting the above-mentioned preferred embodiment, the maximum production of aromatics can be further achieved.

[0050] According to a preferred embodiment of the present invention, the operating conditions of the dry gas removal unit include: an operating temperature of 5-180°C, preferably 10-160°C, preferably 40-70°C, preferably 50-55°C; an operating pressure of 0.1-2.5MPa, preferably 0.15-2.2MPa, preferably 0.17-1.8MPa, preferably 0.18-1.2MPa. By adopting the above-mentioned preferred embodiment, the influence of water on the catalyst of the aromatics production unit is further reduced, and the long-term stability of the device is better maintained.

[0051] According to a preferred embodiment of the present invention, the operating conditions of the quenching unit include: an outlet temperature of 5-80°C, preferably 10-65°C, more preferably 50-55°C; an operating pressure of 0.1-2.2MPa, preferably 0.15-2.0MPa, more preferably 0.45-0.50MPa. By adopting the above-mentioned preferred embodiment, the maximization of the production of aromatics is further achieved.

[0052] According to a preferred embodiment of the present invention, the operating conditions of the aromatic separation unit include: outlet temperature of 0-70°C, preferably 5-65°C, preferably 50-55°C; operating pressure of 0.1-2.0MPa, preferably 0.15-2.0MPa, preferably 0.75-0.8MPa. By adopting the above-mentioned preferred embodiment, the maximization of aromatic production is further achieved.

[0053] According to a preferred embodiment of the present invention, the olefin production unit and the aromatics production unit each adopt a fixed bed, a moving bed or a fluidized bed. By adopting the above-mentioned preferred embodiment, the maximization of the production of aromatics is further achieved.

[0054] According to a preferred embodiment of the present invention, the olefin production unit and the aromatic production unit are coaxially zoned, the olefin production unit is located in the outer zone of the reactor, the aromatic production unit is located in the inner zone of the reactor, and a heat-conducting interlayer is provided between the two units. By adopting the above-mentioned preferred embodiment, the reaction temperature of the aromatic production unit can be better maintained, and efficient use of reaction heat can be achieved.

[0055] The second aspect of the present invention provides an apparatus for producing aromatics from oxygen-containing feedstocks, the apparatus comprising: an olefin production unit ①; an adsorption dehydration unit ②; a dry gas removal unit ③; an aromatics production unit ④; a quenching unit ⑤ and an aromatics separation unit ⑥, which are sequentially connected in series along the flow direction of the logistics, wherein the aromatics separation unit comprises an aromatics logistics outlet and at least two non-aromatics logistics outlets, wherein one non-aromatics logistics outlet is connected to the olefin production unit ①, and one non-aromatics logistics outlet is connected to the dry gas removal unit ③.

[0056] According to the present invention, the olefin production unit ①; the adsorption dehydration unit ②; the dry gas removal unit ③; the aromatics production unit ④; the quenching unit ⑤ and the aromatics separation unit ⑥ can each be provided with multiple outlets and multiple inlets as required, and the present invention has no special requirements for this.

[0057] According to a preferred embodiment of the present invention, the olefin production unit ① contains a bottom inlet, a top outlet and a side wall non-aromatic hydrocarbon stream inlet (generally in the middle of the side wall, but not limited to this position).

[0058] According to a preferred embodiment of the present invention, the adsorption dehydration unit ② comprises a top inlet and a bottom outlet.

[0059] According to a preferred embodiment of the present invention, the dry gas removal unit ③ contains a bottom inlet, a top outlet and a side wall non-aromatic hydrocarbon stream inlet (generally in the middle of the side wall, but not limited to this position).

[0060] According to a preferred embodiment of the present invention, the aromatics production unit ④ contains a top inlet and a bottom outlet.

[0061] According to a preferred embodiment of the present invention, the quenching unit ⑤ comprises a bottom inlet and a top outlet.

[0062] According to a preferred embodiment of the present invention, the aromatic separation unit ⑥ contains a top non-aromatic logistics outlet and a bottom aromatic logistics outlet, and the top non-aromatic logistics outlet is provided with an artificial diversion to return the non-aromatic logistics to the olefin production unit and the dry gas removal unit respectively.

[0063] The present invention provides a device for producing aromatic hydrocarbons from oxygen-containing raw materials. The new device is formed by combining several units and catalysts. The device is used to produce aromatic hydrocarbons from oxygen-containing raw materials and has the advantages of strong adaptability to oxygen-containing raw materials, high aromatic hydrocarbon yield, good long-term stability and low energy consumption.

[0064] according to Figure 1 The process shown,

[0065] The olefin production unit ① has a bottom inlet, a top outlet and a sidewall non-aromatic hydrocarbon stream inlet;

[0066] The adsorption dehydration unit ② has a top inlet and a bottom outlet;

[0067] The dry gas removal unit ③ has a bottom inlet, a top outlet, and a side wall non-aromatic hydrocarbon stream inlet;

[0068] Aromatics production unit ④ contains a top inlet and a bottom outlet;

[0069] The quenching unit ⑤ has a bottom inlet and a top outlet;

[0070] The aromatic separation unit ⑥ comprises a top non-aromatic hydrocarbon logistics outlet, a bottom non-aromatic hydrocarbon logistics outlet, and a side wall aromatic hydrocarbon logistics outlet.

[0071] The export products of the olefin production unit ① are carbon-containing compounds, hydrogen and water. After dehydration by the adsorption dehydration unit ②, the products are mainly carbon-containing compounds and hydrogen, and then enter the dry gas removal unit ③ to remove dry gas; the products after dry gas removal are mainly carbon-containing compounds, and further enter the aromatics production unit ④; the products of the aromatics production unit ④ are mainly aromatics and non-aromatic products, which are successively passed through the quenching unit ⑤ and the aromatics separation unit ⑥ to separate aromatics and non-aromatic products. An artificial diversion is set at the top of the aromatics separation unit to divide the non-aromatic products into two parts, one part of which returns to the olefin production unit ①, and the other part returns to the dry gas removal unit ③, and aromatics are the final products.

[0072] In the present invention, the total yield of aromatics is calculated as follows: total yield of aromatics = total weight of aromatics in the product / (total weight of oxygen-containing feedstock - total weight of product water).

[0073] The total dry gas yield is calculated as follows: total dry gas yield = total weight of dry gas in the product / (total weight of oxygen-containing raw materials - total weight of product water).

[0074] The weight of aromatic hydrocarbons in the product is collected and weighed by organic solvent absorption; the weight of dry gas is measured by flow meter and the total volume is determined by chromatography.

[0075] Example 1

[0076] according to Figure 1 The process shown is as follows:

[0077] 45% methanol + 50% ethanol + 5% water (all in weight percentage) are used as raw materials, and the raw materials are introduced into the bottom inlet of an olefin production unit. A fixed bed reactor and a commercial olefin production catalyst (a methanol conversion catalyst with a brand number of NKC-18 of Nankai Catalyst Factory) are used. Under the conditions of a reaction temperature of 450° C. and a pressure of 0.3 MPa, the following products are generated in the olefin production unit: by mass, 60% of carbon-containing compounds, 3% of hydrogen, and the remaining products are water and oxygen-containing inorganic gas;

[0078] Subsequently, the product generated in the olefin production unit enters the top inlet of the adsorption dehydration unit through the top outlet of the olefin production unit. After dehydration treatment, carbon-containing compounds remain, and hydrogen flows into the bottom inlet of the dry gas removal unit through the bottom outlet of the adsorption dehydration unit. The product after the dry gas is removed is a carbon-containing compound. At this time, the water content of the raw material is less than 600ppm, and then enters the top inlet of the aromatics production unit through the top outlet of the dry gas removal unit. The main components of the product are: by mass, 1% ethylene, 13% C3-C7 light hydrocarbons, 58% aromatics, and the rest are inorganic gases. The aromatics production unit adopts a fixed bed reactor and a commercial aromatization catalyst (from Example 1 of CN201510141378), and 0.2% by weight of phosphorus is added to the catalyst as an additive, and the zeolite with a ten-membered ring channel accounts for 62%; the reaction conditions are: the reaction temperature is 550°C and the pressure is 0.4MPa;

[0079] All products produced by the aromatics production unit are successively introduced into the top inlet of the quenching unit and the aromatics separation unit through the bottom outlet of the aromatics production unit. After cooling and separation, the products are non-aromatic products and aromatics, wherein aromatics are collected as the final product through the bottom aromatics logistics outlet. An artificial diversion is arranged at the top of the aromatics separation unit, and 64 weight % of the non-aromatic products are introduced into the side wall non-aromatics logistics inlet of the olefin production unit through the non-aromatics logistics outlet, and the inlet position is the midpoint of the side wall of the olefin production unit, and the remaining part is returned to the side wall non-aromatics logistics inlet of the dry gas removal unit through the non-aromatics logistics outlet, and the inlet position is the midpoint of the side wall of the dry gas removal unit;

[0080] The operating conditions of the adsorption dehydration unit include: the operating temperature is controlled at 60-65°C; the adsorption pressure is 0.5-0.55MPa.

[0081] The operating conditions of the dry gas removal unit include: operating temperature of 50-55°C; operating pressure of 0.18-1.2MPa.

[0082] The operating conditions of the quenching unit include: outlet temperature of 50-55°C; operating pressure of 0.45-0.50MPa.

[0083] The operating conditions of the aromatic separation unit include: outlet temperature of 50-55°C; operating pressure of 0.75-0.8MPa.

[0084] The preparation process of the aromatization catalyst includes: taking 50 g of HZSM-5 composite carrier, using 50 g of Pt(NH 3 ) 4 Cl 2 , 0.7 mass % phosphoric acid, 4.5 mass % of mixed rare earth chloride (whose oxide composition is 40 mass % lanthanum oxide and 60 mass % cerium oxide) solution was immersed at 25°C for 1 hour, dried at 110°C for 8 hours, and calcined at 400°C for 5 hours to obtain catalyst A.

[0085] Compared with the aromatization catalyst preparation method of Example 1, the difference is that 0.2% by weight of phosphorus is added as an auxiliary agent during the catalyst preparation process, and the addition of praseodymium oxide and neodymium oxide is reduced.

[0086] By adopting the above technical scheme, based on the carbon-based yield of oxygen-containing raw materials, the total yield of aromatics in the product is about 76%, and the dry gas is about 24%. Based on the standard that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 296 days.

[0087] Example 2

[0088] The same as Example 1, except that the non-aromatic hydrocarbon stream returned to the olefin production unit is set to account for 5% of all non-aromatic hydrocarbon streams by artificial diversion at the top of the aromatic hydrocarbon separation unit, and other conditions remain unchanged.

[0089] By adopting the above technical scheme, the total yield of aromatics in the product is 61% and the dry gas is about 39% based on the carbon-based yield. Assuming that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 178 days.

[0090] Example 3

[0091] The same as Example 1, except that the non-aromatic hydrocarbon stream returned to the olefin production unit accounts for 95% of all non-aromatic hydrocarbon streams, and other conditions remain unchanged.

[0092] By adopting the above technical scheme, the total yield of aromatics in the product is 67% and the dry gas is about 33% based on the carbon-based yield. Assuming that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 205 days.

[0093] Example 4

[0094] Same as Example 1, except that the reaction temperature in the olefin production unit is 670° C., and other conditions remain unchanged.

[0095] By adopting the above technical scheme, based on carbon-based yield, the total yield of aromatics in the product is 55%, and the dry gas is about 45%. Assuming that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 155 days.

[0096] Example 5

[0097] Same as Example 1, except that the reaction conditions in the aromatics production unit are: the reaction temperature is 340° C., and other conditions remain unchanged.

[0098] By adopting the above technical scheme, the total yield of aromatics in the product is 53% and the dry gas is about 47% based on the carbon-based yield. Assuming that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 216 days.

[0099] Example 6

[0100] Same as Example 1, except for the aromatization catalyst of the aromatics production unit (from Example 1 of CN201510141378), and the rest is the same as Example 1.

[0101] By adopting the above technical scheme, based on the carbon-based yield, the total yield of aromatics in the product is 70%, and the dry gas is about 30%. Based on the standard that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 180 days.

[0102] Comparative Example 1

[0103] The method of Example 1 is followed, except that the product of the olefin production unit does not pass through the adsorption dehydration unit, and all the non-aromatic hydrocarbon stream products of the aromatic hydrocarbon separation unit are returned to the dry gas removal unit.

[0104] 45% methanol + 50% ethanol + 5% water are used as raw materials, and the raw materials are introduced into the bottom inlet of the olefin production unit. A fixed bed reactor and a commercial olefin production catalyst (same as Example 1) are used. Under the conditions of reaction temperature of 450° C. and pressure of 0.3 MPa, the following products are generated in the olefin production unit: 48% carbon-containing compounds, 3% hydrogen, and the remainder is water.

[0105] Subsequently, the products generated in the olefin production unit are directly fed into the bottom inlet of the dry gas removal unit through the top outlet of the olefin production unit without dehydration. The products after degassing enter the aromatics production unit through the top outlet of the dry gas removal unit. The main components of the products are: 1% ethylene, 43% C3-C7 light hydrocarbons, 30% aromatics, and the rest are inorganic gases and water. ④ The aromatics production unit adopts a fixed bed reactor and an aromatization catalyst (from Example 1 of CN201510141378), and the zeolite molecular sieve with a ten-membered ring channel accounts for 62%; the reaction conditions are: the reaction temperature is 580°C and the pressure is 0.4MPa.

[0106] All products produced by the ④ aromatics production unit flow into the bottom inlet of the ⑤ quenching unit and the ⑥ aromatics separation unit through the bottom outlet of the aromatics production unit. After cooling and separation, the products are non-aromatic products and aromatics. Aromatics are collected as the final product through the bottom aromatics logistics outlet, and 100% of non-aromatic products return to the non-aromatics logistics inlet on the side wall of the ③ dry gas removal unit through the top non-aromatics logistics outlet.

[0107] in,

[0108] The operating conditions of the dry gas removal unit include: operating temperature of 50-55°C; operating pressure of 0.18-1.2MPa.

[0109] The operating conditions of the quenching unit include: outlet temperature of 50-55°C; operating pressure of 0.45-0.50MPa.

[0110] The operating conditions of the aromatic separation unit include: outlet temperature of 50-55°C; operating pressure of 0.75-0.8MPa.

[0111] By adopting the above technical scheme, based on the carbon-based yield, the total yield of aromatics in the product is 35%, and the dry gas yield is 65%. Assuming that the proportion of aromatics in the export of the aromatics production unit decreases by no more than 15%, the aromatics production unit can maintain continuous operation for 71 days.

[0112] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A method for producing aromatic hydrocarbons from oxygen-containing feedstocks, characterized in that: The method includes: Step A: passing an oxygen-containing feedstock into an olefin production unit to generate a product mainly containing carbon-containing compounds, hydrogen and water; Step B: subjecting the product of the olefin production unit to an adsorption dehydration unit to obtain a product mainly containing carbon compounds and hydrogen; Step C: sending the product of the adsorption dehydration unit to a dry gas removal unit to remove dry gas, thereby obtaining a product mainly containing carbon compounds; Step D: sending the product of the dry gas removal unit to the aromatics production unit to obtain a product mainly containing aromatics and non-aromatics; Step E: the product of the aromatics production unit is successively passed through a quenching unit and an aromatics separation unit to separate two streams of materials, one of which is a non-aromatics stream and the other is an aromatics stream, wherein the aromatics stream is the final product; Step F: dividing the non-aromatic hydrocarbon stream of the aromatic hydrocarbon separation unit into at least two parts, one of which is returned to the olefin production unit, and the other is returned to the dry gas removal unit.

2. The method according to claim 1, wherein: In step F, the non-aromatic hydrocarbon stream returned to the olefin production unit accounts for 10-85% of all non-aromatic hydrocarbon streams, preferably 16-80%, by weight percentage.

3. The method according to claim 1 or 2, wherein: Step D, the catalyst used in the aromatics production unit contains, by mass percentage, 0.05-2% of phosphorus as an auxiliary agent, 1-20% of an aromatization active component and 50-95% of a zeolite molecular sieve having a ten-membered ring channel; Preferably, the zeolite molecular sieve having a ten-membered ring channel is selected from one or more of ZSM-22, ZSM-23, ZSM-5, EU-1, and NU-87; Preferably, the aromatization active component contains one or more of platinum, lanthanum, zinc, gallium, copper, copper and cerium.

4. The method according to any one of claims 1 to 3, wherein: The oxygen-containing raw material is one or more of alcohol, ether, oxygen-containing polymer, cellulose and lignin; Preferably, the oxygen-containing feedstock contains 80-99 wt % of organic oxygen-containing compounds and 1-20 wt % of water; preferably 90-98 wt % of organic oxygen-containing compounds and 2-10 wt % of water; More preferably, the organic oxygenate comprises 40-60 wt% of methanol and 40-60 wt% of ethanol and / or propanol.

5. The method according to any one of claims 1 to 4, wherein: The inlet feedstock of the aromatics production unit comes from the dry gas removal unit, and the water content of the inlet feedstock is lower than 1000 ppm, preferably lower than 600 ppm.

6. The method according to any one of claims 1 to 5, wherein: The product of step A contains 30-97% carbon-containing compounds by total mass, and the remainder is hydrogen, water, and oxygen-containing inorganic gases; and / or The product in step D contains, by total mass, 1-20% of ethylene, 2-50% of C3-C7 light hydrocarbons, 45-85% of aromatic hydrocarbons, and the remainder is inorganic gas.

7. The method according to any one of claims 1 to 6, wherein: The operating conditions of the olefin production unit include: a reaction temperature of 240-630°C, preferably 270-550°C; and / or a pressure of 0.05-3.2 MPa; The catalyst contains 50-90 wt% of eight-membered ring and / or ten-membered ring molecular sieve and 10-50 wt% of alumina; Preferably, the eight-membered ring and / or ten-membered ring molecular sieve is selected from ZSM-5 molecular sieve.

8. The method according to any one of claims 1 to 7, wherein: In step D, the operating conditions of the aromatics production unit include: a reaction temperature of 450-680° C., preferably 480-650° C.; and / or a pressure of 0.1-2.8 MPa.

9. The method according to any one of claims 1 to 8, wherein: The operating conditions of the adsorption dehydration unit include: adsorption temperature of 10-150°C, preferably 20-125°C, more preferably 40-70°C, and particularly preferably 60-65°C; adsorption pressure of 0.1-2.8MPa, preferably 0.15-2.5MPa, further preferably 0.4-0.7MPa, and particularly preferably 0.5-0.55MPa; and / or The operating conditions of the dry gas removal unit include: an operating temperature of 5-180°C, preferably 10-160°C, preferably 40-70°C, preferably 50-55°C; an operating pressure of 0.1-2.5MPa, preferably 0.15-2.2MPa, preferably 0.17-1.8MPa, preferably 0.18-1.2MPa; and / or The operating conditions of the quench unit include: an outlet temperature of 5-80°C, preferably 10-65°C, more preferably 50-55°C; an operating pressure of 0.1-2.2MPa, preferably 0.15-2.0MPa, more preferably 0.45-0.50MPa; and / or The operating conditions of the aromatic separation unit include: outlet temperature of 0-70°C, preferably 5-65°C, preferably 50-55°C; operating pressure of 0.1-2.0MPa, preferably 0.15-2.0MPa, preferably 0.75-0.8MPa; and / or The olefin production unit and the aromatics production unit respectively adopt a fixed bed, a moving bed or a fluidized bed.

10. A device for producing aromatic hydrocarbons from oxygen-containing feedstocks, characterized in that: The device comprises: an olefin production unit (①); an adsorption dehydration unit (②); a dry gas removal unit (③); an aromatics production unit (④); a quenching unit (⑤) and an aromatics separation unit (⑥) which are sequentially connected in series along the flow direction of the logistics; the aromatics separation unit (⑥) comprises an aromatics logistics outlet and at least two non-aromatics logistics outlets, wherein one non-aromatics logistics outlet is connected to the olefin production unit (①), and one non-aromatics logistics outlet is connected to the dry gas removal unit (③); Preferably, The olefin production unit (①) comprises a bottom inlet, a top outlet and a sidewall non-aromatic hydrocarbon stream inlet; and / or The adsorption dehydration unit (②) comprises a top inlet and a bottom outlet; and / or The dry gas removal unit (③) comprises a bottom inlet, a top outlet and a side wall non-aromatic hydrocarbon stream inlet; and / or The aromatics production unit (④) has a top inlet and a bottom outlet; and / or The quenching unit (⑤) has a bottom inlet and a top outlet; and / or The aromatic separation unit (⑥) comprises a top non-aromatic logistics outlet and a bottom aromatic logistics outlet. The top non-aromatic logistics outlet is provided with an artificial diversion to return the non-aromatic logistics to the olefin production unit and the dry gas removal unit respectively.

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