A comprehensive utilization method for crude methanol by-produced in MTO

Abstract

The present invention relates to a comprehensive utilization method for by-product crude alcohol in MTO, including pretreatment: dehydrating the mixed by-products; catalytic hydrogenation: subjecting the dehydrated mixed by-products to catalytic hydrogenation; refining stage: rectifying and separating various products; hydrogen production stage: producing hydrogen by methanol reforming, a part of the obtained hydrogen is consumed in the catalytic hydrogenation reaction, and the other part is packaged and sold externally. This not only treats the by-products and avoids occupying the storage space in the factory area, but also can produce important chemical raw materials such as ethanol, isopropanol, and sec-butanol in addition to hydrogen, and can generate greater economic benefits.

Description

Technical Field

[0001] The present invention relates to the technical field of methanol to olefins, and specifically relates to a comprehensive utilization method for by-product crude alcohol in MTO. Background Art

[0002] Methanol to olefins (MTO) is a new C1 chemical process, which refers to a chemical technology that uses methanol synthesized from coal or natural gas as raw materials and produces low-carbon olefins through a fluidized bed reaction form similar to a catalytic cracking unit. In principle, methanol is directly contacted with a catalyst under certain temperature and pressure conditions, so that methanol is dehydrated to form dimethyl ether, and dimethyl ether and raw material methanol form an equilibrium mixture gas, and further catalytic conversion is carried out to gradually convert it into various low-carbon olefins, saturated alkanes, aromatics, aldehydes, ketones, coke and other substances. The current MTO technology features that while producing main products ethylene and propylene (about 80%), about 20% of by-products are accompanied, and the by-products are characterized by a large total amount and miscellaneous varieties.

[0003] In the by-products of MTO, after filtration and fractionation, a mixture containing 30%-40% water, about 30% methanol, and various substances such as acetaldehyde, acetone, butyraldehyde, and butanone is obtained. In industrial production, it is usually called "crude alcohol". Because each component in the crude alcohol is easy to form an azeotrope, it is difficult to separate and reuse. Usually, the by-products are dehydrated and used as fuel oil for heating the reaction kettle, resulting in a large amount of resource waste. Summary of the Invention

[0004] In order to solve the problem that the by-product crude alcohol in MTO cannot be effectively utilized, resulting in a large amount of resource waste, the present invention provides a comprehensive utilization method for by-product crude alcohol in MTO, aiming to utilize the by-product crude alcohol in MTO to generate economic benefits.

[0005] In order to achieve the above object, the technical solution of the present invention is as follows:

[0006] A comprehensive utilization method for by-product crude alcohol in MTO, comprising the following steps:

[0007] A. Pretreatment: The by-product crude alcohol in MTO is introduced into a membrane dehydration separator to remove the water contained in the crude alcohol;

[0008] B. Catalytic hydrogenation: The crude alcohol dehydrated in the pretreatment stage is fully hydrogenated in a hydrogenation reactor in the presence of a catalyst, so that the aldehydes and ketones in the crude alcohol become alcohols through hydrogenation reactions;

[0009] C. Refining stage: The crude alcohol after catalytic hydrogenation is subjected to extractive distillation to separate different products, and the products are: methanol, ethanol, isopropanol, sec-butanol;

[0010] D. Hydrogen production stage: The rectified methanol component is transferred to a reforming reactor, and water vapor is introduced for reforming to produce hydrogen. The mixed gas generated by the reaction is purified to obtain hydrogen after removing carbon dioxide.

[0011] Further, in the catalytic hydrogenation stage, a sector-shaped catalyst is used. The sector-shaped catalysts are spliced and stacked to form a catalyst column. The sector-shaped catalyst is composed of a sector-shaped aluminum foam as the carrier and loaded with nickel, copper, and zinc metal active components.

[0012] Further, the pore diameter of the sector-shaped aluminum foam is 40um - 180um, and the porosity is 80% - 90%.

[0013] Further, the sector-shaped catalyst is prepared by coprecipitation of the sector-shaped aluminum foam and a catalyst mother liquor containing nickel, copper, and zinc. The central angle of the sector-shaped catalyst is 24° - 30°, and multiple sector-shaped aluminum foams are butted to form a disc shape.

[0014] Further, the joints of every two upper and lower sector-shaped catalysts are offset. Coaxial positioning holes are provided on every two adjacent upper and lower sector-shaped catalysts, and positioning rods are inserted into the positioning holes.

[0015] Further, the molar ratio of nickel, copper, and zinc in the catalyst mother liquor is 1:10:5.

[0016] Further, the preparation and regeneration of the sector-shaped catalyst both use a catalyst treatment device. The catalyst treatment device includes a housing and a cover. An inverted "V"-shaped receiving groove is provided inside the housing. The upper end opening of the receiving groove is closed by the cover. When the cover closes the upper end opening of the receiving groove, the cross-section of the receiving groove corresponds to the sector-shaped catalyst. Through holes and overflow grooves are respectively provided at both ends of the receiving groove. A groove corresponding to the overflow groove is provided on the cover. The overflow groove and the groove are butted when the receiving groove is closed by the cover to form a circular overflow hole.

[0017] Further, a coprecipitation mother liquor tank, a TO furnace, and a washing tower are provided outside the catalyst treatment device. The TO furnace and the washing tower are connected in series. The inlet of the TO furnace and the water inlet pipe of the coprecipitation mother liquor tank are connected to the overflow hole through a first solenoid valve. The outlet of the washing tower and the water outlet pipe of the coprecipitation mother liquor tank are connected to the through hole through a second solenoid valve. A blower is provided between the TO furnace and the washing tower. A pump is provided between the water outlet pipe of the coprecipitation mother liquor tank and the second solenoid valve.

[0018] Further, distribution plates are provided at both ends inside the receiving groove. The distribution plates are sector-shaped plate bodies corresponding to the shape of the sector-shaped catalyst. Distribution holes are evenly distributed on the distribution plates, and the fluid flowing through the distribution plates is in a turbulent state.

[0019] Furthermore, there are at least two distribution plates in each end of the accommodation groove. There is a spacing between adjacent distribution plates, and the distribution holes on adjacent distribution plates are offset.

[0020] Through the above technical solutions, the beneficial effects of the present invention are as follows:

[0021] A comprehensive utilization method of by-product crude alcohol in MTO of the present invention can reasonably process the by-product crude alcohol in MTO. Not only are the by-products treated to avoid occupying the storage space in the factory area, but also in addition to hydrogen, important chemical raw materials such as ethanol, isopropanol, and sec-butanol can be produced, which can generate great economic benefits.

[0022] The present invention uses a special catalyst for the deep catalytic hydrogenation reaction of a mixture of alcohols, aldehydes, and ketones. This catalyst is different from conventional catalysts and has good catalytic effects.

[0023] The fan-shaped catalyst of the present invention is simple to manufacture, convenient and fast to use, and is not prone to problems such as coking and carbon deposition during production.

[0024] In the present invention, the same set of catalyst treatment device is used both in the preparation of the catalyst and in the subsequent regeneration treatment, which can greatly reduce the equipment cost. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] Figure 1 is a schematic structural view of the fan-shaped catalyst of the present invention;

[0026] Figure 2 is a schematic structural view of the catalyst column formed by stacking the fan-shaped catalysts of the present invention;

[0027] Figure 3 is a schematic structural view of the catalyst treatment device of the present invention connected to the coprecipitation mother liquor tank, TO furnace, and washing tower;

[0028] Figure 4 is a schematic structural view of the catalyst treatment device of the present invention;

[0029] Figure 5 is a left cross-sectional view of the catalyst treatment device of the present invention.

[0030] The reference numerals in the drawings are: 1, fan-shaped catalyst; 2, catalyst column; 3, housing; 4, cover body; 5, accommodation groove; 6, through hole; 7, overflow groove; 8, coprecipitation mother liquor tank; 9, TO furnace; 10, washing tower; 11, first solenoid valve; 12, second solenoid valve; 13, pump; 14, distribution plate; 15, positioning hole; 16, positioning rod. DETAILED DESCRIPTION OF THE INVENTION

[0031] The present invention will be further described below in conjunction with the drawings and specific embodiments:

[0032] It should be noted that the directional terms such as "front", "rear", "left", "right", "upper", "lower", "bottom surface" and "top surface" used in the following description refer to the directions in the attached drawings, and the terms "inner" and "outer" refer to the directions towards or away from the geometric center of a specific component respectively.

[0033] A comprehensive utilization method for MTO by-product crude alcohol, comprising the following steps:

[0034] A. Pretreatment: The MTO by-product crude alcohol is introduced into a membrane dehydration separator to remove the water contained in the crude alcohol.

[0035] B. Catalytic hydrogenation: The crude alcohol after dehydration in the pretreatment stage is fully hydrogenated in a hydrogenation reactor in the presence of a catalyst, so that the aldehydes and ketones in the crude alcohol are converted into alcohols through hydrogenation reactions.

[0036] C. Refining stage: The crude alcohol after catalytic hydrogenation is subjected to extractive distillation to separate out different products, and the products are: methanol, ethanol, isopropanol, and sec-butanol, wherein ethanol, isopropanol, and sec-butanol are all for external sale.

[0037] D. Hydrogen production stage: The methanol component after distillation is transferred to a reforming reactor, and steam is introduced for reforming hydrogen production. The mixed gas generated by the reaction is purified to obtain hydrogen after removing carbon dioxide. A part of the obtained hydrogen is used for the reaction consumption in step B, and the other part is packaged for external sale.

[0038] Calculated based on the comprehensive treatment of 10,000 tons of crude alcohol per year, about 4.9 million standard cubic meters of hydrogen can be produced annually. 2 million standard cubic meters of hydrogen are used for the self-use of this project and other production activities of this enterprise, and the remaining 2.9 million standard cubic meters of hydrogen are for external sale. Because the hydrogen produced is for self-use and can be used as it is produced, the cost of purchasing external products and the storage and transportation costs are reduced. Not only are the by-products treated, avoiding occupying the storage space in the factory area, but also in addition to hydrogen, important chemical raw materials such as ethanol, isopropanol, and sec-butanol can be produced, which can generate greater economic benefits.

[0039] As Figure 1-2 shown, in the catalytic hydrogenation stage, a sector-shaped catalyst 1 is used. The sector-shaped catalysts 1 are spliced and stacked to form a catalyst column 2. The sector-shaped catalyst 1 is composed of a sector-shaped foam aluminum as a carrier and loaded with nickel, copper, and zinc metal active components. The sector-shaped foam aluminum is an open-cell foam aluminum, and the inner pores of the sector-shaped foam aluminum are interconnected to form channels.

[0040] The inner pore diameter of the sector-shaped foam aluminum is 40um - 180um, and the porosity is 80% - 90%.

[0041] The sector-shaped catalyst 1 is prepared by coprecipitation of sector-shaped aluminum foam and a catalyst mother liquor containing nickel, copper, and zinc. The central angle corresponding to the sector-shaped catalyst is 24°-30°, and multiple sector-shaped aluminum foams are butted to form a disc shape.

[0042] The joints of every two upper and lower layers of the sector-shaped catalysts 1 are staggered. Coaxial positioning holes 15 are provided on every two adjacent upper and lower sector-shaped catalysts 1. A positioning rod 16 is inserted into the positioning holes. The positioning rod 16 penetrates through two adjacent upper and lower sector-shaped catalysts 1 or the positioning rod 16 penetrates through the catalyst column 2 from top to bottom. When the positioning rod penetrates through two adjacent upper and lower sector-shaped catalysts 1, the length of the positioning rod is equal to twice the thickness of the sector-shaped catalyst 1. When the positioning rod penetrates through the catalyst column 2 from top to bottom, the length of the positioning rod is greater than the height of the catalyst column 2.

[0043] In the field of catalytic hydrogenation, the hydrogenation efficiency is the foundation of production. Therefore, the research directions of those skilled in the art are to increase the specific surface area of the catalyst, select more efficient active centers, and improve the conversion rate, etc. The generally recognized easiest and most effective means is to increase the specific surface area of the catalyst. Therefore, those skilled in the art all conduct research by increasing the specific surface area of the catalyst and have currently reached the mesoporous (2nm-50nm) field.

[0044] In the prior art, small particle spherical catalysts need to be supported by porcelain balls and pressed by porcelain balls, otherwise the problem of the catalyst being blown away by the gas flow will occur. Another problem is that although the existing catalyst itself has a very large specific surface area, because the pores inside the catalyst are small and the gaps between adjacent catalysts are large, the reaction gas is difficult to enter the pores inside the catalyst. When there are both large channels (gaps between adjacent catalysts) and mesopores (pores inside the catalyst), the reaction gas mainly passes through the gaps between adjacent catalysts and enters the catalyst interior less. This results in the reaction gas mainly reacting on the surface of the catalyst, and the catalytic area of the catalyst for catalytic hydrogenation is relatively small, causing waste of the catalytic effect. Although mesoporous materials have a very large specific surface area, the pore diameter of the mesopores is already in the same order of magnitude as the molecular diameter. The molecular diameter is about 0.5nm (common gases)-1.5nm (organic matter fractions at 300-500°). Such mesopores not only are not conducive to the passage of the reaction gas but also are very likely to form carbon deposits and cause blockages, resulting in the need to stop the reaction every once in a while for catalyst decoking.

[0045] The sector-shaped catalyst 1 can be conveniently installed and used in the reactor and can fit in with the inner wall of the reactor. Moreover, because the inner holes of the foamed aluminum form a three-dimensional network structure, it has a certain shape and strength. It does not require the use of expanded clay for support and compression, and will not cause displacement and catalyst loss. Even each sector-shaped catalyst can be strengthened by mechanical connection. If various common problems in catalytic hydrogenation occur during the reaction, it can be more convenient to skim the catalyst. It is only necessary to remove the top layer of the sector-shaped catalyst 1. The skimming operation can be completed quickly to improve efficiency.

[0046] The fan-shaped catalyst 1 of the present invention uses foamed aluminum as a carrier, with uniform pores and a larger pore size than that of existing catalysts. Although the specific surface area is smaller than that of traditional catalysts, the fan-shaped catalyst 1 of the present invention can allow all the reaction gases to pass through the pores inside the catalyst, thereby increasing the catalytic area of ​​the reaction gases. Moreover, because the pores inside the foamed aluminum are irregularly shaped channels, the channel pore size is about 40-180um, and the porosity is 80%-90%, which is suitable for the reaction gases to pass through. When the reaction gases pass through the channels, they collide with the channel walls, thereby enhancing the contact opportunities between the reaction gases and the catalysts. All the reaction gases flow through the inner pore channels of the fan-shaped catalysts, with a fast circulation speed, which can quickly take away the reaction heat, is not prone to coking and carbon deposition, and eliminates the disadvantages of traditional particle catalysts. In other words, the present invention uses a catalyst with a smaller specific surface area than that of traditional catalysts, but achieves a better catalytic effect.

[0047] The molar ratio of nickel, copper and zinc in the catalyst mother solution is 1:10:5.

[0048] like Figure 3-5 As shown, the preparation and regeneration of the fan-shaped catalyst 1 both use a catalyst processing device, which includes a shell 3 and a cover 4. The shell 3 is a rectangular box with an opening upward. A "V"-shaped receiving groove 5 is provided inside the shell 3 to accommodate the fan-shaped catalyst 1. The upper end opening of the receiving groove 5 is closed by the cover 4. One side of the cover 4 is hinged to the shell 3 via a hinge shaft, and the other side is detachably connected to the shell 3. When the cover 4 closes the upper end opening of the receiving groove 5, the cross-section of the receiving groove 5 corresponds to the fan-shaped catalyst 1. There is a spacing between the two ends of the receiving groove 5 and the shell 3. A through hole 6 and an overflow groove 7 are respectively provided at both ends of the receiving groove 5. The through hole 6 is connected to the lower end of the left end face of the receiving groove 5, and the overflow groove 7 is located at the upper end of the right end face of the receiving groove 5. A groove corresponding to the overflow groove 7 is provided on the cover. The groove of the overflow groove 7 is connected to each other when the receiving groove 5 is closed by the cover 4 to form a circular overflow hole, and the overflow hole can be connected to a pipeline.

[0049] Outside the catalyst treatment device, there are a coprecipitation mother liquor tank 8, a TO furnace 9 and a washing tower 10. Among them, the TO furnace 9 is connected in series with the washing tower 10. The inlet of the TO furnace 9 and the water inlet pipe of the coprecipitation mother liquor tank 8 are connected to the overflow hole through a first electromagnetic valve 11. The air outlet of the washing tower 10 and the water outlet pipe of the coprecipitation mother liquor tank 8 are connected to the through hole 6 through a second electromagnetic valve 12. There is a fan between the TO furnace 9 and the washing tower 10. A pump 13 is provided between the water outlet pipe of the coprecipitation mother liquor tank 8 and the second electromagnetic valve 12. Both the first electromagnetic valve 11 and the second electromagnetic valve 12 are two-position three-way electromagnetic valves. The pump 13 is a chemical pump in industrial production and a small circulating pump in the laboratory. The opening of the water inlet pipe of the coprecipitation mother liquor tank 8 is higher than the upper opening of the coprecipitation mother liquor tank 8. That is, when preparing the sector catalyst, when the catalyst mother liquor flows back to the coprecipitation mother liquor tank 8, it falls from a high place into the coprecipitation mother liquor tank 8. When the pump rotates in the reverse direction, the catalyst mother liquor in the catalyst treatment device can be pumped back into the coprecipitation mother liquor tank 8.

[0050] Distribution plates 14 are provided at both ends inside the accommodation tank 5. The distribution plates 14 are sector-shaped plate bodies that match the shape of the sector catalyst 1. Distribution holes are evenly distributed on the distribution plates 14. The fluid flowing through the distribution plates 14 is in a turbulent state. The distribution plates 14 make the fluid (catalyst mother liquor or regenerated air flow) evenly distributed in the accommodation tank 5 and uniformly enter the sectoral aluminum foam or the sector catalyst.

[0051] There are at least two distribution plates 14 at each end of the accommodation tank 5. There is a spacing between two adjacent distribution plates 14, and the distribution holes on two adjacent distribution plates 14 are staggered.

[0052] The catalyst treatment device of the present invention can produce and regenerate multiple sector catalysts at one time, and only by switching the first electromagnetic valve and the second electromagnetic valve can the functions of the catalyst treatment device for producing the sector catalyst and regenerating the sector catalyst be changed.

[0053] Example 1:

[0054] Select sectoral aluminum foam with a pore size of 40 - 180 um and a porosity of 80% - 90%, place it in a muffle furnace, heat it to 300 °C, and calcine it for 4 hours under the protection of an inert gas.

[0055] Preparation of the catalyst mother liquor: Take 58 g of nickel nitrate hexahydrate, 375 g of copper nitrate, and 189 g of zinc nitrate, add them to 5000 ml of deionized water, and stir for 2 hours to obtain the catalyst mother liquor.

[0056] Sector-shaped aluminum foam filling: The sector-shaped aluminum foam is filled into the catalyst treatment device and sealed with a cover. Under the stirring state, pump 13 is started to circulate the catalyst mother liquor in the catalyst treatment device and the co-precipitation mother liquor tank 8, so that the sector-shaped aluminum foam is immersed in the catalyst mother liquor, and the catalyst mother liquor flows through the inner holes of the sector-shaped aluminum foam. Circulate for 1 hour at 20 - 60 °C. In this embodiment, the diameter of the sector-shaped aluminum foam is 100 mm, the thickness is 10 mm, and the height of the prepared catalyst column is 200 mm.

[0057] Co-precipitation and aging: While maintaining the stirring state in the co-precipitation mother liquor tank 8, an excessive amount of ammonium bicarbonate aqueous solution is slowly added dropwise to the co-precipitation mother liquor tank 8. After the addition is completed, pump 13 makes the mother liquor continue to circulate for 2 hours.

[0058] Drying: Take out the sector-shaped aluminum foam, dry it at 200 °C, and then calcine it at 430 °C for 2 hours to obtain the sector-shaped catalyst 1 for aldehyde-ketone hydrogenation.

[0059] Example Two:

[0060] Select sector-shaped aluminum foam with a pore size of 40 - 120 um and a porosity of 80% - 85%. Place it in a muffle furnace and heat it to 300 °C and calcine it for 4 hours under inert gas protection.

[0061] Preparation of the catalyst mother liquor: Take 58 g of nickel nitrate hexahydrate, 375 g of copper nitrate, and 189 g of zinc nitrate, add them to 500 ml of deionized water, and stir for 2 hours to obtain the catalyst mother liquor.

[0062] Sector-shaped aluminum foam filling: The sector-shaped aluminum foam is filled into the catalyst treatment device and sealed with cover 4. Under the stirring state, pump 13 is started to circulate the catalyst mother liquor in the catalyst treatment device and the co-precipitation mother liquor tank 8, so that the sector-shaped aluminum foam is immersed in the catalyst mother liquor, and the catalyst mother liquor flows through the inner holes of the sector-shaped aluminum foam. Circulate for 1 hour at 20 - 60 °C. In this embodiment, the diameter of the sector-shaped aluminum foam is 100 mm, the thickness is 10 mm, and the height of the prepared catalyst column is 200 mm.

[0063] Co-precipitation and aging: While maintaining the stirring state in the co-precipitation mother liquor tank 8, an excessive amount of ammonium bicarbonate aqueous solution is slowly added dropwise to the co-precipitation mother liquor tank 8. After the addition is completed, the pump makes the mother liquor continue to circulate for 2 hours.

[0064] Drying: Take out the sector-shaped aluminum foam, dry it at 200 °C, and then calcine it at 430 °C for 2 hours to obtain the sector-shaped catalyst 1 for aldehyde-ketone hydrogenation.

[0065] Example Three:

[0066] Select fan-shaped aluminum foam with a pore size of 80 - 120 um and a porosity of 85% - 90%. Place it in a muffle furnace, heat it to 300 °C, and calcine it for 4 hours under inert gas protection.

[0067] Preparation of the catalyst mother liquor: Take 58 g of nickel nitrate hexahydrate, 375 g of copper nitrate, and 189 g of zinc nitrate, add them to 500 ml of deionized water, and stir for 2 hours to obtain the catalyst mother liquor.

[0068] Packing of the fan-shaped aluminum foam: Pack the fan-shaped aluminum foam into the catalyst treatment device and seal it with the cover 4. Under the stirring state, start the pump 13 to circulate the catalyst mother liquor in the catalyst treatment device and the co-precipitation mother liquor tank 8, submerge the fan-shaped aluminum foam in the catalyst mother liquor, and make the catalyst mother liquor flow through the inner pores of the fan-shaped aluminum foam. Circulate at 20 - 60 °C for 1 hour. In this embodiment, the diameter of the fan-shaped aluminum foam is 100 mm, the thickness is 10 mm, and the height of the prepared catalyst column is 200 mm.

[0069] Co-precipitation and aging: Keep the stirring state in the co-precipitation mother liquor tank 8, slowly drop an excessive amount of ammonium bicarbonate aqueous solution into the co-precipitation mother liquor tank 8. After the dropping is completed, the pump 13 makes the mother liquor continue to circulate for 2 hours.

[0070] Drying: Take out the fan-shaped aluminum foam, dry it at 200 °C, and then calcine it at 430 °C for 2 hours to obtain the fan-shaped catalyst 1 for aldehyde-ketone hydrogenation.

[0071] After pretreatment, the dehydrated MTO by-products are detected by gas chromatography, and the components of the MTO by-products are as follows:

[0072] Water: 2.25%; Acetaldehyde: 9.58%; Propionaldehyde: 1.74%; Acetone: 36.83%; Methyl ethyl ketone: 11.84%; Methanol: 36.55%; The undetected part accounts for 1.21%.

[0073] Using gas chromatography to detect the catalysis, the experimental data for catalytic hydrogenation are as follows:

[0074]

[0075] The data in the above table are the data obtained by detecting the hydrogenation products by gas chromatography after the MTO by-products are hydrogenated.

[0076] This application adopts a nickel-copper-zinc catalytic system, and uses nickel metal to supplement the copper-zinc active centers. Cooperating with the fan-shaped aluminum foam as the catalyst carrier, the catalyst can be used in a complex aldehyde-ketone environment, has strong versatility, makes the hydrogenation reaction proceed more fully, and has a large hydrogenation depth.

[0077] The preferred embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings. However, the present invention is not limited to the above embodiments, and various modifications can be made to the technical solutions of the present invention without departing from the spirit of the present invention, that is, within the scope of disclosure.

Claims

1. A comprehensive utilization method for by-product crude alcohol in MTO, characterized in that, It includes the following steps: A. Pretreatment: The crude alcohol by-produced from MTO is introduced into a membrane dehydration separator to remove the water contained in the crude alcohol; B. Catalytic hydrogenation: The crude alcohol dehydrated in the pretreatment stage is fully hydrogenated in a hydrogenation reactor in the presence of a catalyst, so that the aldehydes and ketones in the crude alcohol are converted into alcohols through hydrogenation reactions; C. Refining stage: The crude alcohol after catalytic hydrogenation is subjected to extractive distillation to separate different products, and the products are: methanol, ethanol, isopropanol, and sec-butanol; D. Hydrogen production stage: The methanol component after distillation is transferred to a reforming reactor, and steam is introduced for reforming hydrogen production. The mixed gas generated by the reaction is purified to obtain hydrogen after removing carbon dioxide; In the catalytic hydrogenation stage, a sector-shaped catalyst (1) is used. The sector-shaped catalysts (1) are spliced and stacked to form a catalyst column (2). The sector-shaped catalyst (1) is composed of a sector-shaped foam aluminum as a carrier and loaded with nickel, copper, and zinc metal active components; The sector-shaped foam aluminum is open-cell foam aluminum, and the inner pores of the sector-shaped foam aluminum communicate with each other to form channels; The pore diameter of the sector-shaped foam aluminum is 40um - 180um, and the porosity is 80% - 90%; The sector-shaped catalyst (1) is prepared by coprecipitation of sector-shaped foam aluminum and a catalyst mother liquor containing nickel, copper, and zinc; The molar ratio of nickel, copper, and zinc in the catalyst mother liquor is 1:10:

5.

2. The comprehensive utilization method of MTO by-product crude alcohol according to claim 1, characterized in that, The central angle of the sector corresponding to the sector-shaped catalyst (1) is 24° - 30°, and multiple sector-shaped foam aluminums are butted to form a disc shape.

3. A comprehensive utilization method of MTO by-product crude alcohol according to claim 1, characterized in that, The joints of every two adjacent upper and lower sector-shaped catalysts (1) are offset. Coaxial positioning holes (15) are provided on every two adjacent upper and lower sector-shaped catalysts (1), and positioning rods (16) are inserted into the positioning holes (15).

4. A comprehensive utilization method of MTO by-product crude alcohol according to claim 1, characterized in that, Both the preparation and regeneration of the sector-shaped catalyst (1) use a catalyst treatment device. The catalyst treatment device includes a housing (3) and a cover body (4). An accommodating groove (5) in the shape of "V" is provided inside the housing (3). The upper end opening of the accommodating groove (5) is closed by the cover body (4). When the cover body (4) closes the upper end opening of the accommodating groove (5), the cross-section of the accommodating groove (5) matches the sector-shaped catalyst (1). Through holes (6) and overflow grooves (7) are respectively provided at both ends of the accommodating groove (5). A groove corresponding to the overflow groove (7) is provided on the cover body (4). The overflow groove (7) and the groove are butted when the accommodating groove (5) is closed by the cover body (4) to form a circular overflow hole.

5. The comprehensive utilization method of the crude alcohol by-produced in MTO according to claim 4, wherein, A coprecipitation mother liquor tank (8), a TO furnace (9), and a washing tower (10) are provided outside the catalyst treatment device. Among them, the TO furnace (9) and the washing tower (10) are connected in series. The inlet of the TO furnace (9) and the water inlet pipe of the coprecipitation mother liquor tank (8) are connected to the overflow hole through a first solenoid valve (11). The air outlet of the washing tower (10) and the water outlet pipe of the coprecipitation mother liquor tank (8) are connected to the through hole (6) through a second solenoid valve (12). A blower is provided between the TO furnace (9) and the washing tower (10). A pump (13) is provided between the water outlet pipe of the coprecipitation mother liquor tank (8) and the second solenoid valve (12).

6. The comprehensive utilization method of crude methanol by-produced in MTO according to claim 4, characterized in that, Distribution plates (14) are provided at both ends inside the accommodation groove (5). The distribution plates (14) are sector-shaped plate bodies that match the shape of the sector-shaped catalyst (1). Distribution holes are evenly distributed on the distribution plates (14), and the fluid flowing through the distribution plates (14) is in a turbulent state.

7. A comprehensive utilization method of MTO by-product crude alcohol according to claim 6, characterized in that, There are at least two distribution plates (14) at each end of the accommodation groove (5). There is a spacing between two adjacent distribution plates (14), and the distribution holes on two adjacent distribution plates (14) are offset.

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