A method for comprehensive utilization of oxide-containing concentrate from MTO production of ethylene

Abstract

This invention discloses a method for the comprehensive utilization of oxide-containing concentrate from MTO (methyl oxytocin) ethylene production. The method includes: concentrating and dehydrating the oxide-containing concentrate from MTO ethylene production; then, hydrogenating the concentrate under the action of a catalyst; and finally, distilling the hydrogenated liquid for separation. This comprehensive utilization method achieves the recovery and reuse of oxides generated in the MTO ethylene production process, with a high oxide recovery rate, which is beneficial for subsequent utilization of these oxides. This invention offers high production efficiency and high economic benefits.

Description

Technical Field

[0001] This invention relates to a method for the comprehensive utilization of oxide-containing concentrate from ethylene production via MTO. Background Technology

[0002] The oxide-containing concentrate produced by the MTO process for ethylene production mainly consists of various oxides, including aldehydes (such as acetaldehyde, propionaldehyde, butyraldehyde, etc.), ketones (such as acetone, butanone, pentanone, etc.), and alcohols (such as methanol, ethanol, n-propanol, butanol, etc.). Since these oxides form azeotropes with water, azeotropes also form between the components of the oxide-containing concentrate. Furthermore, the boiling point difference between some components is small, making it impossible to effectively separate these oxides using conventional methods.

[0003] Currently, domestically, these oxide-containing concentrates are generally sold as fuel at low prices, resulting in a significant waste of resources as a large amount of high-value-added oxides cannot be utilized. International reports suggest returning these oxide-containing concentrates to MTO cracking units for reprocessing to produce corresponding olefins; however, this approach is detrimental to MTO cracking due to the presence of oxides, easily leading to adverse effects such as reaction coking and slagging. Therefore, developing a method for the comprehensive utilization of these oxides is essential. Summary of the Invention

[0004] To at least partially solve the problems in the prior art, the present invention provides the following technical solution:

[0005] This invention provides a method for the comprehensive utilization of oxide-containing concentrate from MTO production of ethylene, comprising:

[0006] The concentrated water containing oxides from MTO-produced ethylene is concentrated and dehydrated, and then hydrogenated under the action of a catalyst. The hydrogenated liquid is then separated by distillation.

[0007] In one or more optional embodiments, the water content of the concentrated and dehydrated ethylene oxide concentrate from the MTO production is less than 20%.

[0008] In one or more optional embodiments, the catalyst is a nickel- or copper-containing catalyst supported on alumina or silica.

[0009] In one or more optional embodiments, the preparation of the catalyst includes:

[0010] The pseudoboehmite or silica powder and the auxiliary element salt are dissolved in water and stirred evenly. Then, 3% nitric acid and guar gum powder are added and extruded into strips. The strips are then dried at 120°C for 12 hours, and then calcined at 600°C for 6 hours. After cooling to room temperature, the carrier is obtained.

[0011] The catalyst is prepared by immersing the support in a salt solution containing nickel or copper for 8 hours, drying it, and calcining it at 500°C for 3 hours.

[0012] In one or more optional embodiments, the auxiliary element is at least one of the elements fluorine, cadmium, cesium, beryllium, hafnium, or tellurium.

[0013] In one or more optional embodiments, the conditions for the hydrogenation reaction are: a reaction pressure of 0.1–5 MPa and a hydrogenation reaction temperature of 120–250 °C.

[0014] In one or more optional embodiments, the hydrogen-to-oil molar ratio is 10–100, and the catalyst space velocity is 0.1–20 h⁻¹. -1 .

[0015] In one or more optional embodiments, the oxides in the oxide concentrate from the MTO ethylene production process are water, alcohols, aldehydes, ketones, and other trace impurities.

[0016] In one or more optional embodiments, the hydrogenation reaction refers to the conversion of the aldehyde and ketone compounds into corresponding alcohol compounds by hydrogenation under the action of a catalyst.

[0017] In one or more alternative embodiments, the hydrogenation reaction is carried out in a hot-walled fixed-bed reactor.

[0018] Based on the above technical solution, the beneficial effects of the present invention compared with the prior art are as follows:

[0019] This invention involves distilling and dehydrating the concentrated oxide-containing water from MTO production, followed by hydrogenation under catalytic conditions to convert aldehydes and ketones in the concentrated oxide-containing water into alcohols. Then, different oxides are separated one by one by distillation. The recovery rate of oxides obtained by this method is greater than 95%, which is beneficial for the subsequent utilization of these oxides. This invention has high production efficiency and high economic benefits. Detailed Implementation

[0020] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Process parameters not specified in the following embodiments are generally performed under conventional conditions.

[0021] The endpoints and any values ​​of the ranges disclosed in this invention 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 the various ranges, the endpoint values ​​of the various ranges and individual point values, and 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 invention.

[0022] Example 1

[0023] The sample was oxide-containing concentrated water produced by the MTO process for ethylene production, with a water content of 55%. The composition data after distillation and concentration to remove some water is shown in Table 1.

[0024] Table 1. Composition and content of oxide concentrate from MTO production of ethylene

[0025] Components methanol acetone Isobutanol propionaldehyde Butanone water other content 35.00％ 41.00％ 0.70％ 0.07％ 4.47％ 17.00％ 1.76％

[0026] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper. The auxiliary agents were elemental fluorine and cadmium. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 100. The hydrogenation reaction temperature was 170℃, the reaction pressure was 0.1 MPa, and the catalyst space velocity was 0.1 h⁻¹. -1 .

[0027] Preparation of the catalyst used in this embodiment:

[0028] (1) Dissolve boehmite with the additives ammonium fluoride and cadmium nitrate in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0029] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0030] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0031] (4) The support obtained in step (3) is immersed in copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0032] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is about 88%.

[0033] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated solution, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0034] Example 2

[0035] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper, with cesium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 100. The hydrogenation reaction temperature was 165℃, the reaction pressure was 1 MPa, and the catalyst space velocity was 0.5 h⁻¹. -1 .

[0036] Preparation of the catalyst used in this embodiment:

[0037] (1) Dissolve silica powder and cesium nitrate additive in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0038] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0039] (3) The dried semi-finished product in step (2) is calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0040] (4) The support obtained in step (3) is immersed in a copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0041] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 91%.

[0042] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0043] Example 3

[0044] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper, with beryllium and cadmium as auxiliary agents. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 70. The hydrogenation reaction temperature was 150°C, the reaction pressure was 2 MPa, and the catalyst space velocity was 1.5 h⁻¹. -1 .

[0045] Preparation of the catalyst used in this embodiment:

[0046] (1) Add boehmite, beryllium nitrate and cadmium nitrate to water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0047] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0048] (3) The dried semi-finished product in step (2) is calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0049] (4) The support obtained in (3) is immersed in copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0050] In this embodiment, acetone in the oxide-containing concentrate of MTO-produced ethylene is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 93%.

[0051] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0052] Example 4

[0053] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper, with hafnium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 70. The hydrogenation reaction temperature was 140℃, the reaction pressure was 3 MPa, and the catalyst space velocity was 2.5 h⁻¹. -1 .

[0054] Preparation of the catalyst used in this embodiment:

[0055] (1) Mix boehmite and hafnium dioxide powder with additives, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0056] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0057] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0058] (4) The support obtained in step (3) is immersed in copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0059] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is about 95%.

[0060] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0061] Example 5

[0062] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper, with elemental tellurium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 50. The hydrogenation reaction temperature was 130℃, the reaction pressure was 4 MPa, and the catalyst space velocity was 3.5 h⁻¹. -1 .

[0063] Preparation of the catalyst used in this embodiment:

[0064] (1) Dissolve boehmite and telluric acid in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0065] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0066] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0067] (4) The support obtained in step (3) is immersed in copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0068] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 97%.

[0069] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0070] Example 6

[0071] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 25% copper, with elemental fluorine and cesium as additives. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 20. The hydrogenation reaction temperature was 120°C, the reaction pressure was 4 MPa, and the catalyst space velocity was 5 h⁻¹. -1 .

[0072] Preparation of the catalyst used in this embodiment:

[0073] (1) Dissolve silica powder with the salts of ammonium fluoride and cesium nitrate in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0074] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0075] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0076] (4) The support obtained in step (3) is immersed in copper nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0077] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 98%.

[0078] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0079] Example 7

[0080] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with elemental fluorine as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 90. The hydrogenation reaction temperature was 170℃, the reaction pressure was 0.1 MPa, and the catalyst space velocity was 0.1 h⁻¹. -1 .

[0081] Preparation of the catalyst used in this embodiment:

[0082] (1) Dissolve boehmite and ammonium fluoride in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0083] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0084] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0085] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0086] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is about 85%.

[0087] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0088] Example 8

[0089] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with cadmium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 90. The hydrogenation reaction temperature was 160℃, the reaction pressure was 1 MPa, and the catalyst space velocity was 0.5 h⁻¹. -1 .

[0090] Preparation of the catalyst used in this embodiment:

[0091] (1) Dissolve boehmite and cadmium nitrate in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0092] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0093] (3) The dried semi-finished product in step (2) is calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0094] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0095] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is about 88%.

[0096] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0097] Example 9

[0098] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with elemental beryllium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 60. The hydrogenation reaction temperature was 150°C, the reaction pressure was 2 MPa, and the catalyst space velocity was 1.5 h⁻¹. -1 .

[0099] In this case, the catalyst and its preparation method include:

[0100] (1) Dissolve boehmite and beryllium nitrate in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0101] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0102] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0103] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0104] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is about 90%.

[0105] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0106] Example 10

[0107] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with elemental tellurium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 50. The hydrogenation reaction temperature was 140℃, the reaction pressure was 3 MPa, and the catalyst space velocity was 2.5 h⁻¹. -1 .

[0108] Preparation of the catalyst used in this embodiment:

[0109] (1) Dissolve silica powder and telluric acid in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0110] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0111] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0112] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0113] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 94%.

[0114] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0115] Example 11

[0116] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with hafnium and cesium as auxiliary agents. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 50. The hydrogenation reaction temperature was 130°C, the reaction pressure was 4 MPa, and the catalyst space velocity was 3.5 h⁻¹. -1 .

[0117] Preparation of the catalyst used in this embodiment:

[0118] (1) Dissolve boehmite, hafnium dioxide powder and cesium nitrate in water, stir evenly, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0119] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0120] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0121] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0122] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 96%.

[0123] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0124] Example 12

[0125] The concentrated ethylene oxide-containing wastewater from MTO production, with a water content of 17% after distillation, concentration, and dehydration as shown in Table 1, was subjected to hydrogenation treatment. The hydrogenation reactor was a hot-walled fixed-bed reactor with dimensions of Ф60×5.5 mm. The reactor material was 15CrMo, and the catalyst was an alumina-supported catalyst containing 20% ​​nickel, with hafnium as the auxiliary agent. 99% industrial hydrogen was used, and the molar ratio of hydrogen to oxides in the concentrated ethylene oxide-containing wastewater from MTO production was 25. The hydrogenation reaction temperature was 120℃, the reaction pressure was 5 MPa, and the catalyst space velocity was 5 h⁻¹. -1 .

[0126] Preparation of the catalyst used in this embodiment:

[0127] (1) Mix boehmite and hafnium dioxide powder with additives, then add 3% nitric acid and guar gum powder and extrude into strips for later use;

[0128] (2) Dry the semi-finished product from step (1) at 120℃ for 12 hours;

[0129] (3) The semi-finished product dried in step (2) is then calcined at 600°C for 6 hours and cooled to room temperature to obtain the desired carrier.

[0130] (4) The support obtained in step (3) is immersed in nickel nitrate solution for 8 hours, then dried and calcined at 500°C for 3 hours to obtain the desired oxidized catalyst.

[0131] In this embodiment, acetone in the oxide-containing concentrate of ethylene produced by MTO is hydrogenated to isopropanol, propionaldehyde is hydrogenated to n-propanol, and butanone is hydrogenated to sec-butanol. The hydrogenation conversion rate is maintained at 99%, and the selectivity is approximately 97%.

[0132] A packed distillation column with a theoretical plate number N=80 was used to distill and separate the above-mentioned hydrogenated material, yielding methanol with a recovery rate of 98.5%, ethanol with a recovery rate of 98%, isopropanol with a recovery rate of 99%, and sec-butanol with a recovery rate of 99%.

[0133] As can be seen from the above examples, increasing the hydrogenation reaction pressure can decrease the reaction temperature, reduce the hydrogen-to-oil ratio, and increase the space velocity. Under the same hydrogenation conversion rate, higher reaction pressure and lower reaction temperature result in higher selectivity for the target product and higher production efficiency. The selectivity for the target product is optimal when the hydrogenation reaction pressure is 5 MPa.

[0134] The above are merely preferred embodiments of the present invention and are not intended to limit the scope of protection of the present invention. All modifications or applications made in accordance with the above embodiments are within the scope of protection of this technical solution.

[0135] Although specific embodiments of the invention have been described in detail, those skilled in the art will understand that various modifications and substitutions can be made to those details based on all the teachings disclosed, and all such changes are within the scope of protection of this invention. The full scope of this invention is given by the appended claims and any equivalents thereof.

Claims

1. A method for comprehensive utilization of oxide-containing concentrate from MTO production of ethylene, characterized in that, include: The concentrated water containing oxides from MTO-produced ethylene is concentrated and dehydrated, and then hydrogenated under the action of a catalyst. The hydrogenated liquid is then separated by distillation. The conditions for the hydrogenation reaction are: reaction pressure of 0.1–5 MPa and hydrogenation reaction temperature of 120–250 °C. The hydrogenation reaction is carried out in a hot-walled fixed-bed reactor; The catalyst is a nickel- or copper-containing catalyst supported on alumina or silica. The preparation of the catalyst includes: The pseudoboehmite or silica powder and the auxiliary element salt are dissolved in water and stirred evenly. Then, 3% nitric acid and guar gum powder are added and extruded into strips. The strips are then dried at 120°C for 12 hours, and then calcined at 600°C for 6 hours. After cooling to room temperature, the carrier is obtained. The catalyst is prepared by immersing the support in a salt solution containing nickel or copper for 8 hours, drying it, and calcining it at 500°C for 3 hours.

2. The method as described in claim 1, characterized in that, The water content of the concentrated and dehydrated oxide concentrate from the MTO-produced ethylene is less than 20%.

3. The method as described in claim 1, characterized in that, The auxiliary element is at least one of the elements fluorine, cadmium, cesium, beryllium, hafnium, or tellurium.

4. The method as described in claim 1, characterized in that, The hydrogen-to-oil molar ratio is 10–100, and the catalyst space velocity is 0.1–20 h⁻¹. -1 .

5. The method as described in claim 1, characterized in that, The oxides in the concentrated ethylene oxide solution produced by MTO consist of water, alcohols, aldehydes, ketones, and other trace impurities.

6. The method as described in claim 5, characterized in that, The hydrogenation reaction refers to the conversion of the aldehyde and ketone compounds into corresponding alcohol compounds under the action of a catalyst.