Catalyst for synthesizing dimethyl oxalate through gas-phase carbonylation as well as preparation method and application of catalyst

Abstract

The invention provides a catalyst for synthesizing dimethyl oxalate through gas-phase carbonylation as well as a preparation method and application of the catalyst, which are used for solving the technical problems of high noble metal content and poor target product selectivity of the existing dimethyl oxalate catalyst. The carrier treated by the competitive adsorbent is used as the active carrier, the active components are effectively adsorbed according to different competitive adsorbents and different distribution positions of active sites on the active carrier, the active components are distributed at different positions of the active carrier according to use requirements, and the active components are different in position during catalysis, so that the catalytic activity of the catalyst is improved. The obtained target products are different, the selectivity of the target products is effectively improved, the treated active center site of the active carrier can carry out targeted effective loading on the precious metal of the catalyst, and a good catalytic effect is obtained on the basis of reducing the content of the precious metal.

Description

technical field

[0001] The invention relates to the technical field of catalyst preparation, in particular to a gas-phase carbonylation catalyst for synthesizing dimethyl oxalate and a preparation method and application thereof. Background technique

[0002] At present, my country's resource pattern can be summarized as short of oil, less gas, and more coal. Clean coal chemical industry can not only make full use of coal resources, reduce waste gas emissions from direct coal combustion, and significantly reduce environmental pressure, it is very beneficial to maintaining energy security and environmental protection, and is a very important research field. For our country, which consumes a lot of energy and is seriously short of oil resources, its significance is even more prominent.

[0003] As one of the five paths of modern coal chemical industry, the development of coal-to-ethylene glycol has always been concerned by the industry. Ethylene glycol is an important chemica...

Examples

Embodiment 1

[0032] A gas-phase carbonylation catalyst for synthesizing dimethyl oxalate comprises an active component and an active carrier, wherein the active component is palladium, the active carrier is a carrier treated by a competitive adsorbent, and the competitive adsorbent is ammonia water.

[0033] Above-mentioned dimethyl oxalate catalyst is used to participate in gas-phase synthesis of dimethyl oxalate reaction, comprising the following steps:

[0034] T1, put the gas-phase carbonylation synthesis dimethyl oxalate catalyst into a fixed reactor, use 5% H 2 / N 2 to restore. Specifically, sieve the prepared catalyst tablet into 40-60 meshes, then take 1ml and put it into a fixed reactor, 2 / N 2 Medium reduction, the total flow rate is controlled at 100ml / min, the reduction temperature is 150°C, and the reduction time is 10 hours.

[0035] T2. After the reduction in step T1, the pressure is 0.2MPa, the HCl content is 100ppm, and the volume space velocity is 8000h -1 , the reac...

Embodiment 2

[0037] A kind of preparation method of gas-phase carbonylation synthetic dimethyl oxalate catalyst, comprises the following steps:

[0038] S1. Add the carrier into the competing adsorbent, seal it after stirring, let it stand for several times, stir and seal it, and filter to obtain the active carrier. Specifically, 5g of α-Al will be weighed 2 o 3 Add it into 200ml of 0.1% ammonia water, stir and seal it, let it stand for 30 minutes, stir and seal it, repeat 6 times, filter and wash to obtain the active carrier.

[0039] S2. Dissolving the palladium salt in the reducing solution, heating and stirring until the palladium salt is completely dissolved, obtaining a mixed solution and constant volume. Specifically, 0.1 g of palladium nitrate was weighed and added to 10 mL of concentrated nitric acid solution, heated and dissolved on an electric furnace until the palladium nitrate was completely dissolved, and cooled to 100 mL to obtain a mixed solution.

[0040] S3. Add the ac...

Embodiment 3

[0046] A catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation. The components of the catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation in this embodiment are the same as those in Example 1, and will not be repeated here.

[0047] In the present embodiment, also provide a kind of preparation method of gas-phase carbonylation synthesis dimethyl oxalate catalyst, comprise the following steps:

[0048] S1. Add the carrier into the competing adsorbent, seal it after stirring, let it stand for several times, stir and seal it, and filter to obtain the active carrier. Specifically, 5g of α-Al will be weighed 2 o 3 Add it into 200ml of 0.1% ammonia water, stir and seal it, let it stand for 30 minutes, stir and seal it, repeat 6 times, filter and wash to obtain the active carrier.

[0049] S2. Dissolving the palladium salt in the reducing solution, heating and stirring until the palladium salt is completely dissolved, obtaining a mixed solution and...

technical field

[0001] The invention relates to the technical field of catalyst preparation, in particular to a gas-phase carbonylation catalyst for synthesizing dimethyl oxalate and a preparation method and application thereof. Background technique

[0002] At present, my country's resource pattern can be summarized as short of oil, less gas, and more coal. Clean coal chemical industry can not only make full use of coal resources, reduce waste gas emissions from direct coal combustion, and significantly reduce environmental pressure, it is very beneficial to maintaining energy security and environmental protection, and is a very important research field. For our country, which consumes a lot of energy and is seriously short of oil resources, its significance is even more prominent.

[0003] As one of the five paths of modern coal chemical industry, the development of coal-to-ethylene glycol has always been concerned by the industry. Ethylene glycol is an important chemica...

Examples

Embodiment 1

[0032] A gas-phase carbonylation catalyst for synthesizing dimethyl oxalate comprises an active component and an active carrier, wherein the active component is palladium, the active carrier is a carrier treated by a competitive adsorbent, and the competitive adsorbent is ammonia water.

[0033] Above-mentioned dimethyl oxalate catalyst is used to participate in gas-phase synthesis of dimethyl oxalate reaction, comprising the following steps:

[0034] T1, put the gas-phase carbonylation synthesis dimethyl oxalate catalyst into a fixed reactor, use 5% H 2 / N 2 to restore. Specifically, sieve the prepared catalyst tablet into 40-60 meshes, then take 1ml and put it into a fixed reactor, 2 / N 2 Medium reduction, the total flow rate is controlled at 100ml / min, the reduction temperature is 150°C, and the reduction time is 10 hours.

[0035] T2. After the reduction in step T1, the pressure is 0.2MPa, the HCl content is 100ppm, and the volume space velocity is 8000h -1 , the reac...

Embodiment 2

[0037] A kind of preparation method of gas-phase carbonylation synthetic dimethyl oxalate catalyst, comprises the following steps:

[0038] S1. Add the carrier into the competing adsorbent, seal it after stirring, let it stand for several times, stir and seal it, and filter to obtain the active carrier. Specifically, 5g of α-Al will be weighed 2 o 3 Add it into 200ml of 0.1% ammonia water, stir and seal it, let it stand for 30 minutes, stir and seal it, repeat 6 times, filter and wash to obtain the active carrier.

[0039] S2. Dissolving the palladium salt in the reducing solution, heating and stirring until the palladium salt is completely dissolved, obtaining a mixed solution and constant volume. Specifically, 0.1 g of palladium nitrate was weighed and added to 10 mL of concentrated nitric acid solution, heated and dissolved on an electric furnace until the palladium nitrate was completely dissolved, and cooled to 100 mL to obtain a mixed solution.

[0040] S3. Add the ac...

Embodiment 3

[0046] A catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation. The components of the catalyst for synthesizing dimethyl oxalate by gas-phase carbonylation in this embodiment are the same as those in Example 1, and will not be repeated here.

[0047] In the present embodiment, also provide a kind of preparation method of gas-phase carbonylation synthesis dimethyl oxalate catalyst, comprise the following steps:

[0048] S1. Add the carrier into the competing adsorbent, seal it after stirring, let it stand for several times, stir and seal it, and filter to obtain the active carrier. Specifically, 5g of α-Al will be weighed 2 o 3 Add it into 200ml of 0.1% ammonia water, stir and seal it, let it stand for 30 minutes, stir and seal it, repeat 6 times, filter and wash to obtain the active carrier.

[0049] S2. Dissolving the palladium salt in the reducing solution, heating and stirring until the palladium salt is completely dissolved, obtaining a mixed solution and...

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