TW201636098A - A catalyst for preparing vinyl chloride and a method for preparing vinyl chloride - Google Patents

Abstract

A catalyst for preparing vinyl chloride comprises a carrier and metal chloride supporting on the carrier. The carrier comprises metal oxide represented by formula (I), wherein M represents alkali metal or alkaline earth metal, L represents rare earth metal, 0.001 ≤ x ≤ 0.5, 0.001 ≤ y ≤ 0.5, 0.1 ≤ z ≤ 0.9. When using the catalyst of this invention for preparing vinyl chloride, the reaction of preparing vinyl chloride can be carried out in one-step under a low temperature, and the yield of the vinyl chloride can also be increased.

Description

Catalyst for preparing vinyl chloride and method for preparing vinyl chloride

This invention relates to a catalyst and its use, and more particularly to a catalyst for the preparation of vinyl chloride, and a process for preparing vinyl chloride using the catalyst.

Vinyl chloride monomer is the main raw material for the synthesis of polyvinyl chloride resin. Therefore, the quality and preparation cost of the vinyl chloride raw material directly affect the quality and preparation cost of the synthesized polyvinyl chloride resin.

At present, industrial production of vinyl chloride is generally carried out by the United States Dow (DOW) company's ethylene balanced oxychlorination process. The ethylene equilibrium oxychlorination process comprises three steps: (1) addition reaction of ethylene and chlorine under the catalysis of a ferric chloride catalyst to form 1,2-dichloroethane; (2) 1,2-dichloroethane The alkane is subjected to a cracking reaction at a high temperature to form a vinyl chloride monomer and hydrogen chloride; and (3) hydrogen chloride and ethylene, and oxygen are reacted under the catalysis of a copper chloride catalyst to form 1,2-dichloroethane and water, and the step ( 3) The obtained 1,2-dichloroethane can be recovered and subjected to the cleavage reaction of the step (2) to form a vinyl chloride monomer.

However, the process of ethylene-balanced oxychlorination to produce vinyl chloride is required. Including multiple steps, resulting in higher production costs, so the world's major chemical companies continue to research and develop how to use ethane as a raw material and prepare vinyl chloride by one-step reaction to reduce production costs. European Ethylene has successfully developed a chloroethylene monomer using ethane as a raw material and direct oxychlorination. Although this method can be carried out in one step, it is necessary to control the reaction in a high temperature environment (450 ° C ~ 470 ° C). It still causes a lot of fuel consumption, so the cost reduction is limited.

In order to solve the disadvantage that the above method needs to be reacted in a high temperature environment, it has been conventionally known that alumina is used as a carrier for carrying a catalyst, and a mixed gas containing ethylene and hydrogen chloride is used as a raw material, and a vinyl chloride is successfully produced in a one-step reaction under a low temperature environment. However, the yield of vinyl chloride obtained by this method is extremely low.

In view of the conventional technology for preparing vinyl chloride in a one-step reaction under a low temperature environment, the yield of vinyl chloride is extremely low, and the applicant has developed a catalyst for preparing vinyl chloride, when the catalyst is used to prepare vinyl chloride. It can be carried out in a one-step reaction in a low temperature environment, and the yield of vinyl chloride can also be increased.

Accordingly, a first object of the present invention is to provide a catalyst for the preparation of vinyl chloride. When the catalyst is used to prepare vinyl chloride, the yield of vinyl chloride can be increased in addition to the one-step reaction in a low temperature environment.

Thus, the catalyst for the preparation of vinyl chloride of the present invention comprises a carrier and a metal chloride supported on the carrier, the carrier comprising a metal oxide of the formula (I): M _x L _y Al _z O (I )

Wherein M is an alkali metal or an alkaline earth metal, and L is a rare earth metal, 0.001 ≦ x ≦ 0.5, 0.001 ≦ y ≦ 0.5, 0.1 ≦ z ≦ 0.9.

Accordingly, a second object of the present invention is to provide a process for producing vinyl chloride which can be carried out in a one-step reaction in a low temperature environment.

The method for producing vinyl chloride of the present invention comprises the step of bringing a mixed gas containing hydrogen chloride, ethylene, oxygen and nitrogen into contact with a catalyst for preparing vinyl chloride as described above.

The effect of the present invention is that since the carrier of the catalyst of the present invention contains a metal oxide as shown in the formula (I), when the vinyl chloride is produced by the catalyst of the present invention, in addition to the one-step reaction in a low temperature environment, Can increase the yield of vinyl chloride.

The contents of the present invention will be described in detail below:

[Catalyst for preparing vinyl chloride]

The catalyst of the present invention comprises a carrier and a metal chloride supported on the carrier. The following describes the carrier, metal chloride and catalyst:

<carrier>

The carrier in the catalyst of the present invention contains a metal oxide as shown in formula (I): M _x L _y Al _z O (I)

Wherein M is an alkali metal or an alkaline earth metal, L is a rare earth metal, 0.001 ≦ x ≦ 0.5, 0.001 ≦ y ≦ 0.5, 0.1 ≦ z ≦ 0.9 (x, y and z points) Do not express the number of moles).

Preferably, M is magnesium metal.

Preferably, L is selected from the group consisting of base metal (Gd), base metal (Eu) or base metal (Y).

Preferably, 0.01 ≦ x ≦ 0.1, 0.01 ≦ y ≦ 0.1, 0.4 ≦ z ≦ 0.7. More preferably, 0.04 ≦ x ≦ 0.08, 0.04 ≦ y ≦ 0.08, 0.4 ≦ z ≦ 0.7.

Preferably, the metal oxide represented by the formula (I) is selected from Mg _0.1 Gd _0.1 Al _0.8 O _1.45 [x of the formula (I) is 0.1/1.45, y is 0.1/1.45, and z is 0.8/1.45. ], Mg _0.1 Eu _0.1 Al _0.8 O _1.45 [x of the formula (I) is 0.1/1.45, y is 0.1/1.45, z is 0.8/1.45], Mg _0.1 Y _0.1 Al _0.8 O _1.45 [x of the formula (I) It is 0.1/1.45, y is 0.1/1.45, z is 0.8/1.45] or a combination of the foregoing.

Preferably, the carrier is obtained by mixing alumina, a first metal oxide and a rare earth metal oxide, and then calcining, the first metal oxide being an alkali metal oxide or an alkaline earth metal oxide. More preferably, the first metal oxide is magnesium oxide, and the rare earth metal oxide is selected from the group consisting of ruthenium oxide (Gd ₂ O ₃ ), ruthenium oxide (Eu ₂ O ₃ ) or ruthenium oxide (Y ₂ O ₃ ). More preferably, the calcination temperature is from 1000 to 1500 °C. More preferably, the calcination time is 1 to 5 hours.

Preferably, the alumina is selected from the group consisting of alpha-alumina, beta-alumina, Y-alumina or a combination of the foregoing.

<metal chloride>

Preferably, the metal chloride is selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides, transition metal chlorides, rare earth metal chlorides or combinations of the foregoing. More preferably, the metal chloride is selected from the group consisting of copper chloride, Potassium chloride, magnesium chloride, barium chloride or a combination of the foregoing.

Preferably, the catalyst further comprises H ₃ (PW ₁₂ O ₄₀ ) carried on the carrier.

Preferably, when the catalyst does not contain H ₃ (PW ₁₂ O ₄₀ ), the content of the metal chloride ranges from 5 to 20% by weight based on 100% by weight of the total weight of the catalyst; when the catalyst comprises In the case of H ₃ (PW ₁₂ O ₄₀ ), the content of the metal chloride and H ₃ (PW ₁₂ O ₄₀ ) is in the range of 5 to 20% by weight based on 100% by weight of the total weight of the catalyst.

<catalyst>

Preferably, the catalyst has a surface area ranging from 0.5 to 10 m ² /g.

Preferably, the metal chloride is supported on the carrier by at least one selected from the group consisting of an impregnation method, an ion exchange method, a coprecipitation method, and a chemical vapor deposition method.

[Method for preparing vinyl chloride]

Preferably, the mixed gas is contacted with the catalyst in a reactor which is a fixed bed reactor or a fluidized bed reactor.

More preferably, when the reactor is a fluidized bed reactor, the catalyst is granular and has an average particle size ranging from 30 to 100 μm.

More preferably, when the reactor is a fixed bed reactor, the catalyst is granular and has an average particle size ranging from 1 to 10 mm.

Preferably, the mixed gas is contacted with the catalyst at 150 to 300 °C.

Preferably, the method for preparing vinyl chloride according to the present invention, wherein the volume ratio of hydrogen chloride, ethylene, oxygen and nitrogen in the mixed gas is 1:1: 0.5: 1.5~1.5: 1.25:0.7:2.5.

Preferably, the mixed gas is in the air velocity range of 100 to 1000 hr ^-1 , the temperature range is 150 to 300 ° C, the pressure range is 0.05 to 0.5 MPa, and the residence time is in the range of 5 to 50 seconds. The inside of the device is in contact with the catalyst.

The present invention will be further illustrated by the following examples, but it should be understood that this embodiment is intended to be illustrative only and not to be construed as limiting.

<Example 1> Catalyst for the preparation of vinyl chloride (carrier: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 )

The catalyst for the preparation of vinyl chloride of Example 1 was prepared according to the following steps:

(1) Preparation of carrier: 0.8 mole of γ-alumina, 0.1 mole of magnesium oxide and 0.1 mole of cerium oxide were uniformly mixed, calcined at 1300 ° C for 3 hours, and then cooled to obtain a Mg _0.1 Gd _0.1 Al _0.8 O _1.45 carrier.

(2) Preparation of catalyst: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 carrier, under atmospheric pressure, first immersed in 100g of solution containing copper chloride and potassium chloride (to the total weight of the solution is 100wt%, copper chloride content In the case of 8 wt%, the potassium chloride content is 1 wt%), after 24 hours, the carrier is taken out and allowed to stand, and then placed in an oven, and baked at 120 ° C for 10 hours to obtain the catalyst (carrier: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 ).

<Example 2> Catalyst for the preparation of vinyl chloride (carrier: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 )

The catalyst for the preparation of vinyl chloride of Example 2 was prepared according to the following steps:

(1) Preparation of carrier: 0.8 mole of α-alumina, 0.1 mole of magnesium oxide and 0.1 mole of cerium oxide were uniformly mixed, calcined at 1300 ° C for 3 hours, and then cooled to obtain a Mg _0.1 Gd _0.1 Al _0.8 O _1.45 carrier.

(2) Preparation of catalyst: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 carrier, under atmospheric pressure, first immersed in 100 g of solution containing copper chloride and H ₃ (PW ₁₂ O ₄₀ ) [to the total weight of the solution is 100 wt% The content of copper chloride is 15 wt%, and the content of H ₃ (PW ₁₂ O ₄₀ ) is 4 wt%]. After 24 hours, the carrier is taken out and allowed to stand, placed in an oven, and baked at 120 ° C for 10 hours. Thereafter, the catalyst (carrier: Mg _0.1 Gd _0.1 Al _0.8 O _1.45 ) was obtained.

<Example 3> Catalyst for the preparation of vinyl chloride (carrier: Mg _0.1 Eu _0.1 Al _0.8 O _1.45 )

The catalyst for the preparation of vinyl chloride of Example 3 was prepared according to the following steps:

(1) Preparation of carrier: 0.8 mole of α-alumina, 0.1 mole of magnesium oxide and 0.1 mole of cerium oxide were uniformly mixed, and calcined at 1200 ° C for 4 hours, followed by cooling to obtain a Mg _0.1 Eu _0.1 Al _0.8 O _1.45 carrier.

(2) Preparation of catalyst: Mg _0.1 Eu _0.1 Al _0.8 O _1.45 carrier, under atmospheric pressure, first immersed in 100g of solution containing copper chloride and potassium chloride (to the total weight of the solution is 100wt%, copper chloride content In the case of 10% by weight, the potassium chloride content is 1% by weight, after 24 hours, the carrier is taken out and allowed to stand, and then placed in an oven, and baked at 120 ° C for 10 hours to obtain the catalyst (carrier: Mg _0.1 Eu _0.1 Al _0.8 O _1.45 ).

<Example 4> Catalyst for the preparation of vinyl chloride (carrier: Mg _0.1 Y _0.1 Al _0.8 O _1.45 )

The catalyst for the preparation of vinyl chloride of Example 4 was prepared according to the following steps:

(1) Preparation of carrier: 0.8 mole of β-alumina, 0.1 mole of magnesium oxide and 0.1 mole of cerium oxide were uniformly mixed, calcined at 1500 ° C for 2 hours, and then cooled to obtain a Mg _0.1 Y _0.1 Al _0.8 O _1.45 carrier.

(2) Preparation of catalyst: Mg _0.1 Y _0.1 Al _0.8 O _1.45 carrier, under atmospheric pressure, first immersed in 100g of solution containing copper chloride and magnesium chloride (to the total weight of the solution is 100wt%, copper chloride content is 10wt %, magnesium chloride content is 2wt%), after 10 hours, the carrier is taken out and left to stand, placed in an oven, and baked at 120 ° C for 24 hours to obtain the catalyst (carrier: Mg _0.1 Y _0.1 Al _0.8 O _1.45 ).

<Comparative Example 1> Catalyst for the preparation of vinyl chloride (carrier: Al ₂ O ₃ )

The catalyst for preparing vinyl chloride of Comparative Example 1 was prepared according to the following steps:

(1) Preparation of catalyst: 1 mole of Y-alumina, under atmospheric pressure, first immersed in 100 g of solution containing copper chloride and magnesium chloride (total weight of solution is 100 wt%, copper chloride content is 10 wt%, magnesium chloride content In 2 wt%), after 24 hours, the carrier was taken out and allowed to stand, placed in an oven, and baked at 120 ° C for 10 hours to obtain the catalyst (carrier: Y-alumina).

It should be noted that the steps of preparing the carrier and the catalyst of the above Examples 1 to 4 and Comparative Example 1 can also be carried out under a vacuum environment.

The average particle diameter of the catalyst of Examples 1 to 4 and Comparative Example 1, the type and surface area of the carrier of the catalyst, and the type and content of the catalyst of the catalyst (based on the total weight of the catalyst: 100% by weight) were respectively summarized in Table 1 below. Show.

<Preparation of vinyl chloride using a fluidized bed reactor> Preparation method of vinyl chloride:

(1) 100 g of the catalysts of Examples 1 to 4 or Comparative Example 1 were placed in a fluidized bed reactor.

(2) a mixed gas containing hydrogen chloride, ethylene, oxygen and nitrogen (volumes as shown in Table 2 below), respectively, under the conditions of Table 3 below, in contact with the catalyst in the fluidized bed reactor, A gaseous product of vinyl chloride.

HCl conversion and vinyl chloride content of vinyl chloride:

The catalysts of Examples 1 to 4 or Comparative Example 1 will be used separately. The gas product obtained by the above method was analyzed by a gas chromatograph (flame ion detector), and the obtained HCl conversion rate and vinyl chloride content (100% by weight of the gas product) were shown in Table 4 below.

Results and discussion:

From the results of Table 4, it was found that Comparative Example 1 using alumina as a catalyst carrier had a vinyl chloride content of only 0.57 wt%, which was much lower than that of Mg _0.1 Gd _0.1 Al _0.8 O _1.45 , Mg _0.1 Eu _{0.1 .} Examples 1 to 4 of Al _0.8 O _1.45 and Mg _0.1 Y _0.1 Al _0.8 O _1.45 as catalyst carriers. In addition, the catalysts of Examples 1 to 4 are all one-step reaction in the preparation of vinyl chloride and the reaction temperature is also below 260 ° C, indicating that the catalyst of the present invention can be used in the one-step reaction to prepare vinyl chloride in a low temperature environment. It is also possible to increase the vinyl chloride content of the produced gas product (i.e., increase the yield of vinyl chloride).

It is particularly worth mentioning that in Examples 1 and 2 using Mg _0.1 Gd _0.1 Al _0.8 O _1.45 as a catalyst carrier, the resulting gas product had a higher vinyl chloride content.

In summary, since the catalysts of Examples 1 to 4 contain Mg _0.1 Gd _0.1 Al _0.8 O _1.45 , Mg _0.1 Eu _0.1 Al _0.8 O _1.45 or Mg _0.1 Y _0.1 Al _0.8 O _1.45 metal oxide carrier, When the catalyst of Examples 1 to 4 was used to prepare vinyl chloride, the yield of vinyl chloride was improved in addition to the one-step reaction in a low temperature environment, and the object of the present invention was indeed achieved.

However, the above is only the embodiment of the present invention, and the scope of the present invention is not limited thereto, that is, the simple equivalent changes and modifications made by the patent application scope and the patent specification of the present invention are still It is within the scope of the patent of the present invention.

Claims (16)

A catalyst for preparing vinyl chloride, comprising a carrier and a metal chloride supported on the carrier, the carrier comprising a metal oxide as shown in formula (I): M _x L _y Al _z O (I) M is an alkali metal or alkaline earth metal, and L is a rare earth metal, 0.001 ≦ x ≦ 0.5, 0.001 ≦ y ≦ 0.5, 0.1 ≦ z ≦ 0.9. The catalyst for preparing vinyl chloride according to claim 1, wherein the metal chloride is selected from the group consisting of alkali metal chlorides, alkaline earth metal chlorides, transition metal chlorides, rare earth metal chlorides, or a combination thereof. The catalyst for preparing vinyl chloride according to claim 1, which further comprises H ₃ (PW ₁₂ O ₄₀ ) supported on the carrier. The catalyst for preparing vinyl chloride according to claim 1, wherein the content of the metal chloride ranges from 5 to 20% by weight based on 100% by weight of the total weight of the catalyst. The catalyst for preparing vinyl chloride according to claim 3, wherein the content of the metal chloride and H ₃ (PW ₁₂ O ₄₀ ) is 5 to 20 wt% based on 100 wt% of the total weight of the catalyst. . The catalyst for preparing vinyl chloride as described in claim 1 has a surface area ranging from 0.5 to 10 m ² /g. The catalyst for preparing vinyl chloride according to claim 1, wherein the carrier is obtained by mixing alumina, a first metal oxide and a rare earth metal oxide, and then calcining, the first metal is oxidized. The substance is an alkali metal oxide or an alkaline earth metal oxide. The catalyst for preparing vinyl chloride according to claim 7, wherein the alumina is selected from the group consisting of α-alumina, β-alumina, γ-alumina or a combination thereof. The catalyst for preparing vinyl chloride according to claim 1, wherein the metal chloride is permeated by at least one selected from the group consisting of an impregnation method, an ion exchange method, a coprecipitation method, and a chemical vapor deposition method. Hosted on the carrier. A process for producing vinyl chloride comprising the step of contacting a mixed gas containing hydrogen chloride, ethylene, oxygen and nitrogen with a catalyst for preparing vinyl chloride as described in any one of claims 1 to 9. A method of producing vinyl chloride according to claim 10, wherein the mixed gas is contacted with the catalyst in a reactor which is a fixed bed reactor or a fluidized bed reactor. The method for producing vinyl chloride according to claim 11, wherein when the reactor is a fluidized bed reactor, the catalyst is granular and has an average particle size ranging from 30 to 100 μm. The method for producing vinyl chloride according to claim 11, wherein when the reactor is a fixed bed reactor, the catalyst is granular and the average particle size ranges from 1 to 10 mm. A method of producing vinyl chloride according to claim 10, wherein the mixed gas is contacted with the catalyst at 150 to 300 °C. A method for producing vinyl chloride according to claim 10, wherein a volume ratio of hydrogen chloride, ethylene, oxygen, and nitrogen in the mixed gas is in the range of 1:1:0.5:1.5 to 1.5:1.25:0.7:2.5. The method for preparing vinyl chloride according to claim 11, wherein the mixed gas is in a space velocity range of 100 to 1000 hr ^-1 , a temperature range of 150 to 300 ° C, a pressure range of 0.05 to 0.5 MPa, and a residence time range of 5 The catalyst was contacted in the reactor under ~50 seconds.