WO2017003014A1 - Method for successively reacting-regenerating and preparing fluid-type olefin after pre-treating with reducing gas - Google Patents

Abstract

The present invention relates to a method for successively reacting-regenerating and preparing a fluid-type olefin after pre-treating with reducing gas, and more specifically, provides a method for successively reacting-regenerating and preparing a fluid-type olefin, the method comprising the steps of: pre-treating a catalyst by supplying reducing gas to the catalyst, the catalyst being for preparing olefin from hydrocarbon (step 1); preparing olefin from hydrocarbon by using the catalyst pre-treated in step 1 (step 2); separating the catalyst used in step 2 and the prepared olefin, then regenerating the separated catalyst (step 3); and recirculating the catalyst regenerated in step 3 to the process in step 1 (step 4), wherein steps 1 to 4 are repeatedly performed so as to successively regenerate the catalyst and prepare olefin. Compared to conventional processes, the preparation method of the present invention adds a process of pre-treating a catalyst by supplying reducing gas thereto, and thus the selectivity and yield of olefin may be enhanced. Further, hydrocarbon may be prevented from being converted into an unnecessary by-product due to contacting with a catalyst at an early stage of a reaction, and thus the process of hydrocarbon being converted into olefin is easily done, and a catalyst may be efficiently utilized.

Description

Continuous reaction-regeneration and flow process for preparing olefin after reducing gas pretreatment

The present invention relates to a process for continuous reaction-regeneration and flow olefins after reducing gas pretreatment.

Olefins such as ethylene and propylene are widely used in the petrochemical industry. Generally these olefins are obtained in the pyrolysis process of naphtha. However, the petrochemical industry requires higher amounts of olefins, so olefins are also produced through dehydrogenation processes using catalysts of lower hydrocarbons.

Catalytic catalytic dehydrogenation processes for the production of olefins utilize various types of lower hydrocarbon compounds as raw materials and show excellent olefin production yields. However, in the early stage of the reaction in which the hydrocarbon is in contact with the catalyst, even though the olefin yield is high, the numerical value decreases with time, and thus there is a problem in that the conversion rate of the hydrocarbon and the yield of the olefin as a whole decrease. In order to solve this problem, a circulating fluidized bed process for shortening the contact time of hydrocarbon and catalyst has been proposed.

However, even in a process in which the contact time of the hydrocarbon and the catalyst is limited, the hydrocarbon generates by-products such as carbon dioxide and carbon monoxide, which are not olefins, rapidly reacting with the catalyst at the initial stage of the reaction. There is this.

Therefore, in the present invention, while studying a method of preparing a continuous reaction-regeneration and a flowable olefin after reducing gas pretreatment, which is more economical and productive than a conventional manufacturing process, by treating the reducing gas in advance before the catalyst reacts with a hydrocarbon, a higher olefin After the reduction gas pretreatment showing selectivity and yield, a process for the continuous reaction-regeneration and flow olefin production was developed and completed.

It is an object of the present invention to provide a continuous reaction-regeneration and fluidized olefin production method after pretreatment of reducing gas.

In order to achieve the above object, the present invention

Pretreatment of the catalyst by supplying a reducing gas to a catalyst for preparing olefins from hydrocarbons (step 1);

Preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 (step 2);

Separating the catalyst used in step 2 from the prepared olefin and regenerating the separated catalyst (step 3); And

Recycling the catalyst regenerated in step 3 to the process of step 1 (step 4); and

The above steps 1 to 4 are repeatedly performed to provide a continuous reaction-regeneration and fluidized olefin production method for continuously regenerating the catalyst and preparing the olefin.

In addition, the present invention

It provides an olefin produced by the above production method.

Furthermore, the present invention

A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon;

A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit;

A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst;

A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit;

A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;

Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And

It provides a continuous reaction-regeneration and fluidized olefin production apparatus for performing the production method comprising a; air reaction unit for regenerating the catalyst separated in the separation unit.

Furthermore, the present invention

A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon;

A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit;

A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst;

A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit;

A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;

Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And

In preparing an olefin using an apparatus comprising a; air reaction unit for regenerating the catalyst separated in the separation unit,

Supplying a reducing gas to the catalyst pretreatment unit to pretreat the catalyst for preparing the olefin from the hydrocarbon (step 1);

Supplying the catalyst pretreated in step 1 to the hydrocarbon reaction part through a catalyst supply part, and supplying a hydrocarbon raw material to a hydrocarbon reaction part through a hydrocarbon supply part to prepare an olefin from a hydrocarbon (step 2);

Separating the catalyst used in step 2 and the prepared olefin in the separation unit, and then introducing the separated catalyst into the air reaction unit to regenerate the catalyst (step 3); And

And introducing the catalyst regenerated in step 3 into the catalyst pretreatment unit (step 4).

The reducing gas is a by-product produced during the preparation of the olefin from the hydrocarbon in step 2, it provides a method for recycling by-products generated during the production of olefin from a hydrocarbon.

In the preparation method of the present invention, a process for supplying a reducing gas to the catalyst and pretreatment is added as compared to the conventional process, thereby improving the selectivity and yield of the olefin. In addition, the hydrocarbon is prevented from contacting the catalyst at the beginning of the reaction to be converted into unnecessary by-products, thereby facilitating the process of converting the hydrocarbon into olefins, and enabling efficient utilization of the catalyst.

1 is a graph showing the results of analyzing the temperature and the reaction product of the catalyst layer according to the propane dehydrogenation reaction in Comparative Example 2;

2 is a schematic representation of an apparatus for implementing the method of the present invention;

3 is a graph showing the temperature change of the catalyst layer after hydrogen pretreatment, which is a reducing gas of the catalyst in Experimental Example 1 of the present invention;

4 is a graph showing the temperature change of the catalyst layer after carbon monoxide pretreatment, which is a reducing gas of the catalyst in Experimental Example 1 of the present invention;

5 is a graph showing the temperature change of the catalyst layer after methane pretreatment, which is a reducing gas of the catalyst in Experimental Example 1 of the present invention;

6 is a graph showing the temperature change of the catalyst layer after ethylene pretreatment, which is a reducing gas of the catalyst in Experimental Example 1 of the present invention;

7 is a graph showing a comparison according to the presence or absence of reducing gas pretreatment of the catalyst in Example 6 and Comparative Example 2 of the present invention.

<Description of the code>

10: hydrocarbon reaction part

20: air reaction part

30: hydrocarbon supply unit

40: catalyst supply unit

50: separator

60 catalyst pretreatment unit

70: reducing gas supply unit

The present invention,

Pretreatment of the catalyst by supplying a reducing gas to a catalyst for preparing olefins from hydrocarbons (step 1);

Preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 (step 2);

Separating the catalyst used in step 2 from the prepared olefin and regenerating the separated catalyst (step 3); And

Recycling the catalyst regenerated in step 3 to the process of step 1 (step 4); and

The above steps 1 to 4 are repeatedly performed to provide a continuous reaction-regeneration and fluidized olefin production method for continuously regenerating the catalyst and preparing the olefin.

Hereinafter, the continuous reaction-regeneration and fluidized olefin production method according to the present invention will be described in detail for each step.

In the method of preparing a continuous reaction-regeneration and fluidized olefin after reducing gas pretreatment according to the present invention, step 1 is a step of pretreating the catalyst by supplying a reducing gas to a catalyst for preparing an olefin from a hydrocarbon.

The production process of the invention relates in particular to a dehydrogenation process for producing olefins from hydrocarbons. At this time, the catalyst is generally used when preparing the olefin, and when preparing the olefin from the hydrocarbon through the catalyst in the prior art as shown in the graph of FIG. It can be seen that the temperature gradually decreases after that.

At this time, when looking at the conversion rate and the olefin selectivity along with the temperature change of the catalyst with time, the conversion rate was found to reach 100% at the beginning of the reaction in which the temperature of the catalyst is increased. It can be seen that most of the carbon dioxide is generated.

That is, it can be seen from the graph of FIG. 1 that the by-products other than olefins are generated from hydrocarbons at the beginning of the reaction in which the temperature of the catalyst increases, and that olefins are prepared from hydrocarbons from the point where the temperature of the catalyst gradually decreases. .

Therefore, referring to the graph of FIG. 1, it can be seen that when preparing an olefin from hydrocarbons, an initial part of the reaction, for example, about 5 seconds from the start of the reaction, corresponds to an unnecessary part for preparing the olefin.

Thus, in the production method of the present invention in the prior art as described above by the reaction zone in which the by-product carbon dioxide is generated, to reduce the efficiency of the catalyst in step 1 by supplying a reducing gas to the catalyst for preparing the olefin from a hydrocarbon The catalyst is pretreated.

For example, the pretreatment of step 1 focuses on the generation of by-products when the temperature of the catalyst increases in the prior art, that is, in the graph of FIG. 1, and a section in which the temperature is increased by pretreatment of the catalyst before being supplied to the hydrocarbon. This is because the olefin can be produced immediately without a by-product section when the catalyst is fed with hydrocarbon.

At this time, the pretreatment of step 1 may be performed by contacting the catalyst and the reducing gas for 0.5 to 5 seconds. The time range during which the contact is carried out, as shown in the graph of FIG. 1, specifies the extent to which the temperature of the catalyst is raised approximately, thereby pretreating the catalyst to an optimal state for olefin production. have.

However, when the contact between the catalyst and the reducing gas is less than 0.5 seconds, the optimization of the catalyst according to the pretreatment of step 1 may not be achieved. When the contact between the catalyst and the reducing gas exceeds 5 seconds, the yield of the olefin is rather increased. Degradation problems may occur.

In this case, the reducing gas of step 1 may include at least one hydrocarbon having a linear or branched C ₁ to C ₄ alkane structure.

Alternatively, the reducing gas of step 1 may include at least one hydrocarbon having a linear or branched C ₁ to C ₄ alkene structure,

Or a hydrocarbon having an alkane structure of C ₁ to C ₄ .

On the other hand, the reducing gas of step 1 may include a gas such as carbon monoxide, hydrogen, ethylene, ethane, methane. The gas, such as carbon monoxide, may react with oxygen on the surface of the highly reactive catalyst to pretreat the catalyst, and the temperature of the catalyst may increase due to the exotherm generated by the pretreatment.

As an example, the catalyst of step 1, for example a metal oxide catalyst, may be a chemical reaction of hydrogen, which is a kind of reducing gas, and M _x O _y + H ₂ → M _{x '} O _{y '} + H ₂ O. The reaction is an exothermic reaction in which water is generated, thereby increasing the temperature of the catalyst.

In addition, the reducing gas of step 1 may be a by-product generated when preparing the olefin from a hydrocarbon. In preparing olefins from hydrocarbons, carbon monoxide, hydrogen, ethylene, ethane, methane and the like are usually generated as by-products. In the production method of the present invention can be used as a reducing gas for pretreatment of the catalyst such as carbon monoxide generated as a by-product, there is an effect that can reduce the cost of the manufacturing process.

In the preparation method of the present invention, step 2 is a step of preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 above.

In the present invention, the catalyst of step 2 is pretreated by a reducing gas before reacting with hydrocarbons, so that the olefin can be produced more efficiently compared to the catalyst in the prior art, that is, a catalyst that has been introduced into the olefin production process without pretreatment. have.

That is, as mentioned above, there was a disadvantage in that unnecessary by-products are generated during a short time when the temperature of the catalyst increases during the preparation of the olefin, but the catalyst in the state of which the temperature is increased through the pretreatment of step 1 may be produced without a by-product section. The olefin can be produced from a hydrocarbon. This not only enables the mass production of olefins, but also increases the efficiency in terms of economics of the process.

When preparing the olefin in step 2, the contact time between the pretreated catalyst and the raw material hydrocarbon may be 0.5 to 10 seconds, preferably 2 to 3 seconds.

If the contact time of the hydrocarbon and the catalyst is less than 0.5 seconds, there is a problem that the conversion rate of the hydrocarbon is lowered, and if the contact time is more than 10 seconds, the amount of active lattice oxygen participating in the reaction among the lattice oxygen of the catalyst is drastically reduced. Problems may occur in which the selectivity of olefins is reduced.

At this time, the catalyst in contact with the hydrocarbon in step 2, that is, the catalyst pretreated in step 1, may be a metal oxide catalyst, in this case, the reaction in which the olefin is prepared from the hydrocarbon may be represented by the following scheme 1.

<Scheme 1>

Lattice oxygen of hydrocarbon + M _x O _y → olefin + H ₂ O + M _{x '} O _y'

(Wherein M _x O _y in the scheme is the catalyst of step 1,

M is at least one metal selected from the group consisting of chromium, vanadium, manganese, iron, cobalt, molybdenum, copper, zinc, cerium and nickel,

y / x> y '/ x')

The catalyst used in the above steps 1 and 2 may be a metal oxide, as shown in the above scheme, for example, may be in a form supported on a carrier. The metal oxide catalyst is an oxygen species carrier, and when the oxygen species carrier is used as a catalyst, a reaction occurs in which lattice oxygen on the catalyst reacts with hydrogen released from the hydrocarbon to generate water and olefins. Accordingly, the olefin selectivity is high, and the oxidative exothermic reaction of the desorbed hydrogen, which compensates for the lack of reaction energy due to the dehydrogenation endothermic reaction, proceeds, and the manufacturing method thereof is also simple, so that there is an advantage in that economical and mass production is possible.

The carrier may be, for example, alumina, but is not limited thereto. The catalyst may be selected by selecting an appropriate material that can be used as a carrier of the catalyst.

In the preparation method according to the present invention, step 3 is a step of separating the catalyst reacted in step 2 with the prepared olefin and regenerating the separated catalyst.

The metal oxide may be regenerated through the catalyst reacted in Step 2, for example, the reaction represented by Scheme 2 below. At this time, M _{x '} O _{y '} of Scheme 2 means a catalyst on which the reaction as in Scheme 1 is carried out, Scheme 2 is a reaction to the reaction with oxygen after the catalyst reacted with the hydrocarbon is separated from the olefin through the separation unit It is shown to be performed by.

<Scheme 2>

M _{x '} O _y' + O ₂ → M _x O _y

In the production method according to the present invention, step 4 is a step of recycling the catalyst regenerated in step 3 to the process of step 1.

By feeding the catalyst regenerated in step 3 of the present invention back to the process of step 1, the catalyst is recycled, thereby making it possible to produce olefins more economically.

 In addition, since the reaction in which the catalyst is regenerated in step 3 is exothermic, it is possible to raise the temperature of the catalyst through the generated heat energy, and thus, pretreatment may be performed more smoothly through the reducing gas in step 1 being recycled.

In other words, in raising the temperature of the catalyst to the temperature required when preparing the olefin from the hydrocarbon, energy is supplied to the catalyst by the regeneration of the step 3 it is possible to raise the temperature of the catalyst more economically.

In this way, the production method of the present invention can not only improve the yield of olefin production through the pretreatment of the catalyst, but also can regenerate and repeatedly use the catalyst used in the production of olefin, thereby further improving the economics of the process. In addition, there is an advantage that the olefin can be continuously produced.

In addition, the present invention,

It provides an olefin produced by the above production method.

As mentioned above, the production method of the present invention is a method that can produce olefins more economically than in the prior art, in which there was no pretreatment for the catalyst. Therefore, in the case of the olefin according to the present invention there is an advantage that is more economical than the prior art.

Furthermore, the present invention,

A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon;

A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit;

A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst;

A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit;

A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;

Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And

It provides a continuous reaction-regeneration and fluidized olefin production apparatus comprising a; air reaction unit for regenerating the catalyst separated in the separation unit.

At this time, it is shown through a schematic diagram of Figure 2 showing an example of the manufacturing apparatus of the present invention, with reference to the drawings will be described in detail the manufacturing apparatus of the present invention.

As shown in FIG. 2, through the reducing gas supply unit 70, a reducing gas capable of causing an exothermic reaction with active oxygen species included in the catalyst is supplied to the catalyst pretreatment unit 60. In this case, the catalyst pretreated by the reducing gas in the catalyst pretreatment unit is supplied to the hydrocarbon reaction unit 30 through a catalyst supply unit 40, and the reaction in which the olefin is generated from the supplied hydrocarbon is performed in the hydrocarbon reaction unit. .

The olefin produced in the hydrocarbon reaction unit may be obtained by being separated from the catalyst used in the separation unit 50, and the catalyst separated in the separation unit may be supplied to the air reaction unit 20 to be regenerated.

In addition, the catalyst regenerated in the air reaction unit 20 may be supplied again to the catalyst pretreatment unit 60, and then supplied to the hydrocarbon reaction unit again after the pretreatment.

That is, the manufacturing apparatus is a device for performing the olefin production method of the present invention as described above, it is possible to produce the olefin from the hydrocarbon while performing the pretreatment process of the catalyst through a reducing gas, by the pre-treatment more than before Olefin can be produced in high yields.

Furthermore, the present invention,

A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon;

A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit;

A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst;

A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit;

A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit;

Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And

In preparing an olefin using an apparatus comprising a; air reaction unit for regenerating the catalyst separated in the separation unit,

Supplying a reducing gas to the catalyst pretreatment unit to pretreat the catalyst for preparing the olefin from the hydrocarbon (step 1);

Supplying the catalyst pretreated in step 1 to the hydrocarbon reaction part through a catalyst supply part, and supplying a hydrocarbon raw material to a hydrocarbon reaction part through a hydrocarbon supply part to prepare an olefin from a hydrocarbon (step 2);

Separating the catalyst used in step 2 and the prepared olefin in the separation unit, and then introducing the separated catalyst into the air reaction unit to regenerate the catalyst (step 3); And

And introducing the catalyst regenerated in step 3 into the catalyst pretreatment unit (step 4).

The reducing gas is a by-product produced during the preparation of the olefin from the hydrocarbon in step 2, it provides a method for recycling by-products generated during the production of olefin from a hydrocarbon.

At this time, the recycling method of the present invention includes the same technical features as described in the method for producing and manufacturing the olefins described above, but relates to a method for recycling the by-product as a reducing gas for pretreatment of the catalyst, Since it is as described above except used as a reducing gas, the description thereof is omitted.

The recycling method of the present invention is to use by-products, ie, by-products of carbon monoxide, hydrogen, methane, ethane, ethylene and the like generated as a reducing gas for pretreatment of the catalyst when preparing olefins from hydrocarbons.

In other words, it is possible to solve the economic loss caused by the disposal of by-products, which can be used for the pretreatment of the catalyst, rather than disposing of unnecessary by-products. Environmental benefits can also be demonstrated.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the following examples are only for the description of the present invention and the scope of the present invention is not limited by the following examples.

<Production example>

Step 1: γ-Al ₂ O ₃ having a size of 45-120 um obtained by spray drying and calcining an alumina sol was prepared as a carrier.

Step 2: To impregnate the metal oxide on the carrier prepared in Step 1, a wet impregnation method was used. Specifically, the alumina carrier prepared in step 1 was immersed in dilute CrO ₃ precursor solution, it was left at room temperature for 12 hours, and then the alumina carrier was dried in a 120 ° C. oven.

The dried carrier was calcined at 700 ° C. for 6 hours, whereby 17.5 wt% Chromium oxide / Alumina (Al ₂ O ₃ ) Catalyst was prepared.

Example 1 Preparation of Olefin 1

Step 1: Pretreatment of hydrogen (H ₂ ) with the catalyst through a reducing gas supply prior to supplying the chromium oxide / alumina (Al ₂ O ₃ ) catalyst prepared in the above preparation to the reaction via the catalyst supply To the temperature, and the temperature of the catalyst passing through the catalyst supply was raised to 660 ℃.

Step 2: The catalyst heated in step 1 was supplied to the hydrocarbon reaction section, and propane was supplied to the hydrocarbon reaction section through the hydrocarbon supply section to prepare propylene.

Step 3: The catalyst reacted with propylene prepared in step 2 was separated in a separation unit to obtain propylene, and the reacted catalyst was fed back into the air reaction unit to regenerate.

Step 4: The catalyst regenerated in the air reaction unit was repeatedly performed in step 1, and then supplied to the hydrocarbon reaction unit.

Example 2 Preparation of Olefin 2

Propylene was prepared in the same manner as in Example 1 except for supplying carbon monoxide (CO) instead of hydrogen as the reducing gas in Step 1 of Example 1 of the present invention.

Example 3 Preparation of Olefin 3

Propylene was prepared in the same manner as in Example 1 except for supplying methane (CH ₄ ) instead of hydrogen as a reducing gas in Step 1 of Example 1 of the present invention.

Example 4 Preparation of Olefin 4

Propylene was prepared in the same manner as in Example 1 except that ethylene (C ₂ H ₄ ) instead of hydrogen was supplied as the reducing gas in Step 1 of Example 1 of the present invention.

Example 5 Preparation of Olefin 5

Propylene was prepared in the same manner as in Example 1 except that ethane (C ₂ H ₆ ) instead of hydrogen was supplied as the reducing gas in Step 1 of Example 1 of the present invention.

Example 6 Preparation of Olefin 6

In the following Comparative Example 2 of the present invention, the flow rate of the reducing gas was 0.11 mol H ₂ / mol Cr, and the furnace temperature was maintained at 680 ° C., in the same manner as in Comparative Example 2, before flowing the propane. To produce propylene.

Comparative Example 1

Propylene was prepared in the same manner as in Example 1 except that no reducing gas was used in Step 1 of Example 1 of the present invention.

Comparative Example 2

Chromium oxide / Alumina (Al ₂ O ₃ ) prepared in the preparation example of the present invention 0.4 g of the catalyst was fixed on a fritz in a reactor made of quartz, and the furnace temperature was maintained at 630 ° C., followed by propane. The space velocity was 8,230 liter _C3 / (kg _cat -hr), through which propylene was produced.

Experimental Example 1 Temperature Change of Catalyst Layer After Pretreatment of Reducing Gas of Catalyst

Hydrogen, carbon monoxide, methane, and ethylene were supplied as reducing gases, and then the temperature of the catalyst bed was analyzed as follows when propane was flowed.

(1) When hydrogen was supplied as the reducing gas, the temperature of the catalyst during the propane dehydrogenation reaction was measured, and the results are shown in FIG. 3.

As shown in FIG. 3, it can be seen that as the amount of hydrogen for pretreatment of the oxygen species carrier increases, the width of the catalyst bed temperature increase due to the rapid combustion reaction in the initial stage of the dehydrogenation reaction decreases.

(2) When carbon monoxide was supplied as the reducing gas, the temperature of the catalyst during the propane dehydrogenation reaction was measured, and the results are shown in FIG. 4.

As shown in FIG. 4, it can be seen that as the amount of carbon monoxide for pretreatment of the oxygen species carrier increases, the width of the catalyst bed temperature increase due to the rapid initial combustion reaction during the dehydrogenation reaction decreases.

(3) When methane was supplied as the reducing gas, the temperature of the catalyst during the propane dehydrogenation reaction was measured, and the results are shown in FIG. 5.

As shown in FIG. 5, it can be seen that as the amount of methane for pretreatment of the oxygen species carrier increases, the width of the catalyst bed temperature increase due to the rapid initial combustion reaction during the dehydrogenation reaction decreases.

(4) When ethylene was supplied as the reducing gas, the temperature of the catalyst during the propane dehydrogenation reaction was measured, and the results are shown in FIG. 6.

As shown in FIG. 6, it can be seen that as the amount of ethylene for pretreatment of the oxygen species carrier increases, the width of the catalyst bed temperature increase due to the initial combustion reaction during the dehydrogenation reaction decreases.

Experimental Example 2 Comparative Analysis According to Pretreatment of Catalysts through Reducing Gas

In Examples 1 to 6 and Comparative Examples 1 and 2 to which the reducing gas pretreatment of the catalyst of the present invention was added, the yield of propylene and the conversion rate of propane were measured and shown in FIG. 7, Tables 1 and 2, respectively.

As shown in FIG. 7, when the catalyst was pretreated with a reducing gas as in Example 6, unlike the results of Comparative Example 2, the yield and selectivity of propylene increased immediately after the contact of propane with the catalyst and the yield of carbon dioxide, a byproduct, decreased It can be seen that.

Comparative Example 1 Example 1 Example 2 Example 3 Example 3 Reducing gas H ₂ CO CH ₄ CH ₄ Reduction Gas Supply (mol / Cr mol) 0.0443 0.0394 0.0361 0.0354 Catalyst Supply Part Catalyst Temperature ( ^o C) 597 660 660 661 660 Catalyst / propane ratio (weight / weight) 31.5 26.2 21 27.6 24.1 Propane Conversion Rate (%) 42.2 49.0 42.32 45.33 39.09 Propylene Yield (%) 30.76 34.15 30.95 34.69 31.04

Example 3 Example 4 Example 5 Reducing gas CH ₄ C ₂ H ₄ C ₂ H ₆ Reduction Gas Supply (mol / Cr mol) 0.0529 0.0537 0.0762 Catalyst Supply Part Catalyst Temperature ( ^o C) 670 670 670 Catalyst / propane ratio (weight / weight) 38.6 38 37.5 Propane Conversion Rate (%) 47.53 51.01 50.01 Propylene Yield (%) 35.19 40.08 44.51

As shown in Tables 1 and 2, the propylene yield increased from 30.76% to 44.51% as the catalyst was pretreated with reducing gas.

Claims (10)

Pretreatment of the catalyst by supplying a reducing gas to a catalyst for preparing olefins from hydrocarbons (step 1); Preparing an olefin from a hydrocarbon using the catalyst pretreated in step 1 (step 2); Separating the catalyst used in step 2 from the prepared olefin and regenerating the separated catalyst (step 3); And Recycling the catalyst regenerated in step 3 to the process of step 1 (step 4); and The above steps 1 to 4 are repeatedly performed to continuously regenerate the catalyst and to produce olefins. The method of claim 1, wherein the pretreatment of step 1 is carried out by contacting the reducing gas with a catalyst for 0.5 to 5 seconds. The method of claim 1, wherein the reducing gas of step 1 comprises at least one hydrocarbon having a linear or branched C ₁ to C ₄ alkane structure. The method of claim 1, wherein the reducing gas of step 1 comprises at least one hydrocarbon having a linear or branched C ₁ to C ₄ alkene structure. The method of claim 1, wherein the reducing gas of step 1 comprises at least one hydrocarbon having an alkane structure of C ₁ to C ₄ . The method of claim 1, wherein the reducing gas of step 1 comprises at least one gas selected from the group consisting of carbon monoxide, hydrogen, ethylene, ethane and methane. . The method of claim 1, wherein the reducing gas of Step 1, Continuous reaction-regeneration and flow olefin production method characterized in that the by-product produced in the preparation of the olefin from the hydrocarbon in step 2. Olefin prepared by the method of claim 1. A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon; A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit; A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst; A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit; A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit; Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And Air reaction unit for regenerating the catalyst separated in the separation unit; comprising a continuous reaction-regeneration and fluidized olefin production apparatus for performing the production method of claim 1. A hydrocarbon reaction unit for preparing an olefin from a hydrocarbon; A hydrocarbon supply unit supplying a hydrocarbon to the hydrocarbon reaction unit; A reducing gas supply unit for supplying a reducing gas capable of causing an exothermic reaction with oxygen species contained in the catalyst; A catalyst pretreatment unit for pretreating the catalyst through a reducing gas supplied from the reducing gas supply unit; A catalyst supply unit supplying the catalyst pretreated in the catalyst pretreatment unit to the hydrocarbon reaction unit; Separation unit for separating the olefin and the catalyst prepared in the hydrocarbon reaction unit; And In preparing an olefin using an apparatus comprising a; air reaction unit for regenerating the catalyst separated in the separation unit, Supplying a reducing gas to the catalyst pretreatment unit to pretreat the catalyst for preparing the olefin from the hydrocarbon (step 1); Supplying the catalyst pretreated in step 1 to the hydrocarbon reaction part through a catalyst supply part, and supplying a hydrocarbon raw material to a hydrocarbon reaction part through a hydrocarbon supply part to prepare an olefin from a hydrocarbon (step 2); Separating the catalyst used in step 2 and the prepared olefin in the separation unit, and then introducing the separated catalyst into the air reaction unit to regenerate the catalyst (step 3); And And introducing the catalyst regenerated in step 3 into the catalyst pretreatment unit (step 4). The reducing gas is a by-product produced during the preparation of the olefin from the hydrocarbon in step 2, characterized in that the recycling of by-products generated during the production of olefin from hydrocarbon.

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