WO2016018097A1

WO2016018097A1 - Naphtha and methanol mixed catalytic cracking reaction process

Info

Publication number: WO2016018097A1
Application number: PCT/KR2015/007989
Authority: WO
Inventors: 강나영; 박용기; 최원춘; 김대진; 서휘민; 박선영; 오주형; 강신철
Original assignee: 한국화학연구원
Priority date: 2014-08-01
Filing date: 2015-07-30
Publication date: 2016-02-04

Abstract

The present invention concerns a naphtha and methanol mixed catalytic cracking reaction process involving a simultaneous cracking reaction of naphtha and methanol by using a circulating fluidized-bed reactor comprising a reactor, a stripper and a regenerator, being a catalytic cracking reaction process wherein: the naphtha is supplied from the bottom part of the reactor, at a position between 0% and 5% of the total length of the reactor; and the methanol is supplied from the bottom part of the reactor, at a position between 10% and 80% % of the total length of the reactor. In the catalytic cracking reaction process according to the present invention, by using the circulating fluidized-bed reactor and by simultaneously cracking the naphtha and methanol that are introduced into the reactor while having different introduction positions for the naphtha and the methanol, the present invention makes it possible to ensure heat neutralisation and thus possible to minimise the amount of energy used, and, in addition, makes it possible to improve the yield of light olefins by suppressing the production of light saturated hydrocarbons such as methane, ethane and propane.

Description

[Specifications

[Name of invention]

Naphtha and Methanol Mixed Catalytic Reaction

Technical Field 1

<οοοι> The present invention relates to a method for producing hard lepin, such as ethylene, propylene, through a naphtha and methanol mixed catalytic reaction process for performing a co-decomposition reaction of naphtha and methanol using a circulating fluidized bed reaction.

<0002>

Background Art

Hard lepine, such as ethylene and propylene, is produced by the high temperature pyrolysis process of more than 800 of naphtha mostly in the basic raw materials of the petrochemical industry, and because of the endothermic reaction, a large amount of energy is used. Recently, the naphtha cracker's competitiveness is falling due to the increase in the weight of natural gas crackers in which ethylene is selectively produced, and the development of Sinulpin manufacturing technology capable of selectively producing propylene is required.

<0004>

<0 (»5) Recently, the Korea Institute of Chemistry, SK Innovat ion, and KBR have developed a catalytic naphtha cracking process and an advanced catalyzed oligophosphate (ACO) process that can improve propylene production by more than 100 ¾ compared to the existing naphtha pyrolysis process. (Korean Patent No. 10-0651329, Korean Patent No. 10-0632563) Alternative Paper (Article 26) <0006>

Meanwhile, as a new olefin production technology, MTO (Methanol To Olef in) technology for producing light olefins from methane after producing methanol through gasification or reforming from coal or natural gas is emerging on the market. The pyrolysis reaction that produces light olefins in naphtha is an endothermic reaction, whereas the MTO reaction that produces light lepine in methanol is an exothermic reaction, which generates a large amount of heat. have. The Γ0 process was developed by U0P in the US and DICP in China, and is in operation for commercial production.

<麵>

As listed above, hydrocarbon reactions are endothermic and methane is an exothermic reaction, so a reaction that combines two reactions for heat neutral i zat ion has been proposed. . Nowak et al. Have shown that methane can be thermally enriched by the addition of C4 hydrocarbons to the conversion process (Appl. Catal. A, 50, (1989) 149-155). The introduction of methane and n-butane in a ratio of 1: 3 suggests that cracking can be promoted for the production of hard lephine without additional energy supply or removal from outside.

<0010>

However, methanol dissolution incineration occurs very fast compared to the decomposition reaction of naphtha, which is a hydrocarbon, so it is disadvantageous to increase the yield of hard lepin by simply producing a lot of side reactions.

<0012> Alternative Paper (Article 26) Thus, the present inventors have been studying the naphtha and methanol combined catalytic cracking reaction process to perform the co-decomposition of naphtha and methanol. Completion of the present invention by performing a co-decomposition reaction of naphtha and methane using a circulating fluidized bed reactor, by adjusting the input position of the naphtha and methanol into the circulating fluidized bed reaction reactor to complete the present invention and completed the present invention It was.

<0014>

Detailed Description of the Invention

[Technical problem]

An object of the present invention is to provide a method for the combined catalytic cracking reaction of naphtha and methane, which is performed due to the high rate of methanol decomposition. It is to provide a method for minimizing the generation of saturated hydrocarbons and improving the yield of hard lepine.

<0016>

Technical Solution

In order to achieve the above object, the present invention

<oois> In a catalytic cracking reaction of naphtha and methanol in which a co-reaction of naphtha and methanol is carried out using a circulating fluidized bed semi-reactor comprising a repeller, a stripper (st r i pper) and a regenerator,

Wherein the naphtha is fed from the bottom of the reactor to a position of 0 ¾ to 5% of the total reactor length, and the methanol is fed from the bottom of the reactor to a position of 10% to 80% of the total reactor length. Provides a catalytic cracking reaction process. Alternative Site (Article 26) <0020>

In addition, the present invention

In the combined catalytic cracking reaction of naphtha and methanol, which performs a simultaneous decomposition reaction of naphtha and methanol using a circulating fluidized bed reactor including a reactor, a stripper and a regenerator,

The naphtha is fed from the bottom of the half hopper to a position of 0 ¾ to 5 ¾ of the length of the full lash, and the methane is

Provides a hard lepine produced by the catalytic cracking reaction process, including feeding to a 10% to 80% position

<0024>

Furthermore, the present invention

<0026> A method for producing hard lephine by a mixed reaction reaction of naphtha and methanol, which performs a simultaneous decomposition reaction of naphtha and methanol using a circulating fluidized bed half vessel including a half container, a stripper, and a regenerator. There is

Wherein the naphtha is supplied from 0 ¾ to 5% of the total half-length of the reaction vessel from the bottom of the semi-container, the methane is supplied from 10% to 80% of the total reactor length from the bottom of the semi-unggi Characterized by a hard to provide a method for improving the pin yield.

<0028>

【Effects of the Invention】

The catalytic cracking reaction process according to the present invention uses a circulating fluidized bed reaction reactor 1, reactor replacement paper (rule 26) By dissolving naphtha methane at the same time by different naphtha and methanol input positions, it is possible to minimize heat consumption by minimizing energy consumption and to minimize energy consumption. The production of light saturated hydrocarbons can be suppressed to improve light olefin yield.

<0030>

[Brief Description of Drawings]

Figure 1 is a schematic diagram showing an example of the circulating fluidized bed bed used in the catalytic cracking process reaction according to the present invention;

2 is carried out under the same conditions as in Comparative Example 1 in the catalytic cracking anti-reflection process while changing the weight ratio of methane to hard naphtha from 0 to ¾ to 100% by weight of the inlet (inl et) A graph of the temperature difference between the outlets (out l et);

3 is a graph showing the yield of methane after performing the process of Examples 1 to 4 ᅳ Comparative Example 1 and Comparative Example 2 according to the present invention;

Figure 4 is a graph showing the yield of the light olefin after performing the process of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 according to the present invention;

5 is a graph illustrating changes in the reactor temperature after performing the processes of Examples 1 to 4, Comparative Example 1 and Comparative Example 2 according to the present invention.

<0036>

[Best form for implementation of the invention]

<0037> The present invention

<oo38> Circulating fluidized bed reactors, including reactors, strippers and regenerators, shall be used as replacement papers (Art. 26). In the catalytic cracking reaction process of naphtha and methanol, which performs the simultaneous reaction of naphtha and methane.

The naphtha is fed from the bottom of the half vessel to 0 ¾ to 5% of the total half vessel length and the methanol is from the bottom of the reactor

Provided is a catalytic cracking reaction process comprising feeding to a 10% to 80% position. 0040>

1 shows an example of a circulating fluidized bed semi-container for carrying out a mixed catalytic cracking process of naphtha and methane.

<0 (M2>) Hereinafter, the catalytic cracking reaction process according to the present invention will be described in detail with reference to a schematic diagram showing an example of a circulating fluidized bed anti-container in FIG. 1.

<0043>

The conventionally proposed techniques propose only concepts for realizing thermal increase to increase energy efficiency in the simultaneous decomposition of naphtha and methane, which have significantly different reaction rates and heats of reaction. However, in order to obtain hard lepin with high yield by inputting two reaction products at the same time, this concept alone is unsatisfactory, and accurate contact time control according to reaction reaction speed is essential.

In order to solve this problem, in the present invention, a circulating fluidized bed anti-tanker was applied, and the position of the hydrocarbon and the methane was adjusted to more precisely control the contact time of naphtha and methanol to a desired time.

<0046>

Hard paper such as ethylene and propylene in the decomposition reaction of naphtha and methanol (Article 26 of the Rule) The pin is an intermediate product, and if the contact time is short, the decomposition does not occur smoothly. If the contact time is too long, the coarseness is intensified to obtain an unwanted product. Therefore, it is very important to precisely control the contact time between the reactant and the catalyst.

In particular, since the decomposition rate of methanol is more than 10 times faster than the decomposition rate of naphtha, which is a hydrocarbon, when the two effluents are added at the same time, the residence time of methanol becomes too long, and thus, the hard saturated hydrocarbons such as methane, ethane, and propane And there is a problem that the amount of BTX production increases. In order to solve this problem, it is preferable to shorten the residence time of methanol in the reactor as compared to naphtha, and for this purpose, it is more preferable to change the position to be introduced into the reactor of the circulating fluidized bed reaction vessel of naphtha and methane. .

<0049>

The circulating fluidized bed reactor 100 used in the catalytic cracking reaction process according to the present invention preferably includes a reaction vessel 10, a stripper 20, and a regenerator 30 as a specific example. .

The reactor 10 is a specific example. It may be a vertical tube (r iser). The vertical tube may have a length of 5 m to 15 m, the diameter may be 1/4 inch to 1 inch, but is not limited thereto. In addition, the reactor 10 may be each formed with a tube to which naphtha and methanol are supplied. In the catalytic cracking reaction process according to the present invention, since the naphtha and methane input positions are different, it is preferable to form tubes for naphtha and methanol at respective positions.

In addition, the stripper 20 is produced value substitute paper produced from naphtha and methanol (Article 26) It may include a cylinder 21 for discharging the product gas. Furthermore, a regenerator 30 is located under the stripper, and may further include a valve 22 for distinguishing the stripper and the regenerator and controlling the circulating flow of catalyst and fuel gas.

The regenerator 30 may include a cylinder 31 for discharging a fuel gas (feul gas) containing naphtha and methane. The regenerator may be filled with a catalyst, and a tube through which air (ai r) may be injected may be formed under the regenerator. In addition, it is preferable that the bottom of the regenerator is connected to the reaction vessel 10, and may further include a valve 32 for distinguishing the regenerator and the reactor and regulating the circulating flow of the catalyst and fuel gas.

<0054>

In the catalytic cracking reaction process according to the present invention, the co-reaction reaction of naphtha and methanol is performed by using the circulating fluidized bed half vessel as described above, wherein the naphtha is supplied to the bottom of the half vessel and the methanol is separated from the bottom. It is preferred to be supplied. The input position of methanol may vary depending on the reaction temperature, the amount of circulation of the catalyst, and the amount of the semi-solution, but it is preferable that the methanol is introduced at a position of 10% to 80% of the length of the entire reactor from the bottom of the semi-container. In this way, if the input position is different, thermal increase can be achieved and the yield of light olefin can be maximized.

In addition, in order to more precisely control the contact time of naphtha and methane with the catalyst of the naphtha is supplied from 0 to 5 ¾ position of the total reactor length from the bottom of the reactor, the methanol is Of the total reactor length from the bottom

It is preferred to be fed to the 10% to 80 3/4 position. More preferably, the methane replacement paper (Article 26) It may be supplied from the bottom of the half vessel to the 15% to 45% position of the total half vessel grinding.

<0057>

In this case, the naphtha used as a _semi- aquaculture may include a saturated hydrocarbon or an unsaturated hydrocarbon having C ₄ to C ₁₂ , and the naphtha may be a full range of naphtha or hard naphtha. light naphtha, raffinate oil, and mixtures thereof. In addition, unlike the pyrolysis process using only saturated hydrocarbons, the circulating-flow-catalytic cracking process using the catalyst may be used as an anti-lephine containing hydrocarbon.

Further, the methanol used as the reaction product can be used not only anhydrous methanol, but also hydrous methanol containing up to 20% of water.

<0060>

In addition, the circulating fluidized bed reaction apparatus 100 is cyclically circulated, wherein the catalyst may use a zeolite-based catalyst. As a specific example, the catalyst may use a shaped spherical or elliptical catalyst having a diameter of 20 / an to 200 including a catalyst component, a binder, and a matrix (matr ix) which is ZSM-5 or SAP0-34. Do not.

<0062>

Further, the naphtha and methanol feed ratio is preferably 0.2 to 1.4 parts by weight of methane per 1 part by weight of naphtha. If the supply of naphtha and methane substitutes (Article 26) If the ratio is less than 0.2 parts by weight of methanol with respect to 1 part by weight of naphtha, the amount of heat generated by the exothermic reaction of methane decreases, which increases the amount of energy used to maintain the reaction temperature. There is a problem that the amount of CO and CH ₄ increases.

<0064>

In addition, the naphtha and methane is preferably performed at a temperature of 600 1: 700 I: and a space velocity range of 5 h-30 h ᅳ ¹ . Furthermore, the residence time of the naphtha and methane in the reaction vessel is preferably 1 second to 5 seconds. If the temperature at which the reaction of the naphtha and methane is performed is less than 600 t, the conversion rate is lowered, so that the yield of the desired product is sharply lowered. There is a problem that the yield of the product is reduced by conversion to coke. In addition, when the space velocity range in which the reaction between the naphtha and methanol is performed is less than 5 h ᅳ ¹ , there is a problem in that the amount of coke production is increased by a fast conversion reaction of methane, and when it exceeds 30 h— ¹ . There is a problem that the conversion rate of naphtha is sharply lowered.

<0066>

In addition, the present invention

Naphtha and Methanol Mixed Contact Substituting Paper for Simultaneous Decomposition of Naphtha and Methane Using Recirculating Fluidized Bed Reactor with Reactor, Stripper and Regenerator (Rule 26) In the sea reaction process,

The naphtha is fed from the bottom of the half vessel to the position 0 ¾ to 5 ¾ of the total half foot length, and the methane is

It provides a light olefin produced by the catalytic cracking reaction process comprising the feed to 10% to 80% position.

<0070>

In the catalytic cracking reaction process according to the present invention, using a circulating fluidized bed half vessel and dissociating naphtha methane at the same time by varying the naphtha and methane input positions, the heat neutralization (heat neutral i zat i on) It is possible to minimize energy consumption and to suppress the production of hard saturated hydrocarbons such as methane, ethane, and propane, thereby improving the yield of hard lepine, and thus making the produced hard lepine economically. Can be used.

<0072>

Furthermore, the present invention

Method for preparing a hard lepine by a mixed reaction reaction of naphtha and methanol, which performs co-lysis of naphtha and methane using a circulating fluidized bed semi-container including a vanizer, a stripper, and a regenerator. To

The naphtha is fed from the bottom of the reactor to a position of 0 to 5 3/4 of the total reaction length and the methanol is from the bottom of the reactor to

It provides a method for improving light olefin yield, characterized in that it is supplied in the 10 ¾ to 80 ¾ position. Alternative Site (Article 26) <0076>

Hereinafter, the method for improving the light olefin yield according to the present invention will be described in detail.

<0078>

Previously proposed techniques only suggest concepts to realize thermal neutralization to increase energy efficiency in naphtha " methane ^ co-reaction reactions with significantly different reaction rates and reaction heat. At the same time, in order to obtain hard olefins with high yield, this concept alone is unsatisfactory, and accurate contact time control according to the reaction rate of reactants is essential.

<oosa> In order to solve this problem, the present invention employs a circulatory fluid caterpillar, and adjusts the position of the hydrocarbon and methanol in order to more precisely control the contact time between naphtha and methanol to the desired time.

<讓>

In the decomposition reaction of naphtha and methane, light olefins such as ethylene, propylene, etc. are extra products, and if the contact time is short, the decomposition does not occur smoothly. If the contact time is too long, the side reaction is intensified to produce an unwanted product. You get Therefore, it is very important to precisely control the contact time between the reactants and the catalyst.

In particular, since the rate of decomposition of methane is 10 times faster than that of naphtha, a hydrocarbon, when two reaction products are added at the same time, the residence time of methanol becomes too long, resulting in hard saturation of methane, ethane, propane, etc. There is a problem in that the amount of hydrocarbon and β? In order to solve this problem, countermeasures to replace methane are compared to naphtha (rule 26). It is preferable to shorten the residence time in the group, and for this purpose, it is more preferable to change the position to be added to the counterunggi of the circulating fluidized bed semi-unggi of naphtha and methanol.

<0084>

The circulating fluidized bed semi-aerator 100 used in the method for improving the yield of hard lepine according to the present invention is a semi-unggi (10) as a specific example. It is preferred to include a stripper (str i pper 20) and a regenerator 30

The reactor 10 may be a vertical pipe (r i ser) as a specific example. The vertical tube may have a length of 5 m to 15 m. The diameter may range from 1/4 inch to 1 inch, but is not limited thereto. In addition, the counterunggi 10 may be formed with a tube supplied with naphtha and methane, respectively. Since the method of improving the yield of light olefins according to the present invention differs in the naphtha and methane input positions, it is preferable to form a tube supplying the naphtha and methane at each position.

In addition, the stripper 20 may include a cylinder 21 for discharging the product gas produced from naphtha and methanol. Furthermore, a regenerator 30 is located below the stripper, and may further include a valve 22 for distinguishing the stripper and the regenerator and controlling circulating flow of catalyst and fuel gas.

The regenerator 30 may include a cylinder 31 for discharging a fuel gas (feul gas) containing naphtha and methane. The regenerator may be filled with a catalyst, and a tube through which air (ai r) may be injected may be formed under the regenerator. In addition, it is preferable that the bottom of the regenerator is connected to the reaction device (10), and the regenerator and the reactionary replacement paper (Article 26) It may further include a valve (32) to distinguish the groups and to control the circulation flow of the catalyst and fuel gas.

<0089>

According to the present invention, a method for improving the yield of hard lepin is circulating as described above.

% ^{■ The} reaction of naphtha and methanol is carried out using a semi-container. The naphtha is preferably supplied to the bottom of the reactor and the methane is supplied at a position away from the bottom. The input position of methanol may vary depending on the reaction temperature, the circulation amount of the catalyst, and the input amount of the reactant, but it is preferable to be introduced at a position of 10% to 80% of the length of the entire reactor from the bottom of the reactor. In this way, if the input position is different, the thermal increase can be achieved and the yield of hard lepine can be maximized.

In addition, in order to more precisely control the contact time of naphtha and methane with the catalyst, the naphtha is fed from the bottom of the reactor to a position of 0 ¾ to 5% of the total reactor length, the methanol is Of the total reactor length from the bottom of

It is preferred to be fed to the 10 ¾ to 80 ¾ position. More preferably, the yield of light olefins can be maximized when the methanol is fed from the bottom of the reactor to 15% to 45% of the total reactor length.

<0092>

In this case, the naphtha used as the counter-agar may include a saturated hydrocarbon or an unsaturated hydrocarbon having C ₄ to C ₁₂ , and the naphtha is a full range of naphtha replacement paper (Rule 26). FuU-range naphtha, light naphtha, raffinate oil, and mixtures thereof, and the like. In addition, unlike the pyrolysis process using only saturated hydrocarbons, the circulating fluid catalytic cracking process using a catalyst can also be used as an olefin containing hydrocarbon.

Further, the methane used as the reaction product can be used not only anhydrous methane, but also hydrous methane containing up to 20% of moisture.

<0095>

In addition, the circulating fluidized bed semi-agitator 100 is a catalyst is circulated, wherein the catalyst may be a zeolite-based catalyst. As a specific example, the catalyst may be a spherical or elliptical catalyst having a diameter of 20 to 200, including but not limited to, ZSM-5 or SAP0-34 catalyst component, binder, and matrix ix.

<0097>

Further, the naphtha and methanol supply ratio is preferably 0.2 to 1.4 parts by weight of methane per 1 part by weight of naphtha. if. When the supply ratio of naphtha and methanol is less than 2 parts by weight of methane relative to 1 part by weight of naphtha, the amount of heat generated by the exothermic reaction of methane decreases, thus increasing the amount of energy used to maintain the reaction temperature. 1.4 If the excess portion is exceeded, there is a problem in that the amount of by-products CO and C¾ is added.

<0099> Alternative Paper (Article 26) <oioo> In addition, it is preferable that the reaction of naphtha and methane is performed at a temperature of 600 ° C. to 700 t 및 and a space velocity range of 5 h ^“1 to 30 γΓ ^1. Furthermore, the reaction of naphtha and methanol is performed. It is preferable that the residence time within is within 1 second to 5 seconds, if the silver content at which the reaction of the naphtha and methanol is performed is less than 600, the conversion rate is lowered, so that the yield of the left product is sharply lowered. In case of exceeding 700 1:, most of the reactants are converted to coke, which lowers the yield of the product, and the space velocity range in which the reaction between naphtha and methane is performed is 5 h ᅳ ^1. If less than one, there is a problem that the coke production rate is increased by the rapid conversion reaction of methane, naphtha 푀 conversion rate is sharply lowered if it exceeds 30 h ᅳ ¹ .

<0101>

[Form for implementation of invention]

Hereinafter, the present invention will be described in detail by the following Examples and Experimental Examples.

<0103>

However, the following Examples and Experimental Examples are only illustrative of the present invention and the scope of the invention is not limited by the Examples and Experimental Examples.

<0105>

<Example 1-4> Catalytic Dissolution Process 1-4

Alternative paper shown in the schematic diagram of FIG. 1 to perform the catalytic cracking reaction process according to the present invention (Article 26) A circulating fluidized bed reaction vessel was prepared as shown.

The circulating fluidized bed reactor is composed of a reactor, a stripper and a regenerator, the reactor is 7 m long and has a diameter of 1/2 inch.

In addition, the ACO-100 catalyst used in the ACO process with HZSM-5 content of 40% by weight was used as a catalyst, and the temperature of 800 t: 100% steam was used to characterize the E-cat. After steaming in the atmosphere for 24 hours, 3 kg of catalyst was loaded into the regenerator.

<0110>

At this time, the various parts of the semi-ungwoong (20% position, 40% position, 60% position, 80 from the lower part of the reactor) to introduce the naphtha and methane (MeOH) at the other positions Methane injection nozzles were installed. Hard naphtha was used as the naphtha introduced into the reactor, and the weight ratio of the hard naphtha and methanol was fixed at 1: 0.25.

The naphtha feeding position supplied to the reactor is the lower part of the counterunggi, and the methanol feeding position is different from the lower portion of the reactor to 20% position, 40% position, 60% position, and 80 ¾ position of the total reactor length. Methanol was fed.

The reciprocating inlet temperature was set to 690 V and the catalyst / oil ratio (Cat / Oi l rat io) to 25.

<0114>

<Comparative Example 1> Alternative Paper (Article 26) <0U6> The circulating fluid caterpillar used in Example 1-4 was used.

<0117>

At this time, the naphtha to be added to the reaction was used hard naphtha, the weight ratio of hard naphtha and methanol was fixed to 1: 0.25.

<011> for the naphtha and methane in the banyonggi half ^■ D it was fed to the bottom of the group § "-.

The reactor inlet temperature is 690 X: and the catalyst / oil ratio is

25 was set.

<0121>

<0122> <Comparative Example 2>

The circulating fluidized bed half vessel used in Example 1-4 was used.

<0124>

The naphtha used in Itti 1, a reactor, used hard naphtha, and did not supply methane.

The reactor was fed naphtha to the bottom of the counterunggi.

<oi27> The half vessel inlet silver degree is 690 t, the catalyst / oil ratio (Cat / Oil ratio) is

35 was set.

<0128>

Experimental Example 1 Thermal Incremental Analysis During Simultaneous Injection of Naphtha and Methanol

In order to confirm the thermal increase phenomenon in the simultaneous decomposition reaction of naphtha and methanol, which is a catalytic cracking reaction according to the present invention, the catalytic cracking reaction is performed under the same conditions as in Comparative Example 1 and the methanol is added to the hard naphtha. Alternative paper in weight ratio of 0 to 100% (Rule Article 26) The fighting was performed while changing to the amount%, and the silver difference between the inlet and the out let of Banunggi was observed, and the results are shown in FIG. 2.

<0131>

As shown in FIG. 2, when the weight ratio of methanol to hard naphtha is about 60% by weight, heat neutralization (heat neutral izat ion) with zero energy consumption may occur. Through this, the catalytic cracking reaction process according to the present invention was found to be possible to simultaneously decompose naphtha and methane in the state of thermal increase.

<0133>

Experimental Example 2 Effect Analysis of Methane-Injected Locations

In order to examine the change according to the input position of methane in the catalytic cracking reaction process according to the present invention, the yield of methane after performing the process of Examples 1 to 4. Comparative Example 1 and Comparative Example 2, The yield of hardpin and the temperature of the counterunggi were analyzed, and the results are shown in FIGS. 3 to 5.

<0136>

3 to 5, the temperature value (ΔΤ) of the reactor was 21 1 after the process of Comparative Example 2, which is a case of decomposing only hard naphtha, and the yield of hard lephine was shown. Showed a 33.5 increase ¾. In addition, the yield of methane was about 10% by weight increase.

On the other hand, after performing the process of Comparative Example 1, which is a case of co-decomposing hydrocarbon light naphtha and methane, the temperature value of the counterunggi is reduced than that of Comparative Example 1, the yield of hard olefins is improved I could confirm that. However, the yield of methane is increased by about 13% by weight of replacement paper (Rule 26). It was confirmed that the very high.

<0139>

On the other hand, after performing the process of Examples 1 to 4 in the case where the position where methane is supplied by the catalytic cracking reaction process according to the present invention was confirmed that the amount of methane produced almost does not increase, It was confirmed that the temperature value of the half vessel was also maintained at a constant level.

<oi4i> In particular, the yield of light olefins (Ethylene + Propylene) was up to about 40% by weight increase than naphtha and methanol at the same time it was confirmed that about 15% increase.

Alternative Site (Article 26)

Claims

[Range of request]

[Claim 1]

In the mixed catalytic reaction reaction of naphtha and methane, which perform co-decomposition of naphtha and methanol using a circulating fluidized bed reactor including a reactor, a stripper, and a regenerator,

The naphtha is fed from the bottom of the counterunggi to positions 0 ¾ to 5 ¾ of the total reactor length. The methanol is a catalytic cracking reaction process comprising the supply from the bottom of the counterunggi to 10 ¾ to 80 ¾ position of the total counterunggi length.

[Claim 2]

The method of claim 1,

The methane is a catalytic cracking reaction comprising being supplied to the position of 15% to 45% of the total reactor length from the bottom of the reactor.

[Claim 3]

The method of claim 1,

The naphtha is a catalytic cracking reaction process comprising a saturated hydrocarbon or unsaturated hydrocarbon having C ₄ to C ₁₂ carbon atoms.

【Claim 4】 Alternative Site (Article 26) The method of claim 1,

The naphtha is at least one selected from the group consisting of full range naphtha, light naphtha, raffinate oil, and combinations thereof. .

[Claim 5]

The method of claim 1,

The circulating fluidized bed reactor is the catalyst is circulated, the catalyst is ZSM-5 or SAPO- 34 catalyst component. A catalytically semi-perforated tablet characterized in that it is a molded spherical or elliptical catalyst of 20 to 200 diameters comprising a binder and a matrix.

[Claim 6]

The method of claim 1,

The naphtha and methanol feed ratio is 0.2 to 1.4 parts by weight of methanol relative to 1 part by weight of naphtha.

[Claim 7]

The naphtha and methane are replaced by a 600 "C to 700 1 temperature and 5 h ¹ to 30 needles (Article 26). Catalytic reaction process, characterized in that the reaction is carried out in the space velocity range.

[Claim 8]

The method of claim 1,

Catalytic cracking reaction process, characterized in that the residence time of the naphtha and methane in the reaction vessel is 1 second to 5 seconds.

[Claim 9]

Reactor. In a mixed contact reaction process for naphtha and methane, which performs a simultaneous decomposition reaction of naphtha and methanol using a circulating fluidized bed reaction device including a stripper and a regenerator,

The naphtha is fed from the bottom of the reactor to a position of 0% to 5 3/4 of the total half vessel length. The methanol is prepared by the catalytic cracking reaction process comprising the methanol supplied from the bottom of the reaction vessel to 10 ¾ to 80% of the total length of the reactor.

[Claim 10]

In a method for producing hard lepinol by mixed catalytic cracking reaction of naphtha and methane which perform co-decomposition of naphtha and methanol using a circulating fluidized bed reactor including a reaction vessel, a stripper and a regenerator, ,

The naphtha is 0% to 5% replacement paper of the total length of the reaction from the bottom of the reaction (rule 26) Is fed to a position, and the methane is

A method for improving the yield of light olefins characterized by being fed at 10% to 80% position.

Alternative Site (Article 26)