KR20090057027A - Recovery of calorific value regenerated during the production of lower olefins from methanol - Google Patents

Abstract

The present invention relates to a method for recovering the amount of heat regenerated in the process of producing lower olefins from methanol as a raw material using a fluid bed process. In this process, the hot catalyst after regeneration is first put into a cracking reaction endothermic zone before contacting with methanol, in which the catalyst is brought into contact with a hydrocarbon. By absorbing a portion of the heat of the high temperature catalyst using a hydrocarbon pyrolysis reaction, the temperature of the catalyst is lowered to meet the temperature requirements of the methanol conversion reaction.

Description

A process for recovering regenerated heat during the production of lower olefins from methanol

The present invention relates to a method for recovering the amount of regenerated heat, and more particularly, to a method for recovering the amount of heat of a high temperature catalyst regenerated in the process of preparing a lower olefin from methanol.

Lower olefins such as ethylene and propylene are the basic raw materials of the chemical industry. Generally, ethylene and propylene are mainly produced from steam cracking of hydrocarbons, and raw materials used are naphtha, light diesel oil and hydrogenation cracking tail oil. As oil prices have risen considerably in recent years, the cost of producing ethylene and propylene from these raw materials is constantly increasing. At the same time, the traditional method of producing ethylene and propylene is relatively high in calorie consumption, mainly due to the high temperature tubular furnace cracking process. These factors are driving the research and development of new processes for producing olefins.

The process for producing lower olefins from non-petroleum raw materials is a process route that has received much attention in recent years. Specifically, a process route for converting coal or natural gas into methanol via a synthesis gas and then converting methanol into lower olefins has been widely received. Among them, the process of selectively converting methanol (or dimethyl ether produced by dehydration of methanol) onto lower (C ₂ -C ₄ ) olefins on a molecular sieve catalyst is generally referred to as MTO process.

In recent years, the fluidized bed MTO process, which takes a continuous reaction-regeneration method, has received much attention. The basic principle of a fluidized bed process is as follows. That is, the raw material methanol and the catalyst are mixed in a reactor to fluidize and convert to a mixture containing products such as ethylene and propylene at a constant temperature, and the catalyst deposits some or all of the carbon by reaction to deposit carbon. Is deactivated. The gaseous reaction product exits the reactor and enters the separator, and the deactivated catalyst is constantly discharged from the reactor and enters the regenerator to be regenerated. In other words, it is burned in an oxygen-containing atmosphere to remove the deposited carbon and then returned to the reactor to contact with the reaction raw materials.

In a fluidized bed process employing the continuous reaction-regeneration method, carbon deposited on the surface of the deactivated catalyst is removed by high temperature combustion. In general, the temperature of the combustion reaction is higher than 600 ° C, the highest can reach 700 ° C or more. If the losses due to heat dissipation are not calculated, the heat generated by the combustion of the deposited carbon is transferred from the regenerator in two ways. In other words, the discharged hot regeneration gas takes a part of the heat and the other part takes the heat of the regenerated hot catalyst.

On the other hand, the heat carried out by the hot regeneration gas is generally recovered and used by the production or generation of steam or the like. For example, US Patent Publication No. US20050238543 A1 discloses a method for recovering heat from regeneration gas, which includes lowering the temperature of the regeneration gas by multiple heat transfers and using the calories obtained for the production of steam. .

On the other hand, the calories left with the regenerated hot catalyst are generally supplied to the reaction. Traditional fluidized bed reaction processes are generally applied to endothermic reactions, such as catalytic cracking of hydrocarbons, and part of the heat of reaction is provided from the hot catalyst regenerated during the regeneration process. That is, the deactivated catalyst is burned in an oxygen-containing atmosphere in the regenerator to remove the deposited carbon, regenerated and heated, and then at least partially provides heat of reaction by transferring heat from the former to the latter while returning to the reactor.

However, this calorie utilization is not suitable for the conversion of methanol to olefins. The causes are as follows. The conversion of methanol to olefins is a strong exothermic reaction and the catalyst is heated in the reactor so that the temperature of the catalyst entering the reactor must be lower than the reaction bed bed temperature to maintain the stability of the reaction temperature. The preferred temperature in the reaction for converting methanol to lower olefins is 350-600 ° C., which is lower than the regeneration temperature of the catalyst charcoaling (600-700 ° C.), ie the temperature of the regenerated catalyst. Therefore, the regenerated high temperature catalyst releases the amount of heat obtained during the regeneration process and must enter the reactor after the temperature is lowered to satisfy the reaction requirement of converting methanol into lower olefins.

It is an object of the present invention to provide a method for recovering the calorific value of a regenerated high temperature catalyst in the process of preparing lower olefins from methanol.

The present inventors have completed the present invention through a deep and delicate study.

The present invention provides a method for recovering the calorific value of the regenerated high temperature catalyst in the process of preparing lower olefins from methanol. This method includes the following steps. That is, the regenerated high temperature catalyst is first introduced into the pyrolysis endothermic zone, and then enters the methanol conversion reactor, where the hydrocarbon is introduced into the pyrolysis endothermic zone and brought into contact with the regenerated high temperature catalyst to cause the pyrolysis reaction to occur. The temperature of the high temperature catalyst after the regeneration is 500-800 ° C.

In the present invention, the catalysts used are silicon aluminum zeolites and / or phosphate molecular sieve catalysts and their elemental modification products, preferably having a pore diameter of 0.3-0.6 nm.

In the present invention, the matrix material of the catalyst is preferably one or several kinds of materials selected from silicon oxide, aluminum oxide or clay.

In the present invention, the temperature of the pyrolysis endothermic zone is preferably 400-700 ° C.

In the present invention, it is preferable that the temperature difference of the catalyst between the inlet and the outlet of the pyrolysis endothermic zone is 50-300 ° C.

In the present invention, the hydrocarbon to be drawn in the thermal decomposition reaction heat absorbing zone is preferably a C ₄ or more products and / or other C ₄ -C ₂₀ hydrocarbons in the reaction to produce olefins from methanol.

In the present invention, the hydrocarbons introduced into the endothermic zone of the pyrolysis reaction are preferably naphtha, gasoline, natural gasoline, light diesel oil, hydrogenated resid and / or kerosene.

In the present invention, it is preferable to merge the product in the endothermic zone of pyrolysis reaction of hydrocarbon with the product obtained in the reaction for producing lower olefins from methanol.

In the present invention, the pyrolysis endothermic zone is preferably one independent reaction zone in the methanol conversion apparatus.

In the present invention, the pyrolysis endothermic zone is preferably a lift zone of the methanol conversion reactor.

The process according to the present invention can recover the heat content of a portion of the regenerated catalyst in the process of preparing the lower olefin from methanol, and also control the temperature requirement of the reaction for converting methanol into the lower olefin by controlling the temperature of the regenerated catalyst. Can satisfy.

In order to achieve the above object, in the method for recovering the heat of regeneration in the process of producing the lower olefin from methanol according to the present invention, the regenerated high temperature catalyst is allowed to flow into the endothermic zone of pyrolysis reaction, and the hydrocarbon catalyst in the endothermic zone. The heat of the catalyst is absorbed by the pyrolysis reaction, and the catalyst temperature is lowered before entering the methanol conversion reactor.

In the process, the catalysts used are silicon aluminum zeolites and / or phosphate molecular sieve catalysts and their elemental modification products, the micropore diameters of which are 0.3-0.6 nm.

In the above method, the substrate material of the catalyst is one or several kinds of materials selected from silicon oxide, aluminum oxide or clay.

In this method, the temperature of the pyrolysis endothermic zone is 400-700 ° C.

In this method, the temperature difference of the catalyst between the inlet and the outlet of the pyrolysis endothermic zone is 50-300 ° C.

In the process, the hydrocarbons introduced into the endothermic zone of the pyrolysis reaction are C ₄ or more products and / or other C ₄ -C ₂₀ hydrocarbons in the production reaction of methanol to olefins.

In the process, the hydrocarbons introduced into the endothermic zone of the pyrolysis reaction are naphtha, gasoline, natural gasoline, light diesel oil, hydrogenated resid and / or kerosene.

In this process, the product containing ethylene and propylene produced in the pyrolysis endothermic zone is merged with the conversion reaction product of methanol.

According to the present invention, it is possible to recover a part of regeneration heat in the process of producing a lower olefin from methanol using a hydrocarbon pyrolysis reaction belonging to the endothermic reaction. The present invention has the following features. That is, in the process of producing lower olefins from methanol, which takes a reaction-regeneration fluidized bed process with continuous reaction characteristics, the regenerated high temperature catalyst is first put into a pyrolysis reaction endothermic zone before contacting methanol, and the C4 within the endothermic zone. -C20 hydrocarbons are introduced into contact with the regenerated high temperature catalyst, the thermal decomposition of the hydrocarbons is used to absorb the heat of the catalyst, the catalyst temperature is lowered to a temperature suitable for the conversion of methanol, and then introduced into the methanol conversion reactor. do. At the same time the lower olefins produced by the pyrolysis reaction can be incorporated into the olefin products produced from methanol.

The present invention provides a method for recovering some of the heat of regeneration in the process of producing lower olefins from methanol. That is, in the process of producing lower olefins from methanol in a fluidized bed process, the methanol raw material and the catalyst are mixed in a reactor to flow and converted to a product mixture containing ethylene, propylene and other hydrocarbons at a constant temperature. Reaction of carbon deposits some or all of the carbon, and the gaseous reaction product is discharged from the reactor to enter the separator, and the deactivated catalyst is continuously discharged from the reactor and introduced into the regenerator to regenerate the deactivated catalyst. Before entering the regenerator, a stream stripper is first passed to remove the remaining hydrocarbons on the catalyst by using an inert gas such as water vapor, and then burned in an oxygen-containing atmosphere in the regenerator to remove the deposited carbon. Work of emitted calories Min is the regeneration gas, and the other mobile part is the regenerated catalyst, and then by using water vapor, such as inert gas, remove the residual oxygen in the heated catalyst in the regenerator 600-700 ℃ thereby pulling the endothermic pyrolysis reaction zone. The reaction endothermic zone may be a single dense-phase reaction zone and at the same time a lift zone for transporting the catalyst to the methanol conversion reactor and at the same time a lift zone for transporting the catalyst to the methanol conversion reactor. In this reaction endothermic zone, the hydrocarbon fuel is contacted with the regenerated catalyst to thermally decompose and absorb the heat of the catalyst. The temperature in the reaction endothermic zone is 400-700 ° C., and the catalyst is discharged from the reaction endotherm and then the temperature is 50-300 ° C. lower than the inlet of this endothermic zone to reach the temperature required by the reactor for converting methanol into olefin. do. The catalyst is again introduced into a reactor that converts methanol into olefins. The product comprising ethylene and propylene produced in the pyrolysis endothermic zone may be combined with a methanol conversion product.

The catalysts include silicon aluminum zeolites with a micropore diameter of 0.3-0.6 nm and / or phosphate molecular sieve catalysts (eg, ZSM-5, ZSM-11, SAPO-11, etc.) and elemental denaturation products thereof. . The catalyst also includes a substrate material, and the substrate material is preferably one or several kinds of materials selected from silicon oxide, aluminum oxide or clay. The number of carbon atoms of the hydrocarbon used in the reaction endothermic zone is 4-20, which may be a product of C4 or more in the reaction for producing olefins from methanol, other C ₄ -C ₂₀ hydrocarbons, naphtha, gasoline, Condensed oil, light diesel oil, hydrogenated residual oil and kerosene and the like.

Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Example 1

Pyrolysis of 2-Butylene over SAPO-34 Molecular Sieve Catalyst.

The method for preparing the catalyst is as follows: a slurry is prepared by mixing SAPO-34 (Dalian Chemical Physics Research Institute, silicon aluminum ratio 0.2), clay, aluminum sol and silicon sol (all purchased from Zhejiang Oda Co., Ltd.) and dispersing it in water. It was. The slurry was spray molded to produce microspheres with a particle diameter distribution of 20-100 μm. The microspheres were roasted at 600 ° C. for 4 hours to obtain a catalyst used in this example. The SAPO-34 molecular sieve content in the catalyst is 30 wt%.

The reaction proceeded in a fluidized bed micro reactor with an internal diameter of 20 mm. The reaction conditions are as follows. That is, the addition amount of the catalyst is 10g, 2-butylene (crude petrochemical company, purity 98%, cis: trans 2-butylene ratio is 1), the mass space velocity of the raw material is 1.0 hr ^-1 , the reaction pressure is 0.1 MPa. The reaction product was analyzed by Varian CP-3800 gas chromatography, Pona column and hydrogen flame detector and the sampling time was 2 minutes.

The heat of reaction was calculated based on the thermodynamic constants of the raw materials and products, of which the thermodynamic data of C5 is the average of the ten alkanes, olefins, dienes and cycloalkanes isomers, and C6 is the twelve alkanes, olefins, dienes and cycloalkanes isomers. Average. Each material was assumed to be an ideal gas all at reaction conditions.

Table 1 shows the results of the conversion reaction and the heat of reaction on the molecular sieve catalyst of 2-butylene. Reaction temperature is 500 degreeC. From the data in Table 1, it can be seen that the selectivity of ethylene and propylene in the reaction product under these reaction conditions is 78.1%, and the endothermic amount of reaction of the pyrolysis reaction under these product distribution conditions is 471 KJ / Kg.

Table 1 Pyrolysis product of 2-butylene of Example 1 and the heat of reaction (500 ° C.)

Product distribution (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₅ C ₆ ⁺ 0.62 18.40 0.25 59.70 10.70 10.01 0.31 ΔH (J / Kmol) endothermic reaction (KJ / Kg) 2.26 × 10 ⁷ 4.71 × 10 ²

C ₆ ⁺ represents a C ₆ and a C ₆ or more product.

Example 2

The procedure of Example 1 was repeated except that the reaction temperature was set at 550 ° C.

The conversion reaction results and the heat of reaction on the molecular sieve catalyst of 2-butylene are shown in Table 2. From the data in Table 2, it can be seen that the selectivity of ethylene and propylene in the reaction product under these reaction conditions is 82.21%, and the endothermic amount of reaction of the pyrolysis reaction under these product distribution conditions is 704 KJ / Kg.

Table 2 Pyrolysis Product of 2-Butylene of Example 2 and Heat of Reaction (550 ° C)

Product distribution (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₅ C ₆ ⁺ 1.01 27.30 0.44 54.91 7.81 5.39 3.14 ΔH (J / Kmol) endothermic reaction (KJ / Kg) 3.38 × 10 ⁷ 7.04 × 10 ²

C ₆ ⁺ represents a C ₆ and a C ₆ or more product.

Example 3

The procedure of Example 1 was repeated except that the reaction temperature was set at 600 ° C.

The conversion reaction results and the heat of reaction on the molecular sieve catalyst of 2-butylene are shown in Table 3. From the data in Table 3, it can be seen that the selectivity of ethylene and propylene in the reaction product under these reaction conditions is 80.97%, and the endothermic amount of reaction of the pyrolysis reaction under these product distribution conditions is 825 KJ / Kg.

Table 3 Pyrolysis Product of 2-Butylene of Example 3 and Heat of Reaction (600 ° C)

Product distribution (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₅ C ₆ ⁺ 4.16 44.03 1.20 36.94 6.40 1.69 5.57 ΔH (J / Kmol) endothermic reaction (KJ / Kg) 3.96 × 10 ⁷ 8.25 × 10 ²

C ₆ ⁺ represents a C ₆ and a C ₆ or more product.

Example 4

Pyrolysis over Kerosene ZSM-5 Molecular Sieve Catalyst

The preparation procedure and reaction operation of the catalyst are the same as in Example 1, among which the SAPO-34 molecular sieve is changed to ZSM-5 (Nam University molecular sieve plant, silicon aluminum ratio is 50), and the raw material is kerosene (No. 3 aviation kerosene, To petrochemicals). The reaction heat calculation method was the same as in Example 1, and the combustion enthalpy of kerosene was -7513 KJ.Kg ^-1 .

Table 4 shows the results of the conversion reaction and the heat of reaction on the molecular sieve catalyst of kerosene. Reaction temperature was 550 degreeC. Other thermodynamic functions of kerosene were calculated with n-dodecane. From the data in Table 4, it can be seen that the selectivity of ethylene and propylene in the reaction product under these reaction conditions is 28.91%, and the endothermic amount of reaction of the pyrolysis reaction under these product distribution conditions is 2238 KJ / Kg.

TABLE 4 Pyrolysis reaction products and heat of reaction of kerosene of Example 4 (550 ℃)

Product distribution (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₄ C ₅ ⁺ 1.70 10.61 2.78 18.30 11.22 22.36 33.03 Endothermic Reaction (KJ / Kg) 22.38 × 10 ²

C ₅ ⁺ represents a C ₅ and C ₅ or more product.

Example 5

The procedure of Example 4 was repeated except that the reaction temperature was set at 600 ° C.

The conversion reaction results and the heat of reaction on the molecular sieve catalyst of kerosene are shown in Table 5. The combustion enthalpy of kerosene was -7513 KJ.Kg ^-1 and the other thermodynamic functions of kerosene were calculated as n-dodecane. From the data in Table 5, it can be seen that the selectivity of ethylene and propylene in the reaction product under these reaction conditions is 36.97%, and the endothermic amount of reaction of the pyrolysis reaction under these product distribution conditions is 2821 KJ / Kg.

TABLE 5 Pyrolysis reaction products and heat of reaction of kerosene of Example 5 (600 ℃)

Product distribution (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₄ C ₅ ⁺ 5.36 14.80 5.12 22.17 4.61 15.16 32.78 Endothermic Reaction (KJ / Kg) 28.21 × 10 ²

C ₅ ⁺ represents a C ₅ and C ₅ or more product.

Example 6

Table 6 shows the conversion reaction results and heat of reaction on the gasoline ZSM-5 molecular sieve catalyst. The catalyst production procedure and reaction operation were the same as in Example 4, in which the raw materials were changed to gasoline (catalytic gasoline of petroleum petrochemical, olefin content of 40%). The reaction temperature was 640 deg. The thermodynamic function of gasoline was calculated from the average of various pentenes. From the data in Table 6, it was found that the yield of ethylene and propylene in the reaction product was 44.01% under these reaction conditions, and the endothermic amount of reaction of the pyrolysis reaction was 361 KJ / Kg under these product distribution conditions.

TABLE 6 Pyrolysis reaction products and heat of reaction of gasoline of Example 6 (640 ℃)

Product yield (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₄ C ₅ ⁺ 2.52 17.22 1.96 26.79 2.18 10.99 38.34 Endothermic Reaction (KJ / Kg) 3.61 × 10 ²

C ₅ ⁺ represents a C ₅ and C ₅ or more product.

Example 7

The procedure of Example 6 was repeated except that the reaction temperature was set at 610 ° C.

Table 7 shows the results of the conversion reaction and the heat of reaction on the molecular sieve catalyst of gasoline. The thermodynamic function of gasoline was calculated from the average of various pentenes. The data in Table 7 shows that the yield of ethylene and propylene in the reaction product under these reaction conditions is 39.66%, and the endothermic amount of the pyrolysis reaction under these product distribution conditions is 367 KJ / Kg.

 TABLE 7 Pyrolysis reaction products and heat of reaction of gasoline of Example 7 (610 ° C)

Product yield (wt%) CH ₄ C ₂ H ₄ C ₂ H ₆ C ₃ H ₆ C ₃ H ₈ C ₄ C ₅ ⁺ 2.28 16.63 1.98 23.05 2.85 9.45 43.76 Endothermic Reaction (KJ / Kg) 3.67 × 10 ²

C ₅ ⁺ represents a C ₅ and C ₅ or more product.

Example 8

Methanol with a 600,000 tonne / year methanol conversion was used for the production of olefins. If the device works normally on average 300 days per year, the daily throughput of methanol is 2000 tons. The conversion unit used a reaction-regeneration fluidized bed process, which mainly included a methanol conversion reactor and a catalytic regenerator, and installed a pyrolysis endothermic reactor on the catalyst transport route that flowed out of the regenerator to the methanol conversion reactor, which took the fluidized bed method. It was. The regenerated hot catalyst first passed through the pyrolysis endothermic zone and then entered the methanol conversion reactor.

The SAPO-34 flow catalyst (catalyst preparation procedure is the same as in Example 1) was used and the catalyst circulation was 2000 tons / day. The temperature of the renewed catalyst (after steam stripping) is 650 ° C. and the temperature must be lowered to 430 ° C. before the catalyst enters the methanol conversion reactor.

In the pyrolysis endothermic reactor, the heat of the regenerated catalyst is absorbed through catalytic pyrolysis of 2-butylene (as in Example 1), and the temperature is lowered to 550 ° C. Since the heat capacity of the catalyst is 840 J / (Kg · K), the amount of heat released by the catalyst is 1.68 × 10 ⁸ KJ / day in the course of decreasing temperature. The catalyst exits the endothermic reactor and passes through a pipeline to disperse before entering the methanol conversion reactor, whereby the temperature is lowered to 430 ° C., and the amount of heat lost is 2.02 × 10 ⁸ KJ / day. Appropriate warming measures are required for the transport conduit of the regenerated catalyst to suppress acid heat loss in the conduit.

2-butylene was preheated to 200 ° C. in a pyrolysis reactor and then supplied thereto, and the reaction temperature was 550 ° C. The heat capacity of 2-butylene was Cp = 1456 J / (Kg · K). The endothermic amount from the supply of Mathene 2-butylene to the complete reaction is 12.14 × 10 ⁵ KJ / Kg, and the once-through conversion rate of 2-butylene is 75%, so the 2-butylene raw material If the feed amount is 184 tons / day, the catalyst temperature can be lowered from 650 ° C to 550 ° C.

The amount of heat that can be recovered by catalytic pyrolysis of 2-butylene in the reaction process is 45% of the heat of the regenerated catalyst, and the recovered heat is used for catalytic pyrolysis of 2-butylene, and 37.8 tons / ethylene is used. It is possible to increase 76.0 tons / day of propylene.

Comparative Example 1

An apparatus for producing olefins with methanol having a methanol conversion scale of 600,000 tons / year was used. If the device works normally on average 300 days per year, the daily throughput of methanol is 2000 tons. This conversion device used a reaction-regeneration fluidized bed process similar to that of Example 8, which mainly includes a methanol conversion reactor and a catalyst regenerator, but without the pyrolysis endothermic zone, and the catalyst is transported directly from the regenerator via Outflow to the conversion reactor.

The SAPO-34 fluid catalyst (the procedure for preparing the catalyst is the same as in Example 1) was used and the catalyst circulation was 2000 tons / day. The temperature of the regenerated catalyst (after steam stiffening) is 650 ° C. and it is necessary to lower the temperature to 430 ° C. before the catalyst enters the methanol conversion reactor.

The catalyst is totally annealed by a pipeline to lower the temperature to 430 ° C., and the heat capacity of the catalyst is 840 J / (Kg · K), and the amount of heat lost during the temperature decrease is 3.70 × 10 ⁸ KJ / It's work.

Claims (10)

As a method of recovering the heat of the regenerated high temperature catalyst in the process of preparing a lower olefin from methanol, Introducing the regenerated high temperature catalyst into the pyrolysis endothermic zone first and then into the methanol conversion reactor; Bringing hydrocarbon into the pyrolysis endothermic zone and bringing it into contact with the regenerated hot catalyst to cause a pyrolysis reaction, wherein the regenerated hot catalyst has a temperature of 500-800 ° C. The recovery method according to claim 1, wherein the catalyst used is a silicon aluminum zeolite and / or a phosphate molecular sieve catalyst and an elementally modified product thereof, and the catalyst has a pore diameter of 0.3-0.6 nm. The recovery method according to claim 1, wherein the matrix material of the catalyst is one or several kinds selected from silicon oxide, aluminum oxide or clay. The method of claim 1, wherein the temperature of the endothermic zone of the pyrolysis reaction is 400-700 ℃. The method of claim 1, wherein the temperature difference of the catalyst between the inlet and the outlet of the pyrolysis endothermic zone is 50-300 ° C. The method according to claim 1, wherein the hydrocarbon introduced into the pyrolysis endothermic zone C ₄ in the reaction to produce olefin from methanol A recovery method wherein the above product and / or other C ₄ -C ₂₀ hydrocarbons. The method of claim 1, wherein the hydrocarbon introduced into the pyrolysis endothermic zone is naphtha, gasoline, natural gasoline, light diesel oil, hydrogenated resid and / or kerosene. The process according to claim 1, wherein the product in the endothermic zone of pyrolysis reaction of the hydrocarbon is combined with the product obtained in the reaction for producing lower olefins from methanol. The method of claim 1, wherein the pyrolysis endothermic zone in the methanol conversion apparatus is one independent reaction zone. The process of claim 1 wherein the pyrolysis endothermic zone is a lift zone of the methanol conversion reactor.