Device and method for producing olefin by using methanol

文档序号：657555 发布日期：2021-04-27 浏览：10次中文

阅读说明：本技术 一种利用甲醇生产烯烃的装置及方法 (Device and method for producing olefin by using methanol ) 是由李晓红金永明王莉王艳学于 2019-10-24 设计创作，主要内容包括：本发明提供一种利用甲醇生产烯烃的装置,包括：甲醇转化反应器、分离装置和还原反应器；其中,所述甲醇转化反应器的出料口与所述分离装置的第一进料口相连接,所述分离装置的第一出料口与所述还原反应器的进料口相连接,所述分离装置的第二出料口与所述甲醇转化反应器的进料口相连接,所述还原反应器的出料口与所述分离装置的第二进料口相连接。本发明所提供的装置实现了富含含氧化合物物流的有效利用,进而使得本发明所提供的利用甲醇生产烯烃的方法具有较高的选择性。(The invention provides a device for producing olefin by using methanol, which comprises: a methanol conversion reactor, a separation device and a reduction reactor; the device comprises a methanol conversion reactor, a separation device, a reduction reactor, a methanol conversion reactor, a reduction reactor and a separation device, wherein a discharge hole of the methanol conversion reactor is connected with a first feed hole of the separation device, a first discharge hole of the separation device is connected with a feed hole of the reduction reactor, a second discharge hole of the separation device is connected with a feed hole of the methanol conversion reactor, and a discharge hole of the reduction reactor is connected with a second feed hole of the separation device. The device provided by the invention realizes the effective utilization of the oxygen-containing compound-rich material flow, so that the method for producing olefin by using methanol provided by the invention has higher selectivity.)

1. An apparatus for producing olefins from methanol, comprising: a methanol conversion reactor, a separation device and a reduction reactor;

the device comprises a methanol conversion reactor, a separation device, a reduction reactor, a methanol conversion reactor, a reduction reactor and a separation device, wherein a discharge hole of the methanol conversion reactor is connected with a first feed hole of the separation device, a first discharge hole of the separation device is connected with a feed hole of the reduction reactor, a second discharge hole of the separation device is connected with a feed hole of the methanol conversion reactor, and a discharge hole of the reduction reactor is connected with a second feed hole of the separation device.

2. A method for producing olefins from methanol, comprising:

a) passing a feed stream comprising methanol to a methanol conversion reactor for a methanol to olefins reaction to produce a first product stream comprising olefins;

b) feeding the first product stream to a separation unit, and separating to obtain an olefin-rich stream and an oxygenate-rich stream;

c) (ii) outputting the olefin-rich stream as a product; and

d) dividing the oxygenate-rich stream into at least two portions, wherein one portion is recycled to the methanol conversion reactor as a recycle stream and the other portion is fed to a reduction reactor as a stream to be reduced for reduction reaction, thereby obtaining a second product stream;

preferably, the method further comprises the following steps:

e) returning the second product stream to the separation unit after gas-liquid separation.

3. A process according to claim 2, wherein the oxygenate-rich stream has a sodium ion content of less than 10ppm, preferably less than 5ppm, more preferably less than 2 ppm; and/or the pH of the oxygenate-rich stream is less than 7, preferably less than 6 and greater than 1.

4. A process according to claim 2 or 3, wherein the oxygenate-rich stream comprises water and oxygenates, the oxygenates comprising methanol and being selected from C₂-C₄Alcohol, C₂-C₄Aldehyde, C₃-C₄Ketones and C₂-C₄At least one compound of a carboxylic acid; preferably, the oxygenate comprises methanol and is selected from C₂-C₄Aldehydes and C₃-C₄At least one compound of a ketone.

5. A method according to claim 4, wherein the water content of the oxygenate-rich stream is from 30 wt% to 80 wt%, and the oxygenate content is from 20 wt% to 70 wt%; preferably, the content of the aldehyde ketone compound in the oxygen-containing compound is 50 wt% to 99 wt%.

6. A method according to any one of claims 2 to 5, wherein the recycle stream comprises from 10% to 70% of the oxygenate-rich stream and the stream to be reduced comprises from 30% to 90% of the oxygenate-rich stream.

7. The process according to any one of claims 2 to 6, wherein in step b) the separation process comprises at least two separation means selected from the group consisting of stripping, water washing and adsorption.

8. The method according to any one of claims 2 to 7, wherein the reduction reactor is packed with a catalyst comprising a carrier, an active component, and a modifying component supported on the active component; the carrier is selected from at least one of alumina, silica, pseudo-boehmite, kaolin and diatomite, the active component is selected from at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZSM-23 molecular sieve, and the modification component is selected from at least one of Ga, Mn, P, La, Ca, Mg and Ce.

9. The method of claim 8, wherein the modifying component is present in an amount of 0.01 wt% to 10 wt% and the active component is present in an amount of 30 wt% to 80 wt%, based on the total mass of the catalyst.

10. The method of any one of claims 2-9, wherein the reduction reaction conditions comprise: the temperature is 250-600 ℃, the pressure is 0-0.3 MPa, and the mass space velocity of the oxygen-containing compound-rich material flow is 0.2h^-1～3.0h^-1。

Technical Field

The invention relates to the technical field of chemical industry, in particular to a device and a method for producing olefin by using methanol.

Background

The traditional olefin production process is the cracking of petroleum feedstocks into olefins. Cracking of petroleum feedstocks is carried out by catalytic cracking, steam cracking, or some combination of the two processes. The olefins produced are typically light olefins such as ethylene and propylene. There is a large market for light olefin products of ethylene and propylene. As petroleum feedstocks from crude oil face ever higher prices, it is advantageous to provide other sources of ethylene and propylene.

Methanol is used as a chemical raw material, and SAPO-34 and ZSM-5 catalysts are adopted to react to obtain ethylene, propylene, aromatic hydrocarbon and gasoline products. The process for preparing methanol from coal or natural gas is mature, and the methanol is cheap due to rich coal resources in China. The catalytic conversion of methanol to ethylene, propylene, aromatic hydrocarbon and gasoline is receiving more and more attention, and related technical researches and patents are very numerous.

No matter what the target product of the catalytic conversion of methanol is, oxygen-containing compounds such as ketones, aldehydes, ethers and the like are inevitably produced as by-products. In the prior art, the part of the oxygen-containing compounds are generally treated as hazardous wastes, and in recent years, the treatment cost is higher and higher. How to effectively utilize the oxygen-containing compounds, change waste into valuable, reduce the carbon-based loss of raw materials and gradually become a difficult problem to be solved urgently in the catalytic conversion process of the methanol.

In current Methanol To Olefins (MTO) technology, this portion of oxygenate and unconverted methanol is returned directly to the MTO reactor. However, this route has a problem of low conversion of the oxygenate.

CN105745012 discloses a process for the enhanced conversion of recycled oxygenates in MTO having two fluidized bed reactors wherein an oxygen-rich stream from a separation unit is reacted in a second reactor with a portion of a regenerated catalyst stream. In this process, the regenerated catalyst is employed in the second reactor, which is essentially still further MTO reacting unreacted methanol, in no substantial difference from the above-described technique of returning oxygenate and unconverted methanol directly to the MTO reactor. In addition, the method has a complex flow because the device is provided with two reactors.

In view of the foregoing, there is a need to develop a new MTO process to increase the utilization of the byproduct oxygen-rich material.

Disclosure of Invention

In view of the problem of low utilization rate of the oxygenate-rich stream in the prior art, the present invention aims to provide an apparatus and a method for producing olefins from methanol, which realize effective utilization of the oxygenate-rich stream, and further enable the method for producing olefins from methanol provided by the present invention to have high selectivity.

In one aspect, the present invention provides an apparatus for producing olefins from methanol, comprising: a methanol conversion reactor, a separation device and a reduction reactor;

According to the invention, the reduction reactor is a fixed bed reactor.

According to the invention, the methanol conversion reactor is used for realizing the reaction of converting methanol into olefin, and the reduction reactor is mainly used for realizing the reaction of converting aldehyde ketone compounds into olefin.

In still another aspect, the present invention provides a method for producing olefins from methanol, comprising:

a) passing a feed stream comprising methanol to a methanol conversion reactor for a methanol to olefins reaction to produce a first product stream comprising olefins;

b) feeding the first product stream to a separation unit, and separating to obtain an olefin-rich stream and an oxygenate-rich stream;

c) (ii) outputting the olefin-rich stream as a product; and

d) the oxygenate-rich stream is split into at least two portions, one of which is recycled to the methanol conversion reactor as recycle stream and the other of which is fed to the reduction reactor as stream to be reduced for reduction reaction to produce a second product stream.

According to the present invention, in the present invention, the term "olefin" includes ethylene and/or propylene.

According to the invention, the reduction reaction refers to that alcohol compounds, aldehyde compounds, ketone compounds and carboxylic acid compounds in the oxygen-containing compound-rich material flow are subjected to aldol condensation reaction under the action of a catalyst to realize carbon chain growth, and then the carbon chain growth is cracked to obtain light hydrocarbons such as ethylene, propylene, carbon tetrahydrocarbon and the like.

According to the present invention, the MTO reaction may be carried out under conditions known in the art as long as the object of the present invention can be achieved.

In some preferred embodiments of the invention, the method further comprises:

e) returning the second product stream to the separation unit after gas-liquid separation.

According to the invention, the second product stream is subjected to a gas-liquid separation to obtain a gas stream and a liquid stream, both of which are returned to the separation device.

According to the invention, the gas stream and the liquid stream are returned to different locations of the separation device.

In some preferred embodiments of the invention, the oxygenate-rich stream has a sodium ion content of less than 10ppm, preferably less than 5ppm, more preferably less than 2 ppm; and/or the pH of the oxygenate-rich stream is less than 7, preferably less than 6 and greater than 1.

According to the present invention, it is advantageous to limit the sodium ion content and the pH of the oxygenate-rich stream to the above-mentioned ranges to protect the catalyst.

In some preferred embodiments of the invention, the oxygenate-rich stream comprises water and oxygenates, the oxygenates comprising methanol and being selected from the group consisting of C₂-C₄Alcohol, C₂-C₄Aldehyde, C₃-C₄Ketones and C₂-C₄At least one compound of carboxylic acid.

In some preferred embodiments of the invention, the oxygenate comprises methanol and is selected from C₂-C₄Aldehydes and C₃-C₄At least one compound of a ketone.

According to the invention, C₂-C₄The alcohol is preferably ethanol, propanol and butanol. C₂-C₄The aldehydes are preferably acetaldehyde, propionaldehyde and butyraldehyde. C₃-C₄The ketones are preferably acetone and butanone. C₂-C₄The carboxylic acids are preferably formic acid, acetic acid and propionic acid.

In some preferred embodiments of the invention, the water content of the oxygenate-rich stream is from 30 wt% to 80 wt%, and the oxygenate content is from 20 wt% to 70 wt%; preferably, the content of the aldehyde ketone compound in the oxygen-containing compound is 50 wt% to 99 wt%.

In some preferred embodiments of the invention, the recycle stream comprises from 10% to 70% of the oxygenate-rich stream and the stream to be reduced comprises from 30% to 90% of the oxygenate-rich stream.

In some preferred embodiments of the present invention, the reduction reactor is filled with a catalyst comprising a carrier, an active component, and a modifying component supported on the active component; the carrier is selected from at least one of alumina, silica, pseudo-boehmite, kaolin and diatomite, the active component is selected from at least one of ZSM-5 molecular sieve, ZSM-11 molecular sieve and ZSM-23 molecular sieve, and the modification component is selected from at least one of Ga, Mn, P, La, Ca, Mg and Ce.

In some preferred embodiments of the present invention, in step b), the method of separation comprises at least two separation modes of stripping, water washing and adsorption.

In some preferred embodiments of the present invention, the modifying component is present in an amount of 0.01 wt% to 10 wt%, and the active component is present in an amount of 30 wt% to 80 wt%, based on the total mass of the catalyst.

In some preferred embodiments of the present invention, the reduction reaction conditions include: the temperature is 250-600 ℃, the pressure is 0-0.3 MPa, and the mass space velocity of the oxygen-containing compound-rich material flow is 0.2h^-1～3.0h^-1。

According to the invention, the reaction pressure is a gauge pressure.

The MTO production device provided by the invention can obtain higher conversion rate of oxygen-containing compounds and higher total selectivity of ethylene, propylene and carbon tetrahydrocarbon.

Drawings

FIG. 1 is a schematic view of a production apparatus in example 1 of the present invention.

Description of reference numerals: 1 is a methanol conversion reactor; 2 is a reduction reactor; 4 is a separation device; 5 is a second product stream; 8 is a feed stream comprising methanol; 9 is an olefin-rich stream; 12 is an oxygenate-rich stream; 14 is the first product stream.

Detailed Description

The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.

In the present invention:

oxygenate conversion of (m1-m2)/m1 x 100%, where m1 refers to the mass of oxygenate in the oxygenate-rich stream 12 and m2 refers to the mass of oxygenate in the second product stream 5.

The selectivity for ethylene + propylene + carbon tetrahydrocarbons in the second product stream 5 is m3/m4 x 100%, where m3 refers to the total mass of ethylene and propylene and carbon tetrahydrocarbons and m4 refers to the total mass of hydrocarbons in the second product stream 5.

In the present invention, the term "C-tetrahydrocarbon" refers to an alkane or an alkene having four carbon atoms.

In the present invention, "the increased overall selectivity of ethylene and propylene and tetracarbon by the oxygenate-rich stream 12" refers to the increased overall selectivity of ethylene and propylene and tetracarbon by subjecting the oxygenate-rich stream 12 to the associated steps in the examples as compared to the direct discharge of the oxygenate-rich stream 12 without entering the reduction reactor 2.

Example 1

Example 1 a production apparatus is shown in fig. 1, the apparatus comprising: a methanol conversion reactor 1, a separation device 4 and a reduction reactor 2;

wherein, the discharge hole of the methanol conversion reactor 1 is connected with the first feed inlet of the separating device 4, the first discharge hole of the separating device 4 is connected with the feed inlet of the reduction reactor 3, the second discharge hole of the separating device 4 is connected with the feed inlet of the methanol conversion reactor 1, and the discharge hole of the reduction reactor 3 is connected with the second feed inlet of the separating device 4.

The method for preparing the olefin by using the device comprises the following steps:

a) feeding a methanol-containing feed stream 8 to a methanol conversion reactor 1 for a methanol-to-olefins reaction to produce a first product stream 14 comprising olefins;

b) the first product material flow 14 enters a separation device 4, and is subjected to steam stripping and water washing separation to obtain an olefin-rich material flow 9 and an oxygen-containing compound-rich material flow 12, wherein the content of sodium ions in the oxygen-containing compound-rich material flow 12 is 1.0ppm, the pH is 5.7, the content of oxygen-containing compounds is 20 wt%, the content of water is 80 wt%, the oxygen-containing compounds comprise methanol, ethanol, propanol, butanol, acetaldehyde, propionaldehyde, butyraldehyde, acetone, butanone, formic acid, acetic acid and propionic acid, and the content of aldehyde ketone compounds in the oxygen-containing compounds is 99 wt%;

c) the olefin rich stream 9 is exported as product; and

d) the oxygenate-rich stream 12 is divided into two parts, of which 20% is recycled as recycle stream to the methanol conversion reactor 1 and 80% is heated as stream to be reduced and enters the reduction reactor 2 for reduction reaction, thereby obtaining a second product stream 5, wherein the reduction reactionA reactor 2 (filled with a reduction catalyst which takes alumina as a carrier, takes ZSM-5 molecular sieve as an active component, takes P as a modified component, the molecular sieve accounts for 70 percent of the total mass of the catalyst, and the modified component accounts for 1.5 percent of the total mass of the catalyst) is a fixed bed reactor, the reaction temperature is 450 ℃, the reaction gauge pressure is 0.15MPa, and the mass space velocity of the oxygen-containing compound-rich material flow 12 is 1h^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 78.0%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 75.1%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 1.1%.

Example 2

The apparatus of example 1 was used.

The method for preparing olefin in the present embodiment includes:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

b) enabling the first product material flow 14 to enter a separation device 4, and obtaining an olefin-rich material flow 9 and an oxygen-containing compound-rich material flow 12 through steam stripping and water washing separation, wherein the content of sodium ions in the oxygen-containing compound-rich material flow 12 is 4.99ppm, the pH value is 6.4, the content of oxygen-containing compounds is 70 wt%, the content of water is 30 wt%, the oxygen-containing compounds comprise methanol, ethanol, propanol, butanol, acetaldehyde, propionaldehyde, butyraldehyde, acetone, butanone, formic acid and acetic acid, and the content of aldehyde ketone compounds in the oxygen-containing compounds is 50 wt%;

c) the olefin rich stream 9 is exported as product; and

d) dividing the oxygen-containing compound-rich material flow 12 into two parts, wherein 20% of the oxygen-containing compound-rich material flow is recycled to a methanol conversion reactor 1 as a circulating material flow, 80% of the oxygen-containing compound-rich material flow is heated as a material flow to be reduced and then enters a reduction reactor 2 for reduction reaction, so as to obtain a second product flow 5, wherein the reduction reactor 2 is filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, and ZSM-5 molecules are used as the reduction catalystThe sieve is an active component, the P is a modified component, the molecular sieve accounts for 70 percent of the total mass of the catalyst, the modified component accounts for 1.5 percent of the total mass of the catalyst) is taken as a fixed bed reactor, the reaction temperature is 450 ℃, the reaction gauge pressure is 0.15MPa, and the mass space velocity of the oxygen-containing compound-rich material flow 12 is 1h^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 83.8%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 87.2%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 1.4%.

Example 3

The apparatus of example 1 was used.

The method for preparing olefin in the present embodiment includes:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

b) enabling the first product material flow 14 to enter a separation device 4, and obtaining an olefin-rich material flow 9 and an oxygen-containing compound-rich material flow 12 through steam stripping and water washing separation, wherein the content of sodium ions in the oxygen-containing compound-rich material flow 12 is 9.99ppm, the pH value is 6.9, the content of oxygen-containing compounds is 30 wt%, the content of water is 70 wt%, the oxygen-containing compounds comprise methanol, ethanol, propanol, acetaldehyde, propionaldehyde, butyraldehyde, acetone, butanone, formic acid and acetic acid, and the content of aldehyde ketone compounds in the oxygen-containing compounds is 90 wt%;

c) the olefin rich stream 9 is exported as product; and

d) dividing the oxygen-containing compound-rich material flow 12 into two parts, wherein 20% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to carry out reduction reaction to obtain a second product flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, a ZSM-5 molecular sieve as an active component, P as a modification component, the molecular sieve accounts for 70% of the total mass of the catalyst, and the modification component accounts for the catalyst1.5 percent of the total mass of the oxidant) is a fixed bed reactor, the reaction temperature is 250 ℃, the reaction gauge pressure is 0MPa, and the mass space velocity of the oxygen-containing compound-rich material flow 12 is 0.2h^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 86.2%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 85.3%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 1.8%.

Example 4

The apparatus of example 1 was used.

The method for preparing olefin in the present embodiment includes:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

b) enabling the first product material flow 14 to enter a separation device 4, and obtaining an olefin-rich material flow 9 and an oxygen-containing compound-rich material flow 12 through steam stripping and water washing separation, wherein the content of sodium ions in the oxygen-containing compound-rich material flow 12 is 1.99ppm, the pH value is 5.8, the content of oxygen-containing compounds is 30 wt%, the content of water is 70 wt%, the oxygen-containing compounds comprise methanol, ethanol, propanol, butanol, acetaldehyde, propionaldehyde, acetone, butanone, formic acid and acetic acid, and the content of aldehyde ketone compounds in the oxygen-containing compounds is 90 wt%;

c) the olefin rich stream 9 is exported as product; and

d) the oxygen-containing compound-rich material flow 12 is divided into two parts, wherein 20 percent of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80 percent of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to carry out reduction reaction to obtain a second product flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, ZSM-5 molecular sieve as an active component, P as a modification component, the molecular sieve accounts for 70 percent of the total mass of the catalyst, and the modification component accounts for 1.5 percent of the total mass of the catalyst) is a fixed bed reactor, the reaction temperature is 600 ℃, the reaction gauge pressure is 0.3MPa, and the oxygen-containing compound-rich material flow isMass space velocity of oxygen compound stream 12 of 3h^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 89.0%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 83.7%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 1.7%.

Example 5

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

b) feeding the first product stream 14 into a separation device 4, and separating by stripping and water washing to obtain an olefin-rich stream 9 and an oxygenate-rich stream 12, wherein the oxygenate-rich stream 12 has a sodium ion content of 0.6ppm and a pH of 5.8;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina and silica as carriers (the weight ratio of the alumina to the silica is 9.5:0.5), a ZSM-5 molecular sieve is taken as an active component, and the molecular sieve accounts for 80% of the total mass of the catalyst) is taken as a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 88.9%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 86.5%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 2.0%.

Example 6

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 30% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 70% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 is filled with a reduction catalyst, the reduction catalyst takes alumina and silica as carriers (the weight ratio of the alumina to the silica is 8:2), a ZSM-5 molecular sieve is taken as an active component, the molecular sieve accounts for 30% of the total mass of the catalyst, P, La is taken as a modified component, La accounts for 0.5% of the total mass of the catalyst, and P accounts for 1% of the total mass of the catalyst) and is taken as a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 90.5%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 87.4%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 2.7%.

Example 7

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to undergo a reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst which takes alumina as a carrier, takes a ZSM-5 molecular sieve as an active component, takes Mn and P as modified components, takes Mn as 0.8% of the total mass of the catalyst, and takes P as 1.2% of the total mass of the catalyst) is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 77.4%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 86.2%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 1.3%.

Example 8

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 is filled with a reduction catalyst, the reduction catalyst takes pseudoboehmite and kaolin as carriers (the mass ratio of the pseudoboehmite to the kaolin is 8:2), a ZSM-23 molecular sieve is taken as an active component, the molecular sieve accounts for 70% of the total mass of the catalyst, P is taken as a modified component, and P accounts for 1.5% of the total mass of the catalyst) and is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 74.5%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 83.7%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 1.2%.

Example 9

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% is heated as a material flow to be reduced and then enters a reduction reactor 2 for reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina and kieselguhr as carriers (the mass ratio of the alumina to the kieselguhr is 5:5), a ZSM-11 molecular sieve is taken as an active component, the molecular sieve accounts for 50% of the total mass of the catalyst, Ga and P are taken as modified components, Ga accounts for 1.1% of the total mass of the catalyst, and P accounts for 0.9% of the total mass of the catalyst) is taken as a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 78.9%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 84.1%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 1.6%.

Example 10

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, a ZSM-5 molecular sieve as an active component, the molecular sieve takes 80% of the total mass of the catalyst, the P, La and Mg as modified components, the P takes 3.3% of the total mass of the catalyst, the La takes 2.4% of the total mass of the catalyst, and the Mg takes 4.3% of the total mass of the catalyst) is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 82.4%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 82.9%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 1.8%.

Example 11

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% is heated as a material flow to be reduced and then enters a reduction reactor 2 for reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 is filled with a reduction catalyst, the reduction catalyst takes alumina, silica and kieselguhr as carriers (the mass ratio of the alumina, the silica and the kieselguhr is 8:1.5:0.5), a ZSM-5 molecular sieve is taken as an active component, the molecular sieve accounts for 60% of the total mass of the catalyst, Ca and P are taken as modified components, Ca accounts for 1.0% of the total mass of the catalyst, and P accounts for 1.5% of the total mass of the catalyst) and is taken as a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 79.8%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 87.6%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 1.5%.

Example 12

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 10% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 90% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 is a fixed bed reactor (filled with a reduction catalyst, the reduction catalyst takes pseudo-boehmite and silicon oxide as carriers (the mass ratio of the pseudo-boehmite to the silicon oxide is 7:3), a ZSM-5 molecular sieve is used as an active component, the molecular sieve accounts for 60% of the total mass of the catalyst, Ce is used as a modified component, and Ce accounts for 0.3% of the total mass of the catalyst);

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 84.5%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 78.9%, and the total selectivity to ethylene, propylene and carbon tetrads for the oxygenate-rich stream 12 is 1.4%.

Comparative example 1

Using the apparatus of example 1, the composition of the oxygenate-rich stream 12 was identical to that of example 3.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) the material flow 12 rich in the oxygen-containing compound is divided into two parts, wherein 20 percent of the material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80 percent of the material flow is heated as a material flow to be reduced and then enters a reduction reactor 2 to carry out reduction reaction, so as to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, ZSM-5 molecular sieve as an active component, P as a modified component, the molecular sieve accounts for 70 percent of the total mass of the catalyst, and the modified component accounts for 1.5 percent of the total mass of the catalyst) is a fixed bed reactor, the reaction temperature is 240 ℃, the reaction gauge pressure is 0MPa, and the mass space velocity of the material flow 12 rich in the oxygen-containing compound is 0.18^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 33.7%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 26.4%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 0.2%.

Comparative example 2

Using the apparatus of example 1, the composition of the oxygenate-rich stream 12 was identical to that of example 3.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) the material flow 12 rich in the oxygen-containing compound is divided into two parts, wherein 20 percent of the material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80 percent of the material flow is heated as a material flow to be reduced and then enters a reduction reactor 2 to carry out reduction reaction, so as to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, ZSM-5 molecular sieve as an active component, P as a modified component, the molecular sieve accounts for 70 percent of the total mass of the catalyst, and the modified component accounts for 1.5 percent of the total mass of the catalyst) is a fixed bed reactor, the reaction temperature is 620 ℃, the reaction gauge pressure is 0.32MPa, and the mass space velocity of the material flow 12 rich in the oxygen-containing compound is 3.5^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 74.2%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 57.0%, and the total selectivity to ethylene, propylene and carbon tetrads for the oxygenate-rich stream 12 is 0.4%.

Comparative example 3

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) heating the oxygen-containing compound-rich material flow 12, and then enabling the oxygen-containing compound-rich material flow to enter a reduction reactor 2 for reduction reaction to obtain a second product flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, a ZSM-5 molecular sieve as an active component, P as a modification component, the molecular sieve accounts for 70% of the total mass of the catalyst, and the modification component accounts for 1.5% of the total mass of the catalyst) is a fixed bed reactor, the reaction temperature is 620 ℃, the reaction gauge pressure is 0.32MPa, and the mass space velocity of the oxygen-containing compound-rich material flow 12 is 3.5h^-1；

e) The second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 61.8%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 59.4%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 0.7%.

Comparative example 4

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 20% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 for reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst which takes alumina as a carrier, takes a ZSM-5 molecular sieve as an active component, takes P as a modification component, takes the molecular sieve accounting for 25% of the total mass of the catalyst, and takes the modification component accounting for 11% of the total mass of the catalyst) is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 58.4%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 66.1%, and the total selectivity to ethylene, propylene and carbon tetrads for the oxygenate-rich stream 12 is 0.6%.

Comparative example 5

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 20% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to perform reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst, the reduction catalyst takes alumina as a carrier, an SAPO-34 molecular sieve as an active component, P as a modification component, the molecular sieve accounts for 70% of the total mass of the catalyst, and the modification component accounts for 1.5% of the total mass of the catalyst) is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 58.2%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 64.9%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 0.4%.

Comparative example 6

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) dividing an oxygen-containing compound-rich material flow 12 into two parts, wherein 20% of the oxygen-containing compound-rich material flow is circulated to a methanol conversion reactor 1 as a circulating material flow, 80% of the oxygen-containing compound-rich material flow is heated and then enters a reduction reactor 2 to undergo a reduction reaction to obtain a second product material flow 5, wherein the reduction reactor 2 (filled with a reduction catalyst which takes silicon oxide as a carrier, takes a ZSM-5 molecular sieve as an active component, takes P as a modification component, takes the molecular sieve to account for 70% of the total mass of the catalyst, and takes the modification component to account for 1.5% of the total mass of the catalyst) is a fixed bed reactor;

e) the second product stream 5 is selectively subjected to gas-liquid separation and returned to different locations of the separation device.

The results show that the oxygenate conversion is 63.9%, the selectivity to ethylene, propylene and carbon tetrads in the second product stream 5 is 63.2%, and the total selectivity to ethylene, propylene and carbon tetrads increased by the oxygenate-rich stream 12 is 0.8%.

Comparative example 7

The composition of the oxygenate-rich stream 12 corresponds to that of example 3, using the apparatus of example 1 and the reaction conditions of the reduction reactor 2.

The remaining steps or conditions include:

a) a methanol-containing feed stream 8 is passed to a methanol conversion reactor 1 for MTO reaction to produce a first product stream 14;

c) the olefin rich stream 9 is exported as product; and

d) the oxygenate-rich stream 12 is totally recycled to the methanol conversion reactor 1.

The results show that the oxygenate conversion is 48.9%, the selectivity to ethylene, propylene and tetracarbon in the second product stream 5 is 43.7%, and the total selectivity to ethylene, propylene and tetracarbon increased by the oxygenate-rich stream 12 is 0.4%.

For convenience of comparison, the reaction conditions and experimental results in examples 1 to 6 are shown in Table 1 below, the reaction conditions and experimental results in examples 7 to 12 are shown in Table 2 below, and the reaction conditions and experimental results in comparative examples 1 to 7 are shown in Table 3 below.

TABLE 1

TABLE 2

TABLE 3

It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.

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Device and method for producing olefin by using methanol

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