CN112680244A - MTBE and naphtha modification combined production system and method - Google Patents
MTBE and naphtha modification combined production system and method Download PDFInfo
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Abstract
The invention discloses an MTBE and naphtha modification combined production system and a method, which relate to the technical field of petrochemical processing, and the MTBE and naphtha modification combined production system comprises the following components: the device comprises a methanol buffer tank, a carbon four buffer tank, an MTBE reactor, an azeotropic tower, a heat exchanger, a heating furnace, an aromatization reactor, an absorption desorption system, a second etherification reactor, a stabilizing tower and a de-heavy tower which are sequentially connected. The invention combines the MTBE production device with the naphtha modification device, cancels an extraction tower and a methanol recovery tower, saves energy consumption, simultaneously fully utilizes isobutene produced by the naphtha modification device, utilizes a newly-added second etherification reactor to produce MTBE, directly mixes unreacted methanol and the produced MTBE with original light aromatic hydrocarbon, can be used for gasoline blending components, realizes production of various products by one set of production line through improving the existing production flow process, and increases production benefits.
Description
Technical Field
The invention relates to the technical field of petrochemical processing, in particular to an MTBE and naphtha modification combined production system and method.
Background
In the processing flow of petrochemical products, a naphtha modifying device and an MTBE (methyl tert-butyl ether) production device are important rings, naphtha modifying raw materials are hydrogenated naphtha and ether carbon four, and the products comprise dry gas, liquefied gas, light aromatic hydrocarbons and heavy aromatic hydrocarbons through an aromatization reactor and an absorption stabilizing system. The raw materials for producing MTBE are methanol and C4, the MTBE is produced by an etherification reactor, unreacted methanol and C4 (C4 after etherification) are separated by an extraction tower, C4 (C4 after etherification) is used as the raw material of a naphtha modifying device, and the methanol is concentrated by a methanol recovery tower and then recycled to produce the MTBE. Methanol can be used as a raw material supplement of a naphtha upgrading device and can provide heat required by the reaction.
Therefore, it is considered that unreacted methanol and C4 (C4 after etherification) are directly sent to a naphtha upgrading device for utilization; meanwhile, the MTBE is produced by utilizing a small amount of isobutene (produced in a naphtha upgrading reactor) in the civil liquefied gas produced by the naphtha upgrading device, and the isobutene is fully utilized, so that the applicant proposes a combined production scheme for upgrading the MTBE and the naphtha, an extraction tower and a methanol recovery tower are omitted, and the energy consumption is saved.
Disclosure of Invention
In order to overcome the defects of related products in the prior art, the invention provides an MTBE and naphtha modification combined production system and method, which reduce an extraction tower and a methanol recovery tower and save energy consumption.
The invention provides an MTBE and naphtha modification combined production system, which comprises: the system comprises a methanol buffer tank, a carbon four buffer tank, an MTBE reactor, an azeotropic tower, a heat exchanger, a heating furnace, an aromatization reactor, an absorption desorption system, a second etherification reactor, a stabilizing tower and a de-heavy tower which are sequentially connected, wherein the methanol buffer tank is also respectively communicated with the azeotropic tower, the aromatization reactor and the second etherification reactor, and the heat exchanger is also respectively communicated with the aromatization reactor and the absorption desorption system; the methanol buffer tank and the carbon four buffer tank are respectively used for storing methanol and carbon four, and the carbon four is isobutane, n-butane and a mixture of isobutene and n-butene; the MTBE reactor comprises an etherification pre-reactor and a first etherification reactor, wherein a methanol buffer tank and a carbon four buffer tank respectively introduce methanol and carbon four into the etherification pre-reactor of the MTBE reactor and remove impurities in raw materials, so that a buffer space is provided to protect the etherification reactor; the etherification pre-reactor feeds purified methanol and the carbon cross into the first etherification reactor to be mixed, and isobutene and methanol are subjected to etherification reaction to generate MTBE; the product after the reaction is fed into the azeotropic tower for separation, MTBE generated by etherification reaction is output from the top of the tower, unreacted carbon four (carbon four without isobutene, also called as carbon four after etherification) and methanol form an azeotrope, the azeotrope is output from the bottom of the tower, and the mixture of hydrogenated naphtha and carbon four and methanol supplemented by a methanol buffer tank are fed into the heat exchanger together for heat exchange (namely the mixture of hydrogenated naphtha and carbon four exchanges heat with the aromatization reaction product), the heat exchanger also provides a part of heat for the absorption and desorption system, the product after heat exchange is melted into a heating furnace and heated to the reaction temperature, and then fed into an aromatization reactor, and aromatization reaction is carried out under the action of a catalyst to obtain dry gas, liquefied gas and aromatic hydrocarbon; and (2) introducing products of aromatization reaction into the absorption desorption system, the second etherification reactor, the stabilizing tower and the de-weighting tower in sequence, separating dry gas products through the absorption desorption system, supplementing methanol according to the content of isobutene in reaction products before feeding into the stabilizing tower, introducing the supplemented methanol into the second etherification reactor for etherification reaction, then introducing the obtained product into the stabilizing tower for separating civil liquefied gas, and finally separating light aromatic hydrocarbons and heavy aromatic hydrocarbons through the de-weighting tower, wherein the light aromatic hydrocarbons are used as gasoline blending components, and the heavy aromatic hydrocarbons are used as diesel blending components.
In some embodiments of the present invention, the purity of the methanol in the methanol buffer tank is 95% or more, and the raw material ratio of the methanol to the carbon four is 1.1 by mole.
In certain embodiments of the present invention, the etherification pre-reactor is a knock down configuration.
The invention also provides an MTBE and naphtha upgrading combined production method, which is applied to any one of the MTBE and naphtha upgrading combined production systems and comprises the following steps:
step a: introducing methanol and C4 into an etherification pre-reactor of an MTBE reactor and removing impurities in raw materials, wherein the purity of the methanol in a methanol buffer tank is more than 95%, the C4 is a mixture of isobutane, n-butane, isobutene and n-butene, and the molar ratio of the methanol to the C4 is 1.1;
step b: the etherification pre-reactor feeds purified methanol and the carbon-four joint into a first etherification reactor of an MTBE reactor for mixing, and isobutene and methanol are subjected to etherification reaction to generate MTBE;
step c: introducing the product after the reaction into an azeotropic tower for separation, outputting MTBE generated by etherification reaction from the top of the tower, forming an azeotrope by unreacted C and methanol, outputting the azeotrope from the bottom of the tower, converging hydrogenated naphtha and supplemented methanol, introducing the naphtha and the supplemented methanol into a heat exchanger for heat exchange, providing a part of heat for an absorption and desorption system by the heat exchanger, melting the product after the heat exchange into a heating furnace, heating to the reaction temperature, introducing the product into an aromatization reactor, and performing aromatization reaction under the action of a catalyst to obtain dry gas, liquefied gas and aromatic hydrocarbon;
step d: and (2) introducing products of aromatization reaction into an absorption desorption system, a second etherification reactor, a stabilizing tower and a heavy hydrocarbon removal tower in sequence, separating dry gas products through the absorption desorption system, supplementing methanol according to the content of isobutene in reaction products before feeding into the stabilizing tower, introducing the supplemented methanol into the second etherification reactor for etherification reaction, then introducing the obtained product into the stabilizing tower for separating civil liquefied gas, and finally separating light aromatic hydrocarbons and heavy aromatic hydrocarbons through the heavy hydrocarbon removal tower.
Compared with the prior art, the invention has the following advantages:
according to the MTBE and naphtha modification combined production system disclosed by the embodiment of the invention, an MTBE production device is combined with a naphtha modification device, an extraction tower and a methanol recovery tower are omitted, energy consumption is saved, isobutene produced by the naphtha modification device is fully utilized, an additional second etherification reactor is utilized to produce MTBE, unreacted methanol and generated MTBE are directly mixed with original light aromatic hydrocarbon and can be used for gasoline blending components, the existing production flow process is improved, the production of various products can be realized by one set of production line, and the production benefit is increased.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is a schematic structural diagram of the MTBE and naphtha upgrading combined production system according to the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and that the following is a description of preferred embodiments of the invention. This invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein, but rather should be construed as broadly as the present disclosure is set forth in order to provide a more thorough understanding thereof.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is explicitly and implicitly understood by one skilled in the art that the embodiments described herein can be combined with other embodiments.
Referring to fig. 1, the MTBE and naphtha upgrading combined production system comprises a methanol buffer tank 1, a carbon four buffer tank 2, an MTBE reactor 3, an azeotropic tower 4, a heat exchanger 5, a heating furnace 6, an aromatization reactor 7, an absorption desorption system 8, a second etherification reactor 9, a stabilizing tower 10 and a de-heavy tower 11 which are sequentially connected, wherein the methanol buffer tank 1 is further respectively communicated with the azeotropic tower 4, the aromatization reactor 7 and the second etherification reactor 9, and the heat exchanger 5 is further respectively communicated with the aromatization reactor 7 and the absorption desorption system 8.
In the embodiment of the invention, the methanol buffer tank 1 and the carbon four buffer tank 2 are respectively used for storing methanol and carbon four, the purity of the methanol in the methanol buffer tank 1 is more than 95%, the carbon four is a mixture of isobutane, n-butane, isobutene and n-butene, and the raw material ratio of the methanol to the carbon four is 1.1 in a molar ratio; the MTBE reactor 3 comprises an etherification pre-reactor 31 and a first etherification reactor 32, the methanol buffer tank 1 and the carbon four buffer tank 2 respectively introduce methanol and carbon four into the etherification pre-reactor 31 of the MTBE reactor 3 and remove impurities in raw materials, the methanol buffer tank and the carbon four buffer tank are used for providing buffer space to protect the etherification reactor, the etherification pre-reactor 31 is of a detachable structure and is convenient to replace according to actual application scenes; the etherification pre-reactor 31 feeds the purified methanol and the carbon cross into the first etherification reactor 32 to be mixed, and isobutylene and methanol are subjected to etherification reaction to generate MTBE; the product after the reaction is introduced into the azeotropic tower 4 for separation, the MTBE generated by the etherification reaction is output from the top of the tower, unreacted carbon four (carbon four without isobutene, also called as carbon four after etherification) and methanol form an azeotrope, the azeotrope is output from the bottom of the tower, and the mixture of the hydrogenated naphtha and the carbon four and the methanol supplemented by the methanol buffer tank 1 are introduced into the heat exchanger 5 together for heat exchange (namely the mixture of the hydrogenated naphtha and the carbon four exchanges heat with the aromatization reaction product), the heat exchanger 5 also provides a part of heat for the absorption desorption system 8, the product after the heat exchange is melted into the heating furnace 6 and heated to the reaction temperature, and then introduced into the aromatization reactor 7, and the aromatization reaction is carried out under the action of a catalyst, so as to obtain dry gas, liquefied gas and aromatic hydrocarbon; the aromatization reaction product is sequentially fed into the absorption desorption system 8, a second etherification reactor 9, a stabilizing tower 10 and a de-heavy tower 11, dry gas products (mainly carbon 2, carbon 1 and hydrogen) are separated out through the absorption desorption system 8, methanol is supplemented according to the content of isobutene in the reaction product before the feed of the stabilizing tower 10 and fed into the second etherification reactor 9 for etherification reaction, then the dry gas products are fed into the stabilizing tower 10 for separating civil liquefied gas (mainly alkane and containing a small amount of isobutene), and light aromatic hydrocarbons (mixed with a small amount of unreacted methanol and generated MTBE) and heavy aromatic hydrocarbons are finally separated out through the de-heavy tower 11, wherein the light aromatic hydrocarbons are used as gasoline blending components, trace methanol can exist in gasoline and do not influence the quality of gasoline products, and the heavy aromatic hydrocarbons are used for blending diesel components.
The MTBE and naphtha modification combined production system disclosed by the embodiment of the invention combines an MTBE production device with a naphtha modification device, an extraction tower and a methanol recovery tower are omitted, energy consumption is saved, isobutene produced by the naphtha modification device is fully utilized, the MTBE is produced by utilizing the newly-added second etherification reactor 9, unreacted methanol and generated MTBE are directly mixed with original light aromatic hydrocarbon and can be used for gasoline blending components, the existing production flow process is improved, the production of various products can be realized by one set of production line, and the production benefit is increased.
On the basis of the above embodiment, the present invention further provides a production method applied to the above MTBE and naphtha upgrading combined production system, including the following steps:
step a: introducing methanol and C4 into an etherification pre-reactor 31 of an MTBE reactor 3 and removing impurities in raw materials, wherein the purity of the methanol in a methanol buffer tank 1 is more than 95%, the C4 is a mixture of isobutane, n-butane, isobutene and n-butene, and the molar ratio of the methanol to the C4 is 1.1;
step b: the etherification pre-reactor 31 feeds the purified methanol and carbon four into a first etherification reactor 32 of the MTBE reactor 3 for mixing, and isobutylene and methanol are subjected to etherification reaction to generate MTBE;
step c: introducing the product after the reaction into an azeotropic tower 4 for separation, outputting MTBE generated by etherification reaction from the top of the tower, forming an azeotrope by unreacted carbon four and methanol, outputting the azeotrope from the bottom of the tower, converging hydrogenated naphtha and supplemented methanol, introducing the naphtha and the supplemented methanol into a heat exchanger 5 for heat exchange, wherein the heat exchanger 5 also provides a part of heat for an absorption and desorption system 8, melting the product after the heat exchange into a heating furnace 6, heating to the reaction temperature, introducing the product into an aromatization reactor 7, and performing aromatization reaction under the action of a catalyst to obtain dry gas, liquefied gas and aromatic hydrocarbon;
step d: the aromatization reaction products are sequentially introduced into an absorption desorption system 8, a second etherification reactor 9, a stabilizing tower 10 and a de-weighting tower 11, dry gas products are separated out through the absorption desorption system 8, methanol is supplemented according to the content of isobutene in the reaction products before the feeding of the stabilizing tower 10, the methanol is introduced into the second etherification reactor 9 for etherification reaction, and then the methanol is introduced into the stabilizing tower 10 for separating civil liquefied gas, and light aromatics and heavy aromatics are finally separated out through the de-weighting tower 11.
The MTBE and naphtha upgrading combined production method applied to the MTBE and naphtha upgrading combined production system in the above embodiment can be implemented, and the MTBE and naphtha upgrading combined production method applied to the MTBE and naphtha upgrading combined production system has the corresponding functional components and beneficial effects applied to the MTBE and naphtha upgrading combined production system in the above embodiment, and specific reference is made to the above embodiment applied to the MTBE and naphtha upgrading combined production system, and the embodiment of the present invention is not described again.
Those not described in detail in this specification are within the skill of the art. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications may be made to the embodiments described in the foregoing detailed description, or equivalent changes may be made in some of the features of the embodiments. All equivalents that can be substituted by the contents of the specification of the present invention and applied directly or indirectly to other related technical fields are within the scope of the present invention.
Claims (4)
1. An MTBE and naphtha upgrading co-production system, comprising: the system comprises a methanol buffer tank, a carbon four buffer tank, an MTBE reactor, an azeotropic tower, a heat exchanger, a heating furnace, an aromatization reactor, an absorption desorption system, a second etherification reactor, a stabilizing tower and a de-heavy tower which are sequentially connected, wherein the methanol buffer tank is also respectively communicated with the azeotropic tower, the aromatization reactor and the second etherification reactor, and the heat exchanger is also respectively communicated with the aromatization reactor and the absorption desorption system; the methanol buffer tank and the carbon four buffer tank are respectively used for storing methanol and carbon four, and the carbon four is isobutane, n-butane and a mixture of isobutene and n-butene; the MTBE reactor comprises an etherification pre-reactor and a first etherification reactor, wherein a methanol buffer tank and a carbon four buffer tank respectively introduce methanol and carbon four into the etherification pre-reactor of the MTBE reactor and remove impurities in raw materials, so that a buffer space is provided to protect the etherification reactor; the etherification pre-reactor feeds purified methanol and the carbon cross into the first etherification reactor to be mixed, and isobutene and methanol are subjected to etherification reaction to generate MTBE; the product after the reaction is fed into the azeotropic tower for separation, MTBE generated by etherification reaction is output from the top of the tower, unreacted carbon four (carbon four without isobutene, also called as carbon four after etherification) and methanol form an azeotrope, the azeotrope is output from the bottom of the tower, and the mixture of hydrogenated naphtha and carbon four and methanol supplemented by a methanol buffer tank are fed into the heat exchanger together for heat exchange (namely the mixture of hydrogenated naphtha and carbon four exchanges heat with the aromatization reaction product), the heat exchanger also provides a part of heat for the absorption and desorption system, the product after heat exchange is melted into a heating furnace and heated to the reaction temperature, and then fed into an aromatization reactor, and aromatization reaction is carried out under the action of a catalyst to obtain dry gas, liquefied gas and aromatic hydrocarbon; and (2) introducing products of aromatization reaction into the absorption desorption system, the second etherification reactor, the stabilizing tower and the de-weighting tower in sequence, separating dry gas products through the absorption desorption system, supplementing methanol according to the content of isobutene in reaction products before feeding into the stabilizing tower, introducing the supplemented methanol into the second etherification reactor for etherification reaction, then introducing the obtained product into the stabilizing tower for separating civil liquefied gas, and finally separating light aromatic hydrocarbons and heavy aromatic hydrocarbons through the de-weighting tower, wherein the light aromatic hydrocarbons are used as gasoline blending components, and the heavy aromatic hydrocarbons are used as diesel blending components.
2. The MTBE and naphtha upgrading co-production system according to claim 1, characterized in that: the purity of the methanol in the methanol buffer tank is more than 95%, and the raw material ratio of the methanol to the C4 is 1.1.
3. The MTBE and naphtha upgrading co-production system according to claim 1, characterized in that: the etherification pre-reactor is of a detachable structure.
4. An MTBE and naphtha upgrading co-production method applied to the MTBE and naphtha upgrading co-production system of any one of claims 1 to 3, characterized by comprising the following steps:
step a: introducing methanol and C4 into an etherification pre-reactor of an MTBE reactor and removing impurities in raw materials, wherein the purity of the methanol in a methanol buffer tank is more than 95%, the C4 is a mixture of isobutane, n-butane, isobutene and n-butene, and the molar ratio of the methanol to the C4 is 1.1;
step b: the etherification pre-reactor feeds purified methanol and the carbon-four joint into a first etherification reactor of an MTBE reactor for mixing, and isobutene and methanol are subjected to etherification reaction to generate MTBE;
step c: introducing the product after the reaction into an azeotropic tower for separation, outputting MTBE generated by etherification reaction from the top of the tower, forming an azeotrope by unreacted C and methanol, outputting the azeotrope from the bottom of the tower, converging hydrogenated naphtha and supplemented methanol, introducing the naphtha and the supplemented methanol into a heat exchanger for heat exchange, providing a part of heat for an absorption and desorption system by the heat exchanger, melting the product after the heat exchange into a heating furnace, heating to the reaction temperature, introducing the product into an aromatization reactor, and performing aromatization reaction under the action of a catalyst to obtain dry gas, liquefied gas and aromatic hydrocarbon;
step d: and (2) introducing products of aromatization reaction into an absorption desorption system, a second etherification reactor, a stabilizing tower and a heavy hydrocarbon removal tower in sequence, separating dry gas products through the absorption desorption system, supplementing methanol according to the content of isobutene in reaction products before feeding into the stabilizing tower, introducing the supplemented methanol into the second etherification reactor for etherification reaction, then introducing the obtained product into the stabilizing tower for separating civil liquefied gas, and finally separating light aromatic hydrocarbons and heavy aromatic hydrocarbons through the heavy hydrocarbon removal tower.
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| CN206751740U (en) * | 2017-05-10 | 2017-12-15 | 山东大齐化工科技有限公司 | The system of methanol, naphtha aromtization production high-knock rating gasoline |
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- 2020-12-09 CN CN202011448070.5A patent/CN112680244A/en active Pending
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4854939A (en) * | 1987-12-08 | 1989-08-08 | Mobil Oil Corporation | Aromatization and etherification process integration |
| CN105195211A (en) * | 2014-06-16 | 2015-12-30 | 中国石油化工股份有限公司 | Methyl alcohol and C4 hydrocarbon aromatization catalyst and aromatization method |
| CN104829435A (en) * | 2015-04-30 | 2015-08-12 | 中建安装工程有限公司 | Apparatus for producing MTBE by using novel catalytic distillation structured packing, and method thereof |
| CN106190217A (en) * | 2016-07-29 | 2016-12-07 | 山东东方宏业化工有限公司 | A kind of hydro carbons overlapping technology of aromatization extends the method that catalyst uses the cycle |
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