CN118812374A - Method for selective superposition of carbon four olefins and system for selective superposition of carbon four olefins - Google Patents
Method for selective superposition of carbon four olefins and system for selective superposition of carbon four olefins Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/06—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups by reactions not involving the formation of carbamate groups
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Abstract
The invention relates to the field of olefin polymerization, and discloses a carbon tetraolefin selective polymerization method and a system for carbon tetraolefin selective polymerization reaction. A process for the selective folding of carbon tetraolefins, the process comprising: (1) In the presence of a reaction regulator, carrying out superposition reaction on the carbon four raw materials; (2) And (3) separating the materials obtained by the superposition reaction in the step (1) in the presence of a separation regulator to obtain the residual raw materials, the reaction regulator, the separation regulator and the superposition product. The carbon tetraolefin selective lamination method has the advantages of high product separation precision and low separation energy consumption.
Description
Technical Field
The invention relates to the field of olefin polymerization, in particular to a carbon tetraolefin selective polymerization method and a system for carbon tetraolefin selective polymerization reaction.
Background
The mixed carbon four-cut fraction produced by catalytic cracking device or catalytic cracking device of oil refinery is mainly composed of n-butane, isobutane, isobutene, 1-butene, cis-2-butene, trans-2-butene and other carbon four-alkanes and olefins, and is usually used as raw material of alkylation device to produce high-octane gasoline after isobutene is removed by methyl tert-butyl ether (MTBE) device.
The mixed carbon four-fraction of the byproduct of the ethylene cracking device for the chemical industry, which is used for extracting and removing butadiene, is mainly composed of the carbon four-alkanes and the alkene such as n-butane, isobutane, isobutene, 1-butene, cis-2-butene, trans-2-butene and the like, but the carbon four-alkanes content is very small, and the carbon four-alkanes is mainly the carbon four-alkene, and the mixed carbon four-fraction is usually used for producing the high-purity 1-butene after the isobutene of the fraction is removed by an MTBE device.
MTBE units are important in the processing of mixed carbon four fractions. After the mixed carbon four fractions produced by the catalytic cracking device or the catalytic cracking device are treated by the MTBE device, not only can the requirements of the alkylation device on the alkane-alkene ratio of the raw materials be better met, but also isobutene which is not a better alkylation raw material can be converted into high-octane gasoline blending component MTBE with higher added value; the mixed carbon four-distillate produced by the ethylene cracking device has higher content of 1-butene, is a raw material for better producing high-purity 1-butene, but the boiling points of isobutene and 1-butene are very close, the separation of the isobutene and the 1-butene is difficult to realize by using a conventional separation method, and the MTBE device realizes the separation of the isobutene and the 1-butene through chemical reaction.
Along with the gradual popularization and use of ethanol gasoline, the MTBE possibly pollutes a ground water source, the productivity of the MTBE is in a descending trend, partial MTBE production devices are subjected to production stopping and production transferring problems, and the selective superposition technology of the carbon tetraolefins is a better MTBE production substitution technology, so that the requirements of the subsequent processing process of the carbon tetrafractions can be met. The carbon tetraolefin selective lamination technology is mainly characterized in that: isobutene in the mixed carbon four fractions is selectively overlapped into an overlapped product with isooctene as a main component under the action of an overlapped catalyst, the obtained overlapped product is a high-octane gasoline component and is also an important chemical raw material, and the residual mixed carbon four fractions after reaction can still be processed by adopting the original technological process.
In the process of the selective polymerization of the carbon tetraolefins, the polymerization of isobutene is easy to occur, and the dry point of the laminated gasoline exceeds standard, so that a reaction regulator is required to be introduced into a reaction system for the selective polymerization of the carbon tetraolefins to control the polymerization of the isobutene, the reaction regulator is basically not consumed in the reaction process, and the cyclic utilization of the reaction regulator is required to be realized through a separation means. CN108976102a discloses a method for recovering isobutene superposition inhibitor and a system device thereof, the application proposes that a catalytic distillation tower is connected behind an isobutene superposition reactor, the recovery and reutilization of the inhibitor are realized by side extraction lines at 10-12 tower plates below a feed inlet of the catalytic distillation tower, or a rectifying tower is added behind the catalytic distillation tower as an inhibitor recovery tower, and the recovery of the inhibitor is completed, but the method has higher reflux of the catalytic distillation tower and high energy consumption of the device; in addition, the temperature of the tower bottom of the catalytic distillation tower is higher, and a heat source with a higher temperature level is needed to provide heat required for separation. CN109354567a discloses an isobutylene superposition system device transformed by methyl tertiary butyl ether device and superposition process method. The isobutene superposition system device comprises a feeding unit, a superposition unit, a catalytic distillation unit and an inhibitor recovery unit, wherein the inhibitor recovery unit is formed by connecting an inhibitor extraction tower and an inhibitor rectification recovery tower, the mixed four and the inhibitor are pre-reacted in a superposition reactor, then the mixed four and the inhibitor are subjected to deep superposition reaction by the catalytic distillation tower, and the inhibitor extraction tower and the inhibitor rectification recovery tower are used for finishing the recovery of the inhibitor and the extraction of a superposition product; in addition, the temperature of the tower bottom of the catalytic distillation tower is higher, and a heat source with a higher temperature level is needed to provide heat required for separation.
In summary, it is necessary to develop a carbon tetraolefin selective lamination method with simple process, feasible and reliable method, high product separation precision and low separation energy consumption.
Disclosure of Invention
The invention aims to solve the problem of high product separation energy consumption in the prior art, and provides a carbon tetraolefin selective polymerization method and a system for the carbon tetraolefin selective polymerization reaction. The carbon tetraolefin selective lamination method has the advantages of high product separation precision and low separation energy consumption.
To achieve the above object, in one aspect, the present invention provides a method for selectively laminating carbon tetraolefins, the method comprising:
(1) In the presence of a reaction regulator, carrying out superposition reaction on the carbon four raw materials;
(2) And (3) separating the materials obtained by the superposition reaction in the step (1) in the presence of a separation regulator to obtain the residual raw materials, the reaction regulator, the separation regulator and the superposition product.
Preferably, the separation modifier is used in an amount of 0.1 to 20%, preferably 2 to 10% of the mass flow of the superimposed product.
In a second aspect, the present invention provides a system for the selective folding of carbon tetraolefins, the system comprising: the superposition reaction unit and the product separation unit are connected in sequence;
the polymerization reaction unit comprises a polymerization reactor for performing polymerization reaction on the carbon tetraolefin;
The product separation unit comprises a residual raw material separation tower and a regulator recovery tower, wherein the residual raw material separation tower is used for carrying out first separation on the materials obtained by the superposition reaction, a second residual raw material is obtained at the tower top, and a tower bottom material containing a separation regulator, a reaction regulator and a superposition product is obtained at the tower bottom;
the regulator recovery tower is used for carrying out second separation on the tower bottom materials of the residual raw material separation tower, the tower top materials containing the separation regulator and the reaction regulator are obtained at the tower top, and the tower bottom products are obtained as superposition products;
The outlet of the regulator recovery tower is connected with the feed inlet of the superposition reactor; or the outlet of the regulator recovery tower is connected with the feed inlet of the residual raw material separation tower and the feed inlet of the superposition reactor.
Through the technical scheme, the beneficial effects of the invention include:
The selective superposition method of the carbon tetraolefins provided by the invention is used for separating products in the presence of the separation regulator, and the separation energy consumption can be reduced by 20-50% compared with the method without introducing the separation regulator under the condition of achieving the same separation precision of the residual raw materials (controlling the residual raw materials to basically contain no reaction regulator). The energy consumption of the first separation tower is about 70% of the total energy consumption, and the whole energy saving effect is obvious.
According to the carbon tetraolefin selective overlapping method provided by the invention, after the separation regulator is introduced, the temperature of the tower bottom of the first separation tower is obviously reduced, and the easily obtained low-temperature heat source can be used as the heat source of the tower bottom reboiler of the residual raw material separation tower, so that the use of the high-temperature heat source as the heat source of the tower bottom reboiler is avoided. Meanwhile, the temperature of the tower bottom of the residual raw material separation tower is close to that of a decarbonization four tower in a conventional Methyl Tertiary Butyl Ether (MTBE) device, is lower than the design temperature (less than or equal to 165 ℃) of the decarbonization four tower in the conventional Methyl Tertiary Butyl Ether (MTBE) device, and the decarbonization four tower and the methanol recovery tower in the conventional MTBE device can be respectively utilized as the residual raw material separation tower and the regulator separation tower, so that the device cost is greatly saved.
Drawings
FIG. 1 is a schematic process flow diagram of a selective carbon tetraolefin polymerization process according to example 1 of the present invention;
FIG. 2 is a schematic process flow diagram of the selective folding method of C2 tetraolefins according to the present invention.
Description of the reference numerals
A. A raw material pretreatment unit; b. A superposition reaction unit; c. A product separation unit;
1. A carbon four feedstock; 2. Demineralized water; 3. Washing water;
4. A washed carbon four raw material; 5. Material obtained by the superposition reaction; 6. Separating the regulator;
7. A second remaining raw material; 8. A reaction modifier; 9. Folding the product;
10. a water washing tower; 11. A superposition reactor; 12. A residual raw material separation tower;
13. And a regulator recovery tower.
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
In the description of the present invention, it should be understood that the terms "top," "bottom," and the like indicate orientations or positional relationships merely to facilitate the description of the invention and simplify the description, and are not meant to indicate or imply that the devices or elements being referred to must have a particular orientation, be configured and operated in a particular orientation, and are not to be construed as limiting the invention.
In the present invention, the unit "ppm (w)" means parts per million by mass, and the unit "ppm (v)" means parts per million by volume.
The first aspect of the invention provides a carbon tetraolefin selective polymerization method, which comprises the following steps:
(1) In the presence of a reaction regulator, carrying out superposition reaction on the carbon four raw materials;
(2) And (3) separating the materials obtained by the superposition reaction in the step (1) in the presence of a separation regulator to obtain the residual raw materials, the reaction regulator, the separation regulator and the superposition product.
The superposition method is carried out in the presence of the separation regulator, thereby being beneficial to reducing energy consumption and saving cost. Meanwhile, the separation regulator is easy to obtain, has good intersolubility with a reactant stream, and does not influence the reaction performance. Preferably, the separation modifier contains at least one of a carbon tetraalkyl alkane, a carbon tetraalkyl alkene, a carbon pentacene, a carbon hexaalkane, and a carbon hexaalkene, preferably at least one of cis 2-butene, trans 2-butene, and isopentane.
In order to reduce the separation energy consumption, the mass content of cis-2-butene, trans-2-butene and isopentane is preferably 40% or more, preferably 70% or more, based on the total mass of the separation regulator.
Particularly preferably, the separation regulator contains cis-2-butene and/or trans-2-butene.
The invention has a wide selection range of specific types of the separation regulator, so long as the separation regulator has the characteristics and the components. Preferably, the separation modifier is selected from light naphtha and/or at least part of the remaining feedstock.
According to the present invention, preferably, the light naphtha has a distillation range of 5 to 80 ℃.
According to the invention, the separation modifier is preferably used in an amount of 0.1 to 20%, for example 0.1％、0.5％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、8％、8.5％、9％、9.5％、10％、10.5％、11％、11.5％、12％、12.5％、13％、13.5％、14％、14.5％、15％、15.5％、16％、17％、17.5％、18％、18.5％、19％、19.5％、20％,, and any value in the range of any two of these values, preferably 2 to 10% of the mass flow of the superimposed product. With the preferred embodiment, the separation energy consumption is more beneficial to be reduced under the same separation precision condition.
The separation controlling agent of the present invention is extremely small in loss in the whole process, and thus the present invention is not particularly limited in the timing of adding the separation controlling agent. Preferably, the separation modifier is added in step (1) and/or in step (2).
According to the present invention, preferably, the separation of step (2) comprises a first separation and a second separation, the first separation being carried out in a residual raw material separation column, the bottom of which is obtained as a bottom material containing a separation regulator, a reaction regulator and a superposition product; the top of the residual raw material separation tower is provided with a second residual raw material;
And introducing the tower bottom material of the residual raw material separation tower into a regulator recovery tower for second separation, obtaining a superposed product at the bottom of the tower, and obtaining a tower top material containing a separation regulator and a reaction regulator at the top of the tower.
When the separation regulator is selected from the residual raw materials, obtaining a bottom material containing the first residual raw materials, the reaction regulator and the superposition product at the bottom of the residual raw material separation tower; and obtaining a second residual raw material at the top of the residual raw material separation tower. In this case, the first remaining raw material is the separation regulator.
The present invention is not particularly limited to the remaining raw material separation column and the regulator recovery column, and may be a fractionating column conventionally used in the art.
The residual raw material separation tower and the regulator recovery tower are respectively provided with a matched reboiler, so that heat is provided for the residual raw material separation tower and the regulator recovery tower, and the residual raw material separation tower and the regulator recovery tower are conventional in the field and are not shown in the drawings of the invention.
According to the invention, preferably the overhead of the regulator recovery column provides at least part of the separation regulator and/or reaction regulator.
The reaction regulator and the separation regulator can be recycled, thereby being beneficial to saving the cost. The reaction regulator and the separation regulator can be recycled together or separately.
When the reaction modifier and separation modifier are recovered for reuse together, preferably, the reaction modifier and separation modifier are returned to step (1) and mixed with the carbon four raw material.
When the reaction modifier and the separation modifier are separately recovered for reuse, preferably, the reaction modifier is returned to step (1) and mixed with the carbon four raw material, and the separation modifier is returned to step (2) and mixed with the material obtained by the superposition reaction.
Preferably, according to the present invention, the polymerization product is a C7-C12 olefin, more preferably isooctene.
According to the present invention, preferably, the conditions of the first separation and the second separation each independently include: the temperature of the tower top is 20-200 ℃, the temperature of the tower bottom is 20-200 ℃, the pressure of the tower top is 0-1MPaG, and the reflux ratio is 0.1-25. In the superposition method provided by the invention, the product separation is carried out under the operation condition of lower reflux ratio, which is beneficial to reducing the energy consumption and saving the equipment investment.
According to the present invention, preferably, the conditions for the first separation include: the column top temperature is 40-70deg.C, such as 40deg.C, 45deg.C, 50deg.C, 55deg.C, 60deg.C, 65deg.C, 70deg.C, and any value in the range of any two of these values; the temperature of the tower bottom is 120-165 ℃, such as 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃, 160 ℃, 165 ℃ and any value in the range formed by any two of the values; the overhead pressure is in the range of 0.3-0.7MPaG, such as 0.3MPaG, 0.4MPaG, 0.5MPaG, 0.6MPaG, 0.7MPaG, and any value in the range of any two of these values; the reflux ratio is 0.2 to 0.6, for example, 0.2, 0.25,0.3, 0.35, 0.4, 0.45, 0.5, 0.55, 0.6, and any value in the range formed by any two of these values. By adopting the preferred embodiment, the residual raw materials are separated under the operation condition of lower reflux ratio, thereby being beneficial to reducing energy consumption and saving cost; the temperature of the tower kettle of the residual raw material separation tower is lower, and a low-temperature heat source can be used as a heat source of a tower kettle reboiler of the residual raw material separation tower, so that the use of a high-temperature heat source as a heat source of the tower kettle reboiler is avoided; the temperature of the tower bottoms of the residual raw material separation tower is lower than that of the decarbonization four tower bottoms of the product separation unit of the conventional MTBE device, and the decarbonization four tower and the methanol recovery tower in the conventional MTBE device can be respectively utilized to be the residual raw material separation tower and the regulator separation tower, so that the device cost is greatly saved.
According to the present invention, preferably, the conditions for the second separation include: the temperature of the tower top is 50-120 ℃, the temperature of the tower bottom is 120-160 ℃, the pressure of the tower top is 0-0.3MPaG, and the reflux ratio is 2-20.
The carbon tetraolefin selective lamination method provided by the invention can achieve higher separation precision of the residual raw materials. Preferably, the second remaining feedstock has a reaction modifier ratio of less than 500ppm, preferably less than 50ppm, more preferably less than 20ppm.
According to the present invention, preferably, the folding reaction of step (1) comprises: and (3) carrying out superposition reaction on the carbon four raw materials under the action of a reaction regulator and a catalyst and optionally a separation regulator.
The conditions for the above-mentioned polymerization reaction are not particularly limited, and may be carried out by referring to a method conventional in the art.
The invention has wider selection range of the types of the carbon four raw materials and can be various carbon four raw materials commonly used in the field. Preferably, the carbon four raw material is a catalytic cracking carbon four fraction and/or an ethylene cracking carbon four fraction.
The reaction modifier of the present invention has a wide selection range of the kind of the reaction modifier, and may be various reaction modifiers commonly used in the art. Preferably, the reaction modifier is selected from at least one of t-butanol, water, methyl t-butyl ether and methanol, more preferably t-butanol. All of the above materials are commercially available.
The invention has a wide selection range of the dosage of the reaction regulator, and preferably, the dosage of the reaction regulator is 0.1-5% of the mass flow of the carbon four raw materials.
The invention has a wide selection range of the types of the catalysts, and can be various catalysts commonly used in the field. Preferably, the catalyst is a sulfonic acid type ion exchange resin catalyst. The catalyst may be obtained commercially or may be prepared according to methods well known to those skilled in the art.
The amount of the catalyst used in the present invention is not particularly limited, and may be carried out according to a method conventional in the art.
According to the invention, preferably, the polymerization reaction is carried out in a polymerization reactor.
Preferably, the polymerization reactor is selected from a fixed bed reactor, a bubble point reactor or a tubular reactor.
In the present invention, the main occurrence in the polymerization reactor is the polymerization of isobutene in the carbon four feedstock. Preferably, a fixed bed or bubble point reactor is employed when the concentration of isobutene in the carbon four feedstock is 15% by weight or less; when the isobutene concentration in the carbon four raw material is more than 15w%, a tubular reactor is adopted.
According to the invention, the carbon-four raw material is preferably pretreated before the carbon-four raw material is subjected to the superposition reaction. With the adoption of the preferred embodiment, metal and alkaline nitride impurities in the carbon four raw materials can be effectively removed.
Preferably, the pretreatment is selected from a water wash treatment and/or a scavenger purification treatment. The pretreatment method is a conventional pretreatment method in the art, and the specific operation can be performed according to a conventional method in the art, and the present invention is not described in detail herein.
When the carbon four feedstock contains unsaturated olefins (e.g., diolefins), the pretreatment preferably also includes selective hydrotreating. With this preferred embodiment, the unsaturated olefin may be saturated.
The selective superposition method of the carbon tetraolefin can adopt a brand-new device as the separation device (the residual raw material separation tower and the regulator separation tower) of the invention, and can also utilize the separation device of the methyl tertiary butyl ether device as the separation device of the invention. The latter can effectively utilize the old device, avoid the wasting of resources, save the cost simultaneously.
According to the present invention, preferably, the residual raw material separation column is derived from a decarbonizing four column in a methyl tertiary butyl ether apparatus.
According to the present invention, preferably, the regulator separation column is from a methanol recovery column in a methyl tertiary butyl ether unit.
In a second aspect, the present invention provides a system for the selective folding of carbon tetraolefins, the system comprising: a superposition reaction unit B and a product separation unit C;
the polymerization unit B comprises a polymerization reactor 11 for performing polymerization reaction on the carbon tetraolefin;
the product separation unit C comprises a residual raw material separation tower 12 and a regulator recovery tower 13, wherein the residual raw material separation tower 12 is used for carrying out first separation on materials obtained by the superposition reaction, a second residual raw material is obtained at the top of the tower, and a tower bottom material containing a separation regulator, a reaction regulator and a superposition product is obtained at the bottom of the tower;
the regulator recovery tower 13 is used for carrying out second separation on the tower bottom material of the residual raw material separation tower 12, the tower top obtains a tower top material containing a separation regulator and a reaction regulator, and the tower bottom obtains a superposed product;
The outlet of the regulator recovery tower 13 is connected with the feed inlet of the superposition reactor 11; or the outlet of the regulator recovery tower 13 is connected with the feed inlet of the residual raw material separation tower 12 and the feed inlet of the superposition reactor 11.
Preferably, the top outlet of the regulator recovery column 13 is connected to the feed inlet of the polymerization reactor 11. Such a preferred embodiment is employed for the recovery and reuse of the reaction moderator along with the separation moderator.
Preferably, the top outlet of the regulator recovery column 13 is connected to the feed inlet of the residual raw material separation column 12, and the side outlet of the regulator recovery column 13 is connected to the feed inlet of the polymerization reactor 11. Such a preferred embodiment is employed for separate recovery and reuse of the reaction modifier and the separation modifier.
According to the present invention, preferably, the residual raw material separation column 12 is further provided with a separation regulator inlet for introducing a separation regulator from outside the system.
In the system provided by the invention, a brand new device can be adopted as the separation unit C (the residual raw material separation tower 12 and the regulator separation tower 13) of the invention, and the separation device of the methyl tertiary butyl ether device can be utilized as the separation unit C of the invention. The latter can effectively utilize the old device, avoid the wasting of resources, save the cost simultaneously.
According to the present invention, preferably, the residual feed separation column 12 is from a decarbonizing four column in a methyl tertiary butyl ether unit.
According to the present invention, preferably, the regulator recovery column 13 is from a methanol recovery column in a methyl tertiary butyl ether unit.
According to the present invention, preferably, the system further comprises: and the raw material pretreatment unit A is connected with the feed inlet of the superposition reaction unit B and is used for pretreating the raw materials.
According to the present invention, preferably, the raw material pretreatment unit a includes a water scrubber 10 and/or a purification tower.
According to one embodiment of the invention, as shown in fig. 1, the carbon four raw material 1 is introduced into the bottom of the water washing tower 10 of the raw material pretreatment unit a, the desalted water 2 is introduced into the upper part of the water washing tower 10, the carbon four raw material 1 is in countercurrent contact with the desalted water 2 inside the water washing tower 10, the water washing water 3 is led out from the bottom of the water washing tower 10, the washed carbon four raw material 4 is introduced into the polymerization reactor 11 of the polymerization reaction unit B from the top of the water washing tower 10, the selective polymerization reaction of isobutene mainly occurs in the polymerization reactor 11, the post-polymerization reaction material 5 at the outlet of the polymerization reactor is introduced into the residual raw material separation tower 12 in the product separation unit C, the top stream of the residual raw material separation tower 12 is the second residual raw material 7, the bottom stream (the first residual raw material, i.e., the separation modifier 6, the reaction modifier 8, the polymerization product 9) is introduced into the modifier recovery tower 13 in the product separation unit C, the top stream of the modifier recovery tower 13 is a mixed stream containing the reaction modifier 8 and the separation modifier 6, the mixed stream is mixed with the post-washed carbon four raw material 4 and returned into the reaction unit B in the polymerization reactor 11, and the top stream of the modifier recovery tower 13 is the polymerization product 13.
The flow direction of the regulator recovery column 13 may also include: the top material flow of the regulator recovery tower 13 is a separation regulator 6, the separation regulator 6 is mixed with the material 5 obtained by the superposition reaction and returns to the residual raw material separation tower 12, the reaction regulator 8 is extracted from the side outlet of the regulator recovery tower 13, the reaction regulator 8 is mixed with the washed carbon four raw material 4 and returns to the superposition reactor 11 of the superposition reaction unit B, and the bottom material flow of the regulator recovery tower 13 is a superposition product 9. For example, reference may be made to fig. 2.
According to one embodiment of the present invention, as shown in fig. 2, the carbon four raw material 1 is introduced into the bottom of the water wash column 10 of the raw material pretreatment unit a, the desalted water 2 is introduced into the upper portion of the water wash column 10, the carbon four raw material 1 is in countercurrent contact with the desalted water 2 in the water wash column, the water wash water 3 is led out from the bottom of the water wash column 10, the washed carbon four raw material 4 is introduced into the polymerization reactor 11 of the polymerization reaction unit B, the selective polymerization reaction of isobutene mainly occurs in the polymerization reactor 11, the post-polymerization material 5 of the polymerization reactor outlet is introduced into the residual raw material separation column 12 in the product separation unit C while the separation regulator 6 is introduced from outside into the residual raw material separation column 12, the overhead stream of the residual raw material separation column 12 is the second residual raw material 7, the overhead stream (separation regulator 6, reaction regulator 8, polymerization product 9) is introduced into the regulator recovery column 13 in the product separation unit C, the overhead stream of the regulator recovery column 13 is the separation regulator 6, the separation regulator 6 is mixed with the material 5 obtained by the polymerization reaction, and is returned to the residual raw material separation column 12 in the polymerization reaction unit B, the overhead stream 8 is returned to the polymerization reaction recovery unit 11 after the regulator is recovered from the side stream of the regulator 8.
The flow direction of the regulator recovery column 13 may also include: the top stream of the regulator recovery tower 13 is a mixture stream containing the reaction regulator 8 and the separation regulator 6, and the mixture stream is mixed with the washed carbon four raw material 4 and returned to the superposition reactor 11 of the superposition reaction unit B, and the bottom stream of the regulator recovery tower 13 is a superposition product 9. For example, reference may be made to fig. 1.
In the present invention, the "first" and "second" do not limit each substance and operation, but only distinguish substances introduced in different steps from each other, and perform operations in different stages.
The present invention will be described in detail by examples.
The superposition catalyst is a commercial product with the brand of KC110 of Kai environmental protection technology Co., ltd.
Example 1
The carbon tetraolefin selective folding method shown in fig. 1 is adopted. The raw materials are carbon four raw materials of a certain refinery, and the mass composition is shown in table 1. The superposition catalyst used is a sulfonic acid type ion exchange resin catalyst. The reaction regulator is tert-butanol, and the dosage is 2% of the mass flow of the carbon four raw materials. The superposition reactor is a fixed bed reactor. The obtained superposition product is C7-C12 olefin fraction with isooctene as main component. The separation regulator is the first residual raw material, and the mass composition is shown in Table 3. The dosage is 5% of the mass flow of the superposed product. The composition of the second remaining feedstock is shown in table 1 and the main operating conditions of the product separation unit fractionation column are shown in table 2.
Example 2
The carbon tetraolefin selective folding method shown in fig. 2 is used. The raw materials are carbon four raw materials of a certain refinery, and the mass composition is shown in table 1. The superposition catalyst used is a sulfonic acid type ion exchange resin catalyst. The reaction regulator is tert-butanol, and the dosage is 2% of the mass flow of the mixed carbon four. The superposition reactor is a tubular reactor. The obtained superposition product is C7-C12 olefin fraction with isooctene as main component. The separation regulator is external reforming topped oil, the mass composition is shown in Table 3, and the dosage is 7% of the mass flow of the superposition product. The composition of the second remaining feedstock is shown in table 1 and the main operating conditions of the product separation unit fractionation column are shown in table 2.
Comparative example 1
The procedure of example 1 was followed, except that the separation regulator was not introduced, namely, the column top stream of the residual raw material separation column 12 was the residual raw material, the column bottom stream (reaction regulator 8, polymerization product 9) was introduced into the regulator recovery column 13 in the product separation unit C, the column top stream of the regulator recovery column 13 was the reaction regulator 8, the reaction regulator 8 was mixed with the washed carbon four raw material 4 and returned to the polymerization reactor 11 of the polymerization reaction unit B, and the column bottom stream was the polymerization product 9.
The composition of the remaining raw materials at the top of the remaining raw material separation column is shown in table 1, and the main operation conditions of the product separation unit fractionation column are shown in table 2.
TABLE 1
TABLE 2
TABLE 3 Table 3
As can be seen from tables 1 and 2: compared with the method without introducing the separation regulator, the superposition method provided by the invention has the advantages that the energy consumption of the product separation unit is obviously reduced and the energy-saving effect is obvious under the separation precision of similar residual raw material separation towers.
In example 1 of the present invention, the total energy consumption of the product separation unit of example 1 was reduced by about 32% and the energy saving effect was remarkable, compared with comparative example 1, in the case where the separation accuracy of the remaining raw material separation column was the same.
In examples 1-2, the bottoms of the residual material separation columns were all low in temperature, and a readily available low temperature heat source could be used as the heat source for the bottoms reboiler. The temperature of the tower bottom of the residual raw material separation tower in comparative example 1 is 172 ℃, the low-temperature heat source is difficult to meet the temperature requirement of the heat source of the tower bottom reboiler, and the heat source with higher temperature is required to be used as the heat source of the tower bottom reboiler.
The temperature of the tower bottom of the residual raw material separation tower in the embodiment 1-2 is lower and is close to that of the tower bottom of the decarburization four tower of the conventional MTBE device, and is lower than the design temperature (less than or equal to 165 ℃) of the decarburization four tower of the conventional MTBE device, so that the decarburization four tower and the methanol recovery tower of the MTBE device can be respectively utilized as the residual raw material separation tower and the regulator recovery tower, thereby avoiding resource waste and saving cost. The temperature of the tower bottom of the residual raw material separation tower in the comparative example 1 is higher than that of the decarbonization four tower of the conventional MTBE device, and is higher than the design temperature of the decarbonization four tower of the conventional MTBE device, so that the decarbonization four tower of the MTBE device and the methanol recovery tower are not available.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
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| CN113024337A (en) * | 2019-12-09 | 2021-06-25 | 中国石油化工股份有限公司 | Method and device for superposing mixed butenes |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| US20210403398A1 (en) * | 2020-06-29 | 2021-12-30 | Lummus Technology Llc | Process for the controlled oligomerization of butenes |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113024337A (en) * | 2019-12-09 | 2021-06-25 | 中国石油化工股份有限公司 | Method and device for superposing mixed butenes |
| CN113582801A (en) * | 2020-04-30 | 2021-11-02 | 中国石油化工股份有限公司 | Process for preparing isooctene by selective superposition of mixed C4 |
| US20210403398A1 (en) * | 2020-06-29 | 2021-12-30 | Lummus Technology Llc | Process for the controlled oligomerization of butenes |
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