CN115925504A - Pre-hydrogenated butadiene extraction device and pre-hydrogenated butadiene extraction method - Google Patents
Pre-hydrogenated butadiene extraction device and pre-hydrogenated butadiene extraction method Download PDFInfo
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Abstract
The invention belongs to the field of cracking carbon four treatment, and relates to a front hydrogenation butadiene extraction device and a front hydrogenation butadiene extraction method. The system comprises a selective hydrogenation system, a first extraction tower system, a first stripping tower system, a water washing tower system and a butadiene refining system which are sequentially arranged, wherein the selective hydrogenation system comprises a selective hydrogenation reactor and a stabilizing tower; a discharge pipeline at the top of the selective hydrogenation reactor is connected with the stabilizing tower; the discharge pipeline at the side part of the stabilizer is connected with the first extraction tower system; a discharge pipeline at the bottom of the first extraction tower system is connected with the first stripping tower system; a discharge pipeline at the top of the first stripping tower system is connected with the water washing tower system; and a discharge pipeline at the top of the water washing tower system is connected with the butadiene refining system. The invention increases the yield of butadiene by arranging the selective hydrogenation system, saves a second extraction system and a second stripping tower system, reduces the comprehensive energy consumption and saves the investment.
Description
Technical Field
The invention belongs to the field of cracking carbon four treatment, and particularly relates to a front hydrogenation butadiene extraction device and a front hydrogenation butadiene extraction method.
Background
The butadiene extraction device adopts a DMF (dimethyl formamide) method or an acetonitrile method, and performs butadiene extraction through a two-stage extraction and carbon four-refining process flow, taking the DMF method as an example, a typical flow is shown in figure 1, wherein the first-stage extraction is to separate mono-olefin and alkane from diene and alkyne, the second-stage extraction is to further separate diene and alkyne to remove alkyne, a water washing system is to remove a solvent, and a refining system is to remove light and heavy components. The traditional butadiene extraction device has long process flow and higher energy consumption and investment due to a two-stage extraction process.
With the mature development and application of the selective hydrogenation catalyst, alkyne in the cracking carbon four raw material is firstly removed by the selective hydrogenation system, and then butadiene is produced by extraction and refining, so that the utilization efficiency of the raw material is improved, the economy of the device is improved, a second extraction tower and a second stripping tower can be eliminated, the energy consumption of the whole device is saved by about 10-15%, and the selective hydrogenation system is an exothermic reaction and adds a small amount of energy consumption. Therefore, the acetylene hydrocarbon removal rate and the butadiene loss rate are controlled within a reasonable range, the selective hydrogenation system is coupled with the traditional butadiene extraction device, the economical efficiency and the environmental protection property of the device are greatly improved, the comprehensive energy consumption of the device is reduced, and the comprehensive utilization value of carbon four is increased.
Two key steps exist in the front-end hydrogenation technology, and a hydrogenation reactor ensures the selectivity and the conversion rate of alkyne through a catalyst and operation conditions and reduces the loss of butadiene; heavy component removal (the heavy component influences the polymerization of dialkene and alkyne) and purge gas can be realized before the carbon four raw material enters the extraction device through the process flow. CN101172929 realizes the action of releasing gas through a light component removal tower, but heavy components are not removed, and the reaction adopts a palladium noble catalyst, so that the economic benefit is low, and meanwhile, the process does not provide a reflux setting, the reaction temperature rise is large, the catalyst performance is influenced, and the long-period operation is not favorable.
Disclosure of Invention
The invention aims to solve the problems of long flow, high energy consumption and low raw material utilization rate of the conventional butadiene device, and provides a front hydrogenation butadiene extraction device. The acetylene hydrocarbon selective hydrogenation system is coupled with the traditional butadiene extraction device, so that the purposes of eliminating a second extraction system and a second stripping system are achieved. The defects of the traditional butadiene device are overcome, and the economic benefit of the device is increased.
In order to achieve the above object, a first aspect of the present invention provides a front hydrogenation butadiene extraction device, which includes a selective hydrogenation system, a first extraction tower system, a first stripping tower system, a water washing tower system, and a butadiene refining system, which are sequentially arranged, where the selective hydrogenation system includes a selective hydrogenation reactor and a stabilizer;
the selective hydrogenation reactor is provided with a bottom feeding pipeline of the selective hydrogenation reactor and a top discharging pipeline of the selective hydrogenation reactor, and the top discharging pipeline of the selective hydrogenation reactor is connected with the stabilizing tower;
the stabilizing tower is provided with a stabilizing tower top discharge pipeline, a stabilizing tower bottom discharge pipeline and a stabilizing tower side discharge pipeline; the discharge pipeline at the side part of the stabilizer is connected with the first extraction tower system;
the first extraction tower system is provided with a first extraction tower system top discharge pipeline and a first extraction tower system bottom discharge pipeline, and the first extraction tower system bottom discharge pipeline is connected with the first stripping tower system;
the first stripping tower system is provided with a first stripping tower system top discharge pipeline and a first stripping tower system bottom discharge pipeline, and the first stripping tower system top discharge pipeline is connected with the water washing tower system;
the washing tower system is provided with a washing tower system top discharging pipeline, and the washing tower system top discharging pipeline is connected with the butadiene refining system.
The second aspect of the invention provides a method for extracting front hydrogenated butadiene, which is performed by using the front hydrogenated butadiene extraction device and comprises the following steps:
after mixing the cracking carbon four raw material and hydrogen, carrying out selective hydrogenation reaction in the selective hydrogenation reactor, feeding the reacted material into the stabilizing tower, optionally partially refluxing, separating out purge gas at the top of the stabilizing tower and feeding out, separating out heavy components at the bottom of the stabilizing tower and feeding out, and separating out the side material of the stabilizing tower at the side and feeding into a first extraction tower system;
and (2) feeding the material at the side part of the stabilizer into a first extraction tower system, extracting monoolefine and alkane raffinate from the top of the first extraction tower system, feeding the material at the bottom of the first extraction tower system into a first stripping tower system, returning the material at the bottom of the first stripping tower system to the first extraction tower system, feeding the material at the top of the first stripping tower system into a washing tower system, and feeding the material at the top of the washing tower system into a butadiene refining system to obtain a butadiene product.
The invention has the beneficial effects that:
1) The comprehensive utilization efficiency of the carbon four is increased by arranging a selective hydrogenation system;
2) The selective hydrogenation system is arranged to convert vinyl acetylene into butadiene, so that the yield of butadiene is increased, and the economy of the device is improved;
3) A second extraction system and a second stripping tower system are omitted by arranging the selective hydrogenation system, so that the comprehensive energy consumption is reduced, and the investment is saved;
4) By arranging the stabilizing tower, non-condensable gas, carbon five, polymer and other heavy components generated in the reaction process can be removed, the stability of the operation of the extraction device is ensured, and the polymerization risk is reduced;
5) Through the reflux arrangement of the reaction materials, the concentration of vinyl acetylene in the raw materials can be reduced, the reaction temperature rise is reduced, the reaction regeneration time is prolonged, and the long-period operation is ensured;
6) The invention selects nickel-based catalyst, which has outstanding economic benefit;
7) The device can be used for modifying all the traditional butadiene extraction devices.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The above and other objects, features and advantages of the present invention will become more apparent by describing in more detail exemplary embodiments thereof with reference to the attached drawings.
FIG. 1 is a flow chart of a conventional DMF butadiene extraction device.
FIG. 2 is a flow diagram of a front hydrogenation butadiene extraction device of the present invention.
FIG. 3 is a flow diagram of an embodiment of the selective hydrogenation system of the present invention.
FIG. 4 is a flow diagram of another embodiment of the selective hydrogenation system of the present invention.
Description of the reference numerals:
the system comprises a first extraction tower system 1, a first stripping tower system 2, a second extraction tower system 3, a second stripping tower system 4, a water washing tower system 5, a butadiene refining system lightness-removing tower 6, a butadiene refining system heavy-removing tower 7, a selective hydrogenation system 8, a selective hydrogenation reactor 9, a stabilizer tower 10, a stabilizer tower top condenser 11, a stabilizer tower kettle reboiler 12, a hydrogenation separation tank 13, a tail gas condenser 14, a reflux pump 15 and a reflux cooler 16; raw material 17, heavy component 18, purge gas 19, carbon four discharge 20 and hydrogen 21.
Detailed Description
Preferred embodiments of the present invention will be described in more detail below. While the following describes preferred embodiments of the present invention, it should be understood that the present invention may be embodied in various forms and should not be limited by the embodiments set forth herein.
The invention aims to solve the problems of long flow, high energy consumption and low raw material utilization rate of the conventional butadiene extraction device, and provides a front hydrogenation butadiene extraction device. The acetylene hydrocarbon selective hydrogenation system is coupled with the traditional butadiene extraction device, so that the purposes of eliminating a second extraction system and a second stripping system are achieved. The defects of the traditional butadiene device are overcome, and the economic benefit of the device is increased.
In order to achieve the above object, a first aspect of the present invention provides a front hydrogenation butadiene extraction device, which includes a selective hydrogenation system, a first extraction tower system, a first stripping tower system, a water washing tower system, and a butadiene refining system, which are sequentially arranged, where the selective hydrogenation system includes a selective hydrogenation reactor and a stabilizer;
the selective hydrogenation reactor is provided with a bottom feeding pipeline of the selective hydrogenation reactor and a top discharging pipeline of the selective hydrogenation reactor, and the top discharging pipeline of the selective hydrogenation reactor is connected with the stabilizing tower;
the stabilizing tower is provided with a stabilizing tower top discharge pipeline, a stabilizing tower bottom discharge pipeline and a stabilizing tower side discharge pipeline; the discharge pipeline at the side part of the stabilizer is connected with the first extraction tower system;
the first extraction tower system is provided with a first extraction tower system top discharge pipeline and a first extraction tower system bottom discharge pipeline, and the first extraction tower system bottom discharge pipeline is connected with the first stripping tower system;
the first stripping tower system is provided with a first stripping tower system top discharge pipeline and a first stripping tower system bottom discharge pipeline, and the first stripping tower system top discharge pipeline is connected with the water washing tower system;
the washing tower system is provided with a washing tower system top discharge pipeline, and the washing tower system top discharge pipeline is connected with the butadiene refining system.
In the invention, the stabilizing tower can separate more than 99 percent of C five in the raw materials, and C five is an important influence factor causing butadiene polymerization, thereby providing high-quality raw materials for extraction and refining units.
According to the invention, the selective hydrogenation system can realize that vinyl acetylene in unsaturated components in the cracking carbon four raw material can be converted into butadiene and a small amount of butene-1, and butyne is converted into butene-1 to obtain a butadiene-rich carbon four product, so that the yield of butadiene is increased, light components such as non-condensable gas and heavy components such as carbon five and green oil are removed by arranging the stabilizing tower, a high-quality raw material is provided for extraction, and the polymerization risk is reduced. The discharge pipeline at the top of the selective hydrogenation reactor can be directly connected with the stabilizing tower, and can also be provided with a reflux device, the discharge pipeline at the top of the selective hydrogenation reactor is firstly connected with the reflux device and then connected with the stabilizing tower, for example, a reflux pump is optionally added, partial reacted materials can be selected to reflux, and the concentration of carbon-tetra-alkyne at the inlet of the reactor is reduced. The regeneration frequency can be extended and the long-period operation can be maintained. The method is suitable for the extraction process of butadiene such as acetonitrile, N-dimethylformamide, N-methylpyrrolidone, N-formylmorpholine and the like, is not limited to NMP (N-methylpyrrolidone), and has better applicability and popularization.
Specifically, as shown in fig. 3, the selective hydrogenation system of the present invention includes a cracking carbon four-material connection selective hydrogenation reactor inlet to join with hydrogen, a selective hydrogenation reactor outlet to connect with a stabilizer inlet, a stabilizer top purge gas to be delivered, a stabilizer bottom heavy component to be delivered, and a stabilizer side line to connect with an extraction column system.
Another selective hydrogenation system of the present invention is shown in fig. 4, and comprises a selective hydrogenation reactor for hydrogenation and a stabilizer for removing heavy components and non-condensable gas. And a reflux device (comprising a hydrogenation separation tank, a reflux pump and a reflux cooler) is arranged behind the reactor. Wherein: the cracking carbon four raw material and hydrogen are converged and connected with an inlet of a selective hydrogenation reactor, an outlet of the selective hydrogenation reactor is connected with a gas-liquid separation tank, after non-condensable gas is separated, part of materials are connected with an inlet of a stabilization tower through a reflux pump, purge gas at the top of the stabilization tower is sent out, heavy components at the bottom of the stabilization tower are sent out, and a side line of the stabilization tower is connected with an extraction tower system. And part of materials of the reflux pump are connected with a feeding pipeline to dilute the concentration of the vinyl acetylene in the pyrolysis carbon four feeding material.
In the invention, a first extraction tower system, a first stripping tower system, a water washing tower system and a butadiene refining system in the butadiene extraction device are typically arranged in a conventional butadiene extraction device.
According to the invention, preferably, the bottom feeding pipeline of the selective hydrogenation reactor comprises a hydrogen feeding pipeline and a cracking carbon four-raw material feeding pipeline, the top discharging pipeline of the selective hydrogenation reactor is connected with the stabilizing tower, the top discharging pipeline of the stabilizing tower is connected with the stabilizing tower top condenser and then divided into two branches, one branch is used as a product discharging pipeline, and the other branch is connected with the upper part of the stabilizing tower; and a stabilizer kettle reboiler is arranged at the bottom of the stabilizer tower.
According to the invention, preferably, a discharge pipeline at the top of the selective hydrogenation reactor is connected with a hydrogenation separation tank, the hydrogenation separation tank is provided with a discharge pipeline at the top of the hydrogenation separation tank and a discharge pipeline at the bottom of the hydrogenation separation tank, the discharge pipeline at the top of the hydrogenation separation tank is connected with a tail gas condenser, the tail gas condenser is provided with a tail gas condenser discharge pipeline and a tail gas condenser circulation pipeline, the tail gas condenser discharge pipeline is converged with a stable tower top condenser product discharge pipeline, and the tail gas condenser circulation pipeline is connected with the hydrogenation separation tank; the bottom discharge pipeline of the hydrogenation separation tank is connected with a reflux pump and then divided into two pipelines, one pipeline is connected with the stabilizing tower, and the other pipeline is connected with a reflux cooler and then converged with the bottom feed pipeline of the selective hydrogenation reactor.
According to the present invention, preferably, the butadiene refining system comprises a butadiene refining system light component removal tower and a butadiene refining system heavy component removal tower;
the butadiene refining system light component removal tower is provided with a butadiene refining system light component removal tower top discharge pipeline and a butadiene refining system light component removal tower bottom discharge pipeline, and the butadiene refining system light component removal tower bottom discharge pipeline is connected with the butadiene refining system heavy component removal tower;
the de-weighting tower of the butadiene refining system is provided with a de-weighting tower top discharge pipeline of the butadiene refining system and a de-weighting tower bottom discharge pipeline of the butadiene refining system.
The second aspect of the invention provides a method for extracting butadiene through front hydrogenation, which is carried out by adopting the device for extracting butadiene through front hydrogenation and comprises the following steps:
mixing a cracking carbon four raw material with hydrogen, carrying out selective hydrogenation reaction in the selective hydrogenation reactor, feeding the reacted material into the stabilizing tower, optionally partially refluxing, separating out purge gas at the top of the stabilizing tower, feeding out heavy components at the bottom of the stabilizing tower, and feeding the side material of the stabilizing tower into a first extraction tower system;
and (2) feeding the material at the side part of the stabilizer into a first extraction tower system, extracting monoolefine and alkane raffinate from the top of the first extraction tower system, feeding the material at the bottom of the first extraction tower system into a first stripping tower system, feeding the material at the bottom of the first stripping tower system back to the first extraction tower system, feeding the material at the top of the first stripping tower system into a washing tower system, and feeding the material at the top of the washing tower system into a butadiene refining system to obtain a butadiene product.
According to the invention, preferably, the material at the top of the washing tower system is sent to a light component removal tower of a butadiene refining system, light components separated from the tower top are sent to the outside, the material at the bottom of the light component removal tower of the butadiene refining system separated from the tower bottom is sent to a heavy component removal tower of the butadiene refining system, heavy components are separated from the tower bottom, and a butadiene product is obtained at the tower top.
According to the present invention, preferably, the cracking carbon four raw material is a carbon four raw material rich in butadiene and vinyl alkyne; wherein, the content of butadiene is 20wt percent to 70wt percent, and the content of vinyl acetylene is 0.1wt percent to 10wt percent; preferably, the butadiene content is 40wt% to 55wt% and the vinylacetylene content is 0.5wt% to 5wt%.
According to the present invention, preferably, the catalyst used in the selective hydrogenation reactor is a nickel-based catalyst and/or a palladium-based catalyst, preferably a nickel-based catalyst; the operating conditions of the selective hydrogenation reactor include: the temperature is 20-40 ℃, the operation pressure is 0.5-1.0 MPaG, the reaction temperature is 5-25 ℃, the molar ratio of the hydrogen to the alkyne is 0.5-5:1, the circulation ratio is 0-3:1, and the volume space velocity of the catalyst is 0.2-3.
According to the present invention, preferably, the operating conditions of the stabilizer column comprise: the pressure is 0.4-1.0 MPaG, the operation temperature at the top of the tower is 35-80 ℃, the number of tower plates is 20-80, and the reflux ratio is 5-50.
According to the present invention, preferably, the extraction solvent is at least one of acetonitrile, N-dimethylformamide, N-methylpyrrolidone and N-formylmorpholine.
In the invention, the effective removal rate (product of selectivity and conversion rate for producing butadiene) of vinyl acetylene in the selective hydrogenation system cracking carbon four raw material is more than 99wt%, preferably more than 99.9wt%, and the loss rate of butadiene in the selective hydrogenation system cracking carbon four raw material cannot exceed 5wt%, preferably not more than 3wt%.
Example 1
The device shown in fig. 2 is adopted in this embodiment to perform the method, and includes a selective hydrogenation system, a first extraction tower system, a first stripping tower system, a water scrubber system, and a butadiene refining system, which are sequentially arranged, where the selective hydrogenation system includes a selective hydrogenation reactor, a stabilizer, and an optional reflux pump; the selective hydrogenation reactor is provided with a bottom feeding pipeline of the selective hydrogenation reactor and a top discharging pipeline of the selective hydrogenation reactor, the top discharging pipeline of the selective hydrogenation reactor is optionally connected with a reflux pump and then is divided into two pipelines, one pipeline is connected with the stabilizing tower, and the other pipeline is converged with the bottom feeding pipeline of the selective hydrogenation reactor; the bottom feeding pipeline of the selective hydrogenation reactor comprises a hydrogen pipeline and a cracking carbon four-raw material pipeline, and the top discharging pipeline of the selective hydrogenation reactor is optionally connected with a hydrogenation separation tank; the hydrogenation separation tank is provided with hydrogenation separation tank top discharge pipeline and hydrogenation separation tank bottom discharge pipeline, hydrogenation separation tank top discharge pipeline connects the tail gas condenser, the tail gas condenser is provided with tail gas condenser exhaust line and tail gas condenser circulating line, tail gas condenser circulating line connects the lateral part of hydrogenation separation tank. The bottom discharge pipeline of the hydrogenation separation tank is connected with the reflux pump and is divided into two pipelines, one pipeline is connected with the stabilizing tower, and the other pipeline is connected with the reflux condenser and then is converged with the bottom feed pipeline of the selective hydrogenation reactor;
the stabilizing tower is provided with a stabilizing tower top discharge pipeline, a stabilizing tower bottom discharge pipeline and a stabilizing tower side discharge pipeline; the discharge pipeline at the side part of the stabilizer is connected with the first extraction tower system; the discharge pipeline at the top of the stabilizing tower is connected with a condenser at the top of the stabilizing tower and then divided into two branches, one branch is converged with the discharge pipeline of the tail gas condenser, and the other branch is connected with the upper part of the stabilizing tower; a reboiler is arranged at the bottom of the stabilizing tower;
the first extraction tower system is provided with a first extraction tower system top discharge pipeline and a first extraction tower system bottom discharge pipeline, and the first extraction tower system bottom discharge pipeline is connected with the first stripping tower system; the first stripping tower system is provided with a first stripping tower system top discharge pipeline and a first stripping tower system bottom discharge pipeline, and the first stripping tower system top discharge pipeline is connected with the water washing tower system; the washing tower system is provided with a washing tower system top discharge pipeline, and the washing tower system top discharge pipeline is connected with the butadiene refining system; the butadiene refining system comprises a butadiene refining system light component removal tower and a butadiene refining system heavy component removal tower; the butadiene refining system light component removing tower is provided with a butadiene refining system light component removing tower top discharge pipeline and a butadiene refining system light component removing tower bottom discharge pipeline, and the butadiene refining system light component removing tower bottom discharge pipeline is connected with the butadiene refining system heavy component removing tower; the de-weighting tower of the butadiene refining system is provided with a de-weighting tower top discharge pipeline of the butadiene refining system and a de-weighting tower bottom discharge pipeline of the butadiene refining system.
The front hydrogenation butadiene extraction method comprises the following steps:
after mixing the cracking carbon four raw material and hydrogen, carrying out selective hydrogenation reaction in the selective hydrogenation reactor, feeding the reacted material into the stabilizing tower, optionally partially refluxing, separating out purge gas at the top of the stabilizing tower and feeding out, separating out heavy components at the bottom of the stabilizing tower and feeding out, and separating out the side material of the stabilizing tower at the side and feeding into a first extraction tower system; the cracking carbon four raw material is 30t/h, and the composition is shown in Table 1, wherein the content of butadiene is 50wt%, and the content of vinyl acetylene is 1wt%; the selective hydrogenation reaction is controlled by a catalyst and process conditions, the catalyst adopts a nickel-based catalyst, the temperature of the selective hydrogenation operation conditions is 30 ℃, the operation pressure is 0.6MPaG, the reaction temperature is 5 ℃, the molar ratio of hydrogen to alkyne (the sum of alkyne and dialkene) is 1, the circulation ratio is 1:1, and the volume space velocity of the catalyst is 0.5; the operating conditions of the stabilizer column include: the pressure is 0.6MPaG, the operation temperature at the top of the tower is 40 ℃, the number of tower plates is 50, and the reflux ratio is 20;
sending the material at the side part of the stabilizer into a first extraction tower system, extracting monoolefine and alkane raffinate from the top of the first extraction tower system, sending the material at the bottom of the first extraction tower system into a first stripping tower system, returning the material at the bottom of the first stripping tower system to the first extraction tower system, sending the material at the top of the first stripping tower system into a washing tower system, and sending the material at the top of the washing tower system into a butadiene refining system to obtain a butadiene product; and (3) feeding the material at the top of the washing tower system into a light component removal tower of a butadiene refining system, separating out light components at the tower top and sending the light components to the outside, separating out the material at the tower bottom of the light component removal tower of the butadiene refining system and sending the material into a heavy component removal tower of the butadiene refining system, separating out heavy components at the tower bottom and obtaining a butadiene product at the tower top.
TABLE 1 cracking carbon four feedstock composition
| Phase state | Liquid phase |
| Constituent Unit | wt％ |
| Allene | 0.01 |
| N-butane | 12.70 |
| Isobutane | 0.72 |
| 1-butene | 11.49 |
| Isobutene | 16.52 |
| Cis-butenediol-2 | 2.57 |
| Butene-2 | 3.66 |
| 1,3-butadiene | 50.10 |
| 1,2-butadiene | 0.52 |
| Methylacetylene | 0.19 |
| Water (W) | 0.00 |
| Ethyl acetylene | 0.26 |
| Vinyl acetylene | 1.040 |
| C5 | 0.187 |
| Isoprene (I) | 0.018 |
| Cyclopentadiene | 0.019 |
| Molecular weight | 55.100 |
The selective hydrogenation system can realize that vinyl acetylene in unsaturated components in the cracking carbon four raw material can be converted into butadiene and a small amount of butene-1, and butyne is converted into butene-1 to obtain a butadiene-rich carbon four product, wherein the effective removal rate of the vinyl acetylene (the product of the selectivity and the conversion rate for producing butadiene) is 99.95wt%. The loss rate of butadiene in the cracking C four raw material is 2wt%.
Therefore, the product purity of the front hydrogenation butadiene extraction device can be calculated, and the requirement of polymerization grade can be met.
Purity of butadiene product: 99.9 wt.%
Therefore, the economic benefit of the front hydrogenated butadiene extraction device can be preliminarily calculated, the second extraction tower system and the second stripping tower system account for about 15% of the energy consumption of the total device, the energy consumption of the original butadiene extraction device is 220kg standard oil/t product, and the energy consumption can be saved by 220 multiplied by 15% =33kg standard oil/t product after the front hydrogenated butadiene extraction device is modified; the effective removal rate of vinyl acetylene is 99.95wt%, and the content of butadiene in the product of the modified front hydrogenated butadiene extraction device is improved by 0.3t/h compared with that of the original butadiene extraction device; butadiene loss: 30 × 50% × 2% =0.3t/h. Thus butadiene losses and increases can be offset; the equipment investment cost of the selective hydrogenation system is offset with that of the second extraction system and the second stripping tower system; the increase in energy consumption of selective hydrogenation systems is limited and negligible. Therefore, the front hydrogenation butadiene extraction device can realize energy consumption saving of 33kg standard oil/t product, namely 33kg standard oil/t product multiplied by 5 yuan/kg standard oil multiplied by 15t product multiplied by 8000 hours =1980 ten thousand/year, and has considerable energy saving and consumption reduction effects and economic benefits.
Comparative example 1
The device of the comparative example is different from the device of the example 1 in that the selective hydrogenation system only comprises a selective hydrogenation reactor and a light component removal tower, the hydrogenation reactor is connected with the light component removal tower, the light component removal tower is provided with a light component removal tower top discharge pipeline and a light component removal tower kettle discharge pipeline, and the light component removal tower kettle discharge pipeline is connected with the first extraction tower system; the method is different from the method of the embodiment 1 in that the cracking carbon four raw material is sent into a selective hydrogenation reactor for hydrogenation reaction, then sent into a light component removal tower for removing light components, light components including hydrogen, methane, propane and the like are discharged from the top of the tower, and the bottom of the tower isObtaining light component removed C 4 The distillate is sent to a first extraction tower system.
The effective removal rate of vinyl acetylene (product of selectivity and conversion to butadiene) was 99.95wt%. The loss rate of butadiene in the cracking carbon four raw material is 3wt%, and carbon five in the cracking carbon four raw material is not removed.
Purity of butadiene product: 99.7wt%.
While embodiments of the present invention have been described above, the above description is illustrative, not exhaustive, and not limited to the disclosed embodiments. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
Claims (10)
1. The front hydrogenation butadiene extraction device is characterized by comprising a selective hydrogenation system, a first extraction tower system, a first stripping tower system, a water washing tower system and a butadiene refining system which are sequentially arranged, wherein the selective hydrogenation system comprises a selective hydrogenation reactor and a stabilizing tower;
the selective hydrogenation reactor is provided with a bottom feeding pipeline of the selective hydrogenation reactor and a top discharging pipeline of the selective hydrogenation reactor, and the top discharging pipeline of the selective hydrogenation reactor is connected with the stabilizing tower;
the stabilizing tower is provided with a stabilizing tower top discharge pipeline, a stabilizing tower bottom discharge pipeline and a stabilizing tower side discharge pipeline; the discharge pipeline at the side part of the stabilizer is connected with the first extraction tower system;
the first extraction tower system is provided with a first extraction tower system top discharge pipeline and a first extraction tower system bottom discharge pipeline, and the first extraction tower system bottom discharge pipeline is connected with the first stripping tower system;
the first stripping tower system is provided with a first stripping tower system top discharge pipeline and a first stripping tower system bottom discharge pipeline, and the first stripping tower system top discharge pipeline is connected with the water washing tower system;
the washing tower system is provided with a washing tower system top discharge pipeline, and the washing tower system top discharge pipeline is connected with the butadiene refining system.
2. The front hydrogenated butadiene extraction device of claim 1, wherein the bottom feed line of the selective hydrogenation reactor comprises a hydrogen feed line and a cracking carbon four-raw-material feed line, the top discharge line of the selective hydrogenation reactor is connected with a stabilizer, the top discharge line of the stabilizer is connected with a stabilizer overhead condenser and then divided into two branches, one branch is used as a product discharge line, and the other branch is connected with the upper part of the stabilizer; and a stabilizer kettle reboiler is arranged at the bottom of the stabilizer tower.
3. The front hydrogenation butadiene extraction device of claim 2, wherein the selective hydrogenation reactor top discharge line is connected to a hydrogenation separation tank, the hydrogenation separation tank is provided with a hydrogenation separation tank top discharge line and a hydrogenation separation tank bottom discharge line, the hydrogenation separation tank top discharge line is connected to a tail gas condenser, the tail gas condenser is provided with a tail gas condenser discharge line and a tail gas condenser circulation line, the tail gas condenser discharge line merges with a stabilizer overhead condenser product discharge line, and the tail gas condenser circulation line is connected to the hydrogenation separation tank; and the discharge pipeline at the bottom of the hydrogenation separation tank is connected with a reflux pump and then divided into two pipelines, one pipeline is connected with the stabilizing tower, and the other pipeline is connected with a reflux cooler and then converged with the feed pipeline at the bottom of the selective hydrogenation reactor.
4. The front hydrogenation butadiene extraction device of claim 1, wherein the butadiene refining system comprises a butadiene refining system light component removal tower and a butadiene refining system heavy component removal tower;
the butadiene refining system light component removing tower is provided with a butadiene refining system light component removing tower top discharge pipeline and a butadiene refining system light component removing tower bottom discharge pipeline, and the butadiene refining system light component removing tower bottom discharge pipeline is connected with the butadiene refining system heavy component removing tower;
the de-weighting tower of the butadiene refining system is provided with a de-weighting tower top discharge pipeline of the butadiene refining system and a de-weighting tower bottom discharge pipeline of the butadiene refining system.
5. A method for extracting butadiene through front hydrogenation, which is characterized by adopting the front hydrogenation butadiene extraction device of claims 1-4, and comprises the following steps:
mixing a cracking carbon four raw material with hydrogen, carrying out selective hydrogenation reaction in the selective hydrogenation reactor, feeding the reacted material into the stabilizing tower, optionally partially refluxing, separating out purge gas at the top of the stabilizing tower, feeding out heavy components at the bottom of the stabilizing tower, and feeding the side material of the stabilizing tower into a first extraction tower system;
and (2) feeding the material at the side part of the stabilizer into a first extraction tower system, extracting monoolefine and alkane raffinate from the top of the first extraction tower system, feeding the material at the bottom of the first extraction tower system into a first stripping tower system, returning the material at the bottom of the first stripping tower system to the first extraction tower system, feeding the material at the top of the first stripping tower system into a washing tower system, and feeding the material at the top of the washing tower system into a butadiene refining system to obtain a butadiene product.
6. The front hydrogenation butadiene extraction method of claim 5, wherein the top material of the water scrubber system is sent to a light component removal tower of a butadiene refining system, light components separated from the top of the tower are sent to the outside, the bottom material of the light component removal tower of the butadiene refining system separated from the bottom of the tower is sent to a heavy component removal tower of the butadiene refining system, heavy components are separated from the bottom of the tower, and a butadiene product is obtained at the top of the tower.
7. The front hydrogenated butadiene extraction process of claim 5, wherein the cracked C four feedstock is a C four feedstock rich in butadiene and vinyl acetylenes; wherein, the content of butadiene is 20wt percent to 70wt percent, and the content of vinyl acetylene is 0.1wt percent to 10wt percent; preferably, the butadiene content is 40wt% to 55wt% and the vinylacetylene content is 0.5wt% to 5wt%.
8. The front hydrogenation butadiene extraction method according to claim 5, wherein the catalyst adopted by the selective hydrogenation reactor is a nickel-based catalyst and/or a palladium-based catalyst, preferably a nickel-based catalyst; the operating conditions of the selective hydrogenation reactor include: the temperature is 20-40 ℃, the operation pressure is 0.5-1.0 MPaG, the reaction temperature is 5-25 ℃, the molar ratio of the hydrogen to the alkyne is 0.5-5:1, the circulation ratio is 0-3:1, and the volume space velocity of the catalyst is 0.2-3.
9. The front hydrogenated butadiene extraction process of claim 5, wherein the stabilizer column operating conditions comprise: the pressure is 0.4-1.0 MPaG, the operation temperature at the top of the tower is 35-80 ℃, the number of tower plates is 20-80, and the reflux ratio is 5-50.
10. The method for extracting pro-hydrogenated butadiene according to claim 5, wherein the extraction solvent is at least one of acetonitrile, N-dimethylformamide, N-methylpyrrolidone, and N-formylmorpholine.
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