CN112321382B - 1-butene refining energy-saving process and device with heat pump heat integration - Google Patents
1-butene refining energy-saving process and device with heat pump heat integration Download PDFInfo
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- CN112321382B CN112321382B CN202011007779.1A CN202011007779A CN112321382B CN 112321382 B CN112321382 B CN 112321382B CN 202011007779 A CN202011007779 A CN 202011007779A CN 112321382 B CN112321382 B CN 112321382B
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Abstract
The invention relates to the technical field of 1-butene refining, in particular to an energy-saving process and device for 1-butene refining with heat pump heat integration. According to the energy-saving 1-butene refining process with heat pump heat integration, after the ether post-carbon four mixture of MTBE is subjected to selective hydrogenation reaction, a 1-butene-containing mixture with main components of hydrogen, water, methanol, carbon three, 1-butene, isobutane, n-butane, trans-2-butene and cis-2-butene is obtained, heavy components containing n-butane, trans-2-butene and cis-2-butene are removed through a de-heavy tower, light components containing isobutane and carbon three are removed through a light component removal tower, and 1-butene is obtained from the bottom of the light component removal tower. The energy-saving process and the energy-saving device for refining the 1-butene, which are disclosed by the invention, have the advantages that the energy integration of the heat pump rectification system of the heavy component removal tower and the light component removal tower and the waste heat reutilization is realized by utilizing the technical means with the heat pump heat integration, the obvious energy-saving characteristic is realized, and the economic benefit is improved.
Description
Technical Field
The invention relates to the technical field of 1-butene refining, in particular to an energy-saving process and device for 1-butene refining with heat pump heat integration.
Background
The 1-butene is carbon tetraolefin, can be used as a polyethylene comonomer, and can also be used for producing fine chemical products such as methyl ethyl ketone, valeraldehyde, isodecanol and the like, and the application is very wide. The polymerization grade 1-butene can be produced by ethylene dimerization, the ethylene is expensive, so the production cost is high, and the large-scale industrial application cannot be realized, and the mixed carbon four generated in the petroleum hydrocarbon cracking process is an excellent raw material for producing the high-purity 1-butene after 1, 3-butadiene is removed by extraction, and the carbon four is subjected to the removal of the ether of the isobutene by the etherification reaction. Therefore, how to extract 1-butene from mixed C4 is a hot problem to be researched. At present, most of 1-butene comes from mixed C4 and is mainly obtained by extractive distillation and ultra-precise distillation separation.
The processes for separating 1-butene by extractive distillation are more extensive, and are more typical than a two-tower process for extracting n-butene proposed by Krupp Uhde company in Germany. The process adopts a mixture of morpholine and N-methylmorpholine as an extracting agent, wherein the mixture of morpholine and N-methylmorpholine is mixed in a mass ratio of 1:1, a carbon-containing material containing 45-53 wt% of N-butene is fed into an extraction and rectification tower, a butane component is separated out at the top of the tower, a material rich in N-butene at the bottom of the tower is fed into a stripping tower for solvent recovery, more than 97% of N-butene is obtained at the top of the stripping tower, and high-purity 1-butene can be obtained through further separation. However, the process has long flow, high energy consumption, poor chemical stability of the extractant and easy decomposition at high temperature.
In China, mainly the university of tobacco terrace, researches on the extraction process of 1-butene, and a process for separating 1-butene by using a mixture of methyl ethyl ketone and a polar solvent as an extracting agent has been developed. The process adopts a two-tower extraction rectification flow, the four carbon materials containing butylene are removed by an extraction rectification tower, and the solvent recovery is completed in an analytical tower. The extractive distillation tower and the analysis tower are operated under pressure, the temperature of the tower bottom is lower than 170 ℃, cheap steam can be used for heating, and the purity of the butene product is higher than 97%. However, the selectivity of the extractant is not good enough, and the consumption of the extractant is large.
The domestic market mainly adopts an ultra-precise rectification separation method, which comprises a light component removal tower and a heavy component removal tower, wherein the light component removal tower removes carbon III with medium and low boiling points, isobutane and an azeotrope with water, the bottom product is removed with high boiling point n-butane and 2-butene through the heavy component removal tower, and the top of the tower obtains 1-butene with the mass fraction of more than 99.5%. Although the process has simple flow, the required number of tower plates is large, the reflux ratio is large, the energy consumption is also high, and the mass fraction of the produced 1-butene is more than 99 percent.
Patent CN2014101190893 discloses an energy-saving process flow for 1-butene separation and purification, in which after the etherified carbon-carbon four mixture from MTBE is subjected to selective hydrogenation reaction, a lighter isobutane component is removed through a deisobutanizer rectification tower, and simultaneously, H is removed2、H2O, methanol and hydrocarbons form low-boiling-point azeotrope to be removed from the tower top, then heavier components of n-butane, trans-2-butene and cis-2-butene are removed through a 1-butene rectifying tower, high-purity 1-butene can be obtained from the tower top, and the whole process utilizes a process integration means to realize heat integration of a deisobutanizer and a 1-butene refining tower, so that an energy-saving 1-butene precise separation process is obtained, but the energy-saving effect of the process flow of the method needs to be further improvedHigh.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a 1-butene refining energy-saving process and a device with heat pump heat integration, which realize the energy integration of a heat pump rectification system of a heavy component removal tower and a light component removal tower and the waste heat recycling by using a technical means with heat pump heat integration, reduce the consumption of public works by using an air cooler, have the obvious characteristic of energy saving, reduce the consumption of steam and circulating water, have low working pressure of the tower and simple operation, and improve the economic benefit of the 1-butene refining process.
According to the 1-butene refining energy-saving process with heat pump heat integration, after ether and carbon four mixtures of MTBE are subjected to selective hydrogenation reaction, a 1-butene-containing mixture with the main components of hydrogen, water, methanol, carbon three, 1-butene, isobutane, normal butane, trans-2-butene and cis-2-butene is obtained, heavy components containing normal butane, trans-2-butene and cis-2-butene are removed through a heavy component removing tower, light components containing isobutane and carbon three are removed through a light component removing tower, and 1-butene is obtained from the bottom of the light component removing tower;
wherein, the heavy components removed from the bottom of the heavy component removal tower and the 1-butene removed from the bottom of the light component removal tower are used as heat source media to heat the mixture containing the 1-butene;
and heating and pressurizing the light component evaporated from the top of the heavy component removal tower to obtain a heating medium for a tower bottom reboiler of the light component removal tower and an intermediate reboiler of the heavy component removal tower.
Specifically, the 1-butene refining energy-saving process with heat pump heat integration comprises the following steps:
(1) after the ether post-carbon-four mixture of MTBE is subjected to selective hydrogenation reaction, a 1-butene-containing mixture with the main components of hydrogen, water, methanol, carbon three, 1-butene, isobutane, n-butane, trans-2-butene and cis-2-butene is obtained, the 1-butene-containing mixture is divided into two paths and is heated by a 1# heat exchanger and a 2# heat exchanger respectively, then the two paths are converged and enter a de-weighting tower for rectification, heavy components containing n-butane, trans-2-butene and cis-2-butene are removed from the bottom of the de-weighting tower, and the heavy components are cooled by the 2# heat exchanger and then are sent out of the device;
(2) a reboiler at the bottom of the heavy component removal tower is heated by steam, steam condensate is introduced into a 3# heat exchanger to be used as a heating medium, light components containing 1-butene and isobutane are evaporated from the top of the heavy component removal tower, the light components are sequentially heated by the 3# heat exchanger and are divided into two paths after being adiabatically compressed by a compressor, one path of the light components enters the reboiler at the bottom of the light component removal tower to be used as the heating medium, the other path of the light components enters an intermediate reboiler of the heavy component removal tower to be used as the heating medium, the light components are cooled by the two paths of the light components and then are converged to enter an air cooler to be further cooled to be in a supercooled state, and the light components are decompressed by a throttle valve and enter a 1# reflux tank to finish the rectification process of the heat pump;
(3) a part of mixed liquid in the 1# reflux tank enters the top of a heavy component removal tower to be used as reflux, the rest of mixed liquid enters a light component removal tower to be rectified, light components containing carbon, three and isobutane are evaporated from the top of the light component removal tower and condensed by a condenser to enter the 2# reflux tank, non-condensable gas containing a small amount of carbon, three and hydrogen is sent out of a device from the top of the 2# reflux tank, a part of liquid material enters the top of the light component removal tower to be used as reflux, the rest of liquid material is used as a light carbon, four and rich in isobutane to be sent out of the device, 1-butene is removed from the bottom of the light component removal tower, and the liquid material is sent out of the device after being cooled by a 1# heat exchanger.
The pressure at the top of the de-heavy tower is 0.45-1 MPaG, the temperature at the top of the de-heavy tower is 45-65 ℃, the pressure at the bottom of the de-heavy tower is 0.55-1.1 MPaG, the temperature at the bottom of the de-heavy tower is 65-85 ℃, and the reflux ratio at the top of the de-heavy tower is 8-20.
The tower top pressure of the lightness-removing tower is 0.5-1.1 MPaG, the tower top temperature is 45-65 ℃, the tower bottom pressure is 0.6-1.2 MPaG, the tower bottom temperature is 60-80 ℃, and the tower top reflux ratio is 100-300.
The temperature of the mixture containing 1-butene is 50-60 ℃ after heating.
And heating and pressurizing the light components evaporated from the top of the heavy component removal tower at 75-95 ℃ under 1.05-1.65 MPaG.
The flow ratio of the 1-butene-containing mixture entering the 1# heat exchanger to the 2# heat exchanger is 0.05-0.2.
The flow ratio of the light components entering a tower bottom reboiler of the light component removal tower and an intermediate reboiler of the heavy component removal tower is 0.8-1.8.
The invention relates to a 1-butene refining energy-saving device with heat pump heat integration, which comprises a heat exchange unit, a rectification unit, a compression unit and a fluid conveying unit; the heat exchange unit comprises a reboiler, a heat exchanger, a condenser and an air cooler; the rectification unit comprises a heavy component removing tower and a light component removing tower.
Specifically, the 1-butene refining energy-saving device with heat pump heat integration comprises a feeding pipe, a heavy component removal tower and a light component removal tower; the feeding pipe is divided into two paths which are respectively connected with a No. 1 heat exchanger and a No. 2 heat exchanger, and then one path is synthesized and connected with a feeding port of the de-weighting tower; a discharge hole at the bottom of the tower of the heavy component removal tower is connected with a No. 2 heat exchanger; a discharge port at the top of the heavy component removal tower is sequentially connected with a 3# heat exchanger and a compressor, and then is divided into two paths, one path is connected with a 3# reboiler at the bottom of the light component removal tower, the other path is connected with a 2# reboiler in the middle of the heavy component removal tower, then the two paths are synthesized, and the one path is connected with a 1# reflux tank after passing through an air cooler and a throttle valve; a 1# reboiler at the bottom of the heavy component removal tower is connected with a 3# heat exchanger; the No. 1 reflux tank is respectively connected with a top reflux port of the heavy component removal tower and a feed port of the light component removal tower; a discharge hole at the bottom of the light component removal tower is connected with a 1# heat exchanger; the discharge port at the top of the light component removing tower is sequentially connected with a condenser and a 2# reflux tank, and the 2# reflux tank is connected with the reflux port at the top of the light component removing tower.
The No. 2 heat exchanger is also connected with a heavy component recovery pipeline.
The 1# heat exchanger is also connected with a 1-butylene recovery pipeline.
The 2# backflow tank is connected with a noncondensable gas pipeline.
The discharge hole at the bottom of the tower of the de-heavy tower is connected with the No. 2 heat exchanger through the No. 1 tower bottom pump.
The discharge hole at the bottom of the light component removal tower is connected with the No. 1 heat exchanger through the No. 2 tower bottom pump.
The No. 1 reflux tank is respectively connected with a top reflux port of the heavy component removal tower and a feed port of the light component removal tower through a No. 1 reflux pump.
And the 2# reflux tank is respectively connected with a reflux opening at the top of the light component removal tower and a light carbon four-recovery pipeline through a 2# reflux pump.
The working process of the energy-saving device for refining 1-butene with heat pump heat integration is as follows:
the etherified C-C mixture from MTBE is subjected to selective hydrogenation reaction, and the main components of the etherified C-C mixture are hydrogen, water, methanol, C-C, 1-butene, isobutane, n-butane, trans-2-butene and cis-2-butene. The mixture is divided into two paths according to a certain proportion, and the two paths of the mixture are subjected to heat exchange through a No. 1 heat exchanger and a No. 2 heat exchanger respectively, and then are converged and enter a de-weighting tower for rectification, wherein heavy components such as n-butane, trans-2-butene and cis-2-butene are removed from the bottom of the de-weighting tower, are pumped out through a No. 1 tower bottom pump, enter the No. 2 heat exchanger for heat exchange and are cooled, and then are introduced into a heavy component recovery pipeline.
And a No. 1 reboiler at the bottom of the heavy component removal tower is heated by steam, and steam condensate is introduced into a No. 3 heat exchanger to serve as a heat source medium. Light components such as 1-butene, isobutane and the like are evaporated from the top of the heavy component removal tower, the light components are heated through a 3# heat exchanger and then enter a compressor, the pressure and the temperature of gas at the top of the tower are improved after adiabatic compression, the gas is divided into two paths, one path of the gas enters a 3# reboiler at the bottom of the light component removal tower and serves as a heat source medium, and the other path of the gas returns to a 2# reboiler in the middle of the heavy component removal tower and serves as a heat source medium. The temperature of light component substances is reduced after two paths of heat exchange to form a full liquid phase, the light component substances are converged and then enter an air cooler to be further cooled to a supercooled state, and the light component substances are decompressed through a throttle valve and enter a No. 1 return tank to finish the heat pump rectification process.
After the pressure of the liquid cooled in the No. 1 reflux tank is increased by the No. 1 reflux pump, one part of the liquid is used as reflux and returned to the top of the heavy component removal tower, and the other part of the liquid enters the light component removal tower for rectification. And (3) evaporating light components such as carbon III, isobutane and the like from the top of the light component removal tower, condensing the light components by a condenser, and then feeding the light components into a No. 2 reflux tank. And (3) introducing noncondensable gas containing a small amount of light components such as carbon, hydrogen and the like into a noncondensable gas pipeline at the top of the No. 2 reflux tank, pumping out the liquid material by a No. 2 reflux pump, refluxing one part of the liquid material to the top of the light component removal tower, and introducing the other part of the liquid material serving as light carbon four rich in isobutane into a light carbon four recovery pipeline. The material at the bottom of the light component removal tower is 1-butene, which is pumped out by a No. 2 tower bottom pump, and is introduced into a No. 1 heat exchanger for cooling and then is introduced into a 1-butene recovery pipeline.
Compared with the prior art, the invention has the following beneficial effects:
(1) the whole process and the device realize the energy integration of the heat pump rectification system of the heavy component removal tower and the light component removal tower and the waste heat recycling by using the technical means of heat pump heat integration, reduce the consumption of public works by using the air cooler, have the obvious characteristic of energy conservation, reduce the consumption of steam and circulating water, have low working pressure of the tower, are simple to operate and improve the economic benefit of the device;
(2) the invention changes the traditional mode of removing light and heavy firstly and then removing heavy, firstly removes heavy components such as normal butane, trans-2-butene and cis-2-butene and the like through a heavy removal tower, then removes light components such as isobutane and carbon, and the like, and can obtain high-purity 1-butene from the tower bottom.
Drawings
FIG. 1 is a schematic diagram of the structure of a 1-butene refining energy-saving device with heat pump heat integration of the invention;
in the figure: 1. a feed pipe; 2. a 1-butene recovery line; 3. 1# heat exchanger; 4. a heavy component recovery line; 5. 2# heat exchanger; 6. a de-heavy tower; 7. 3# heat exchanger; 8. a compressor; 9. a light component removal tower; 10. a condenser; 11. 2# reflux tank; 12. a noncondensable gas pipeline; 13. a No. 2 tower bottom pump; 14. 1# bottom pump; 15. a # 1 reboiler; 16. a # 2 reboiler; 17. an air cooler; 18. a throttle valve; 19. 1# reflux tank; 20. 1# reflux pump; 21. a # 3 reboiler; 22. 2# reflux pump; 23. and a light carbon four recovery pipeline.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited thereto.
Example 1
As shown in figure 1, the 1-butene refining energy-saving device with heat pump heat integration comprises a feed pipe 1, a heavy component removal tower 6 and a light component removal tower 9; the feeding pipe 1 is divided into two paths which are respectively connected with a No. 1 heat exchanger 3 and a No. 2 heat exchanger 5, and then one path is synthesized and connected with a feeding hole of a de-weighting tower 6; a discharge hole at the bottom of the tower of the de-heavy tower 6 is connected with a No. 2 heat exchanger 5; a discharge port at the top of the heavy component removal tower 6 is sequentially connected with a 3# heat exchanger 7 and a compressor 8, and then is divided into two paths, one path is connected with a 3# reboiler 21 at the bottom of the light component removal tower 9, the other path is connected with a 2# reboiler 16 in the middle of the heavy component removal tower 6, then the two paths are synthesized, and the one path is connected with a 1# reflux tank 19 after passing through an air cooler 17 and a throttle valve 18; a 1# reboiler 15 at the bottom of the heavy component removal tower 6 is connected with a 3# heat exchanger 7; the 1# reflux tank 19 is respectively connected with a tower top reflux port of the heavy component removal tower 6 and a feed port of the light component removal tower 9; a discharge hole at the bottom of the light component removal tower 9 is connected with a No. 1 heat exchanger 3; a discharge port at the top of the light component removal tower 9 is sequentially connected with a condenser 10 and a 2# reflux tank 11, and the 2# reflux tank 11 is connected with a reflux port at the top of the light component removal tower 9.
The # 2 heat exchanger 5 is also connected with a heavy component recovery pipeline 4.
The 1# heat exchanger 3 is also connected with a 1-butene recovery pipeline 2.
The 2# return tank 11 is connected with a non-condensable gas pipeline 12.
The discharge hole at the bottom of the heavy component removal tower 6 is connected with the No. 2 heat exchanger 5 through the No. 1 tower bottom pump 14.
The discharge hole at the bottom of the light component removal tower 9 is connected with a No. 1 heat exchanger 3 through a No. 2 tower bottom pump 13.
The 1# reflux tank 19 is respectively connected with a reflux port at the top of the heavy component removing tower 6 and a feed port of the light component removing tower 9 through a 1# reflux pump 20.
The 2# reflux tank 11 is connected with a top reflux port of the light component removal tower 9 and a light carbon four-recovery pipeline 23 through a 2# reflux pump 22 respectively.
The working process of the energy-saving device for refining 1-butene with heat pump heat integration is as follows:
the etherified C-C mixture from MTBE is subjected to selective hydrogenation reaction, and the main components of the etherified C-C mixture are hydrogen, water, methanol, C-C, 1-butene, isobutane, n-butane, trans-2-butene and cis-2-butene. The mixture is divided into two paths according to a certain proportion, and the two paths of the mixture are subjected to heat exchange through a No. 1 heat exchanger 3 and a No. 2 heat exchanger 5 respectively, and then are converged to enter a de-weighting tower 6 for rectification, wherein heavy components such as n-butane, trans-2-butene and cis-2-butene are removed from the bottom of the de-weighting tower 6, are pumped out through a No. 1 tower bottom pump 14, enter a No. 2 heat exchanger 5 for heat exchange and are cooled, and then are introduced into a heavy component recovery pipeline 4.
After the pressure of the liquid cooled in the 1# reflux tank 19 is increased by the 1# reflux pump 20, one part of the liquid is returned to the top of the heavy component removal tower 6 as reflux, and the other part of the liquid enters the light component removal tower 9 for rectification. Light components such as carbon, isobutane and the like are evaporated from the top of the light component removal tower 9, condensed by a condenser 10 and then enter a No. 2 reflux tank 11. The noncondensable gas containing a small amount of light components such as carbon, hydrogen and the like enters a noncondensable gas pipeline 12 at the top of a No. 2 reflux tank 11, the liquid material is pumped out by a No. 2 reflux pump 22, one part of the liquid material reflows to the top of a light component removal tower 9, and the other part of the liquid material serving as light carbon four rich in isobutane enters a light carbon four recovery pipeline 23. The material at the bottom of the light component removal tower 9 is 1-butene, which is pumped out by a No. 2 tower bottom pump 13, and is introduced into a No. 1 heat exchanger 3 for cooling and then introduced into a 1-butene recovery pipeline 2.
Example 2
The 1-butene refining energy-saving device with heat pump heat integration in the embodiment 1 is used for refining 1-butene, and the specific process flow is as follows:
the etherified C-C mixture from MTBE was subjected to a selective hydrogenation reaction to obtain a 1-butene-containing mixture having the main components hydrogen, water, methanol, C-C, 1-butene, isobutane, n-butane, trans-2-butene and cis-2-butene, the 1-butene-containing mixture having a temperature of 40 ℃ and a flow rate of 5507.41kg/h and having the composition shown in Table 1.
TABLE 1 composition of the 1-butene-containing mixtures
| Make up of | Hydrogen gas | Water (W) | Carbon III | Isobutane | N-butane | 1-butene | Isobutene |
| kg/h | 0.3333 | 4.626 | 18.906 | 172.044 | 1138.344 | 3397.1 | 2.968 |
| Composition of | Cis-2-butene | Trans-2-butene | Butadiene | Vinyl acetylene | Methanol | MTBE | Dimethyl ether |
| kg/h | 443.866 | 327.587 | 0.055 | 0.048 | 0.249 | 0.00095 | 1.283 |
Firstly, dividing a mixture containing 1-butene into two paths according to the proportion of about 1.2:1, respectively exchanging heat through a 1# heat exchanger and a 2# heat exchanger, raising the temperature to 56 ℃, converging the two paths, and entering a de-heavy tower for rectification, wherein the pressure at the top of the de-heavy tower is 0.6MPaG, the temperature at the top of the de-heavy tower is 55.5 ℃, the temperature at the bottom of the de-heavy tower is 70.9 ℃, the pressure at the bottom of the de-heavy tower is 0.71MPaG, and the reflux ratio is 12.6. Heavy components (the flow rate is 1925.72kg/h, the temperature is 70.9 ℃) containing n-butane, trans-2-butene and cis-2-butene are removed from the bottom of the de-weighting tower, are pumped out by a No. 1 tower bottom pump, and are sent out of the device after heat exchange and temperature reduction by a No. 2 heat exchanger.
The reboiler at the bottom of the heavy component removal tower is heated by steam, and the steam condensate flow (the flow rate is 7158kg/h, and the temperature is 145 ℃) is introduced into a No. 3 heat exchanger as a heating medium. The light component (the flow is 48806.6kg/h, the temperature is 55.5 ℃) containing 1-butene and isobutane is evaporated from the top of the heavy component removal tower, the light component is heated by a 3# heat exchanger and compressed by a compressor in an adiabatic way, the temperature is increased to 86.2 ℃ and the pressure is 1.2MpaG, then the light component is divided into two paths, one path (the flow is 43601.8kg/h) enters a reboiler at the bottom of the light component removal tower to be used as a heating medium, the other path (the flow is 5204.8kg/h) enters an intermediate reboiler of the heavy component removal tower to be used as a heating medium, the temperature of the light component is reduced to about 76 ℃ after the two paths are cooled, the light component is converged and enters an air cooler to be further cooled to be in a supercooled state, the pressure is reduced to 42.5 ℃ through a throttle valve, the pressure is reduced to 0.57MpaG, the light component enters a 1# reflux tank, and the rectification process is completed through a heat pump;
after the pressure of the mixed liquid in the No. 1 reflux tank is increased by a No. 1 reflux pump, a part (the flow rate is 45201.2kg/h) enters the top of a heavy component removal tower to be used as reflux, the rest (the flow rate is 3579.75kg/h) enters a light component removal tower to be rectified, the pressure of the top of the light component removal tower is 0.65MPaG, the temperature of the top of the light component removal tower is 48.8 ℃, the temperature of the bottom of the light component removal tower is 64.8 ℃, the pressure of the bottom of the light component removal tower is 0.76MPaG, and the reflux ratio is 170.
The method comprises the following steps of evaporating light components containing carbon, three and isobutane (the flow is 35981.2kg/h, the temperature is 48.8 ℃) from the top of a light component removal tower, condensing the light components through a condenser, reducing the temperature to 45 ℃, feeding the light components into a 2# reflux tank, feeding noncondensable gas containing a small amount of carbon, three and hydrogen out of a device from the top of the 2# reflux tank, feeding a part (the flow is 35771.4kg/h) of liquid materials into the top of the light component removal tower to serve as reflux, feeding the rest (the flow is 101.8kg/h) of liquid materials to serve as a light carbon four delivery device rich in isobutane, removing 1-butene (the flow is 3369.95kg/h, the temperature is 64.8 ℃) from the bottom of the light component removal tower, pumping the liquid materials through a 2# tower bottom pump, cooling a 1# heat exchanger to the temperature of about 50 ℃, and delivering the light components out of the device. The purity of the obtained 1-butene product was 99.8%.
The composition of the main streams in the above process scheme is shown in table 2.
TABLE 2 composition of the major streams in the Process
Comparative example 1
In this comparative example, a mixture containing 1-butene was purified by the conventional rectification method of removing light and heavy components, wherein the mixture containing 1-butene was the same as in example 2, the temperature was 40 ℃ and the flow rate was 5507.41kg/h, and the composition was as shown in Table 1.
The rectification method comprises the following steps: firstly, removing low-boiling-point carbon three, isobutane and azeotrope with water by using a light component removal tower, wherein the top pressure of the light component removal tower is 0.65MPaG, the temperature at the top of the tower is 46.5 ℃, the pressure at the bottom of the tower is 0.76MPaG, the temperature at the bottom of the tower is 67.7 ℃, and the reflux ratio at the top of the tower is 195; then removing high-boiling-point n-butane and 2-butene by a de-heavy tower, wherein the pressure at the top of the de-heavy tower is 0.5MPaG, the temperature at the top of the de-heavy tower is 50 ℃, the pressure at the bottom of the de-heavy tower is 0.61MPaG, the temperature at the bottom of the de-heavy tower is 65.3 ℃, and the reflux ratio at the top of the de-heavy tower is 12.9; finally, 1-butene with the purity of 99.8 percent is obtained from the top of the de-heavy tower; all the equipment needing to be heated is heated by adopting steam, and all the equipment needing to be cooled is cooled by adopting circulating condensed water.
Comparative example 2
This comparative example used a rectification process of heavy ends removal followed by light ends removal without heat pump heat integration to purify and refine the 1-butene-containing mixture, wherein the 1-butene-containing mixture was the same as in example 2, the temperature was 40 ℃, the flow rate was 5507.41kg/h, and the composition was as shown in table 1.
The rectification method comprises the following steps: firstly, removing heavy components containing n-butane, trans-2-butene and cis-2-butene by using a de-heavy tower, wherein the pressure at the top of the de-heavy tower is 0.6MPaG, the temperature at the top of the de-heavy tower is 55.5 ℃, the pressure at the bottom of the de-heavy tower is 0.71MPaG, the temperature at the bottom of the de-heavy tower is 70.9 ℃, and the reflux ratio at the top of the de-heavy tower is 12.6; removing light components containing carbon, three and isobutane by using a light component removal tower, wherein the top pressure of the light component removal tower is 0.65MPaG, the temperature of the top of the light component removal tower is 48.9 ℃, the pressure of the bottom of the light component removal tower is 0.76MPaG, the temperature of the bottom of the light component removal tower is 64.8 ℃, and the reflux ratio of the top of the light component removal tower is 170; finally, 1-butene with the purity of 99.8 percent is obtained from the bottom of the light component removal tower; all the equipment needing heating is heated by adopting steam, and all the equipment needing cooling is cooled by adopting circulating condensed water.
Comparative example 3
The 1-butene-containing mixture was purified and refined by the rectification method of patent CN2014101190893, wherein the temperature of the 1-butene-containing mixture was 40 ℃, the flow rate was 5507.41kg/h, and the composition is shown in table 1. The process parameters were calculated by simulations exactly according to the data disclosed in example 1 thereof.
The top pressure of the lightness-removing column is 1.2MPaG, the temperature at the top of the column is 70.6 ℃, the pressure at the bottom of the column is 1.31MPaG, the temperature at the bottom of the column is 90.6 ℃, and the reflux ratio at the top of the column is 414.9.
The pressure at the top of the de-heavy tower is 1.7MPaG, the temperature at the top of the de-heavy tower is 99.9 ℃, the pressure at the bottom of the de-heavy tower is 1.81MPaG, the temperature at the bottom of the de-heavy tower is 112.3 ℃, and the reflux ratio at the top of the de-heavy tower is 48.3.
The results of comparing example 2 and comparative examples 1 to 3, in which the energy consumption consumed by the distillation methods of example 2 and comparative examples 1 to 3 was converted into standard oil by simulation with chemical engineering simulation software Aspen Plus and conversion with GB/T50441-.
TABLE 3 comparison of energy consumption consumed by the rectification Processes of example 2 and comparative examples 1-3
As can be seen from Table 3, the energy-saving process for refining 1-butene with heat pump heat integration has the obvious energy-saving characteristic when the 1-butene-containing mixture with the main components of hydrogen, water, methanol, carbon three, 1-butene, isobutane, normal butane, trans-2-butene and cis-2-butene is obtained after the carbon four mixture is subjected to selective hydrogenation reaction after the ether from MTBE is treated. Compared with the conventional rectification process of removing light and heavy firstly and then in comparison with the comparative example 1, the energy consumption is reduced by about 43 percent; compared with the rectification process without heat pump heat integration, which is used for removing heavy components first and then removing light components, the energy consumption is reduced by about 38 percent; compared with the rectification method in the prior patent CN2014101190893, the energy consumption is reduced by about 56%.
Claims (8)
1. A1-butene refining energy-saving process with heat pump heat integration is characterized in that: the method comprises the following steps:
(1) after the ether post-carbon four mixture of MTBE is subjected to selective hydrogenation reaction, a 1-butene-containing mixture with the main components of hydrogen, water, carbon three, isobutane, n-butane, 1-butene, cis-2-butene, trans-2-butene and methanol is obtained, the 1-butene-containing mixture is divided into two paths, is heated by a No. 1 heat exchanger and a No. 2 heat exchanger respectively, then is converged and enters a de-weighting tower for rectification, heavy components containing n-butane, trans-2-butene and cis-2-butene are removed from the bottom of the de-weighting tower, and is sent out of the device after being cooled by the No. 2 heat exchanger;
(2) a reboiler at the bottom of the heavy component removal tower is heated by steam, steam condensate is introduced into a 3# heat exchanger to be used as a heating medium, light components containing 1-butene and isobutane are evaporated from the top of the heavy component removal tower, the light components are sequentially heated by the 3# heat exchanger and are divided into two paths after being adiabatically compressed by a compressor, one path of the light components enters the reboiler at the bottom of the light component removal tower to be used as the heating medium, the other path of the light components enters an intermediate reboiler of the heavy component removal tower to be used as the heating medium, the light components are cooled by the two paths of the light components and then are converged to enter an air cooler to be further cooled to be in a supercooled state, and the light components are decompressed by a throttle valve and enter a 1# reflux tank to finish the rectification process of the heat pump;
(3) a part of mixed liquid in the No. 1 reflux tank enters the top of a heavy component removal tower to be used as reflux, the rest enters a light component removal tower to be rectified, light components containing carbon, three and isobutane are evaporated from the top of the light component removal tower, the light components are condensed by a condenser and then enter the No. 2 reflux tank, noncondensable gas containing a small amount of carbon, three and hydrogen is sent out of a device from the top of the No. 2 reflux tank, a part of liquid material enters the top of the light component removal tower to be used as reflux, the rest is used as a light carbon, four, rich in isobutane, 1-butene is removed from the bottom of the light component removal tower, and the liquid material is sent out of the device after being cooled by a No. 1 heat exchanger.
2. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: the pressure at the top of the de-heavy tower is 0.45-1 MPaG, the temperature at the top of the de-heavy tower is 45-65 ℃, the pressure at the bottom of the de-heavy tower is 0.55-1.1 MPaG, the temperature at the bottom of the de-heavy tower is 65-85 ℃, and the reflux ratio at the top of the de-heavy tower is 8-20.
3. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: the top pressure of the light component removal tower is 0.5-1.1 MPaG, the temperature of the top of the tower is 45-65 ℃, the pressure of the bottom of the tower is 0.6-1.2 MPaG, the temperature of the bottom of the tower is 60-80 ℃, and the reflux ratio of the top of the tower is 100-300.
4. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: the temperature of the mixture containing 1-butene is 50-60 ℃ after heating.
5. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: and heating and pressurizing the light components evaporated from the top of the heavy component removal tower at 75-95 ℃ under 1.05-1.65 MPaG.
6. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: the flow ratio of the mixture containing 1-butene entering the 1# heat exchanger to the 2# heat exchanger is 0.05-0.2.
7. The energy-saving process for refining 1-butene with heat pump heat integration according to claim 1, characterized in that: the flow ratio of the light components entering a tower bottom reboiler of the light component removal tower and an intermediate reboiler of the heavy component removal tower is 0.8-1.8.
8. The device for 1-butene refining energy-saving process with heat pump heat integration of claim 1 is characterized in that: comprises a feeding pipe (1), a heavy component removing tower (6) and a light component removing tower (9); the feeding pipe (1) is divided into two paths which are respectively connected with a 1# heat exchanger (3) and a 2# heat exchanger (5), and then one path is synthesized and connected with a feeding hole of a de-weighting tower (6); a discharge port at the bottom of the tower of the heavy component removal tower (6) is connected with a No. 2 heat exchanger (5) through a No. 1 tower bottom pump (14), and the No. 2 heat exchanger (5) is also connected with a heavy component recovery pipeline (4); a discharge port at the top of the heavy component removal tower (6) is sequentially connected with a 3# heat exchanger (7) and a compressor (8), then the heavy component removal tower is divided into two paths, one path is connected with a 3# reboiler (21) at the bottom of the light component removal tower (9), the other path is connected with a 2# reboiler (16) in the middle of the heavy component removal tower (6), then the two paths are synthesized, and the one path is connected with a 1# reflux tank (19) after passing through an air cooler (17) and a throttle valve (18); a 1# reboiler (15) at the bottom of the heavy component removal tower (6) is connected with a 3# heat exchanger (7); the 1# reflux tank (19) is respectively connected with a reflux port at the top of the heavy component removal tower (6) and a feed inlet of the light component removal tower (9) through a 1# reflux pump (20); a discharge hole at the bottom of the light component removal tower (9) is connected with a No. 1 heat exchanger (3) through a No. 2 tower bottom pump (13), and the No. 1 heat exchanger (3) is also connected with a 1-butylene recovery pipeline (2); a discharge port at the top of the light component removal tower (9) is sequentially connected with a condenser (10) and a 2# reflux tank (11), the 2# reflux tank (11) is respectively connected with a reflux port at the top of the light component removal tower (9) and a light carbon four-recovery pipeline (23) through a 2# reflux pump (22), and the 2# reflux tank (11) is also connected with a noncondensable gas pipeline (12).
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