CN103058812A - Olefin separation system and olefin separation method - Google Patents
Olefin separation system and olefin separation method Download PDFInfo
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- CN103058812A CN103058812A CN2013100331014A CN201310033101A CN103058812A CN 103058812 A CN103058812 A CN 103058812A CN 2013100331014 A CN2013100331014 A CN 2013100331014A CN 201310033101 A CN201310033101 A CN 201310033101A CN 103058812 A CN103058812 A CN 103058812A
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Abstract
The invention provides an olefin separation system and an olefin separation method. The olefin separation system comprises a demethanation unit. The demethanation unit comprises a primary demethanation tower, a pressure swing adsorption system and a secondary demethanation tower. A first gas-phase flow pipeline is arranged between the outlet located on the top of the primary demethanation tower and the inlet of the pressure swing adsorption system; and a hydrocarbon-rich gas flow pipeline is arranged between the outlet located on the top of the pressure swing adsorption system and the inlet of the secondary demethanation tower. The gas to be separated is unclearly cut or clearly cut via the primary demethanation tower, so that the first gas-phase flow obtained by a manner of processing the gas to be separated via the primary demethanation tower can be effectively divided into a hydrocarbon-rich gas flow and a hydrogen-rich flow after being adsorbed by the pressure swing adsorption system, CH4/H2 molecular ratio in the hydrocarbon-rich gas flow entering the primary demethanation tower is enlarged, the differential pressure of CH4 on the top part of the primary demethanation tower is increased, and the energy consumption required by temperature reduction and the investment and the operation cost on olefin separation are reduced.
Description
Technical field
The present invention relates to the gas delivery field, in particular to a kind of olefin separation system and alkene separation method.
Background technology
In oil gas, oil refinery dry gas and the methanol-to-olefins gas product except containing ethene, propylene, also contain a large amount of other compositions, such as hydrogen, methane, acetylene, propane and nitrogen etc., because ethene, propylene are important industrial chemicals, therefore can adopt above oil gas, oil refinery dry gas and methanol-to-olefins gas product is that raw material separates ethene and propylene wherein, at present, deep cooling separating method is the most ripe, adopts at most.
There are many shortcomings in typical conventional deep cooling separating method, such as usually requiring unstripped gas is carried out 4 to 5 grades of compressions, need a large amount of low-temperature cooling medias, separating the refrigeration system that needs below-100 ℃ such as methane-hydrogen cools off, therefore, the energy consumption of conventional deep cooling separating method is higher, and is also high to the requirement of equipment, and the separating effect that wants to realize ideal has to strengthen investment.In the low temperature separation process process, hydrogen and methane separation are maximum one of energy consumption and cost consumption in the whole separation system, and complex process.Because, CH in the unstripped gas
4/ H
2Molecule ratio is very large on ethylene loss impact in the tail gas, and this is because H because of the demethanizing tower item
2Reduced CH with the existence of other rare gas element
4Dividing potential drop only is improved pressure or the reduction temperature just satisfies cat head to the requirement of dew point, improves pressure and is isolating CH with the reduction temperature
4The time, part ethene also can with CH
4Together be separated, cause the loss of ethene, above-mentioned impact is by the decision that balances each other, and stage number and reflux ratio what do not depend on, therefore at temperature and pressure condition one timing, CH in the unstripped gas
4/ H
2Molecule ratio is less, and ethylene loss is just larger in the tail gas, otherwise then little, energy consumption is also lower.Therefore, how from splitting gas or olefine mixing gas, separate hydrogen is as much as possible, cause people's extensive concern with the energy consumption that reduces the hydrogen methane separation.
Existing Lu Musi technology is one of technology more advanced in the deep cooling separation of olefins, the structural representation of Lu Musi alkene low temperature separation process system as shown in Figure 1: enter depropanizing tower 51 ' after the unstripped gas drying device 52 ' drying, the top gaseous phase of depropanizing tower 51 ' separates through the laggard promoting the circulation of qi liquid of the overhead condenser 54 ' partial condensation of depropanizing unit, the liquid that condensation is got off is as the backflow of depropanization system, all the other gas phases that contain carbon three hydro carbons and carbon three following hydrocarbon components enter compressor 53 ' boost after, successively through the second reboiler 192 ', enter demethanizing tower 11 ' after the first cryogen chiller 161 ' and the second cryogen chiller 162 ' a series of heat exchange process of cooling; Depropanizing tower 51 ' bottom product is that carbon four and carbon four above components are sent to debutanizing tower 61 '.The overhead condenser of demethanizing unit utilizes propylene (or ethene) to make cryogen, the overhead stream of partial condensation enters (overhead condenser and the return tank of not shown demethanizing unit among Fig. 1) behind the return tank, the liquid phase that return tank is separated is as the backflow of demethanizing tower 11 ', gas phase is (take hydrogen and methane as main, be called the hydrogen methane gas stream) through after the ice chest 142 ' heat exchange, deliver to the outer gas ductwork of device.The logistics that contains C2 hydrocarbon class and carbon three hydrocarbon compositions at the bottom of the demethanizing tower 11 ' tower enters deethanizing column 31 ', the overhead stream of deethanizing column 31 ' passes through at first that hydrogenation acetylene removal reactor 21 ' changes into ethene with the alkynes class in the logistics (mainly being acetylene) and then ethane enter ethylene rectification tower 22 ', the top gaseous phase of ethylene rectification tower 22 ' is as ethylene product feeder tank field, and ethane is sent into fuel gas system and acted as a fuel and use or recycle and process at the bottom of the tower of ethylene rectification tower 22 ' after interchanger heating vaporization.The tower base stream of deethanizing column 31 ' enters the propylene rectification cell; the cat head propylene product of propylene rectification tower 41 ' refluxes the Partial Liquid Phase material through return tank of top of the tower 42 ' through overhead water cooler 43 ' condensation rear section; remove behind methyl alcohol, oxide compound and other impurity as propylene product feeder Propylene Tank Farm, partial reflux propylene rectification tower 41 ' through product protection bed (not shown in figure 1) again.Propane logistics at the bottom of the propylene rectification tower 41 ' tower is through ice chest 142 ' and hydrogen methane gas stream heat exchange cooling, the methane that the cat head of introducing demethanizing tower 11 ' is located with absorption demethanizing tower 11 ' after the 3rd cryogen chiller 163 ' is by the cryogen Quench, the ethene in the hydrogen gas stream; Entering gas ductwork after another stock-traders' know-how ice chest 142 ' heat exchange uses as combustion gas.The material of the isolated carbon containing four of propylene rectification cell and above component enters debutanizing tower 61 ' separation of carbon, four hydro carbons and carbon four above hydrocarbon productss.
Above-mentioned conventional cryogenics and Lu Musi technology are owing to all being to adopt a demethanizing to process the molecule ratio that is difficult to obtain desirable methane and hydrogen, therefore cause that tail gas energy consumption in the process of separating ethene is high, the ethylene loss amount large and invest high shortcoming, the present invention mainly is in order to realize reducing energy consumption, to reduce ethylene loss and improvement that the Lu Musi technology is made on the basis of Lu Musi technology.
Summary of the invention
The present invention aims to provide a kind of olefin separation system and alkene separation method, has reduced the energy consumption in the olefin separation process.
To achieve these goals, according to an aspect of the present invention, a kind of olefin separation system is provided, this olefin separation system comprises the demethanizing unit, the demethanizing unit comprises just demethanizing tower, pressure swing adsorption system and inferior demethanizing tower, is provided with the first gaseous stream pipeline between the tower top outlet of first demethanizing tower and the import of pressure swing adsorption system; Be provided with rich hydrocarbon stream pipeline between the import of the tower top outlet of pressure swing adsorption system and time demethanizing tower.
Further, above-mentioned demethanizing unit also comprises the first compressor, the first ice chest, First Heat Exchanger, the second interchanger, the first cryogen chiller and decompressor, has the second gaseous stream pipeline between the tower top outlet of inferior demethanizing tower and the import of decompressor; The first compressor is arranged on the rich hydrocarbon stream pipeline; The first ice chest has: stream in the first gaseous stream the first ice chest is serially connected in the first gaseous stream pipeline; Stream in rich hydrocarbon stream the first ice chest is serially connected in the rich hydrocarbon stream pipeline between the import of the first compressor and inferior demethanizing tower; First Heat Exchanger has: stream in the rich hydrocarbon stream First Heat Exchanger is serially connected in the rich hydrocarbon stream pipeline between the import of stream and inferior demethanizing tower in rich hydrocarbon stream the first ice chest; Stream in the second liquid phase logistics First Heat Exchanger is connected with the tower bottom outlet of inferior demethanizing tower, and heat exchange is carried out in rich hydrocarbon stream and second liquid phase logistics in First Heat Exchanger; The second interchanger has: stream in rich hydrocarbon stream the second interchanger is serially connected in the rich hydrocarbon stream pipeline between the import of stream and inferior demethanizing tower in the rich hydrocarbon stream First Heat Exchanger; Stream in the second gaseous stream the second interchanger is connected with the outlet of decompressor, and rich hydrocarbon stream and the second gaseous stream carry out heat exchange in the second interchanger; The first cryogen chiller is arranged between the import of the interior stream of rich hydrocarbon stream the second interchanger and time demethanizing tower.
Further, above-mentioned demethanizing unit also comprises: the first reboiler, and being connected with the first tower bottom outlet of first demethanizing tower and linking to each other with the tower reactor of first demethanizing tower forms the first circulation line; The second reboiler, being connected with the second tower bottom outlet of first demethanizing tower and linking to each other with the tower reactor of first demethanizing tower forms the second circulation line.
Further, above-mentioned olefin separation system also comprises the ethylene distillation unit, and the ethylene distillation unit comprises: hydrogenation acetylene removal reactor has: the hydrogen gas stream import, and have the hydrogen rich stream pipeline between the outlet of the hydrogen rich stream of pressure swing adsorption system; The hydrocarbon material import, and have second liquid phase logistics pipeline between the tower bottom outlet of inferior demethanizing tower; The ethylene product outlet; Ethylene rectification tower is connected with the ethylene product outlet.
Further, above-mentioned olefin separation system also comprises deethanizing unit and propylene rectification cell, the deethanizing unit comprises deethanizing column, and deethanizing column has: the first liquid phase stream import, and have the first liquid phase stream pipeline between the 3rd tower bottom outlet of first demethanizing tower; The deethanizer overhead stream outlet, and have hydro carbons acetylene removal Location Detection of Medium Transportation Pipeline between the hydrocarbon material import of hydrogenation acetylene removal reactor; The propylene rectification cell comprises: propylene rectification tower has: the 3rd liquid phase stream import, and have the 3rd liquid phase stream pipeline between the tower bottom outlet of deethanizing column; The outlet of cat head propylene; Return tank of top of the tower is connected with the outlet of the cat head propylene of propylene rectification tower and consists of the 3rd circulation line with propylene rectification tower, and the first reboiler or the second reboiler have propylene import and the propylene outlet that is connected with the 3rd circulation line.
Further, also be provided with control valve on the 3rd circulation line between aforesaid propylene rectifying tower and the return tank of top of the tower, control valve and the first reboiler or the second reboiler are arranged in parallel.
Further, above-mentioned olefin separation system also comprises the second ice chest, and the second ice chest has the second gas phase liquid and flows stream in the second ice chest, and the second gas phase liquid flows the interior stream of the second ice chest and is connected with the interior stream of the second gaseous stream second interchanger of the second interchanger; Have two article of the 4th liquid phase stream pipeline between propylene rectification tower and the second ice chest, be connected with gas ductwork after one article of the 4th liquid phase stream pipeline wherein passes the second ice chest; Another article the 4th liquid phase stream pipeline passes to extend to first demethanizing tower behind the second ice chest and is connected, olefin separation system also comprises the second cryogen chiller, and the second cryogen chiller is arranged on the second ice chest and just on the 4th liquid phase stream pipeline between the demethanizing tower.
Further, above-mentioned olefin separation system also comprises: the depropanizing unit comprises: depropanizing tower, the tower top outlet of depropanizing tower with just be provided with just degassed phase logistics pipeline between the demethanizing tower; Moisture eliminator is connected with the import of depropanizing tower and carries unstripped gas to be separated to depropanizing tower; The second compressor is arranged on depropanizing tower and the first first degassed phase logistics pipeline between the demethanizing tower; The 3rd cryogen chiller, be arranged on the second compressor and the first first degassed phase logistics pipeline between the demethanizing tower, the first ice chest has the first degassed phase logistics import and the first degassed phase logistics that are connected with first degassed phase logistics pipeline between the 3rd cryogen chiller with the second compressor and exports; The debutylize unit comprises: debutanizing tower, and be provided with the first liquid phase stream pipeline that takes off between the depropanizing tower; Overhead condenser has the import that is connected with the tower top outlet of debutanizing tower and the outlet of flowing out for the condensation after product.
According to a further aspect in the invention, a kind of alkene separation method also is provided, this alkene separation method comprises that separating main component is the process of the gas mixture of hydrogen, carbon three hydro carbons and carbon three following hydro carbons, process comprises: first demethanizing process: make gas mixture just carry out the first gaseous stream and the first liquid phase stream that non-clear cutting obtains being separated from each other in the demethanizing process, the first gaseous stream comprises hydrogen, methane and C2 hydrocarbon class, and the first liquid phase stream comprises C2 hydrocarbon class and carbon three hydro carbons; Pressure-swing adsorption process: make the first gaseous stream carry out rich hydrocarbon stream and hydrogen rich stream that pressure-variable adsorption obtains being separated from each other; Inferior demethanizing process: make rich hydrocarbon stream in inferior demethanizing, carry out the second gaseous stream and second liquid phase logistics that clear cutting obtains being separated from each other.
Further, contain volume percent in the first gaseous stream that above-mentioned just demethanizing process obtains and be 15～90% C2 hydrocarbon class; The volume percent of hydrogen is 85～99.99% in the hydrogen rich stream that pressure-swing adsorption process obtains, and the volume of hydrogen accounts for 40～70% of hydrogen cumulative volume in the first gaseous stream in the hydrogen rich stream; The volume content of ethene≤2% in the second gaseous stream that inferior demethanizing process obtains.
Further, said process also comprises: make gas mixture successively through carrying out heat exchange, carry out carrying out just demethanizing process after the heat exchange with cryogen with the first gaseous stream that is obtained by non-clear cutting; Make rich hydrocarbon stream successively through processed compressed, with by isolated the first gaseous stream of first demethanizing process carry out heat exchange, with by the isolated second liquid phase logistics of inferior demethanizing carry out heat exchange, with carry out the laggard places demethanizing of heat exchange process by isolated the second gaseous stream of inferior demethanizing; Make by isolated the second gaseous stream of inferior demethanizing and rich hydrocarbon stream and carry out the cooling of expanding before the heat exchange; Part the first liquid phase stream is separated by reheating boiling by first demethanizing process repeat just demethanizing process.
Further, above-mentioned alkene separation method also comprises: make unstripped gas to be separated carry out compressing to form gas mixture after depropanizing is processed; Make part the first liquid phase stream carry out the deethanizing processing and obtain deethanizer overhead stream and the 3rd liquid phase stream; Make deethanizer overhead stream and rich hydrocarbon stream and/or external hydrogen carry out the hydrogenation acetylene removal and react to such an extent that contain mixture of ethylene after the acetylene removal, will contain again mixture of ethylene rectifying and obtain ethylene product; The 3rd liquid phase stream rectifying is obtained the 4th gaseous stream and the mutually logistics of the 4th liquid phase, the 4th gaseous stream and part the first liquid phase stream heat exchange are processed by the further removal of impurity formed propylene product; After making the 4th liquid phase stream and the second gaseous stream carry out heat exchange, the 4th liquid phase stream after a part of heat exchange and cryogen are further carried out being used for absorbing after the heat exchange first demethanizing process wish form ethene in the gaseous substance of the first gaseous stream, the 4th liquid phase stream after another part heat exchange is carried as combustion gas.
Use technical scheme of the present invention, first demethanizing tower, pressure swing adsorption system and time demethanizing tower coordinating operation, through after the sub-zero treatment of first demethanizing tower, cat head working temperature and the pressure of rationally controlling first demethanizing tower by temperature control component and pressure control valve carry out non-clear cutting or clear cutting to gas to be separated, the not carbon containing three and carbon three above hydro carbons the first gaseous streams that obtain after gas to be separated is processed through first demethanizing tower further are divided into rich hydrocarbon stream and hydrogen rich stream with the first gaseous stream effectively through after the absorption of pressure swing adsorption system, have increased the CH in the rich hydrocarbon stream that enters time demethanizing tower
4/ H
2Molecule ratio, and then increased the inferior demethanizer column overhead CH of place
4Dividing potential drop, therefore only the temperature of inferior demethanizing tower need to be reduced to higher dew point and can isolate CH
4And H
2, the required energy consumption of cooling has reduced in sepn process so; And, because therefore increasing so that only have few in the second gaseous stream that inferior demethanizer column overhead is separated or even do not have ethene of dew point reduced the loss of ethene; Simultaneously, the realization of above-mentioned technique effect can greatly reduce investment and the running cost of separation of olefins.
Description of drawings
The Figure of description that consists of the application's a part is used to provide a further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not consist of improper restriction of the present invention.In the accompanying drawings:
Fig. 1 shows the structural representation according to the Lu Musi alkene low temperature separation process system of prior art; And
Fig. 2 shows the structural representation according to the olefin separation system in a kind of preferred embodiment of the present invention.
Embodiment
Need to prove, in the situation that do not conflict, embodiment and the feature among the embodiment among the application can make up mutually.Describe below with reference to the accompanying drawings and in conjunction with the embodiments the present invention in detail.
As shown in Figure 2, in a kind of typical embodiment of the present invention, a kind of olefin separation system is provided, this olefin separation system comprises the demethanizing unit, the demethanizing unit comprises just demethanizing tower 11, pressure swing adsorption system 12 and inferior demethanizing tower 17, is provided with the first gaseous stream pipeline between the import of the tower top outlet of first demethanizing tower 11 and pressure swing adsorption system 12; Be provided with rich hydrocarbon stream pipeline between the import of the tower top outlet of pressure swing adsorption system 12 and time demethanizing tower 17.
Olefin separation system with said structure, adopt just demethanizing tower 11, pressure swing adsorption system 12 and time demethanizing tower 17 are used in conjunction with, through after the sub-zero treatment of first demethanizing tower 11, rationally control just cat head working temperature and the pressure of demethanizing tower 11 is carried out non-clear cutting or clear cutting to gas to be separated, obtain after gas to be separated is processed through first demethanizing tower 11 not that the first gaseous stream of carbon containing three and carbon three above hydro carbons further is divided into rich hydrocarbon stream and hydrogen rich stream with the first gaseous stream effectively through after the absorption of pressure swing adsorption system 12, increased the CH in the rich hydrocarbon stream that enters time demethanizing tower 17
4/ H
2Molecule ratio, and then increased inferior demethanizing tower 17 CH of cat head place
4Dividing potential drop, therefore only the temperature of inferior demethanizing tower 17 need to be reduced to higher dew point and can isolate CH
4And H
2, the required energy consumption of cooling has reduced in sepn process so; And, because the increasing so that only need the lower cold just can be so that only have few in the second gaseous stream that inferior demethanizing tower 17 cats head separate or even do not have ethene of dew point, so reduced the loss of ethene; Simultaneously, the realization of above-mentioned technique effect can greatly reduce the investment of separation of olefins.
As shown in Figure 2, in a kind of preferred embodiment of the present invention, above-mentioned demethanizing unit also comprises the first compressor 131, the first ice chest 141, First Heat Exchanger 151, the second interchanger 152, the first cryogen chiller 161 and decompressor 18, has the second gaseous stream pipeline between the import of the tower top outlet of inferior demethanizing tower 17 and decompressor 18; The first compressor 131 is arranged on the rich hydrocarbon stream pipeline; The first ice chest 141 has stream and the interior stream of rich hydrocarbon stream the first ice chest in the first gaseous stream the first ice chest, and stream is serially connected in the first gaseous stream pipeline in the first gaseous stream the first ice chest; Stream is serially connected in the rich hydrocarbon stream pipeline between the import of the first compressor 131 and inferior demethanizing tower 17 in rich hydrocarbon stream the first ice chest; First Heat Exchanger 151 has in the rich hydrocarbon stream First Heat Exchanger stream in the stream and second liquid phase logistics First Heat Exchanger, and stream is serially connected in the rich hydrocarbon stream pipeline between the import of stream and inferior demethanizing tower 17 in rich hydrocarbon stream the first ice chest in the rich hydrocarbon stream First Heat Exchanger; Stream is connected with the tower bottom outlet of time demethanizing tower 17 in the second liquid phase logistics First Heat Exchanger, and heat exchange is carried out in rich hydrocarbon stream and second liquid phase logistics in First Heat Exchanger 151; The second interchanger 152 has in rich hydrocarbon stream the second interchanger stream in the stream and the second gaseous stream the second interchanger, and stream is serially connected in the rich hydrocarbon stream pipeline between the import of stream and inferior demethanizing tower 17 in the rich hydrocarbon stream First Heat Exchanger in rich hydrocarbon stream the second interchanger; Stream is connected with the outlet of decompressor 18 in the second gaseous stream the second interchanger, and rich hydrocarbon stream and the second gaseous stream carry out heat exchange in the second interchanger 152; The first cryogen chiller 161 is arranged between the import of the interior stream of rich hydrocarbon stream the second interchanger and time demethanizing tower 17.
In above-mentioned olefin separation system, reduce from the rich hydrocarbon stream of pressure swing adsorption system 12 temperature after carrying out heat exchange with the first gaseous stream from first demethanizing tower 11 in the first ice chest 141 after the 131 compression superchargings of the first compressor, temperature reduces after the second gaseous stream heat exchange that temperature sharply descends after then entering First Heat Exchanger 151 and heat-eliminating medium and carrying out continuing to enter the second interchanger 152 and expand through decompressor 18 after the again heat exchange; Subsequently rich hydrocarbon stream continue to enter the first cryogen chiller 161 and cryogen carry out heat exchange further cooling enter time demethanizing tower 17 with lower temperature and again carry out low temperature separation process, a series of heat exchange that rich hydrocarbon stream carries out are reduced temperature significantly, have further reduced the energy consumption of low temperature separation process in the inferior demethanizing tower 17.
As shown in Figure 2, the demethanizing unit comprises also that the first reboiler 191 and the second reboiler 192, the first reboilers 191 are connected with the first tower bottom outlet of first demethanizing tower 11 and links to each other with first demethanizing tower 11 tower reactors and forms the first circulation line; The second reboiler 192 is connected with the second tower bottom outlet of first demethanizing tower 11 and links to each other with first demethanizing tower 11 tower reactors and forms the second circulation line.
The first liquid phase stream that part is flowed out by the first tower bottom outlet of first demethanizing tower 11 and the second tower bottom outlet becomes gas phase and returns in the tower reactor of first demethanizing tower 11 after the first reboiler 191 or 192 heating of the second reboiler, and with the reverse contact mass transfer of the liquid phase stream that is stayed by cat head, reach the purpose of cryogenic rectification.
As shown in Figure 2, olefin separation system also comprises the ethylene distillation unit, the ethylene distillation unit comprises hydrogenation acetylene removal reactor 21 and ethylene rectification tower 22, hydrogenation acetylene removal reactor 21 has hydrogen gas stream import, hydrocarbon material import and ethylene product outlet, has the hydrogen rich stream pipeline between the hydrogen rich stream outlet of hydrogen gas stream import and pressure swing adsorption system 12; Has second liquid phase logistics pipeline between the tower bottom outlet of hydrocarbon material import and time demethanizing tower 17; Ethylene rectification tower 22 is connected with the ethylene product outlet.
Carry out after the heat exchange temperature rising and then enter hydrogenation acetylene removal reactor 21 carrying out hydrogenation reaction as the heat-eliminating medium of First Heat Exchanger 151 and the first gaseous stream take the C2 hydrocarbon class as main second liquid phase logistics by inferior demethanizing tower 17 is isolated, hydrogen derives from pressure swing adsorption system 12 isolated hydrogen rich streams and/or external hydrogen in hydrogenation acetylene removal reactor 21, and the material that obtains after hydrogenation is finished forms ethylene product after ethylene rectification tower 22 rectifying.Isolated hydrogen is rationally utilized, reduced the external hydrogen gas consumption of acetylene hydrogenation, saved the acetylene hydrogenation cost.
As shown in Figure 2, olefin separation system also comprises deethanizing unit and propylene rectification cell, the deethanizing unit comprises deethanizing column 31, deethanizing column 31 has the first liquid phase stream import and deethanizer overhead stream outlet, has the first liquid phase stream pipeline between the 3rd tower bottom outlet of the first liquid phase stream import and first demethanizing tower 11; Has hydro carbons acetylene removal Location Detection of Medium Transportation Pipeline between the hydrocarbon material import of deethanizer overhead stream outlet and hydrogenation acetylene removal reactor 21; The propylene rectification cell comprises propylene rectification tower 41 and return tank of top of the tower 42, and propylene rectification tower 41 has the 3rd liquid phase stream import and the outlet of cat head propylene, has the 3rd liquid phase stream pipeline between the tower bottom outlet of the 3rd liquid phase stream import and deethanizing column 31; Return tank of top of the tower 42 is connected with the outlet of the cat head propylene of propylene rectification tower 41 and consists of the 3rd circulation line with propylene rectification tower 41, and the first reboiler 191 or the second reboiler 192 have propylene import and the propylene outlet that is connected with the 3rd circulation line.
In above-mentioned olefin separation system, the ethene gas mixture take ethene as main component of just demethanizing tower 11 isolated the first liquid phase streams formation after deethanizing column 31 is processed can be used as the charging of hydrogenation acetylene removal reactor 21, to remove a small amount of alkynes type organic wherein; Simultaneously because time demethanizing tower 17 isolated second liquid phase logistics nearly all are C-2-fraction, so this burst logistics need not to enter deethanizing column 31, only having the first liquid phase stream that first demethanizing tower 11 contains carbon two and carbon three components to enter deethanizing column 31 separates, thereby greatly alleviated the load of deethanizing column 31, be conducive to reduce energy consumption and the investment cost of deethanizing column 31; Deethanizing column 31 is isolated to be entered the first reboiler 191 that cat head propylene product that propylene rectification tower 41 carries out obtaining after the rectifying enters the demethanizing unit or the second reboiler 192 and the first liquid phase stream and carries out lowering the temperature after the heat exchange take propylene as the 3rd main liquid phase streams, the heat of while cat head propylene product is become gas phase by rear the first liquid phase stream of the first liquid phase stream absorption and returns in the tower reactor of first demethanizing tower 11, and with the reverse contact mass transfer of the liquid phase stream that is stayed by cat head, the purpose that reaches cryogenic rectification utilizes the alternative hot steam of cat head propylene product and the first liquid phase stream to carry out heat exchange like this in the first reboiler 191 or the second reboiler 192, take full advantage of remaining heat and cold in the system, reduced the consumption of hot steam and water, save energy consumption and water resources, saved the use of water coolant and the facility investment of overhead water cooler.Cooled cat head propylene product obtains qualified propylene product after removing wherein a small amount of methyl alcohol, oxide compound and other impurity through devices such as product protection beds.
For heat exchange and just demethanizing tower 11 operations (such as service temperature) of adjusting of effectively controlling the cat head propylene product, as shown in Figure 2, also be provided with control valve 43 on the 3rd circulation line between propylene rectification tower 41 and the return tank of top of the tower 42, control valve 43 and the first reboiler 191 or the second reboiler 192 are arranged in parallel, in order to the flow through amount of propylene product of the first reboiler 191 or the second reboiler 192 of adjusting.
As shown in Figure 2, olefin separation system also comprises the second ice chest 142, the second ice chest 142 has the second gas phase liquid and flows stream in the second ice chest, and the second gas phase liquid flows the interior stream of the second ice chest and is connected with the interior stream of the second gaseous stream second interchanger of the second interchanger 152; Have two article of the 4th liquid phase stream pipeline between propylene rectification tower 41 and the second ice chest 142, one article of the 4th liquid phase stream pipeline wherein is connected with gas ductwork after passing the second ice chest 142; Another article the 4th liquid phase stream pipeline passes to extend to first demethanizing tower 11 behind the second ice chest 142 and is connected, olefin separation system comprises also that the second cryogen chiller 162, the second cryogen chillers 162 are arranged on the second ice chest 142 and just on the 4th liquid phase stream pipeline between the demethanizing tower 11.
In above-mentioned olefin separation system, cooled off through decompressor 18 expansions by the second gaseous stream from inferior demethanizing tower 17, in the second ice chest 142, cool off the 4th liquid phase stream as heat-eliminating medium after the cooling of the rich hydrocarbon stream that passes through in the second interchanger 152, on the one hand the second gaseous stream temperature after heat exchange rises to some extent and transfers out the olefin separation system use that acts as a fuel, the cat head of demethanizing tower 11 partly was used for absorbing the just ethene of cat head place first gaseous stream of demethanizing tower 11 at the beginning of cooled part the 4th liquid phase stream entered after the second cryogen chiller 162 further Quench more on the other hand, and another part the 4th liquid phase stream can be sent into gas ductwork and use as combustion gas.
As shown in Figure 2, olefin separation system also comprises depropanizing unit and debutylize unit, the depropanizing unit comprises depropanizing tower 51, moisture eliminator 52, the second compressor 132 and the 3rd cryogen chiller 163, the tower top outlet of depropanizing tower 51 with just be provided with just degassed phase logistics pipeline between the demethanizing tower 11; Moisture eliminator 52 is connected with the import of depropanizing tower 51 and carries unstripped gas to be separated to depropanizing tower 51; The second compressor 132 is arranged on depropanizing tower 51 and the first first degassed phase logistics pipeline between the demethanizing tower 11; The 3rd cryogen chiller 163 is arranged on the second compressor 132 and the first first degassed phase logistics pipeline between the demethanizing tower 11, and the first ice chest 141 has the first degassed phase logistics import and the first degassed phase logistics that are connected with first degassed phase logistics pipeline between the 3rd cryogen chiller 163 with the second compressor 132 and exports; The debutylize unit comprises debutanizing tower 61 and overhead condenser 62, is provided with between debutanizing tower 61 and the depropanizing tower 51 just to take off the liquid phase stream pipeline; Overhead condenser 62 has the import that is connected with the tower top outlet of debutanizing tower 61 and the outlet of flowing out for the condensation after product.
Preferably separation for gases such as the oil gas that satisfies complicated component, oil refinery dry gas, methanol-to-olefins gas products, in above-mentioned olefin separation system, be provided with depropanizing unit and debutylize unit, utilize depropanizing tower 51 that carbon four hydro carbons in the gas to be separated and carbon four above hydro carbons and carbon three hydro carbons and carbon three following hydro carbons are separated to form and contain the first degassed phase logistics of carbon three hydro carbons and carbon three following hydro carbons and contain carbon four hydro carbons and the first liquid phase stream that takes off of carbon four above hydro carbons.First degassed phase logistics wherein enters above-mentioned demethanizing unit and carries out separating treatment, and, before first degassed phase logistics is entering just demethanizing tower 11 successively in the first ice chest 141 with just demethanizing tower 11 isolated the first gaseous stream heat exchange, in the 3rd cryogen chiller 163 with after the cryogen heat exchange, lowered the temperature significantly, therefore, reduced the energy consumption that first demethanizing tower 11 carries out low temperature separation process.Wherein first takes off liquid phase stream and enters debutanizing tower 61 and separate and obtain carbon four-product and carbon five products, realized fully careful separation of unstripped gas is conducive to the utilization of unstripped gas.
The typical embodiment of another kind according to the present invention, a kind of alkene separation method also is provided, this alkene separation method comprises that separating main component is the process of the gas mixture of hydrogen, carbon three hydro carbons and carbon three following hydro carbons, this process comprises just demethanizing process, pressure-swing adsorption process and inferior demethanizing process, make gas mixture just carry out the first gaseous stream and the first liquid phase stream that non-clear cutting obtains being separated from each other in the demethanizing process, the first gaseous stream comprises hydrogen, methane and C2 hydrocarbon class, and the first liquid phase stream comprises C2 hydrocarbon class and carbon three hydro carbons; Make the first gaseous stream carry out rich hydrocarbon stream and hydrogen rich stream that pressure-variable adsorption obtains being separated from each other; Make rich hydrocarbon stream in inferior demethanizing process, carry out clear the second gaseous stream and the second liquid phase logistics of cutting to get.
Above-mentioned alkene separation method adopts non-clear cutting method to substitute clear cutting method commonly used at present at the cat head place of first demethanizing tower 11, has reduced cold load and thermal load required in the first demethanizing sepn process and has namely reduced energy consumption.Take first demethanizing tower 11 and time demethanizing tower 17 as example illustrates above-mentioned alkene separation method, so-called non-clear cutting is that the content to the C2 hydrocarbon class of the cat head component of first demethanizing tower 11 does not need to reach below 5% of clear cutting, but a part of C2 hydrocarbon class of first demethanizing tower 11 is separated as the first gaseous stream with the light constituent of cat head, and another part C2 hydrocarbon class and carbon three hydro carbons are separated at the bottom of the tower as the first liquid phase stream, do not contain like this carbon three and carbon three above hydro carbons in tower the first gaseous stream, thereby the volume of carbon three hydro carbons of loss accounts for below 0.01% of carbon three cumulative volumes in first demethanizing tower 11, and those skilled in the art can be according to the temperature and pressure of the suitable non-clear cutting of the tolerable temperature of device and pressure selection.The pressure swing adsorption process that above-mentioned alkene separation method adopts obtains rich hydrocarbon stream and hydrogen rich stream with the hydrogen effective separation of the hydro carbons in the first gaseous stream, wherein can be used for sorbent material of the present invention and includes but not limited to acticarbon, activated alumina etc.CH in the isolated rich hydrocarbon stream of pressure-variable adsorption
4/ H
2Molecule ratio is larger, and then has increased inferior demethanizing tower 17 CH of cat head place
4Dividing potential drop, therefore only the temperature of inferior demethanizing tower 17 need to be reduced to higher dew point and can isolate CH
4And H
2, the required energy consumption of cooling has reduced in sepn process so; And, because increasing so that only have few in the second gaseous stream that inferior demethanizing tower 17 cats head separate or even do not have ethene of dew point do not have hydrogen and methane in the second liquid phase logistics, therefore reduced the loss of ethene; Simultaneously, the realization of above-mentioned technique effect can greatly reduce the investment of separation of olefins.
In the another kind of preferred embodiment of the present invention, contain volume percent in the first gaseous stream that first demethanizing process obtains and be 15～90% C2 hydrocarbon class; Pressure-swing adsorption process, the volume percent of hydrogen is 85～99.99% in the hydrogen rich stream, the volume of hydrogen accounts for 40～70% of hydrogen cumulative volume in the first gaseous stream in the hydrogen rich stream; The volume content of ethene≤2% in inferior demethanizing process the second gaseous stream.Those skilled in the art can be according to the composition of handled unstripped gas and the used rational pressure and temperature of Array selection, the result of non-clear cutting, pressure-variable adsorption and the clear cutting that obtains envisioning is conducive to the control of the product that whole alkene separation method obtains.
Be that the process of the gas mixture of hydrogen, carbon three hydro carbons and carbon three following hydro carbons also comprises and makes gas mixture successively through carrying out heat exchange, carry out carrying out first demethanizing process after the heat exchange with cryogen with the first gaseous stream that is obtained by non-clear cutting in order rationally to use heat and the cold that produces in the sepn process, above-mentioned separation main component; Make rich hydrocarbon stream successively through processed compressed, with by isolated the first gaseous stream of first demethanizing process carry out heat exchange, with by the isolated second liquid phase logistics of inferior demethanizing process carry out heat exchange, with carry out the laggard places demethanizing of heat exchange process by isolated the second gaseous stream of inferior demethanizing process; Make by isolated the second gaseous stream of inferior demethanizing and rich hydrocarbon stream and carry out the cooling of expanding before the heat exchange; Part the first liquid phase stream is separated by reheating boiling by first demethanizing repeat described just demethanizing process.
In olefin separation process, the first gaseous stream that gas mixture to be separated and the first isolated temperature of demethanizing process is lower carries out heat exchange, rich hydrocarbon stream and the first gas gas-phase objects, second liquid phase thing and the second gaseous stream and carries out heat exchange, all be to utilize the heat exchange that the difference of heat is carried out in the separating step in the sepn process, therefore can reduce the input of external heat-eliminating medium, save separation costs.
In another preferred embodiment of the present invention, above-mentioned alkene separation method also comprises makes unstripped gas to be separated carry out progressively compressing after depropanizing is processed the separation temperature that obtains to suit; Make part the first liquid phase stream carry out the deethanizing processing and obtain deethanizer overhead stream and the 3rd liquid phase stream; Make deethanizer overhead stream and rich hydrocarbon stream and/or external hydrogen carry out hydrogenation reaction and carry out acetylene removal and obtain the mixture of ethylene that contains after the acetylene removal, will contain again mixture of ethylene rectifying and obtain ethylene product; The 3rd liquid phase stream rectifying is obtained the 4th gaseous stream and the mutually logistics of the 4th liquid phase, the 4th gaseous stream and part the first liquid phase stream heat exchange are processed by the further removal of impurity formed propylene product; After making the 4th liquid phase stream and the second gaseous stream carry out heat exchange, the 4th liquid phase stream after a part of heat exchange and cryogen are further carried out heat exchange be used for absorbing ethene in the gaseous substance that first demethanizing process wish forms described the first gaseous stream, the 4th liquid phase stream after another part heat exchange is carried as combustion gas.It is in order to obtain the gas mixture of suitable separation temperature that unstripped gas to be separated is carried out recompressing after depropanizing is processed, because separation temperature raises along with pressure rise, so raw gas pressure infinitely can not be raise, otherwise energy consumption also sharply raises thereupon, so between general exert pressure to 2.0 with gas mixture～4.0MPA.
Can be used for unstripped gas to be separated of the present invention and include but not limited to oil gas, oil refinery dry gas, methanol-to-olefins gas product, the utilization sources of hydrogen that isolated hydrogen rich stream reacts as acetylene hydrogenation from unstripped gas, reduce the consumption of external hydrogen, saved the synthetic cost of ethene.And, not carbon containing three and carbon three above hydro carbons in the first gaseous stream that the just non-clear cutting of demethanizing process forms, therefore only having the first liquid phase stream need to carry out the deethanizing processing gets final product, so that the energy consumption that deethanizing is processed and load will reduce, and then investment and the running cost of deethanizing device can correspondingly be reduced.
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various modifications and variations.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (12)
1. olefin separation system, described olefin separation system comprises the demethanizing unit, it is characterized in that, described demethanizing unit comprises just demethanizing tower (11), pressure swing adsorption system (12) and inferior demethanizing tower (17),
Be provided with the first gaseous stream pipeline between the tower top outlet of described just demethanizing tower (11) and the import of described pressure swing adsorption system (12);
Be provided with rich hydrocarbon stream pipeline between the import of the tower top outlet of described pressure swing adsorption system (12) and described demethanizing tower (17).
2. olefin separation system according to claim 1, it is characterized in that, described demethanizing unit also comprises the first compressor (131), the first ice chest (141), First Heat Exchanger (151), the second interchanger (152), the first cryogen chiller (161) and decompressor (18)
Has the second gaseous stream pipeline between the import of the tower top outlet of described demethanizing tower (17) and described decompressor (18);
Described the first compressor (131) is arranged on the described rich hydrocarbon stream pipeline;
Described the first ice chest (141) has:
Stream in the first gaseous stream the first ice chest is serially connected in described the first gaseous stream pipeline;
Stream in rich hydrocarbon stream the first ice chest is serially connected in the rich hydrocarbon stream pipeline between the import of described the first compressor (131) and described demethanizing tower (17);
Described First Heat Exchanger (151) has:
Stream in the rich hydrocarbon stream First Heat Exchanger is serially connected in the described rich hydrocarbon stream pipeline between the import of stream and described demethanizing tower (17) in described rich hydrocarbon stream the first ice chest;
Stream in the second liquid phase logistics First Heat Exchanger is connected with the tower bottom outlet of described demethanizing tower (17), and described rich hydrocarbon stream and described second liquid phase logistics are carried out heat exchange in described First Heat Exchanger (151);
Described the second interchanger (152) has:
Stream in rich hydrocarbon stream the second interchanger is serially connected in the described rich hydrocarbon stream pipeline between the import of stream and described demethanizing tower (17) in the rich hydrocarbon stream First Heat Exchanger;
Stream in the second gaseous stream the second interchanger is connected with the outlet of described decompressor (18), and described rich hydrocarbon stream and described the second gaseous stream carry out heat exchange in described the second interchanger (152);
Described the first cryogen chiller (161) is arranged between the import of the interior stream of described rich hydrocarbon stream the second interchanger and described demethanizing tower (17).
3. olefin separation system according to claim 2 is characterized in that, described demethanizing unit also comprises:
The first reboiler (191), formation the first circulation line is connected with the first tower bottom outlet of described just demethanizing tower (11) and links to each other with the described just tower reactor of demethanizing tower (11);
The second reboiler (192), formation the second circulation line is connected with the second tower bottom outlet of described just demethanizing tower (11) and links to each other with the described just tower reactor of demethanizing tower (11).
4. olefin separation system according to claim 3 is characterized in that, described olefin separation system also comprises the ethylene distillation unit, and described ethylene distillation unit comprises:
Hydrogenation acetylene removal reactor (21) has:
The hydrogen gas stream import, and have the hydrogen rich stream pipeline between the outlet of the hydrogen rich stream of described pressure swing adsorption system (12);
The hydrocarbon material import, and have second liquid phase logistics pipeline between the tower bottom outlet of described demethanizing tower (17);
The ethylene product outlet;
Ethylene rectification tower (22) is connected with described ethylene product outlet.
5. olefin separation system according to claim 4 is characterized in that, described olefin separation system also comprises deethanizing unit and propylene rectification cell,
Described deethanizing unit comprises deethanizing column (31), and described deethanizing column (31) has:
The first liquid phase stream import, and have the first liquid phase stream pipeline between the 3rd tower bottom outlet of described just demethanizing tower (11);
The deethanizer overhead stream outlet, and have hydro carbons acetylene removal Location Detection of Medium Transportation Pipeline between the hydrocarbon material import of described hydrogenation acetylene removal reactor (21);
Described propylene rectification cell comprises:
Propylene rectification tower (41) has:
The 3rd liquid phase stream import, and have the 3rd liquid phase stream pipeline between the tower bottom outlet of described deethanizing column (31);
The outlet of cat head propylene;
Return tank of top of the tower (42), be connected with the outlet of the cat head propylene of described propylene rectification tower (41) and consist of the 3rd circulation line with described propylene rectification tower (41), described the first reboiler (191) or the second reboiler (192) have propylene import and the propylene outlet that is connected with described the 3rd circulation line.
6. olefin separation system according to claim 5, it is characterized in that, also be provided with control valve (43) on described the 3rd circulation line between described propylene rectification tower (41) and the described return tank of top of the tower (42), described control valve (43) is arranged in parallel with described the first reboiler (191) or the second reboiler (192).
7. olefin separation system according to claim 5 is characterized in that, described olefin separation system also comprises the second ice chest (142),
Described the second ice chest (142) has the second gas phase liquid and flows stream in the second ice chest, and described the second gas phase liquid flows the interior stream of the second ice chest and is connected with the interior stream of the second gaseous stream second interchanger of described the second interchanger (152);
Have two article of the 4th liquid phase stream pipeline between described propylene rectification tower (41) and described the second ice chest (142),
One article of the 4th liquid phase stream pipeline wherein is connected with gas ductwork after passing described the second ice chest (142);
Another article the 4th liquid phase stream pipeline passes to extend to behind described the second ice chest (142) with described just demethanizing tower (11) and is connected, described olefin separation system also comprises the second cryogen chiller (162), and described the second cryogen chiller (162) is arranged on described the second ice chest (142) and described just the 4th liquid phase stream pipeline between the demethanizing tower (11).
8. olefin separation system according to claim 7 is characterized in that, described olefin separation system also comprises:
The depropanizing unit comprises:
Depropanizing tower (51), the tower top outlet of described depropanizing tower (51) and the described just degassed phase logistics pipeline that just is provided with between the demethanizing tower (11);
Moisture eliminator (52) is connected with the import of described depropanizing tower (51) and carries unstripped gas to be separated to described depropanizing tower (51);
The second compressor (132) is arranged on the described just degassed phase logistics pipeline between described depropanizing tower (51) and the described just demethanizing tower (11);
The 3rd cryogen chiller (163), be arranged on the described just degassed phase logistics pipeline between described the second compressor (132) and the described just demethanizing tower (11), described the first ice chest (141) has the first degassed phase logistics import and the first degassed phase logistics that are connected with described just degassed phase logistics pipeline between described the 3rd cryogen chiller (163) with described the second compressor (132) and exports;
The debutylize unit comprises:
Debutanizing tower (61), and be provided with the first liquid phase stream pipeline that takes off between the described depropanizing tower (51);
Overhead condenser (62) has the import that is connected with the tower top outlet of described debutanizing tower (61) and the outlet of flowing out for the condensation after product.
9. an alkene separation method is characterized in that, described alkene separation method comprises that separating main component is the process of the gas mixture of hydrogen, carbon three hydro carbons and carbon three following hydro carbons, and described process comprises:
First demethanizing process: make described gas mixture just carry out the first gaseous stream and the first liquid phase stream that non-clear cutting obtains being separated from each other in the demethanizing process described, described the first gaseous stream comprises hydrogen, methane and C2 hydrocarbon class, and described the first liquid phase stream comprises C2 hydrocarbon class and carbon three hydro carbons;
Pressure-swing adsorption process: make described the first gaseous stream carry out rich hydrocarbon stream and hydrogen rich stream that pressure-variable adsorption obtains being separated from each other;
Inferior demethanizing process: make described rich hydrocarbon stream in described demethanizing, carry out the second gaseous stream and second liquid phase logistics that clear cutting obtains being separated from each other.
10. alkene separation method according to claim 9 is characterized in that,
Contain volume percent in described the first gaseous stream that described just demethanizing process obtains and be 15～90% described C2 hydrocarbon class;
The volume percent of hydrogen is 85～99.99% in the described hydrogen rich stream that described pressure-swing adsorption process obtains, and the volume of hydrogen accounts for 40～70% of hydrogen cumulative volume in described the first gaseous stream in the described hydrogen rich stream;
The volume content of ethene≤2% in described the second gaseous stream that described demethanizing process obtains.
11. alkene separation method according to claim 9 is characterized in that, described process also comprises:
Make described gas mixture successively through carrying out heat exchange, carry out carrying out just demethanizing process after the heat exchange with cryogen with the first gaseous stream that is obtained by described non-clear cutting;
Make described rich hydrocarbon stream successively through processed compressed, with undertaken by described just isolated the first gaseous stream of demethanizing process heat exchange, with undertaken by the isolated second liquid phase logistics of described demethanizing heat exchange, with undertaken carrying out the demethanizing process described time after the heat exchange by isolated the second gaseous stream of described demethanizing;
Make by isolated the second gaseous stream of described demethanizing and described rich hydrocarbon stream and carry out the cooling of expanding before the heat exchange;
Described the first liquid phase stream of part is separated by reheating boiling by described just demethanizing process repeat described just demethanizing process.
12. alkene separation method according to claim 9 is characterized in that, described alkene separation method also comprises:
Make unstripped gas to be separated carry out compressing to form described gas mixture after depropanizing is processed;
Make described the first liquid phase stream of part carry out the deethanizing processing and obtain deethanizer overhead stream and the 3rd liquid phase stream;
Make described deethanizer overhead stream and described rich hydrocarbon stream and/or external hydrogen carry out the hydrogenation acetylene removal and react to such an extent that contain mixture of ethylene after the acetylene removal, contain mixture of ethylene rectifying and obtain ethylene product described again;
Described the 3rd liquid phase stream rectifying is obtained the 4th gaseous stream and the mutually logistics of the 4th liquid phase, described the first liquid phase stream heat exchange of described the 4th gaseous stream and part is processed by the further removal of impurity formed propylene product;
After making described the 4th liquid phase stream and described the second gaseous stream carry out heat exchange, described the 4th liquid phase stream after a part of heat exchange and cryogen are further carried out being used for after the heat exchange absorbing ethene in the gaseous substance that described just demethanizing process wish forms described the first gaseous stream, described the 4th liquid phase stream after another part heat exchange is carried as combustion gas.
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