CN103087772A - Device and method for separating refinery dry gas through oil absorption - Google Patents
Device and method for separating refinery dry gas through oil absorption Download PDFInfo
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Abstract
The invention discloses a device and a method for separating refinery dry gas through oil absorption. The device comprises a C4 absorption tower and a C4 desorption tower. A gasoline absorption tower is arranged after the C4 absorption tower. A top outlet of the C4 absorption tower is connected to the lower part of the gasoline absorption tower. The bottom and the top of the gasoline absorption tower respectively communicate with the outside world. The method comprises the steps that: catalytic dry gas is subjected to compression and cooling, and is delivered into the C4 absorption tower and is absorbed by using a C4 absorption agent; the tower kettle material of the C4 absorption tower is delivered into the C4 desorption tower; the tower kettle material of the C4 desorption tower is delivered back to the C4 absorption tower; tower top gas of the C4 absorption tower is delivered into the gasoline absorption tower and is absorbed by a gasoline absorption agent. According to the invention, no equipment such as ethylene cooling machine, expansion machine, or cold box is needed, such that investment and energy consumption are reduced.
Description
Technical field
The present invention relates to the organic chemical industry field, say further, relate to a kind of device and method that adopts oily absorption extraction oil refinery dry gas.
Background technology
Plant catalytic dry gas derives from catalytic cracking process, and the ethylene content in dry gas is about 12～20 % by mole usually, and ethane content is about 15～24 % by mole, also contains alkene, the alkane such as propylene, propane, butane.Plant catalytic dry gas is burnt mainly as fuel at present, and utility value is lower.If alkene, alkane in catalysis drying gas are reclaimed, be sent to ethylene plant as the raw material of producing ethene, can save a large amount of cracking stock oil, production cost of ethylene is significantly descended, thereby make enterprise obtain economic benefit preferably.
The method that reclaims at present ethene from plant catalytic dry gas mainly contains separation by deep refrigeration, middle cold oil absorption process, Separation by Complexation method, pressure swing adsorption process etc., and the whole bag of tricks differs from one another.The separation by deep refrigeration technical maturity, Recovery rate of ethylene is high, but investment is large, is used for rare ethylene recovery energy consumption higher; The Separation by Complexation method, Recovery rate of ethylene is higher, but strict to the impurity in raw material, and the pre-treatment expense is higher, needs special complexes absorption; Pressure swing adsorption process is simple to operate, and energy consumption is lower, but product purity is low, and Recovery rate of ethylene is low, and floor space is large.
Middle cold oil absorption process is mainly to utilize absorption agent to come separating gas mixture to the different solubility of each component in gas, the general absorption agent that first utilizes absorbs C2 and the above heavy constituent of C2, isolate the non-condensable gasess such as methane, hydrogen, then use each component in the agent of rectification method separate absorbent.The method has the characteristics such as small scale, strong adaptability, investment cost are low, can be used for from splitting gas the separation of olefins, reclaims the technique such as lighter hydrocarbons from Sweet natural gas.Middle cold oil absorption process can be used for the recovery of low-concentration ethane in catalytic cracked dry gas, but in traditional routine, the loss of cold oil absorption technique absorption agent is large, Recovery rate of ethylene is lower, and the rate of recovery only has 85% left and right usually.
CN 1640992 has proposed a kind ofly to be applicable to reclaim liquefied gas from associated gas or Sweet natural gas to install self-produced stable light hydrocarbon as the refrigeration oil absorption process of absorption agent, and the C3 yield recovery process of having relatively high expectations.Adopt the absorption process of this refrigeration oil, can obtain higher light hydrocarbon recovery rate, and technique be simple with less absorption agent, reduce energy consumption, increase economic efficiency.But the method is only applicable to reclaim liquefied gas from associated gas or Sweet natural gas, can not reclaim the C2 cut, can't be used for the recovery of plant catalytic dry gas.
CN 1414067 proposed a kind of after the shallow cold technique of Sweet natural gas grafting oil absorption technique, thereby improve the method for light hydrocarbon recovery rate.The method enters gains after the shallow cold technique of Sweet natural gas to carry out gas-liquid separation in the secondary triphase separator, makes gas enter the bottom on absorption tower and absorption agent and carries out the gas-liquid exchange and obtain reclaiming after C3, C4 component; Enter after lighter hydrocarbons in liquid and secondary triphase separator mix and deviate from methane and ethane in desorption tower, the desorption liquid of formation is entered reclaim after desorption tower cuts out C3, C4 component.The method can improve the light hydrocarbon recovery rate in Sweet natural gas, increases lighter hydrocarbons output.But the method is only applicable to reclaim lighter hydrocarbons from Sweet natural gas, and is not suitable for the recovery of plant catalytic dry gas.
US 5502971 discloses a kind of C2 of recovery and has reached the more low-pressure low-temperature technique of heavy hydrocarbons, is applicable to the recovery of oil refinery dry gas.This technique has been cancelled traditional high pressure scheme, changes and adopts low-voltage technology, and recovered temperature just can remain on the temperature that the nitric acid resin generates like this, has avoided dangerous Potential feasibility, can also keep higher olefin yields simultaneously.Although this process using the low pressure scheme, temperature is still low reaches-100 ℃, still belongs to a kind of of deep cooling process for separating, therefore investment is larger, energy consumption is higher.
US 6308532 has proposed a kind of technique that reclaims ethene and propylene from oil refinery dry gas, this technique comprises from absorbing tower reactor extracts C3, C4, C5, C6 liquid out and part tower bottoms phase materials is circulated to tower top, thereby keep the freezing temp of overhead condenser to be not less than-95 ℃, be rich in propylene or ethylene-propylene zone extraction gas phase side line simultaneously in the absorption tower.Although this technique is unlikely too low to tower top with the maintenance tower top temperature with part tower reactor Matter Transfer, tower top temperature is still low reaches-95 ℃, still belongs to a kind of of deep cooling process for separating, and therefore investment is larger, and energy consumption is higher.
CN 101063048A discloses the method for cold oil absorption process separating plant catalytic dry gas in a kind of the employing, this technique by compression, remove the steps such as sour gas, drying and purification, absorption, desorb, cold recovery and rough segmentation and form, it is with low cost that the method has absorption agent, loses the advantages such as low.But still need in this technique dry gas to be cooled to-30 ℃～-40 ℃, cold separating technology in belonging to, therefore investment is larger, and energy consumption is higher.
CN101812322A discloses a kind of method that adopts the oil-absorption process separating plant catalytic dry gas, and as absorption agent, keep absorption temperature is 5-15 ℃ to the method with C-4-fraction, and adopts decompressor and ice chest to reclaim cold.The method significantly improves the rate of recovery of alkene and alkane, has reduced simultaneously internal circulating load and the loss amount of absorption agent, has reduced energy consumption, but needs the equipment such as decompressor and ice chest, invests higher.
CN101759518A discloses a kind of method of oily absorption extraction plant catalytic dry gas, the method of this invention uses C-4-fraction as absorption agent, in absorption compression, cooled catalysis drying gas, the C2 cut reaches more heavy component in main absorption tower, the tower reactor logistics on main absorption tower is delivered to desorption tower and is processed, the C2 concentrated gas that is recycled by the desorption tower tower top.Use method of the present invention, because absorption temperature is high, do not need ethene, propylene refrigeration compressor and decompressor, have that energy consumption is low, a less investment, the characteristics such as simple to operate, but carbon four absorption agents losses are larger in absorption process.
In sum, all there is the problem that investment is large, energy consumption is high and the absorption agent loss is large in the existing technique that reclaims ethene and propylene from oil refinery dry gas.
Summary of the invention
Have for solving the technique that reclaims ethene and propylene from oil refinery dry gas that exists in prior art the problem that investment is large, energy consumption is high and the absorption agent loss is large, the invention provides a kind of device and method that adopts oily absorption extraction oil refinery dry gas.As absorption agent, reclaim ethene in oil refinery dry gas, propylene with C-4-fraction and gasoline fraction, keeping absorption temperature is more than 10 degree, does not need the equipment such as ethylene refrigeration machine, decompressor, ice chest, has reduced investment and energy consumption.
One of purpose of the present invention is to provide a kind of device that adopts oily absorption extraction oil refinery dry gas.
Comprise carbon four absorption towers and carbon four desorption towers, carbon four bottoms, absorption tower connect the catalysis drying gas inlet line, be provided with compressor and water cooler on the catalysis drying gas inlet line, carbon four bottoms, absorption tower connect carbon four desorption towers, carbon four connection carbon four tops, absorption tower, desorption tower bottom, carbon four desorption tower top connections out-of-bounds
Behind described carbon four absorption towers, naphtha scrubber is set, carbon four absorption tower top exits connect naphtha scrubber bottoms, and described naphtha scrubber bottom and top are communicated with out-of-bounds respectively.
Two of purpose of the present invention is to provide a kind of method that adopts oily absorption extraction oil refinery dry gas.
Comprise:
Catalysis drying gas is compressed to be entered carbon four absorption towers after cooling and is absorbed by carbon four absorption agents, and carbon four absorption tower tower reactor materials enter carbon four desorption towers, and carbon four desorption tower tower reactor materials return to carbon four absorption towers; Carbon four absorption tower overhead gas enter naphtha scrubber and are absorbed by the gasoline absorption agent.
Specifically comprise the following steps:
(1) compression: will bring up to 4.0～6.0MPa from the pressure of the catalysis drying gas of plant catalytic cracking unit (FCC);
(2) cooling: the catalysis drying gas after compressing is cooled to 5 ℃～20 ℃;
(3) carbon four absorbs: adopt C-4-fraction as absorption agent, described absorption agent enters carbon four absorption towers from top of tower, in the absorption catalysis drying gas, the C2 cut reaches more heavy component, and the overhead stream on absorption tower enters the gasoline absorption system of back, and carbon four desorption towers are delivered in the tower reactor logistics on absorption tower;
(4) carbon four desorbs: the tower reactor logistics on described carbon four absorption towers enters carbon four desorption towers, the C2 concentrated gas that tower top is recycled, and tower reactor obtains the C-4-fraction absorption agent after desorb, returns to carbon four absorption towers after cooling and recycles;
(5) gasoline absorbs: the top gaseous phase logistics on described carbon four absorption towers enters in naphtha scrubber, and the gasoline absorption agent enters from tower top, absorbs carbon four absorption agents of carrying secretly in gaseous stream, naphtha scrubber top tail gas discharger, tower reactor logistics carrying device.
Pressure from the catalysis drying gas of plant catalytic cracking unit in step (1) generally is about 0.7～0.9MPa, generally need to improve step by step pressure to 4.0～6.0MPa.In the method for the invention, to the compression hop count there is no particular limitation, preferably adopt three sections compressions.
In described step (2), the catalysis drying gas after preferably compressing is cooled to 5 ℃～20 ℃.In concrete enforcement of the present invention, refrigeration agent can be selected the cold water of 5 ℃ of left and right, is provided by lithium-bromide absorption-type refrigerating machine.What lithium bromide refrigerator adopted is absorption refrigeration technology, take the waste hot steam of refinery as thermal source, has advantages of that energy consumption is low.
In described step (3), described carbon four absorption agents can adopt carbon four or other C-4-fraction after the mixed c 4 of refinery or ether, are preferably the C-4-fraction of 2-butylene of 1-butylene, the 5～70%wt of the normal butane that comprises 10～40%wt, 3～15%wt; The C-4-fraction of cis-2-butene that more preferably comprises Trans-2-butene, the 25～35%wt of 1-butylene, the 20～35%wt of normal butane, the 5～10%wt of 20～35%wt; When concrete enforcement of the present invention, the mixed c 4 fraction of preferred refinery, its chief component is generally carbon 3 0.5% (wt%, as follows), normal butane 25%, butene-1 6%, butene-2 62%, carbon 5 6.5%.
In described step (3), the number of theoretical plate on described carbon four absorption towers is preferably 35～45, and working pressure is preferably 3.5～5.5MPa, and tower top temperature is preferably 5～20 ℃, and the tower reactor temperature is preferably 100～125 ℃.
In described step (4), the number of theoretical plate of described carbon four desorption towers is preferably 20～35, and working pressure is preferably 1.5～2.5MPa, and tower top temperature is preferably 35～60 ℃, and the tower reactor temperature is preferably 100～130 ℃, and reflux ratio is 0.5～2.0.
In described step (5), described gasoline absorption agent is gasoline commonly used, preferably from the gasoline products of refinery.The number of theoretical plate of described naphtha scrubber is preferably 15～25, and working pressure is preferably 3.5～4.5MPa a little less than carbon four absorption tower pressure, and tower top temperature is preferably 15～25 ℃, and the tower reactor temperature is preferably 30～40 ℃.
With reference to Fig. 1, be described as follows:
The pressure of the catalysis drying gas 1 that the plant catalytic cracking unit is next is brought up to 4.0～6.0MPa through three sections compressors 7; Be cooled to 5～20 ℃ through the plant catalytic dry gas after three sections compressions through water cooler, preferred 12 ℃ of left and right, cooled catalysis drying gas enters carbon four absorption towers 8;
In carbon four absorption towers 8, adopt the mixed c 4 cut as absorption agent 2, temperature is 5～20 ℃, the C-4-fraction of the 2-butylene of the preferred 1-butylene that uses the normal butane that contains 10～40%wt, 3～15%wt, 45～70%wt and the C5 of 0～10%wt; More preferably use the C-4-fraction of the C5 of the cis-2-butene of Trans-2-butene, 25～35%wt of 1-butylene, the 20～35%wt of the normal butane comprise 20～35%wt, 5～10%wt and 0～10%wt.Carbon four absorption agents 2 spray into from 8 tops, carbon four absorption tower, absorb C2 cut and heavier component in described catalysis drying gas 1, at the bottom of the gaseous stream that tower top contains unabsorbed gases methane, hydrogen, carbon four enters naphtha scrubber 9 towers; Gasoline absorption agent 3 sprays into from tower top, absorbs the carbon fourth class component in gaseous stream, and unabsorbed methane, hydrogen tail gas 4 are discharged from tower top and is sent to the fuel gas pipe network, contain the gasoline stream 5 of carbon four from the tower reactor extraction.
The still liquid temp that absorbs tower reactor from carbon four is 100～125 ℃, pressure 3.5～5.5MPa, pressured difference enters carbon four desorption tower 10 middle parts, the concentrated C2 cut 6 that the desorb tower top is recycled, its chief component is ethene 25～35%, ethane 30～40%, carbonic acid gas 5～10%, propylene 0～15%, C4 and heavy constituent 0～15% more, the tower reactor absorption agent returns to carbon four absorption towers 8 and recycles after water cooler is cooling; The C2 concentrated gas that the desorb tower top obtains can be sent to the ethylene plant after deoxidation alkaline cleaner further separates.
In the method for the invention, the top gaseous phase logistics on described carbon four absorption towers is mainly not to be absorbed gas such as methane, the hydrogen etc. that agent absorbs, carbon four absorption agents that wherein also contain a small amount of C2 cut and carry secretly.For reducing the loss of carbon four absorption agents, this strand gaseous stream is introduced in naphtha scrubber, adopt the gasoline absorption agent that carbon four absorption agents are absorbed.The naphtha scrubber top gaseous phase logistics that is mainly methane, hydrogen is sent to the fuel gas pipe network as tail gas, contains the gasoline stream carrying device of carbon four.
Device and method of the present invention has following characteristics:
(1) reclaim C2 fraction in catalysis drying gas with the mixed c 4 component of refinery and gasoline fraction as absorption agent in the method for the invention, raw sorbent easily obtains, with low cost, and do not need ethene, propylene refrigeration compressor, less investment, simple to operate;
(2) carbon four absorption agents that finish up back and forth and carry secretly in gas as absorption agent with gasoline, and carbon four components that reclaim can further recycle, and the absorption agent loss is few;
(3) method Recovery rate of ethylene of the present invention improves, greater than 90%;
(4) in method of the present invention, carbon four absorption agents and catalysis drying gas are cooled to 5～20 ℃, can select lithium bromide refrigerator to provide cryogen to freeze, and energy consumption is low;
(5) in the method for the invention, the minimum operation temperature of device is not less than 5 ℃, and equipment and pipeline can adopt common low-temperature steel, have saved great amount of investment.
Description of drawings
Fig. 1 device schematic flow sheet of the present invention.
Description of reference numerals:
1 catalysis drying gas; 2 carbon four absorption agents; 3 gasoline absorption agents; 4 tail gas; 5 gasoline; 6 C2 concentrated gas; 7 compressors; 8 carbon four absorption towers; 9 naphtha scrubbers; 10 carbon four desorption towers
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment:
as shown in Figure 1, a kind of device that adopts oily absorption extraction oil refinery dry gas, comprise carbon four absorption towers 8 and carbon four desorption towers 10, 8 bottoms, carbon four absorption tower connect the catalysis drying gas inlet line, be provided with compressor 7 and condenser on the catalysis drying gas inlet line, 8 bottoms, carbon four absorption tower connect carbon four desorption towers 10, carbon four desorption tower 10 bottoms connect 8 tops, carbon four absorption tower, carbon four desorption tower 10 tops connections out-of-bounds, behind described carbon four absorption towers 8, naphtha scrubber 9 is set, carbon four absorption tower 8 top exits connect naphtha scrubber 9 bottoms, described naphtha scrubber 9 bottoms and top are communicated with out-of-bounds respectively.
Detailed process is as follows:
From the catalysis drying gas 1 that the plant catalytic cracking unit comes, pressure 0.8MPa through three sections compressions, is increased to 4.8MPa with pressure.Catalysis drying gas after supercharging is cooled to 12 ℃ through water cooler, then sends in carbon four absorption towers 8.In carbon four absorption towers, the hybrid C 4 cut that adopts the refinery to produce sprays into from tower top as absorption agent 2, absorbs C2 and heavier component in catalysis drying gas.The number of theoretical plate on absorption tower is 40, and working pressure is 4.0MPa, and tower top temperature is 18.2 ℃, and the tower reactor temperature is 105.1 ℃.The carbon four absorption agent materials that tower reactor is rich in C2 are delivered to carbon four desorption towers 10 and are processed, and the tower top unabsorbed gases enters naphtha scrubber 9.In naphtha scrubber, adopt the gasoline products of refinery's production as absorption agent 3, spray into from tower top, absorb the carbon fourth class component in gas.The number of theoretical plate of naphtha scrubber is 20, and working pressure is 3.8MPa, and tower top temperature is 19.2 ℃, 33.6 ℃ of tower reactor temperature.The methane of tower top, hydrogen tail gas 4 are discharged into the fuel gas pipe network, gasoline 5 carrying devices of tower reactor.
The carbon that the is rich in C2 four pressured differences of absorption agent that absorb tower reactors from carbon four enter carbon four desorption tower 10 middle parts.The number of theoretical plate of desorption tower is 31, and working pressure is 2.0MPa, and tower top temperature is 38.2 ℃, and the tower reactor temperature is 110 ℃, and reflux ratio is 1.2.The desorption tower tower reactor adopts the low-pressure steam heating, obtains concentrated C2 cut 6 from tower top.Poor carbon four absorption agents of desorb tower reactor return to carbon four and absorb the tower top recycle through being cooled to 12 ℃.
In the present embodiment, Recovery rate of ethylene is 91.8%.
Each main streams is listed in table 1 with the composition that separates rear product.
Table 1
| Name | 1 | 2 | 3 | 4 | 5 | 6 |
| Temperature [C] | 40 | 12 | 12 | 19.2 | 33.6 | 38.2 |
| Pressure [MPa] | 0.78 | 4.48 | 4.26 | 3.8 | 3.85 | 2.0 |
| Mass rate [kg/h] | 13495 | 45000 | 9000 | 7049.2 | 11353 | 7725 |
| Massfraction % | ||||||
| Hydrogen | 3.58 | 0 | 0 | 6.81 | 0.03 | 0 |
| Nitrogen | 22.06 | 0 | 0 | 41.67 | 0.35 | 0 |
| Oxygen | 1.35 | 0 | 0 | 2.49 | 0.04 | 0.02 |
| Carbon monoxide | 1.22 | 0 | 0 | 2.29 | 0.03 | 0 |
| Carbonic acid gas | 4.95 | 0 | 0 | 2.77 | 0.2 | 5.83 |
| Methane | 22.09 | 0 | 0 | 34.26 | 0.9 | 6.02 |
| Ethene | 19.69 | 0 | 0 | 2.75 | 0.28 | 31.57 |
| Ethane | 20.38 | 0.08 | 0 | 0.28 | 0.04 | 35.4 |
| Propylene | 2.5 | 0.99 | 0 | 0.63 | 0.41 | 4.42 |
| Propane | 0.38 | 0.38 | 0 | 0.18 | 0.15 | 1.06 |
| Trimethylmethane | 0.28 | 23.97 | 0 | 0.03 | 6.88 | 8.6 |
| Normal butane | 0.16 | 11.16 | 0 | 0 | 2.36 | 0.73 |
| 1-butylene | 0.13 | 25.75 | 0 | 0 | 6.32 | 4.86 |
| Trans-2-butene | 0.17 | 15.66 | 0 | 0 | 3.07 | 0.94 |
| Cis-2-butene | 0.19 | 14.71 | 0 | 0 | 2.67 | 0.51 |
| Iso-pentane | 0.31 | 6.66 | 0 | 0 | 0.57 | 0 |
| Skellysolve A | 0.01 | 0.18 | 0 | 0 | 0.01 | 0 |
| The 1-amylene | 0.03 | 0.46 | 0 | 0 | 0.04 | 0 |
| Water | 0.52 | 0 | 0 | 0.03 | 0 | 0 |
| Gasoline | 0 | 0 | 100 | 0 | 75.56 | 0 |
Claims (9)
1. device that adopts oily absorption extraction plant catalytic dry gas, comprise carbon four absorption towers and carbon four desorption towers, carbon four bottoms, absorption tower connect the catalysis drying gas inlet line, be provided with compressor and water cooler on the catalysis drying gas inlet line, carbon four bottoms, absorption tower connect carbon four desorption towers, carbon four connection carbon four tops, absorption tower, desorption tower bottom, carbon four desorption tower top connections out-of-bounds is characterized in that:
Behind described carbon four absorption towers, naphtha scrubber is set, carbon four absorption tower top exits connect naphtha scrubber bottoms, and described naphtha scrubber bottom and top are communicated with out-of-bounds respectively.
2. method that adopts separating plant catalytic dry gas device as claimed in claim 1 comprises:
Catalysis drying gas is compressed to be entered carbon four absorption towers after cooling and is absorbed by carbon four absorption agents, and carbon four absorption tower tower reactor materials enter carbon four desorption towers, and carbon four desorption tower tower reactor materials return to carbon four absorption towers; Carbon four absorption tower overhead gas enter naphtha scrubber and are absorbed by the gasoline absorption agent.
3. method as claimed in claim 2 is characterized in that:
The number of theoretical plate on described carbon four absorption towers is 35～45, and working pressure is 3.5～5.5MPa, and tower top temperature is 5～20 ℃, and the tower reactor temperature is 100～125 ℃.
4. method as claimed in claim 2 is characterized in that:
The number of theoretical plate of described naphtha scrubber is 15～25, and working pressure is 3.5～4.5MPa, and tower top temperature is 15～25 ℃, and the tower reactor temperature is 30～40 ℃.
5. method as described in one of claim 2～4 is characterized in that:
Described catalysis drying gas after compression to pressure be 4.0～6.0MPa; It is 5 ℃～20 ℃ through being cooled to temperature.
6. method as claimed in claim 5 is characterized in that:
Described boil down to multistage compression;
The refrigeration agent of described cooling middle employing is cold water.
7. method as described in one of claim 2～4 is characterized in that:
Described carbon four desorption tower tower reactor materials return to carbon four absorption tower recycles after being cooled to 5～20 ℃.
8. method as claimed in claim 2 is characterized in that:
Carbon four or other C-4-fraction after the mixed c 4 that described carbon four absorption agents are the refinery or ether; Described gasoline absorption agent is the gasoline products that is selected from the refinery.
9. method as claimed in claim 8 is characterized in that:
Described carbon four absorption agents are the C-4-fraction of 2-butylene of 1-butylene, the 5～70%wt of the normal butane that comprises 10～40%wt, 3～15%wt.
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