CN103752129A - Device and process for separating and recycling non-methane total hydrocarbons and hydrogen gas from refinery dry gas - Google Patents
Device and process for separating and recycling non-methane total hydrocarbons and hydrogen gas from refinery dry gas Download PDFInfo
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- CN103752129A CN103752129A CN201310443567.1A CN201310443567A CN103752129A CN 103752129 A CN103752129 A CN 103752129A CN 201310443567 A CN201310443567 A CN 201310443567A CN 103752129 A CN103752129 A CN 103752129A
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Abstract
The invention provides a device for separating and recycling hydrocarbon components and hydrogen gas from refinery dry gas and a process for separating and recycling the hydrocarbon components and the hydrogen gas by adopting the device. After treatment by the method, C2 and C2+ light hydrocarbon components in the mixture gas can be recycled, moreover, H2 in the mixture gas can be concentrated and purified, so that the additional value of the mixture gas is maximized, ideal economic benefits can be produced, Chinese energy development strategies are met, and besides, carbon dioxide emissions are reduced.
Description
Technical field
That patent of the present invention relates to is a kind of two-part pressure-variable adsorption (PSA-C that adopts
2 +/ R and PSA-H
2) separate the C in the dry gas that reclaims the discharge of refinery or olefin polymerization production process
2and C
2 +gas product and gas product H
2technique, be specially adapted to reclaim in oil refinery dry gas C
2and C
2 +gas product, H
2valuable component.
Background technology
The torch gas of the oil refinery dry gas of oil plant discharge and polyolefin device discharge contains a large amount of C
2, C
2 +light hydrocarbon component and H
2component, mainly contains CH in light hydrocarbon component
4(～10.49%), C
2h
4(～8.55%), C
2h
6(～2.41%), C
3h
6(～1.52%), C
4with C
4 +(～3.18%), H
2(～23.46%).These parts are as fuel gas, and a part is transported to flare vent system burning.If do not reclaim C wherein
2, C
2 +, H
2component, causes a large amount of light hydrocarbon components and H
2the wasting of resources, if can be by the N in oil refinery dry gas
2, CO, CO
2deng Impurity removal, and by C
2and C
2 +and H
2reclaim respectively and be reused for each production link of refinery or polyolefin device factory, the added value of oil refinery dry gas can be maximized, not only there is considerable economic benefit, can also reduce in a large number greenhouse gases CO
2discharge capacity, environmental benefit is obvious.
The method of oil refinery dry gas lighter hydrocarbons recovery mainly contains at present: oily absorption and separation method, separation by deep refrigeration, membrane separation process.Oil absorption and separation method has the organic efficiency of absorption low (≤70%) and can not reclaim purification H
2the shortcoming of gas; The operating temperature of separation by deep refrigeration is-100 ℃ of left and right, has investment and operating cost is high, operation easier is large, equipment corrosion is serious shortcoming, and the NO of the minute quantity in oil refinery dry gas
xcohesion accumulation at low temperatures, NO
xunder the condition of-80 ℃ with C
4, C
5diolefin reaction spanning tree mucilage binding itrated compound, this itrated compound character is extremely unstable, once be subject to the large-minded amplitude fluctuation of oil refinery dry gas and be subject to thermal shock, very likely blasts, and just there is explosion accident in an ethylene plant of France's nineties in 20th century.Membrane separation process is to C
3with C
3 +separation organic efficiency can reach more than 90%, but to C
2h
4, C
2h
6separation organic efficiency be difficult to exceed 75%, but also exist investment and the high shortcoming of equipment maintenance cost, same membrane separation process also exists and cannot reclaim H
2shortcoming.
Above-mentioned technique and method are mainly to reclaim hydrocarbon component in oil refinery dry gas, but have ignored the H in purification and recover oil refinery dry gas
2component, H in oil refinery dry gas
2content very high (20-30%), and H
2raw materials for production very important in refinery's production process, by the H in oil refinery dry gas
2purification, direct reuse, in the production link of refinery, has not only reduced H
2the waste of resource, reduces the environmental pollution in hydrogen production process, and can also reduce unit consumption of product and cost.
In recent years, although pressure swing adsorption also starts to set foot in, reclaim oil refinery dry gas field, only relate to the ethene composition reclaiming in oil refinery dry gas, and the rate of recovery is not high.But in oil refinery dry gas, ethylene gas is only sub-fraction wherein, its content often only have 10% less than.Relative, in oil refinery dry gas, but conventionally contain the hydrocarbons such as the propylene of total amount more than 30%, butylene, total institute is known, the material such as propylene, butylene is all very important refinery raw material, if can reclaim in the lump, there is to very important effect refinery, to the benefit contribution of refinery obviously.But, search out the relevant absorbing process of absorption hydrocarbons compounds and suitable absorption, with regard to existing technology, fail accomplished.So, in existing report, often lay particular emphasis on and only separate and reclaim ethylene gas, and abandoned other hydrocarbon components.
Summary of the invention
In view of above defect, the object of the invention is to overcome above-mentioned deficiency, provide a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas.Thereby realized from mainly containing C
2, C
2 +hydro carbons and H
2in the oil refinery dry gas of component, separate and reclaim C
2, C
2 +hydro carbons and highly purified H
2component.
For achieving the above object, the present invention has adopted following structure.
The invention provides and a kind ofly for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that, comprise the equipment of pressure-variable adsorption hydrocarbon component and two parts of hydrogen psa.
The equipment of pressure-variable adsorption hydrocarbon component comprises: at least one hydrocarbon component adsorption tower, half gas product surge tank, suitable pans, the C put
2and C
2 +resolution gas surge tank, C
2and C
2 +gas product surge tank, displacement compressor and vavuum pump A.
In the present invention, the preferred 4-8 of hydrocarbon component adsorption tower.
In the present invention, be provided with along putting pans, its role is to, when certain adsorption tower forward bleeds off pressure, this adsorption tower is communicated with and carries out equal pressure drop, the higher concentration C that the adsorption tower forward bleeding off pressure discharges with pans forward
2and C
2 +gas product enters along putting pans, when at other adsorption tower of follow-up period when boosting, along putting pans, be communicated with this adsorption tower, suitablely put the higher concentration C in pans
2and C
2 +gas product enters in this adsorption tower and is adsorbed the adsorbent absorption in tower, reaches and improves C
2and C
2 +the object of product recovery rate.
In the present invention, the effect of displacement compressor is, impurity displacement in this adsorption tower is discharged to this adsorption tower, and makes to be full of in this adsorption tower highly purified C
2and C
2 +gas product, has so just improved the follow-up reverse C obtaining with vacuum analysis that bleeds off pressure
2and C
2 +the purity of gas product.
The bottom of hydrocarbon component adsorption tower is provided with oil refinery dry gas input channel.
Also in parallelly on hydrocarbon component adsorption tower be provided with four pipelines: pipeline respectively with half gas product surge tank, along putting pans, C
2and C
2 +resolution gas surge tank is connected with vavuum pump A.
Wherein, the pipeline being connected with half gas product surge tank is preferably disposed on the upper end of hydrocarbon component adsorption tower, thereby unabsorbed gases is flowed out by upper end.
C
2and C
2 +gas product surge tank and C
2and C
2 +resolution gas surge tank is by pipeline communication, and centre is provided with valve to control inflow and the outflow of gas.
Displacement compressor parallel is in hydrocarbon component adsorption tower and C
2and C
2 +on the connected pipeline of resolution gas surge tank, one end is communicated with hydrocarbon component adsorption tower, the other end and C
2and C
2 +resolution gas surge tank is communicated with.
The equipment of hydrogen psa comprises: at least one foreign gas adsorption tower, H
2product surge tank, fuel resolution gas surge tank, fuel gas surge tank and vavuum pump B.
In the present invention, the preferred 6-12 of foreign gas adsorption tower.
Foreign gas adsorption tower bottom is provided with the pipeline being connected with half gas product surge tank.
Also in parallelly on foreign gas adsorption tower be provided with three pipelines: three pipelines respectively with H
2product surge tank, fuel resolution gas surge tank are connected with vavuum pump B.
Fuel gas surge tank and fuel resolution gas surge tank are by pipeline communication, and centre is provided with valve to control inflow and the outflow of gas.
Hydrocarbon component adsorption tower is provided with the adsorbent one that can adsorb non-methane class total hydrocarbon, is provided with the adsorbent two that can adsorb the foreign gas except hydrogen in foreign gas adsorption tower.
It should be noted that all parallel pipeline starting points place is equipped with sequencing valve.
Provided by the invention for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, also there is such technical characterictic: adsorbent one and adsorbent two are all selected from two or more the combination in 4 kinds of adsorbents of active carbon, aluminium oxide, silica gel, molecular sieve with middle microcellular structure.
In the process of producing, often, according to different exhaust gas constituents compositions, kind and combination to adsorbent are adjusted.
In the present invention, owing to being the absorption process that oil refinery dry gas is carried out, therefore, in adsorbent one and adsorbent two, the volume percent content of each component materials is preferably modified activated carbon 70-90%, aluminium oxide 5%-20%, silica gel 0-5%, molecular sieve 0-10%.
In addition, the present invention also provides a kind of technique of using said apparatus to separate and reclaim hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that, comprises pressure-variable adsorption hydrocarbon component (PSA-C
2 +/ R) and hydrogen psa (PSA-H
2) Liang Ge workshop section.
At pressure-variable adsorption hydrocarbon component (PSA-C
2 +/ R) workshop section in, oil refinery dry gas experiences successively absorption, 2-4 equal pressure drop at hydrocarbon component adsorption tower, forward bleeds off pressure, gas product displacement, reversely bleed off pressure, vacuumize, boost, 2-4 equal voltage rise and the operation of finally boosting obtain hydrocarbon component, meanwhile, hydrocarbon component adsorption tower is discharged the gas not adsorbed by this workshop section.In this workshop section, the material of absorption process absorption is hydrocarbon component.The operating pressure of the workshop section of pressure-variable adsorption hydrocarbon component is 0.5-0.6MPa.
At (the PSA-H of workshop section of hydrogen psa
2) in, by the gas of the workshop section of pressure-variable adsorption hydrocarbon component absorption, through the operation of foreign gas adsorption tower absorption, do not obtained highly purified hydrogen.In this workshop section, the material of absorption process absorption is the gas except hydrogen.The operating pressure of the workshop section of hydrogen psa is 0.4-0.5MPa.
Experience absorption, 2-3 the equal pressure drop successively in foreign gas adsorption tower of gas except hydrogen, reversely bleed off pressure, vacuumize, 2-3 equal voltage rise and the operation of finally boosting obtain fuel gas.
In addition, before gas enters hydrocarbon component adsorption tower, mist (the 0-20KPa of the torch gas of the oil refinery dry gas of refinery's discharge and polyolefin device discharge, gauge pressure) need through compressor compresses, the pressure of the gas after compression can be 0.1-1.0MPa(gauge pressure), the gas after compression is priority process PSA-C after point flow container dehydration
2 +/ R and PSA-H
2liang Ge workshop section.
Concrete operation step and the principle of above-mentioned Liang Ge workshop section are as follows:
pSA-C
2
+
/ R workshop section adsorption process:
At PSA-C
2 +in/R workshop section, C
2and C
2 +hydrocarbon component is adsorbed and is reclaimed and obtained C by inverse put and the parsing of finding time
2and C
2 +gas product; The H not being adsorbed
2, O
2, N
2, CH
4, CO, CO
2etc. component from adsorption tower port of export output, as half gas product, enter follow-up PSA-H
2workshop section further separates.
(1) absorption A
Contain C
2and C
2 +hydrocarbon component mist (gauge pressure pressure is 0.5-0.6MPa) entering through inverse put, find time to resolve in the adsorption tower of regeneration and adsorb from bottom to top, in adsorption tower, adsorbent is to C
2and C
2 +hydrocarbon component adsorbs, and from adsorption tower top exit, obtains C
2and C
2 +half gas product that hydrocarbon content is lower, this gas is transported to follow-up PSA-H
2h in the further adsorbing separation purifying gas of workshop section
2.The quantity of the adsorption tower in adsorption step can be adjusted according to actual condition demand simultaneously, can be 2-6 adsorption tower.
(2) all pressure drops (ED)
Gas in adsorption tower is discharged to the adsorption tower of the equal voltage rise of needs, reclaim the gas in adsorption tower, meanwhile, C in adsorption tower
2and C
2 +the concentration of hydrocarbon component is enhanced.All pressure drop also can be carried out to the lower pressure surge tank of pressure, and all the number of times of pressure drop can be 2-4 time.Each all pressure drops can be carried out continuously or separately carry out.
(3) forward bleed off pressure (PP)
Residual gas in adsorption tower is discharged to the higher concentration C that the adsorption tower forward bleeding off pressure discharges from top of tower outlet
2and C
2 +gas product enters along putting pans, when at other adsorption tower of follow-up period when boosting, along putting pans, be communicated with this adsorption tower, suitablely put the higher concentration C in pans
2and C
2 +gas product enters in this adsorption tower and is adsorbed the adsorbent absorption in tower, reaches and improves C
2and C
2 +the object of product recovery rate.
(4) gas product displacement (RP)
By a part of C
2and C
2 +gas product passes in adsorption tower from adsorption tower bottom after replacing air compressor machine supercharging, and discharges replaced gas from top, and replaced gas enters along putting pans.Displacement step can be by the C in adsorption tower
2and C
2 +hydrocarbon component is further concentrated, makes inverse put and vacuumizes the C obtaining in resolving
2and C
2 +the purity of gas product is improved, and is conducive to recycle.
(5) reverse bleeding off pressure (D)
C is emitted and be stored into the direction that gas in adsorption tower is entered against gaseous mixture from adsorption tower outlet at bottom
2and C
2 +resolution gas surge tank is also inputted C by decompression
2and C
2 +gas product surge tank, final output is out-of-bounds recycled.The reverse step that bleeds off pressure can be by a part of C being adsorbed in adsorption tower
2and C
2 +hydrocarbon component is resolved and is reclaimed.
(6) vacuumize (V)
With vavuum pump, A vacuumizes adsorption tower, by dead space in adsorption tower and adsorbent C
2and C
2 +hydrocarbon component parses.Evacuation step is divided into V1, V2, V3 three phases.Wherein, the V2 stage is the rinsing step of finding time, and, when this adsorption tower carrying out evacuation step, a small amount of half gas product is passed into adsorption tower from the top exit of adsorption tower, and adsorption tower is rinsed when vacuumizing.After evacuation step finishes, C
2and C
2 +hydrocarbon component is resolved to be reclaimed, and meanwhile, adsorption tower is regenerated.
(7) voltage rise (R)
To the adsorption tower that completes regeneration first with having it being boosted and make C along venting and displacement gas of certain pressure in pans along putting
2and C
2 +hydrocarbon component is adsorbed agent absorption, increases C
2and C
2 +the hydrocarbon component rate of recovery.
(8) all voltage rises (ER)
The adsorption tower and another adsorption tower or the higher pressure surge tank of pressure in equal pressure drop that complete the step of boosting are communicated with, make its isostasy, the pressure of adsorption tower is progressively raise.In pressure equalizing, gas passes into adsorption tower from adsorption tower top exit.All the number of times of voltage rise is consistent with the number of times of all pressure drops, according to actual conditions, can be 2-4 time.
(9) (FR) finally boosts
After all voltage rise step finishes, the pressure when operating pressure of adsorption tower does not also reach absorption work, now utilize half gas product of adsorption tower outlet finally to boost to adsorption tower, the pressure while making the pressure of adsorption tower approach absorption work, and prepare to enter next adsorption cycle.So far, adsorption tower has carried out 1 complete adsorption cycle, so circulation.
pSA-H
2
workshop section's adsorption process:
At PSA-H
2in workshop section, remove H
2o in addition
2, N
2, CH
4be adsorbed agent absorption thereby in adsorption tower outlet, to obtain purity be 99.99% gas product H Deng impurity
2, by inverse put and the parsing of finding time, can obtain by CO, N
2, CH
4deng the fuel gas of remaining ingredient composition.
(1) absorption A
From PSA-C
2 +h is contained in/R workshop section
2, O
2, N
2, CH
4etc. half gas product (gauge pressure pressure is 0.1-1.0MPa) of component entering through inverse put, find time to resolve in the adsorption tower of regeneration and adsorb from bottom to top, in adsorption tower, adsorbent is to except H
2o in addition
2, N
2, CH
4deng impurity, adsorb, from adsorption tower top exit obtain concentration be 99.99%(V%) gas product H
2.When the absorption forward position of adsorption zone is moved upwards up to certain position, can be considered that this adsorbent has arrived this absorption terminal, now, stop adsorption tower bottom inflow and top and give vent to anger, stop absorption.The quantity of the adsorption tower in adsorption step can be adjusted according to actual condition demand simultaneously, can be 1-3 adsorption tower.
(2) all pressure drops (ED)
Gas in adsorption tower is discharged to the adsorption tower of the equal voltage rise of needs, reclaim the gas in adsorption tower, reduce H in this adsorption tower
2concentration.All pressure drop also can be carried out to the lower pressure surge tank of pressure, and all the number of times of pressure drop can be 2-3 time, can consider whether to need to arrange the pressure surge tank of all pressing use according to actual conditions.All press number of times more, the pressure in adsorption tower is lower, H
2the rate of recovery is higher.Each all pressure drops can be carried out continuously or separately carry out.
(3) reverse bleeding off pressure (D)
The direction that gas in adsorption tower is entered against half gas product emits and is stored into fuel gas resolution gas surge tank and input fuel gas surge tank by decompression from adsorption tower outlet at bottom, and final output is out-of-bounds recycled.By the reverse step that bleeds off pressure, the resolved recovery of gas that a part is adsorbed obtains fuel gas.
(4) vacuumize (V)
With vavuum pump, B vacuumizes adsorption tower, by dead space in adsorption tower and adsorbent O
2, N
2, CH
4deng gas, further parse.Evacuation step is divided into V1, V2, V3 three phases.Wherein the V2 stage is the rinsing step of finding time, when this adsorption tower carrying out evacuation step, by a small amount of gas product H
2from the top exit of adsorption tower, pass into adsorption tower, adsorption tower is rinsed when vacuumizing.After evacuation step finishes, the resolved recovery of gas being adsorbed in adsorption tower obtains fuel gas, and meanwhile, adsorption tower is regenerated.
(5) all voltage rises (ER)
The adsorption tower and another adsorption tower or the higher pressure surge tank of pressure in equal pressure drop that complete the step of boosting are communicated with, make its isostasy, the pressure of adsorption tower is progressively raise.In pressure equalizing, gas passes into adsorption tower from adsorption tower top exit.All the number of times of voltage rise is consistent with the number of times of all pressure drops, according to actual conditions, can be 2-3 time.
(6) (FR) finally boosts
After all voltage rise step finishes, the pressure when operating pressure of adsorption tower does not also reach absorption work, the gas product H that now utilizes adsorption tower to export
2adsorption tower is finally boosted, the pressure while making the pressure of adsorption tower approach absorption work, and prepare to enter next adsorption cycle.So far, adsorption tower has carried out 1 complete adsorption cycle, so circulation.
Contain a large amount of C
2and C
2 +the mist of the torch gas of the oil refinery dry gas of light hydrocarbon component and polyolefin device discharge, after said method separating treatment of the present invention, can obtain three strands of product gas that purposes is different, they respectively: be rich in C
2and C
2 +gas product, gas product H
2and fuel gas.According to operating mode, can adjust operating parameter, can make C
2and C
2 +c in gas product
2and C
2 +component volume content is 15%-90%, C
2and C
2 +the rate of recovery of light hydrocarbon component reaches more than 94%, gas product H
2middle H
2purity can reach more than 99.99%.Main component in fuel gas after separation is CH
4, CO, N
2deng composition, can output to the pipe network that out-of-bounds burns.
effect of the present invention
The present invention, by the selection to adsorbent in variety classes adsorption tower, realizes the gas that adsorbs various combination in different adsorption towers.Particularly, realized in hydrocarbon component pressure-variable adsorption workshop section and adsorbed all paraffin gas except methane gas, realize the ethylene gas not only reclaiming with in separate traditional handicraft, can also be recovered to other hydrocarbon mixed gas, thereby improved the recovery utilization rate of waste gas.
The present invention is also by downflow releasing tank in the middle of arranging and two equipment of displacement compressor, and coordinates relevant process, thereby improved the purity of hydrocarbon mixed gas.
In addition, absorbing process used in the present invention can also be according to different actual demands, adjust operating parameter and increase and all press the modes such as number of times suitably to improve C
2and C
2 +c in gas product
2and C
2 +the concentration of hydrocarbon component.
Therefore,, after processing by the inventive method, not only can make C in gaseous mixture
2and C
2 +hydrocarbon component is recycled, can also be by H wherein
2concentrated purification, maximizes the added value of mist, can produce desirable economic benefit, meets the energy development strategy of China, reduces CO2 emissions simultaneously.
Accompanying drawing explanation
Fig. 1 be the present embodiment provide for separate and reclaim the structural representation of the device of hydrocarbon component and hydrogen from oil refinery dry gas;
In Fig. 1: the equipment of 100-pressure-variable adsorption hydrocarbon component, the equipment of 200-hydrogen psa, M-oil refinery dry gas, A-C
2and C
2 +hydrocarbon component gas, B-hydrogen, C-fuel gas, 1-separatory surge tank, 2-compressor, 10-half gas product surge tank, 21-adsorption tower A, 22-adsorption tower B, 23-adsorption tower C, 24-adsorption tower D, 25-adsorption tower E, 26-adsorption tower F, 30-is along putting pans, 41-C
2and C
2 +resolution gas surge tank, 42-C
2and C
2 +gas product surge tank, 50-vavuum pump A, 60-replaces compressor, 210-adsorption tower H, 211-adsorption tower I, 212-adsorption tower J, 213-adsorption tower K, 214-adsorption tower L, 220-H
2gas product surge tank, 231-fuel resolution gas surge tank, 232-fuel gas surge tank, 240-vavuum pump B.
Fig. 2 is used the device for separate and reclaim hydrocarbon component and hydrogen from oil refinery dry gas that the present embodiment provides to reclaim C
2and C
2 +the sequential chart of light hydrocarbon component pressure-variable adsorption.
Fig. 3 is the sequential chart that concentrates the pressure-variable adsorption of hydrogen for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas that uses the present embodiment to provide.
The specific embodiment
Now by reference to the accompanying drawings and specific embodiment, the present invention is further detailed explanation.These accompanying drawings are the schematic diagram of simplification, and basic structure of the present invention is only described in a schematic way, and therefore it only shows the formation relevant with the present invention.
The present embodiment is from the torch gas of oil refinery dry gas discharge, to separate to reclaim C
2and C
2 +the pressure swing adsorption method of light hydrocarbon component concentrated hydrogen, gas flow is 3000Nm
3/ h, its gas componant forms into as shown in table 1:
Mixed gas composition composition (V%) before table 1 separates and reclaims
The present embodiment pressure swing adsorption system is by PSA-C
2 +/ R and PSA-H
2liang Ge workshop section composition.Unstripped gas is successively through PSA-C
2 +/ R and PSA-H
2liang Ge workshop section, at PSA-C
2 +in/R workshop section, C
2and C
2 +hydrocarbon component is adsorbed and is reclaimed and obtained C by parsing
2and C
2 +gas product; At PSA-H
2in workshop section, in gaseous mixture, remove H
2o in addition
2, N
2, CH
4thereby be adsorbed agent and absorb in adsorption tower outlet and obtain the gas product H that purity is higher etc. component
2, by resolving the fuel gas that can obtain remaining ingredient composition.
PSA-C
2 +/ R workshop section is by 6 hydrocarbon component adsorption towers (adsorption tower A-adsorption tower F), 1 suitable pans, 1 C put
2and C
2 +resolution gas surge tank, 1 C
2and C
2 +gas product surge tank, 1 half gas product surge tank, 1 vavuum pump A, 1 displacement air compressor machine and corresponding program-controlled valve, pipeline are formed by connecting, and have 2 adsorption towers simultaneously in adsorbed state at every turn.In order to guarantee higher C
2and C
2 +c in the rate of recovery of hydrocarbon component and gas product
2and C
2 +the concentration of hydrocarbon component, PSA-C
2 +the each adsorption tower of/R workshop section is selected 2 equal pressure drops, and increases along putting and displacement step in inverse put with before finding time to resolve.Stable in order to maintain system pressure, after resolving, adopt boost (R), 2 equal voltage rises (ER) and (FR) step of finally boosting, make it progressively reach adsorptive pressure, adsorptive pressure is about 0.6MPa.
Below take adsorption tower A as example is to PSA-C
2 +the technical process of/R workshop section is illustrated in conjunction with Fig. 1, Fig. 2:
1, absorption A:
Oil refinery dry gas enters PSA-C through compressor compresses to 0.6MPa and except after free water
2 +/ R workshop section, escapes and enter half gas product surge tank through sequencing valve KV101A from the bottom inflow of adsorption tower A and from the KV102A of top of tower.In adsorption tower, adsorbent is to C
2and C
2 +hydrocarbon component adsorbs, and from adsorption tower top exit, obtains C
2and C
2 +half gas product that hydrocarbon content is lower.Close sequencing valve KV101A and KV102A, adsorption step finishes.Half gas product enters half gas product surge tank by pressure regulation to 0.5MPa.
Adsorbent is: modified activated carbon 85%, aluminium oxide 5%, silica gel 5%, molecular sieve 5%.
2, one all falls E1D:
After absorption A step finishes, open sequencing valve KV103A and KV103D, by adsorption tower A with to be ready carrying out an adsorption tower D who all rises E1R step and to be communicated with, make to be all depressed between two towers pressure balance.One all falls after end, closes sequencing valve KV103A and KV103D.
3, two all fall E2D:
One all falls after E1D step finishes, and opens sequencing valve KV104A and KV104E, by adsorption tower A with to be ready carrying out the two adsorption tower E that all rise E2R step and to be communicated with, make to be all depressed between two towers pressure balance.Two all fall after end, close sequencing valve KV104E.
4, forward bleed off pressure PP:
Two all fall after E2D step finishes, and keep sequencing valve KV104A in opening, and open sequencing valve KV107, make adsorption tower A and are communicated with along putting pans, and in tower, residual gas continuation out enters suitable pans to the two pressure tower balance of putting from top.
5, gas product displacement RP:
For guaranteeing the purity of gas product, after forward bleeding off pressure PP step and finishing, keep sequencing valve KV104A and KV107 in opening, and open sequencing valve KV105A and KV109, a part is entered at the bottom of tower through displacement compressor compresses gas product later, foreign gas component residual in tower is cemented out and entered along putting pans.After displacement RP step finishes, close sequencing valve KV104A, KV107 and KV109.
6, the reverse D that bleeds off pressure:
After gas product displacement RP step finishes, keep sequencing valve KV105A in opening and open sequencing valve KV110, C is resolved and entered to the most of gas product component being now adsorbed by inverse put step
2and C
2 +resolution gas surge tank, finally enters C by pressure regulation
2and C
2 +gas product surge tank.Reverse bleed off pressure step and finish after, close sequencing valve KV105A and KV110.
7, the V that finds time:
After the reverse D of bleeding off pressure step finishes, adsorbent bedly contain a part of gas product and do not resolved completely, now by evacuation step, it is further resolved.Evacuation step comprises 3 stage: V1, V2 and V3 altogether, and wherein V2 is the rinsing step of finding time, and refers in the parsing of finding time, and a part of half gas product is entered from top of tower, product component is developed, to guarantee the higher gas product rate of recovery.Open sequencing valve KV106A and enter evacuation step V1, after certain hour, open sequencing valve KV103A and KV108 and enter evacuation step V2, V2 step arrives closes sequencing valve KV103A after setting-up time and KV108 enters evacuation step V3, after finishing, evacuation step V3 closes sequencing valve KV106A, so far whole evacuation step finishes, and in tower, product component is resolved and reclaims and enter C
2and C
2 +gas product surge tank.
8, voltage rise R:
After the V step of finding time finishes, open sequencing valve KV104A and KV107, by higher with pressure adsorption tower A being communicated with along putting surge tank, make to be all depressed into pressure balance between two towers, reclaim along putting the product component in surge tank.After finishing, voltage rise R closes sequencing valve KV107.
9, two all rise E2R:
After voltage rise R step finishes, keep sequencing valve KV104A in opening, open sequencing valve KV104C, by adsorption tower A with to be ready carrying out the two adsorption tower C that all fall E2D step and to be communicated with, make to be all depressed between two towers pressure balance.Two all rise E2R finish after, close sequencing valve KV104A and KV104C.
10, isolation I:
Two all rise E2R step finish after, all valves of adsorption tower gateway are all failure to actuate, and wait pending next step, with meet 6 towers on working procedure mutually coupling.
11, one all rise E1R:
After isolation I step finishes, open sequencing valve KV103A and KV103D, by adsorption tower A with to be ready carrying out an adsorption tower D who all falls E1D step and to be communicated with, make to be all depressed between two towers pressure balance.One all rises E1R finish after, close sequencing valve KV103A and KV103D.
12, the FR that finally boosts:
Through the pressure in the adsorption tower A of voltage rise R step and twice equal voltage rise ER, do not reach yet absorption operating pressure, now by opening sequencing valve KV102A, half higher pressure gas product is passed in adsorption tower A from top of tower, make its pressure progressively approach absorption operating pressure.When pressure reaches adsorptive pressure, the step of finally boosting finishes.
Complete after above-mentioned steps, adsorption tower A has completed the cycling of one-period, PSA-C
2 +the circulation step of other 5 towers of/R workshop section is identical with adsorption tower A, just mutually staggers in time, to guarantee having at any time 2 adsorption towers adsorbing the operation of A step, thereby guarantees that adsorbent equipment moves continuously.At the C of this workshop section
2and C
2 +gas product is recovered, and half gas product not being adsorbed continues to enter follow-up PSA-H
2workshop section carries out purifying hydrogen of hydrogen.
PSA-H
2workshop section is by 5 foreign gas adsorption towers (adsorption tower H-adsorption tower L), 1 fuel resolution gas surge tank, 1 fuel gas surge tank, 1 H
2gas product surge tank, 1 vavuum pump B and corresponding program-controlled valve, pipeline are formed by connecting, and have 2 adsorption towers simultaneously in adsorbed state at every turn.PSA-H
2the each adsorption tower of workshop section is selected 2 equal pressure drops.Stable in order to maintain system pressure, after resolving, adopt 2 equal voltage rises (ER) and (FR) step of finally boosting, make it progressively reach adsorptive pressure, adsorptive pressure is about 0.5MPa.
Below take adsorption tower H as example is to PSA-H
2the technical process of workshop section is illustrated in conjunction with Fig. 1, Fig. 3:
1, absorption A:
Half gas product escapes and enter H through sequencing valve KV201A from the bottom inflow of adsorption tower H and from the KV202A of top of tower
2gas product surge tank.In adsorption tower, adsorbent is to removing H
2component is in addition adsorbed, and from adsorption tower top exit, obtains the H that purity is 99.99%
2gas product.Close sequencing valve KV201A and KV202A, adsorption step finishes.
Adsorbent is: modified activated carbon 75%, aluminium oxide 20%, molecular sieve 5%.
2, one all falls E1D:
After absorption A step finishes, open sequencing valve KV203A and KV203D, by adsorption tower H with to be ready carrying out an adsorption tower K who all rises E1R step and to be communicated with, make to be all depressed between two towers pressure balance.One all falls after end, closes sequencing valve KV203A and KV203D, still has certain pressure in tower.
3, two all fall E2D:
One all falls after E1D step finishes, and opens sequencing valve KV204A and KV204E, by adsorption tower H with to be ready carrying out the two adsorption tower L that all rise E2R step and to be communicated with, make to be all depressed between two towers pressure balance.Two all fall after end, close sequencing valve KV204A and KV204E.
4, the reverse D that bleeds off pressure:
Two all fall after E2D step finishes, and open sequencing valve KV205A, and fuel resolution gas surge tank is resolved and entered to the most of component being now adsorbed by inverse put step, by pressure regulation, finally enters fuel gas surge tank.Reverse bleed off pressure step and finish after, close sequencing valve KV205A.
5, the V that finds time:
After the reverse D of bleeding off pressure step finishes, adsorbent bed interior some gas is not resolved completely, now by evacuation step, it is further resolved.Evacuation step comprises 3 stage V1/V2/V3 altogether, and wherein V2 step is in the parsing of finding time, by a part of gas product H
2from top of tower, enter, impurity composition is developed.Open sequencing valve KV206A and enter evacuation step V1, after certain hour, open sequencing valve KV204A and KV207 and enter evacuation step V2, V2 step arrives closes sequencing valve KV204A after setting-up time and KV207 enters evacuation step V3, after finishing, evacuation step V3 closes sequencing valve KV206A, so far whole evacuation step finishes, and in tower, impurity composition is resolved and reclaims and enter fuel gas surge tank.
6, two all rise E2R:
After the V step of finding time finishes, open sequencing valve KV204A and KV204B, by adsorption tower H with to be ready carrying out the two adsorption tower I that all fall E2D step and to be communicated with, make to be all depressed between two towers pressure balance.Two all rise E2R finish after, close sequencing valve KV204A and KV204B.
7, isolation I:
Two all rise E2R step finish after, all valves of adsorption tower gateway are all failure to actuate, and wait pending next step, with meet 5 towers on working procedure mutually coupling.
8, one all rise E1R:
After isolation I step finishes, open sequencing valve KV203A and KV203C, by adsorption tower H with to be ready carrying out an adsorption tower J who all falls E1D step and to be communicated with, make to be all depressed between two towers pressure balance.One all rises E1R finish after, close sequencing valve KV203A and KV203C.
9, the FR that finally boosts:
Through the pressure in the adsorption tower H of twice equal voltage rise ER, do not reach yet absorption operating pressure, now by opening sequencing valve KV202A, by gas product H higher pressure
2from top of tower, pass in adsorption tower H, make its pressure progressively approach absorption operating pressure.When pressure reaches adsorptive pressure, the step of finally boosting finishes.
Complete after above-mentioned steps, adsorption tower H has completed the cycling of one-period, PSA-H
2the circulation step of 4 towers of other of workshop section is identical with adsorption tower H, just mutually staggers in time, to guarantee having at any time 2 adsorption towers adsorbing the operation of A step, thereby guarantees that adsorbent equipment moves continuously.In this workshop section, remove H
2it is 99.99% H that component is in addition adsorbed and obtains purity
2gas product.The impurity composition reclaiming by parsing is as fuel gas.
In sum, after native system separating treatment, obtain 3 gangs of gas: C
2and C
2 +gas product, gas product H
2and fuel gas, its gas composition is as shown in table 2:
After table 2 separates and reclaims, product gas becomes to be grouped into (V%)
The C obtaining after this routine separating treatment
2and C
2 +the purity of gas product is 85.94%(V%); C in fuel gas after separation
2and C
2 +the gas content of component is only 1.375%(V%); The gas product H obtaining after separation
2purity be 99.99%(V%); C in gaseous mixture
2and C
2 +the cycles of concentration of component is about 5 times, the rate of recovery>=94%.
Without departing from the idea case in the present invention described above, various replacements and the change according to ordinary skill knowledge and customary means, made, include within the scope of the invention.
It is worthy of note, according to the gas feed of difference composition, should adjust the adsorbent in different workshop sections adsorption tower.But, according to the volume range of the constituent of conventional oil refinery dry gas and each composition, for reaching the good adsorption effect of each workshop section, adsorbent should be selected from modified activated carbon, aluminium oxide, silica gel, molecular sieve 4, and the scope of its volumn concentration should be selected in modified activated carbon 70-90%, aluminium oxide 5%-20%, silica gel 0-5%, molecular sieve 0-10%.
the effect of the present embodiment
The hydrocarbon mixture gas finally obtaining by the method for the present embodiment, purity is high, and the rate of recovery reaches more than 90%.The present invention has realized the target that reclaims all hydrocarbon component gas except methane gas, and the added value of mist is maximized, and has improved the regeneration rate of the energy.
In addition, by the method for the present embodiment, can also purify concentrated, the hydrogen purity finally obtaining, up to 99.99%, can produce desirable economic benefit, meets the energy development strategy of China, reduces CO2 emissions simultaneously.
Claims (10)
1. for separate and reclaim a device for hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that, comprise the equipment of pressure-variable adsorption hydrocarbon component and two parts of hydrogen psa,
Wherein, the equipment of described pressure-variable adsorption hydrocarbon component comprises: at least one hydrocarbon component adsorption tower, half gas product surge tank, suitable pans, the C put
2and C
2 +resolution gas surge tank, C
2and C
2 +gas product surge tank, displacement compressor and vavuum pump A;
The bottom of described hydrocarbon component adsorption tower is provided with oil refinery dry gas input channel;
On described hydrocarbon component adsorption tower, go back in parallel four pipelines that are provided with;
Described four pipelines respectively with half gas product surge tank, along putting pans, C
2and C
2 +resolution gas surge tank is connected with vavuum pump A;
Described C
2and C
2 +gas product surge tank and C
2and C
2 +resolution gas surge tank passes through pipeline communication;
Described displacement compressor parallel is in hydrocarbon component adsorption tower and C
2and C
2 +on the connected pipeline of resolution gas surge tank, one end is communicated with hydrocarbon component adsorption tower, the other end and C
2and C
2 +resolution gas surge tank is communicated with;
The equipment of described hydrogen psa comprises: at least one foreign gas adsorption tower, H
2product surge tank, fuel resolution gas surge tank, fuel gas surge tank and vavuum pump B;
Described foreign gas adsorption tower bottom is provided with the pipeline being connected with half gas product surge tank;
On described foreign gas adsorption tower, go back in parallel three pipelines that are provided with;
Described three pipelines respectively with H
2product surge tank, fuel resolution gas surge tank are connected with vavuum pump B;
Described fuel gas surge tank and fuel resolution gas surge tank pass through pipeline communication;
Described hydrocarbon component adsorption tower is provided with the adsorbent one that can adsorb non-methane class total hydrocarbon;
In foreign gas adsorption tower, be provided with the adsorbent two that can adsorb the foreign gas except hydrogen.
2. as claimed in claim 1 a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that: the parallel pipeline starting point place of described hydrocarbon component adsorption tower, foreign gas adsorption tower and displacement compressor is equipped with sequencing valve.
3. as claimed in claim 1 a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that: the preferred 4-8 of described hydrocarbon component adsorption tower;
4. as claimed in claim 1 a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that: the preferred 6-12 of described foreign gas adsorption tower.
5. as claimed in claim 1 a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that: described adsorbent one is for having two or more the combination in 4 kinds of adsorbents of active carbon, aluminium oxide, silica gel, molecular sieve of middle microcellular structure;
Described adsorbent two is for having two or more the combination in 4 kinds of adsorbents of modified activated carbon, aluminium oxide, silica gel, molecular sieve of middle microcellular structure.
6. as claimed in claim 1 a kind of for separate and reclaim the device of hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that: in described adsorbent one, the volume percent content of each component materials is modified activated carbon 70-90%, aluminium oxide 5%-20%, silica gel 0-5%, molecular sieve 0-10%; In adsorbent two, the volume percent content of each component materials is modified activated carbon 70-90%, aluminium oxide 5%-20%, silica gel 0-5%, molecular sieve 0-10%.
7. the device of use as described in as arbitrary in claim 1 to 6 separates and reclaims a technique for hydrocarbon component and hydrogen from oil refinery dry gas, it is characterized in that, comprises pressure-variable adsorption hydrocarbon component and hydrogen psa Liang Ge workshop section;
In the workshop section of described pressure-variable adsorption hydrocarbon component, oil refinery dry gas experiences successively absorption, 2-4 equal pressure drop at hydrocarbon component adsorption tower, forward bleeds off pressure, gas product displacement, reversely bleed off pressure, vacuumize, boost, 2-4 equal voltage rise and the operation of finally boosting obtain hydrocarbon component, meanwhile, hydrocarbon component adsorption tower is discharged the gas not adsorbed by this workshop section;
In the workshop section of described hydrogen psa, by the gas of the workshop section of pressure-variable adsorption hydrocarbon component absorption, through the operation of foreign gas adsorption tower absorption, do not obtained highly purified hydrogen;
Wherein, in the workshop section of described pressure-variable adsorption hydrocarbon component, the material of absorption process absorption is hydrocarbon component;
In the workshop section of described hydrogen psa, the material of absorption process absorption is the gas except hydrogen.
8. a kind of technique that separates from oil refinery dry gas and reclaim hydrocarbon component and hydrogen as claimed in claim 7, is characterized in that: the operating pressure of the workshop section of described pressure-variable adsorption hydrocarbon component is 0.5-0.6MPa.
9. a kind of technique that separates from oil refinery dry gas and reclaim hydrocarbon component and hydrogen as claimed in claim 7, is characterized in that: the operating pressure of the workshop section of described hydrogen psa is 0.4-0.5MPa.
10. a kind of technique that separates from oil refinery dry gas and reclaim hydrocarbon component and hydrogen as claimed in claim 7, is characterized in that: experience absorption, 2-3 the equal pressure drop successively in foreign gas adsorption tower of described gas except hydrogen, reversely bleed off pressure, vacuumize, 2-3 equal voltage rise and the operation of finally boosting obtain fuel gas.
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