CN104624022A - Double-absorption and double-desorption hydrogen gas and light hydrocarbon comprehensive recovery system - Google Patents
Double-absorption and double-desorption hydrogen gas and light hydrocarbon comprehensive recovery system Download PDFInfo
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- CN104624022A CN104624022A CN201310554076.4A CN201310554076A CN104624022A CN 104624022 A CN104624022 A CN 104624022A CN 201310554076 A CN201310554076 A CN 201310554076A CN 104624022 A CN104624022 A CN 104624022A
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 238000010521 absorption reaction Methods 0.000 title claims abstract description 135
- 229930195733 hydrocarbon Natural products 0.000 title claims abstract description 121
- 150000002430 hydrocarbons Chemical class 0.000 title claims abstract description 121
- 238000011084 recovery Methods 0.000 title claims abstract description 70
- 239000004215 Carbon black (E152) Substances 0.000 title claims abstract description 23
- 238000003795 desorption Methods 0.000 title abstract description 7
- 239000001257 hydrogen Substances 0.000 claims abstract description 165
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 165
- 239000007789 gas Substances 0.000 claims abstract description 84
- 239000012528 membrane Substances 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 21
- 239000003921 oil Substances 0.000 claims description 79
- 239000002250 absorbent Substances 0.000 claims description 22
- 230000002745 absorbent Effects 0.000 claims description 22
- 239000002737 fuel gas Substances 0.000 claims description 12
- 150000002431 hydrogen Chemical class 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 10
- 230000004087 circulation Effects 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 230000001839 systemic circulation Effects 0.000 claims description 4
- 239000000047 product Substances 0.000 abstract description 39
- 239000012465 retentate Substances 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 23
- 230000008569 process Effects 0.000 description 16
- 238000005265 energy consumption Methods 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 15
- 238000000746 purification Methods 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 7
- 238000009835 boiling Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 238000005194 fractionation Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 3
- 239000000498 cooling water Substances 0.000 description 3
- 235000019628 coolness Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011027 product recovery Methods 0.000 description 3
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000006477 desulfuration reaction Methods 0.000 description 2
- 230000023556 desulfurization Effects 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000008929 regeneration Effects 0.000 description 2
- 238000011069 regeneration method Methods 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 239000002918 waste heat Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
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- 239000010779 crude oil Substances 0.000 description 1
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- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
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- 230000002779 inactivation Effects 0.000 description 1
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- 229910002027 silica gel Inorganic materials 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
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- 239000002699 waste material Substances 0.000 description 1
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- Hydrogen, Water And Hydrids (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The present invention provides a double-absorption and double-desorption hydrogen gas and light hydrocarbon comprehensive recovery system, which comprises: a membrane separation device for treating refinery gas being rich in hydrogen gas and light hydrocarbons and separating the refinery gas into the hydrogen product and the retentate gas, wherein the hydrogen product is subjected to hydrogen recovery, and the retentate gas is conveyed into the inlet on the bottom portion of a first absorption tower or a second absorption tower; a PSA device for treating a stream containing high-purity hydrogen and low-purity light hydrocarbons; and an oil absorption device for carrying out light hydrocarbon recovery, wherein the oil absorption device comprises the first absorption tower, the second absorption tower, a first desorption tower, a second desorption tower and a subsequent product separation unit, wherein the first absorption tower is used for treating a stream having high hydrogen content and containing rich light hydrocarbons, the second absorption tower is used for treating a stream having low hydrogen content and containing rich light hydrocarbons, and the requirement of the liquefied gas product on the C2 content can be met with the double-desorption tower device.
Description
Technical field
The present invention relates to a kind of hydrogen recovery system, also relate to a kind of light hydrocarbon recovery system, particularly a kind of hydrogen and lighter hydrocarbons comprehensive recovery system.
Background technology
Along with the heaviness and peracid of processing crude oil are high-sulfurized, hydrogen becomes more and more important for the production of guarantee qualified products in refinery, and high product hydrogen cost and hydrogen production bioreactor investment, make the recovery of hydrogen particularly important.Current in the recovery technology technique relative maturity situation of high-purity hydrogen, seem more have realistic meaning for how effectively reclaiming medium and low-purity hydrogen discharge stream stock economically.Meanwhile, owing to forming containing other high value lighter hydrocarbons in these discharge stream stocks, consider the synthetical recovery of hydrogen and lighter hydrocarbons, to making rational use of resources, strengthening effects of energy saving and emission reduction, increasing economic efficiency significant.
Reclaim for independent hydrogen, considerable oil plant utilizes pressure swing adsorption method, membrane separation process to reclaim the purification that the oil refinery dry gas of higher degree has carried out hydrogen.The high score that this part oil refinery dry gas is generally hydrogenation plant is vented outward, desulfurization low point of gas etc.Pressure swing adsorption method utilizes the solid absorbent such as active carbon, molecular sieve, silica gel be contained in vertical pressure vessel, carries out selective absorption, thus reach the object of gas separaion to the various impurity in mist.Membrane separation process be with the partial pressure difference of film both sides for motive force, utilize the difference of gas with various infiltration rate in film, make its film two lateral enrichment with realize be separated process.
Lighter hydrocarbons recovery independent in refinery is common in the absorption stabilizing apparatus in the devices such as Atmospheric vacuum, catalytic cracking and delayed coking, for absorbing the tower overhead gas discharged in this device, as Atmospheric vacuum three top gas, catalytic cracking rich gas, rich tail gas of coking plant etc.Employing " absorption tower-desorber-stabilizer " three tower fractionation process flow process, is separated lighter hydrocarbons by absorption and desorption, to obtain the products such as the qualified stable gasoline of qualified dry gas, liquefied gas and vapour pressure.Traditional oils absorption process is applicable to the C3+ lighter hydrocarbons recovery of middle and small scale.
Cold separation technology, is traditional low temperature recovery process, usually runs at elevated pressures, utilizes the boiling temperature difference of feed component to reach separating effect.The occasion that this technology is applicable on a large scale, multicomponent reclaims simultaneously, has the advantage that ratio defective product is high, separation purity is high.But for nitrogen, refinery gas that methane content is higher, need extremely low condensation temperature, separating energy consumption and equipment investment are very high.
In above-mentioned three kinds of techniques, only have cold separation technology can consider the synthetical recovery of hydrogen and lighter hydrocarbons, due to its equipment investment and separating energy consumption higher, it is applicable to large-scale occasion, is not suitable for the stream stock that the compositional purity such as hydrogen, nitrogen and methane are relatively high.Its isolated ethane product generally can as ethylene raw, but this technology domestic is immature.
Because hydrogen purification device is to the restriction of hydrogen purity in unstripped gas, make to be recycled by UF membrane or psa unit compared with the hydrogen resources in the oil refinery dry gas of low-purity.Meanwhile, if there is the heavy hydrocarbon (C3+ lighter hydrocarbons) of higher degree in UF membrane and pressure-variable adsorption raw material, for UF membrane, retentate side lime set may be caused and cause the permanent damage of film, and for pressure-variable adsorption, likely cause the inactivation of adsorbent, thus impact operation.Meanwhile, pressure swing adsorption is relatively applicable to the stream stock that process hydrogen purity is greater than 50v%, and generally its rate of recovery is about 90%, and product hydrogen purity can reach more than 99.9%.UF membrane can process the lower stream stock of hydrogen purity, but its product purity is up to 98v%, and the rate of recovery is 80-92%.
For the lighter hydrocarbons recovery technology of current widely used oil-absorption process, C3+ light hydrocarbon product can only be reclaimed, hydrogen product wherein cannot be reclaimed, simultaneously, due to the restriction of absorption process, if the lighter hydrocarbons in the stream stock that recover hydrogen purity is relatively high, will have a strong impact on its assimilation effect, reduce the light hydrocarbon product rate of recovery.
Summary of the invention
The invention provides the two desorb hydrogen of a kind of biabsorption and lighter hydrocarbons comprehensive recovery system, object is oily absorption of light hydrocarbon recovery technology to combine with technology for hydrogen purification, realizes the comprehensive reutilization of lighter hydrocarbons and hydrogen to the stream stock of different hydrogen purity in refinery.
For achieving the above object, the technical solution used in the present invention is:
The two desorb hydrogen of a kind of biabsorption and lighter hydrocarbons comprehensive recovery system, it is characterized in that, it comprises:
Membrane separation device, its entrance communicates with first strand of oil refinery dry gas, and for being separated into hydrogen production and ooze residual air, described hydrogen production gives hydrogen and reclaims, described in ooze residual air and will send into the bottom inlet of following first absorption tower or second absorption tower;
Oil absorption plant, it comprises the first absorption tower, second absorption tower, the first desorber, the second desorber and light hydrocarbon product separative element, wherein:
The bottom inlet on described first absorption tower is connected with second strand of oil refinery dry gas, the bottom inlet of described second absorption tower is connected with the 3rd strand of oil refinery dry gas, the lean absorption oil of systemic circulation enters the tower top on described first absorption tower and the tower top of described second absorption tower, at the bottom of the tower on described first absorption tower and the tower bottom flow of described second absorption tower go out after merge into rich absorbent oil, described rich absorbent oil enter described first desorber and complete first time desorb after, flow into described second desorber again to complete second time desorb and to become lean absorption oil, described lean absorption oil goes out from the tower bottom flow of described second desorber again, after cooling pressurization, be back to the tower top on described first absorption tower and the tower top of described second absorption tower, to form circulation,
The tower overhead gas of described second desorber connects with described light hydrocarbon product separative element.
Also comprise psa unit or another membrane separation device, its entrance is connected with the 4th strand of oil refinery dry gas, and the 4th strand of oil refinery dry gas is separated into High Purity Hydrogen and stripping gas, and described High Purity Hydrogen gives hydrogen and reclaims, and described stripping gas gives fuel gas and reclaims.
The tower overhead gas on described first absorption tower is connected with the entrance of described psa unit or another membrane separation device.
The tower overhead gas of described second absorption tower gives fuel gas and reclaims.
The tower overhead gas of described first desorber connects with the bottom inlet of described second absorption tower.
Described rich absorbent oil is divided into two strands, and wherein one enters the tower top of described first desorber, and one enters the middle and upper part of described first desorber in addition.
Boil again from the lean absorption oil stage casing that is first and the first desorber that the tower bottom flow of described second desorber goes out and carry out the first heat exchange, then the second heat exchange is carried out with described light hydrocarbon product separative element, then carry out the 3rd heat exchange and the 4th heat exchange respectively with two strands of described rich absorbent oils, then pump into the tower top on described first absorption tower and the tower top of described second absorption tower.
Described light hydrocarbon product separative element is the arbitrary or any combination of depropanizing tower, debutanizing tower, depentanizer.
Described first strand of oil refinery dry gas is higher degree hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, described second strand of oil refinery dry gas is medium purity hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, described 3rd strand of oil refinery dry gas is low-purity hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, and described 4th strand of oil refinery dry gas is higher degree hydrogen and the stream stock of lower C3+ lighter hydrocarbons content.
Higher degree hydrogen, medium purity hydrogen and low-purity hydrogen refer to that concentration is more than or equal to the hydrogen of 50v%, concentration is more than or equal to 30v% respectively and are less than the hydrogen that the hydrogen of 50v% and concentration is less than 30v%; Described higher C3+ lighter hydrocarbons content refers to that C3+ content is more than or equal to 5v%, and described lower C3+ lighter hydrocarbons content refers to that C3+ content is less than 5v%.
Generally speaking, the present patent application adopts technique scheme, and compared with old product, tool has the following advantages:
1, technology for hydrogen purification and lighter hydrocarbons recovery technology organically combine by the present invention, take into full account influencing each other of hydrogen and lighter hydrocarbons, oil refinery dry gas is considered to the synthetical recovery of hydrogen and lighter hydrocarbons, effectively raise the rate of recovery of hydrogen and lighter hydrocarbons, improve the utilization rate of device.
2, the present invention is according to oil refinery dry gas feature, to supply raw materials multiple entry, optimum choice stream stock feed entrance point, thus effectively can reclaim the stream stock of each different hydrogen purity range and lighter hydrocarbons content, effectively can not only reclaim high-purity hydrogen, more low-purity hydrogen stream stock is reclaimed and become practical, thus improve refinery hydrogen utilization ratio.
3, heat-exchange network coupling is not rationally one of major reason causing energy consumption larger.The present invention again heat exchanging network is optimized coupling.The present invention adopts heat integrated, takes into full account the waste heat recovery of circulation lean absorption oil and 3.5MPag steam, reduces steam and cooling water public work consumption, thus reduces energy consumption.
4, the present invention adopts the regeneration of lean absorption oil device inside, thus does not rely on other devices, the independence of assurance device.
Accompanying drawing explanation
Fig. 1 is the structural representation of the two desorb hydrogen of biabsorption provided by the invention and lighter hydrocarbons comprehensive recovery system;
Fig. 2 is the stream stock information table in application example of the present invention;
Fig. 3 be in application example of the present invention hydrogen lighter hydrocarbons synthetical recovery with reclaim product recovery rate contrast table respectively;
Fig. 4 be in application example of the present invention hydrogen lighter hydrocarbons synthetical recovery with reclaim energy consumption comparison table respectively;
Fig. 5 be in application example of the present invention hydrogen lighter hydrocarbons synthetical recovery with reclaim Efficiency Comparison table respectively.
Description of reference numerals: first-class stock 11; Second stock 12; 3rd stream stock 13; 4th stream stock 14; Membrane separation device 20; Hydrogen reclaims 21; Psa unit 30; Fuel gas reclaims 31; First absorption tower 41; Second absorption tower 42; First desorber 43; Second desorber 44; Depropanizing tower 45; Debutanizing tower 46; Light naphthar 51; C3 product 52; C4 product 53; First heat exchange 61; Second heat exchange 62; 3rd heat exchange 63; 4th heat exchange 64; Jet chimney 70.
Detailed description of the invention
First, the present invention, according to the feature of hydrogen and C3+ lighter hydrocarbons content, as above classifies to oil refinery dry gas.
According to the classification to oil refinery dry gas, the present invention proposes the two desorb hydrogen of biabsorption and lighter hydrocarbons comprehensive recovery system, technology for hydrogen purification and oily absorption techniques organically combine by the present invention, make full use of influencing each other of hydrogen and C3+ lighter hydrocarbons, be provided with four feed(raw material)inlets, it processes higher degree hydrogen and the first-class stock 11(of higher C3+ lighter hydrocarbons content and classification 1 respectively), medium purity hydrogen and the second stock 12(of higher C3+ lighter hydrocarbons content and classification 2), low-purity hydrogen and the 3rd of higher C3+ lighter hydrocarbons content the stream stock 13(and classification 3), higher/medium purity hydrogen and the 4th of lower C3+ lighter hydrocarbons content the stream stock 14(and classification 4 and classification 5).
As shown in Figure 1, the two desorb hydrogen of biabsorption provided by the invention and lighter hydrocarbons comprehensive recovery system schematic diagram, it comprises:
Membrane separation device 20, its entrance with higher degree hydrogen and the first-class stock 11(of higher C3+ lighter hydrocarbons content and classification 1) be connected, what this first-class stock 11 is separated into hydrogen production (purity is up to 98v%) and enrichment C3+ lighter hydrocarbons oozes residual air, described hydrogen production can send into separately the relatively low pipe network of hydrogen purity, such as reformation hydrogen pipe network, or give hydrogen again together with merging with the hydrogen product that following psa unit 30 produces and reclaim 21, described in ooze residual air and will send into the bottom inlet on following first absorption tower 41;
Psa unit 30, its entrance is with relatively high-purity hydrogen and the 4th of lower C3+ lighter hydrocarbons content the flow stock 14(and classification 4) be connected, 4th stream stock is separated into the stripping gas of High Purity Hydrogen (hydrogen purity > 99.9%) and a small amount of C3+ lighter hydrocarbons, described High Purity Hydrogen can give hydrogen and reclaim 21, described stripping gas gives fuel gas and reclaims 31 after pressure-raising, also directly can drain into refinery's low pressure gas system;
Oil absorption plant, it comprises the first absorption tower 41, second absorption tower 42, first desorber 43, second desorber 44 and light hydrocarbon product separative element (as depropanizing tower 45 and debutanizing tower 46), wherein:
The bottom inlet on described first absorption tower 41 with medium purity hydrogen and the second stock 12(of higher C3+ lighter hydrocarbons content and classification 2) and membrane separation device 20 in produce described in ooze residual air and be connected, the bottom inlet of described second absorption tower 42 is with low-purity hydrogen and the 3rd of higher C3+ lighter hydrocarbons content the flow stock (i.e. classification 3) and be connected, the lean absorption oil of systemic circulation enters the described tower top on the first absorption tower 41 and the tower top of described second absorption tower 42, after respectively flowing the C3+ lighter hydrocarbons of stock in each self-absorption respective absorption tower, at the bottom of the tower on described first absorption tower 41 and the tower bottom flow of described second absorption tower 42 go out after merge into rich absorbent oil, described rich absorbent oil is divided into two strands, wherein one enters the tower top of described first desorber 43, one enters the middle and upper part of described first desorber 43 in addition, described first desorber 43 arranges stage casing reboiler and tower bottom reboiler, tower top does not arrange backflow, make two strands of rich absorbent oils after the first desorber 43 completes first time desorb, flow into described second desorber 44 again to complete second time desorb and to become lean absorption oil, described lean absorption oil goes out from the tower bottom flow of described second desorber 44 again, after cooling pressurization, be back to the described tower top on the first absorption tower 41 and the tower top of described second absorption tower 42, to form circulation,
Enter the medium purity hydrogen of the stream stock on described first absorption tower 41, methane, ethane enrichment be tower overhead gas, described tower overhead gas is connected with the entrance of described psa unit 30, to carry out hydrogen purification recovery; In addition, described first absorption tower 41 is provided with two stage casing backflow coolings, can improve absorption efficiency;
Described second absorption tower 42 also arranges stage casing backflow cooling; Enter the low-purity hydrogen of the stream stock of described second absorption tower 42, methane, ethane enrichment be tower overhead gas, the described stripping gas that the tower overhead gas of described second absorption tower 42 and described psa unit 30 produce merges, and gives fuel gas together and reclaims 31;
The tower overhead gas of described first desorber 43 can connect with the bottom inlet of described second absorption tower 42, does recycling again;
The tower overhead gas of described second desorber 44 is connected to light hydrocarbon product separative element, as required the tower overhead gas of the second desorber 44 is separated into the light hydrocarbon product of different brackets.Such as in the present embodiment, the tower overhead gas of described second desorber 44 connects with depropanizing tower 45 and debutanizing tower 46 successively, C3 product 52 is wherein separated from the tower top of described depropanizing tower 45, C4 product 53 is wherein separated from the tower top of described debutanizing tower 46, and isolates light naphthar 51 from the tower bottom of described debutanizing tower 46.
As shown in the above, the present invention is directed to different classes of oil refinery dry gas, adopt different recycling modes:
Reclaim for hydrogen, UF membrane and pressure swing adsorption combine by the present invention, and for the stream stock that hydrogen content is higher, such as classification 1, considers that hydrogen does lighter hydrocarbons recovery after reclaiming, and it is also conceivable to hydrogen recovery after lighter hydrocarbons recovery.
For lighter hydrocarbons recovery, consider scale and reclaim C3+ lighter hydrocarbons, adopting traditional oil-absorption process technology, on absorption tower is arranged, according to different hydrogen purity, being provided with double absorption column and two desorber.Wherein: the first absorption tower 41 processes the relatively high stream stock of hydrogen content, after the first absorption tower 41, in tower overhead gas, hydrogen will by enrichment, and C3+ lighter hydrocarbons will enrichment at the bottom of tower, and the tower overhead gas of high hydrogen purity can be sent to pressure-variable adsorption and do hydrogen purification.Second absorption tower 42 processes the relatively low stream stock of hydrogen content, this tower overhead gas by carrying device, as hydrogen feedstock or fuel gas.The setting of two desorber mainly considers that liquefied gas 52 product be separated is to the content requirement of C2.
In addition, invention also contemplates that heat is integrated, to reduce energy consumption.As shown in Figure 1, the present invention is provided with jet chimney 70, and boiling in the bottom of itself and the second desorber 44, boil in the bottom of the first desorber 43 and boils in the bottom of depropanizing tower 45 again again again carries out heat exchange, successively for oily absorption plant provides the heat needed for work.And in order to reduce the energy consumption of described jet chimney 70, the heat that the lean absorption oil that the present invention utilizes the tower bottom flow of described second desorber 44 to go out is rich in, make it first boil again with the stage casing of the first desorber 43 and carry out the first heat exchange 61, then the second heat exchange 62 is carried out with described light hydrocarbon product separative element (boiling again in the bottom as debutanizing tower 46 wherein), carry out the 3rd heat exchange 63 and the 4th heat exchange 64 respectively with two strands of described rich absorbent oils again, make it after supercooling, just pump into the described tower top on the first absorption tower 41 and the tower top of described second absorption tower 42.Now, because two strands of described rich absorbent oils enter the first desorber 43 again after above-mentioned 3rd heat exchange 63 and the 4th heat exchange 64, and described first desorber 43 has also carried out above-mentioned first heat exchange 61, institute's calorific requirement of the first desorber can be made significantly to reduce, saved the energy.In like manner, due to the heat that described debutanizing tower 46 utilizes above-mentioned second heat exchange 62 to produce, alternative steam provides heat for it.The utilization of cyclic absorption oil heat effectively can reduce the public work such as cooling water and steam consumption.
In traditional handicraft, through UF membrane ooze residual air due to hydrogen purity lower, often directly carry out fuel gas recovery, but its pressure ratio is higher, just there is certain kinetic energy waste, and the residual air of oozing produced due to membrane separation device 20 in the present invention is sent to the first absorption tower 41, not only can improve the rate of recovery of C3+ lighter hydrocarbons, more effectively make use of the high pressure that UF membrane oozes residual air, save the energy.
Generally speaking, the present patent application adopts technique scheme, and compared with old product, tool has the following advantages:
1, technology for hydrogen purification and lighter hydrocarbons recovery technology organically combine by the present invention, take into full account influencing each other of hydrogen and lighter hydrocarbons, oil refinery dry gas is considered to the synthetical recovery of hydrogen and lighter hydrocarbons, effectively raise the rate of recovery of hydrogen and lighter hydrocarbons, improve the utilization rate of device.
2, the present invention is according to oil refinery dry gas feature, to supply raw materials multiple entry, optimum choice stream stock feed entrance point, thus effectively can reclaim the stream stock of each different hydrogen purity range and lighter hydrocarbons content, effectively can not only reclaim high-purity hydrogen, more low-purity hydrogen stream stock is reclaimed and become practical, thus improve refinery hydrogen utilization ratio.
3, heat-exchange network coupling is not rationally one of major reason causing energy consumption larger.The present invention again heat exchanging network is optimized coupling.The present invention adopts heat integrated, takes into full account the waste heat recovery of cyclic absorption oil, reduces steam and cooling water public work consumption, thus reduces energy consumption.
4, the present invention adopts the regeneration of lean absorption oil device inside, thus does not rely on other devices, the independence of assurance device.
5, the present invention is very flexible:
(1) according to refinery's actual conditions, effectively can select and change unit wherein, such as according to the requirement to hydrogen product, psa unit 30 can be replaced by membrane separation device 20.
(2) hydrogen purity of oozing residual air that can produce according to membrane separation device 20, selects feeding first absorption tower 41 or second absorption tower 42.
(3) if there is no relatively high-purity hydrogen and be rich in the stream stock of C3+ lighter hydrocarbons, can cancel the membrane separation device 20 in technological process;
(4) when the first absorption tower 41 tower overhead gas hydrogen purity is lower and there is not high hydrogen purity and the less stream stock of C3+ lighter hydrocarbons, psa unit 30 can be cancelled;
(5) absorb oil can select flexibly as the case may be, as diesel oil, heavy naphtha, boat coal etc.;
(6) according to separation of products requirement, light hydrocarbon product separative element can be the arbitrary or any combination in depropanizing tower, debutanizing tower, depentanizer.
Instance analysis:
With the data of a certain refinery for case: the present invention utilizes the bilingual suction flow process of biabsorption to hydrogen, lighter hydrocarbons synthetical recovery, carry out the hydrogen of lighter hydrocarbons recovery with traditional absorption-desorb-systems stabilisation, lighter hydrocarbons reclaim respectively and contrast.
Refer to the stream stock information table shown in Fig. 2, oil refinery dry gas is divided into hydrogen purity scope not homogeneous turbulence stock, hydrogen purity is at more than 50v%, and the less stream stock 1,2 of C3+ component directly sends into psa unit 30, the High Purity Hydrogen of psa unit 30 output gives hydrogen and reclaims 21, the stripping gas of psa unit 30 output gives fuel gas through pressure-raising and reclaims 31, or directly enters low pressure gas system.
The compressed heat exchange of stream stock 3-7 that hydrogen purity is rich in lighter hydrocarbons at more than 50v% simultaneously enters UF membrane, and UF membrane hydrogen production purity is 98v%, is mixed into PSA purifies further with absorption tower top gas, obtains the High Purity Hydrogen of hydrogen purity > 99.9%.
Hydrogen purity oozes with film together with residual air at the stream stock 8-13 of 30-50v% and enters at the bottom of the first absorption tower 41 tower after desulfurization, compression, cooling, the lean absorption oil of systemic circulation sends into the first absorption tower 41 tower top, first absorption tower 41 arranges two stage casing backflow coolings, to improve absorption efficiency.First absorption tower 41 tower overhead gas is sent into psa unit 30 and is carried out hydrogen purification recovery.After rich absorbent oil at the bottom of rich absorbent oil at the bottom of first absorption tower 41 tower and second absorption tower 42 tower merges after heating pressure-raising point two stream stocks, directly the first desorber 43 tower top is sent into after one of them stream stock is heated to 70 DEG C, another one stream stock-traders' know-how cross with lean absorption oil stream stock heat exchange to 110 DEG C after, send into the first desorber 43 middle and upper part.First desorber 43 arranges stage casing reboiler and tower bottom reboiler, and tower top does not arrange backflow.
Hydrogen purity is at below 20v% and the stream stock 14-18 being rich in lighter hydrocarbons sends at the bottom of second absorption tower 42 tower together with the first desorber 43 tower overhead gas, and tower top sends into the lean absorption oil of circulation.Second absorption tower 42 also arranges stage casing backflow cooling.Second absorption tower 42 tower overhead gas sends into refinery's fuel gas pipe network together with the Utilization of PSA Relief Gas of pressure-raising.
The second desorber 44 separate absorbent oil and light hydrocarbon component is delivered to after oil heating at the bottom of first desorber 43 tower.Light hydrocarbon component is distillated by tower top, circulation lean absorption oil at the bottom of tower for the first desorber 43 stage casing boil again, boil again at the bottom of debutanizing tower, the first desorber 43 part charging, depropanizing tower charging, the first desorber 43 combined feed heat is provided after temperature be down to 82 DEG C, be cooled with circulating water 40 DEG C again, pressurizeed by pump, send into the first absorption tower 41 with second absorption tower 42 as poor absorbent.Second desorber 44 tower top distillates lighter hydrocarbons and obtains C3 product 52, C4 product 53 and light naphthar 51 through depropanizing tower, debutanizing tower.
Heat is integrated:
3.5MPag steam boils for boiling at the bottom of the second desorber 44 tower, at the bottom of the first desorber 43 tower again again, boil at the bottom of depropanizing tower tower again, depropanizing tower charging provides heat, and hot water finally goes out device with 60 DEG C.
Circulation naphtha for the first desorber 43 stage casing boil again, boil again at the bottom of debutanizing tower tower, the first desorber 43 part charging, the first desorber 43 combined feed provide heat, now temperature is down to 82 DEG C, be cooled with circulating water 40 DEG C again, pressurization feeding first absorption tower 41 and second absorption tower 42 top are as absorbent.
As a comparison, the stream stock 1-8 PSA containing more hydrogen, less lighter hydrocarbons is carried out hydrogen recovery by us.The stream stock 9-18 being rich in lighter hydrocarbons is carried out lighter hydrocarbons recovery by traditional absorption-desorb-systems stabilisation, is first entered absorption tower, and absorption tower arranges two stage casing backflow coolings, to improve absorption efficiency.Absorption tower top gas is sent to fuel gas pipe network, at the bottom of tower rich absorbent oil through heating pressure-raising after be divided into two flow stocks, one of them stream stock directly send into desorber tower top, another one stream stock-traders' know-how cross with the heat exchange of lean absorption oil stream stock after, send into desorber middle and upper part.In order to improve desorption efficiency, desorber arranges stage casing reboiler and tower bottom reboiler, and tower top does not arrange backflow.The tower overhead gas of desorber is sent back to bottom absorption tower, oil at the bottom of desorber enters light ends fractionation tower and fractionates out lighter hydrocarbons, after the circulation lean absorption oil at the bottom of tower and the reboiler heat exchange of desorber stage casing, with desorber charging heat exchange respectively, pressurizeed by pump after cooling, send into absorption tower as poor absorbent.Lighter hydrocarbons, through follow-up depropanizing tower, debutanizing tower, obtain C3 product, C4 product and light naphthar.
Heat is integrated:
3.5MPag jet chimney boils for boiling at the bottom of light ends fractionation tower, at the bottom of desorber again again, boil at the bottom of debutanizing tower again, desorber section charging provides heat, and hot water finally goes out device with 87 DEG C.
Circulation naphtha for boiling again at the bottom of the charging of light ends fractionation tower, depropanizing tower, boil in desorber stage casing, desorber section charging, depropanizing tower charging provide heat again, now temperature reduces to 92 DEG C, be cooled with circulating water 40 DEG C again, pressurization sends into top, absorption tower as absorbent.
Refer to Fig. 3, hydrogen lighter hydrocarbons synthetical recovery and reclaim product recovery rate contrast table respectively, and consult Fig. 4, hydrogen lighter hydrocarbons synthetical recovery and reclaim energy consumption comparison table (energy consumption index basis GB/T50441-2007 " petrochemical industry designs energy consumption calculation standard ") respectively, consulting Fig. 5 again, is hydrogen lighter hydrocarbons synthetical recovery and reclaim Efficiency Comparison table respectively.
As can be seen from the above results, the heat that the synthetical recovery of hydrogen lighter hydrocarbons takes full advantage of recycle oil and steam is to material and boil and provide thermal source, after heat exchange, hot water goes out device with 60 DEG C, recycle oil is cooled to 82 DEG C, greatly optimize heat exchange process, can energy recovery rate be improved, reduce the public work such as low-temperature receiver and thermal source consumption.The specific energy consumption that hydrogen lighter hydrocarbons reclaim respectively is 194kg/t, and synthetical recovery specific energy consumption is 171.7kg/t, and specific energy consumption decreases.
Although the running cost of synthetical recovery increases to some extent, but reclaim respectively relative to hydrogen lighter hydrocarbons, lighter hydrocarbons after hydrogen can effectively reclaim by synthetical recovery in tail gas, and the hydrogen after lighter hydrocarbons recovery in tail gas reclaims, significantly improve product recovery rate (all more than 85%), many recovery C3 products 5800 tons/year, C4 product 12264 tons/year, light naphthar 5628 tons/year, hydrogen 1,205 ten thousand mark stands/year, thus makes economic benefit add 5,053 ten thousand yuan/year.Flow process of the present invention hydrogen effectively in convection current stock, lighter hydrocarbons can carry out synthetical recovery, creates more economic worth.
Hydrogen lighter hydrocarbons synthetical recovery equipment investment expense is 1.25 times of respectively reclaimer investment cost, and investment cost difference payoff period is 0.98.
More than illustrate just illustrative for the purpose of the present invention; and nonrestrictive, those of ordinary skill in the art understand, when not departing from the spirit and scope that claim limits; many amendments, change or equivalence can be made, but all will fall within protection scope of the present invention.
Claims (10)
1. the two desorb hydrogen of biabsorption and a lighter hydrocarbons comprehensive recovery system, it is characterized in that, it comprises:
Membrane separation device, its entrance communicates with first strand of oil refinery dry gas, and for being separated into hydrogen production and ooze residual air, described hydrogen production gives hydrogen and reclaims, described in ooze residual air and will send into the bottom inlet of following first absorption tower or second absorption tower;
Oil absorption plant, it comprises the first absorption tower, second absorption tower, the first desorber, the second desorber and light hydrocarbon product separative element, wherein:
The bottom inlet on described first absorption tower is connected with second strand of oil refinery dry gas, the bottom inlet of described second absorption tower is connected with the 3rd strand of oil refinery dry gas, the lean absorption oil of systemic circulation enters the tower top on described first absorption tower and the tower top of described second absorption tower, at the bottom of the tower on described first absorption tower and the tower bottom flow of described second absorption tower go out after merge into rich absorbent oil, described rich absorbent oil enter described first desorber and complete first time desorb after, flow into described second desorber again to complete second time desorb and to become lean absorption oil, described lean absorption oil goes out from the tower bottom flow of described second desorber again, after cooling pressurization, be back to the tower top on described first absorption tower and the tower top of described second absorption tower, to form circulation,
The tower overhead gas of described second desorber connects with described light hydrocarbon product separative element.
2. the two desorb hydrogen of biabsorption according to claim 1 and lighter hydrocarbons comprehensive recovery system, it is characterized in that: also comprise psa unit or another membrane separation device, its entrance is connected with the 4th strand of oil refinery dry gas, 4th strand of oil refinery dry gas is separated into High Purity Hydrogen and stripping gas, described High Purity Hydrogen gives hydrogen and reclaims, and described stripping gas gives fuel gas and reclaims.
3. the two desorb hydrogen of biabsorption according to claim 2 and lighter hydrocarbons comprehensive recovery system, is characterized in that: the tower overhead gas on described first absorption tower is connected with the entrance of described psa unit or another membrane separation device.
4. the two desorb hydrogen of biabsorption according to claim 2 and lighter hydrocarbons comprehensive recovery system, is characterized in that: the tower overhead gas of described second absorption tower gives fuel gas and reclaims.
5. the two desorb hydrogen of biabsorption according to claim 1 and lighter hydrocarbons comprehensive recovery system, is characterized in that: the tower overhead gas of described first desorber connects with the bottom inlet of described second absorption tower.
6. the two desorb hydrogen of biabsorption according to claim 1 and lighter hydrocarbons comprehensive recovery system, it is characterized in that: described rich absorbent oil is divided into two strands, wherein one enters the tower top of described first desorber, and one enters the middle and upper part of described first desorber in addition.
7. the two desorb hydrogen of biabsorption according to claim 6 and lighter hydrocarbons comprehensive recovery system, it is characterized in that: boil again from the lean absorption oil stage casing that is first and the first desorber that the tower bottom flow of described second desorber goes out and carry out the first heat exchange, then the second heat exchange is carried out with described light hydrocarbon product separative element, then carry out the 3rd heat exchange and the 4th heat exchange respectively with two strands of described rich absorbent oils, then pump into the tower top on described first absorption tower and the tower top of described second absorption tower.
8. the two desorb hydrogen of biabsorption according to claim 1 and lighter hydrocarbons comprehensive recovery system, is characterized in that: described light hydrocarbon product separative element is the arbitrary or any combination of depropanizing tower, debutanizing tower, depentanizer.
9. the two desorb hydrogen of biabsorption according to claim 2 and lighter hydrocarbons comprehensive recovery system, it is characterized in that: described first strand of oil refinery dry gas is higher degree hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, described second strand of oil refinery dry gas is medium purity hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, described 3rd strand of oil refinery dry gas is low-purity hydrogen and the stream stock of higher C3+ lighter hydrocarbons content, and described 4th strand of oil refinery dry gas is higher degree hydrogen and the stream stock of lower C3+ lighter hydrocarbons content.
10. the two desorb hydrogen of biabsorption according to claim 9 and lighter hydrocarbons comprehensive recovery system, is characterized in that: higher degree hydrogen, medium purity hydrogen and low-purity hydrogen refer to that concentration is more than or equal to the hydrogen of 50v%, concentration is more than or equal to 30v% respectively and is less than the hydrogen that the hydrogen of 50v% and concentration is less than 30v%; Described higher C3+ lighter hydrocarbons content refers to that C3+ content is more than or equal to 5v%, and described lower C3+ lighter hydrocarbons content refers to that C3+ content is less than 5v%.
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| CN112299942A (en) * | 2019-08-02 | 2021-02-02 | 中国石化工程建设有限公司 | Method and system for recovering carbon dioxide fraction in refinery dry gas |
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| CN104624022B (en) | 2017-04-05 |
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