CN109173583A - A kind of medium temperature vacuum pressure swing adsorption system and method - Google Patents
A kind of medium temperature vacuum pressure swing adsorption system and method Download PDFInfo
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- CN109173583A CN109173583A CN201811160591.3A CN201811160591A CN109173583A CN 109173583 A CN109173583 A CN 109173583A CN 201811160591 A CN201811160591 A CN 201811160591A CN 109173583 A CN109173583 A CN 109173583A
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- 238000001179 sorption measurement Methods 0.000 claims abstract description 353
- 238000000034 method Methods 0.000 claims abstract description 127
- 230000008569 process Effects 0.000 claims abstract description 93
- 238000011010 flushing procedure Methods 0.000 claims abstract description 59
- 239000003463 adsorbent Substances 0.000 claims abstract description 30
- 238000003795 desorption Methods 0.000 claims abstract description 25
- 230000006837 decompression Effects 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 285
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 17
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 16
- 239000001257 hydrogen Substances 0.000 claims description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 14
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 8
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 6
- 239000001569 carbon dioxide Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 238000000926 separation method Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000013022 venting Methods 0.000 claims 9
- 230000008929 regeneration Effects 0.000 claims 2
- 238000011069 regeneration method Methods 0.000 claims 2
- 238000007599 discharging Methods 0.000 claims 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims 1
- 238000011946 reduction process Methods 0.000 claims 1
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 72
- 230000002411 adverse Effects 0.000 description 44
- 230000001174 ascending effect Effects 0.000 description 44
- 238000010521 absorption reaction Methods 0.000 description 42
- 238000004080 punching Methods 0.000 description 31
- 238000012163 sequencing technique Methods 0.000 description 28
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000000746 purification Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 239000000446 fuel Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000000274 adsorptive effect Effects 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000002808 molecular sieve Substances 0.000 description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- GJEAMHAFPYZYDE-UHFFFAOYSA-N [C].[S] Chemical compound [C].[S] GJEAMHAFPYZYDE-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000002309 gasification Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000007420 reactivation Effects 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000003009 desulfurizing effect Effects 0.000 description 1
- 238000001784 detoxification Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002955 isolation Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- -1 vapor Chemical compound 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
- B01D53/04—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography with stationary adsorbents
- B01D53/047—Pressure swing adsorption
- B01D53/0476—Vacuum pressure swing adsorption
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Separation Of Gases By Adsorption (AREA)
Abstract
本发明公开了一种中温真空变压吸附系统及方法。系统包括吸附塔、产品气罐、顺冲气罐、冲洗气罐、逆放气罐等。系统设置多个吸附塔或均压罐。方法包括吸附、恒压顺冲、逆放以及冲洗和/或真空解吸等工序。多塔或塔罐运行中，恒压顺冲工序后的吸附塔进入均压降压工序，同时与该吸附塔连接的另一吸附塔或均压罐进入均压升压工序。降压后的吸附塔进入冲洗和/或真空解吸使吸附剂再生后进入均压升压，同时连接的另一吸附塔或均压罐进入均压降压。恒压顺冲包括高压顺冲和低压顺冲。本发明通过加入高压顺冲、低压顺冲等恒压顺冲步骤，使得吸附结束后吸附塔内的有效气体仍能进入产品气罐，明显改善变压吸附气体回收率，同时产品气纯度仍然可以达到要求。
The invention discloses a medium temperature vacuum pressure swing adsorption system and method. The system includes adsorption tower, product gas tank, forward gas tank, flush gas tank, reverse gas tank, etc. The system is equipped with multiple adsorption towers or pressure equalizing tanks. The method includes processes such as adsorption, constant pressure forward flushing, reverse deposition, and flushing and/or vacuum desorption. In multi-tower or tower-tank operation, the adsorption tower after the constant pressure flushing process enters the pressure equalization and decompression process, and at the same time, another adsorption tower or pressure equalization tank connected to the adsorption tower enters the pressure equalization and boosting process. The depressurized adsorption tower enters into flushing and/or vacuum desorption to regenerate the adsorbent and then enters into pressure equalization and boosting, and at the same time, another connected adsorption tower or pressure equalization tank enters into equalization and decompression. Constant pressure forward flushing includes high pressure forward flushing and low pressure forward flushing. In the present invention, by adding constant pressure forward flushing steps such as high pressure forward flushing, low pressure forward flushing, etc., the effective gas in the adsorption tower can still enter the product gas tank after the adsorption is completed, the recovery rate of the pressure swing adsorption gas is obviously improved, and the purity of the product gas can still be Meet the requirements.
Description
Technical field
The present invention relates to a kind of medium temperature vacuum pressure swing adsorption system and methods, belong to gas purification technical field.
Background technique
In the fields such as chemical industry, power generation, need to carry out all kinds of mixed gas to need in isolation of purified, such as ammonia synthesis process
It will be to the CO in synthesis gas2、H2S etc. is removed, and the hydrogen for being made pure is synthesized with being used to react with nitrogen.Conventional hybrid gas
Body purification style is washed for low-temp methanol, and this method cools down firstly the need of to gas, and gas after cooling enters absorption tower,
Middle CO2、H2S by low temperature liquid methanol absorption, remaining gas through cold recovery, again heat after continue subsequent handling.Gas
Cooling and reheating process can bring the waste of energy, and need complicated heat exchange and refrigerating plant.
The method of pressure swing adsorption purge be it is a kind of various gases can be separated and recovered, obtain high-purity specific components gas
The effective ways of body.Traditional pressure swing adsorption technique is mainly used for air separation and gas purification recycling, and operating temperature is normal
Temperature, purity of product gas and yield are difficult to reach higher level simultaneously, need by process modification and promoted performance of the adsorbent come
Develop skill index.CN102351147A discloses a kind of for CO2、H2S and H2The medium temperature pressure-variable adsorption side of mixed gas separation
Method, directly to remove CO under medium temperature2、H2The sour gas such as S avoid in medium temperature gas purification process due to the bring that cools down
Energy loss improves energy utilization efficiency.But H in this method2The rate of recovery is lower, CO2Removing precision it is to be improved.
Summary of the invention
The purpose of the present invention is to provide a kind of medium temperature vacuum pressure swing adsorption system and methods.
The invention is realized by the following technical scheme:
A kind of medium temperature vacuum pressure swing adsorption system, including adsorption tower, product gas tank, suitable qi of chong channel ascending adversely tank, flushing gas tank, reverse gas
Tank；It is equipped with unstripped gas entrance, reverse gas outlet below the adsorption tower and is all provided with along qi of chong channel ascending adversely entrance, and above each adsorption tower
There are product port, pressure mouth and rinses gas entrance；Adsorbent is filled in the adsorption tower；The product gas tank passes through connecting tube
Road is connected with the product port of the adsorption tower, and the suitable qi of chong channel ascending adversely tank, inverse put gas tank enter with the suitable qi of chong channel ascending adversely of the adsorption tower respectively
Mouth, reverse gas outlet are connected；The flushing gas tank is connected by connecting pipe with the flushing gas entrance of the adsorption tower.
In above-mentioned technical proposal, the suitable qi of chong channel ascending adversely tank include high pressure along qi of chong channel ascending adversely tank and low pressure along qi of chong channel ascending adversely tank；The product gas
Tank includes high-voltage product gas tank and low voltage product gas tank.
In above-mentioned technical proposal, the system setting includes at least multiple adsorption towers of adsorption tower A and adsorption tower B, described
It is connected between multiple adsorption towers by pressure mouth.
Alternatively, the equalizer tank is connected with the pressure mouth of the adsorption tower the system also includes equalizer tank.
A kind of medium temperature vacuum pressure swing absorption process, including absorption, constant pressure are along punching, inverse put and flushing and/or vacuum desorption
Etc. processes, comprising:
The product port of adsorption tower is opened, is connected to adsorption tower with product gas tank, inversely boosts to absorption setting pressure,
Adsorption tower is set to enter absorption process；
Absorption: being connected to the product port of adsorption tower with product gas tank, and is in the unstripped gas entrance of adsorption tower and opens
State；So that unstripped gas is entered adsorption tower by the unstripped gas entrance of adsorption tower, passes through the selective absorption of adsorbent in adsorption tower
Easy adsorbed gas is separated, difficult adsorbed gas is made to enter product gas tank from the product port of adsorption tower；
Constant pressure is along punching: being in close state the unstripped gas entrance of adsorption tower, is in the product port of adsorption tower and opens
State, and the suitable qi of chong channel ascending adversely entrance of adsorption tower is opened, make adsorption tower and product gas tank, be respectively at connected state along qi of chong channel ascending adversely tank；Make
Enter adsorption tower along qi of chong channel ascending adversely body；Under the propulsion along qi of chong channel ascending adversely body, the difficult adsorbed gas at the top of adsorption tower enters production from product port
Product gas tank；Make absorption tower pressure interior force constant in the process along punching；
Inverse put: opening the reverse gas outlet of adsorption tower, be connected to it with atmosphere or inverse put gas tank, along absorption opposite direction release
Gas in adsorption tower is depressurized to adsorption tower inversely identical as environmental pressure, exports easy adsorbed gas by reverse gas and enters
Inverse put gas tank；
Entering flushing and/or vacuum desorption after being depressured adsorption tower inverse put obtains the adsorbent in adsorption tower again
It is raw, and easy adsorbed gas component is made to release adsorption tower；And
It rinses: rinsing in process, so that the reverse gas of adsorption tower is exported and rinse gas entrance and open, make to rinse gas from adsorption tower
Top enters, and is exported and is flowed out by reverse gas, so that adsorbent is regenerated, and easy adsorbed gas component is gone out with air-flow is rinsed
Adsorption tower；And/or
Vacuum desorption: make the reverse gas port opening of adsorption tower, and be connected with vacuum pump inlet, make to inhale by vacuumizing
Gas so that adsorption tower is further inversely depressured, and is obtained along absorption opposite direction release at vacuum pump outlet in attached tower
Easy adsorbed gas, regenerates adsorbent；
After adsorption tower flushing and/or vacuum desorption, the product port of adsorption tower is opened, connects adsorption tower and product gas tank
It is logical, absorption setting pressure is inversely boosted to, adsorption tower is made to enter absorption process.
The method also includes:
The system setting includes at least multiple adsorption towers of adsorption tower A and adsorption tower B；Or the system comprises multiple suctions
Attached tower and multiple equalizer tanks；
So that one of adsorption tower is inversely boosted to absorption setting pressure, sequentially enters absorption and constant pressure along rushing process；It is permanent
Under pressure condition, the propulsion of suitable qi of chong channel ascending adversely body is so that the difficult adsorbed gas at the top of adsorption tower enters product gas tank from product port；
It opens the pressure mouth of two adsorption towers or adsorption tower and equalizer tank and it is made to be interconnected, make to complete constant pressure along punching
Adsorption tower be in drop pressure process and be forward depressured, while so that another adsorption tower or an equalizer tank is in pressure and rising
Pressure process is inversely boosted；
Make after the adsorption tower of drop pressure enters and rinses process and/or vacuum desorption process completion adsorbent reactivation,
Into boost pressure process；So that two adsorption towers or adsorption tower is opened and is connected to the pressure mouth of equalizer tank, makes to complete to adsorb
The regenerated adsorption tower of agent carries out reverse boost pressure, while another adsorption tower or an equalizer tank being made to carry out forward equal pressure drop
Pressure；
After adsorption tower boost pressure reaches predetermined pressure, the product port of adsorption tower is opened, adsorption tower and product gas are made
Tank connection, makes adsorption tower reenter absorption process.
In above-mentioned technical proposal, the constant pressure along punching include high pressure along punching and low pressure along punching, the method also includes:
High pressure is along punching: entering high pressure after absorption process along process is rushed, the product port of adsorption tower is made to be in opening state
State, and the suitable qi of chong channel ascending adversely entrance of adsorption tower is opened, so that adsorption tower and high-voltage product tank, high pressure is kept connected state respectively along qi of chong channel ascending adversely tank
State；So that high pressure is entered adsorption tower along qi of chong channel ascending adversely body, obtains the satisfactory difficult adsorbed gas of purity in high-voltage product gas tank at this time；
Drop pressure: high pressure enters drop pressure process after journey along breaking through；Open two adsorption towers or a suction
Attached tower and the pressure mouth of an equalizer tank are simultaneously connected to it, so that one of adsorption tower is in drop pressure process and are forward dropped
Pressure, and another adsorption tower or an equalizer tank are in boost pressure process and are inversely boosted；
Low pressure is along punching: so that the adsorption tower after drop pressure is entered low pressure along process is rushed, makes the product port of adsorption tower
It is opened with along qi of chong channel ascending adversely entrance, and keeps connected state along qi of chong channel ascending adversely tank with low voltage product tank and low pressure respectively；Low pressure enters along qi of chong channel ascending adversely
Adsorption tower obtains the satisfactory difficult adsorbed gas of purity in the low voltage product gas tank of device at this time；
Inverse put: make by low pressure along punching adsorption tower enter inverse put process, open adsorption tower reverse gas outlet, make its with
Atmosphere or the connection of inverse put gas tank, the gas along absorption opposite direction release adsorption tower, are depressurized to adsorption tower inversely and environmental pressure
It is identical, so that easy adsorbed gas is entered inverse put gas tank by reverse gas outlet.
In above-mentioned technical proposal, medium temperature vacuum pressure swing adsorption system used in method is provided with including adsorption tower A and suction
Multiple adsorption towers of attached tower B, and the multiple adsorption tower in drop pressure and boost pressure is to correspond.
In above-mentioned technical proposal, the easy adsorbed gas includes hydrogen sulfide, carbon dioxide, carbon monoxide, methane, water steaming
One of gas, oxygen or a variety of mixtures.
In above-mentioned technical proposal, the hardly possible adsorbed gas includes one of hydrogen, nitrogen, rare gas or a variety of mixing
Object.
In above-mentioned technical proposal, the suitable qi of chong channel ascending adversely body is selected being easy to separate with product gas and is not easy to be adsorbed by adsorbent
Gas, including nitrogen, vapor or argon gas.
The present invention has the following advantages and beneficial effects: by the way that high pressure is added along punching, low pressure along punching, so that absorption
After available gas in adsorption tower still can enter product gas tank, hence it is evident that improve the PSA Gas rate of recovery, while product
Gas purity still can achieve requirement.
Detailed description of the invention
Fig. 1 is a kind of medium temperature vacuum pressure swing adsorption system schematic diagram according to the present invention.
Fig. 2 is the pressure swing adsorption system schematic diagram of embodiment synthetic-ammonia transformation gas purification according to the present invention.
Fig. 3 is embodiment methanol steam reforming H according to the present invention24 tower pressure swing adsorption system schematic diagrames of purification.
In figure: 1-rinses gas tank；2-product gas tanks；3-raw material gas tanks；4-inverse put gas tanks；5-along qi of chong channel ascending adversely tank；6―
Vacuum pump；7-adsorption tower A；8-adsorption tower B；9-solenoid valves.
Specific embodiment
A specific embodiment of the invention and the course of work are further described with reference to the accompanying drawing.
The positional terms such as the upper, lower, left, right, front and rear in present specification be positional relationship based on the figure and
It establishes.Attached drawing is different, then corresponding positional relationship is also possible to change therewith, therefore cannot be interpreted as with this to protection model
The restriction enclosed.
As shown in Figure 1, a kind of medium temperature vacuum pressure swing adsorption system, including adsorption tower, product gas tank 2, suitable qi of chong channel ascending adversely tank 5, punching
Scrubber tower 1, inverse put gas tank 4.Unstripped gas entrance, reverse gas outlet and suitable qi of chong channel ascending adversely entrance, and adsorption tower are equipped with below adsorption tower
Top is equipped with product port, pressure mouth and rinses gas entrance, controls its unlatching by solenoid valve 9.
Adsorbent is filled in adsorption tower.
Product gas tank is connected by connecting pipe with the product port of adsorption tower.Along qi of chong channel ascending adversely tank 5, inverse put gas tank 4 respectively with
The suitable qi of chong channel ascending adversely entrance of adsorption tower, reverse gas outlet are connected.Rinse the flushing gas entrance phase that gas tank passes through connecting pipe and adsorption tower
Even.
Along qi of chong channel ascending adversely tank 5 include high pressure along qi of chong channel ascending adversely tank and low pressure along qi of chong channel ascending adversely tank, corresponding product gas tank includes high-voltage product gas
Tank and low voltage product gas tank.
When only adsorption tower is arranged in system, two, including adsorption tower A7 and adsorption tower B8 is at least arranged in adsorption tower.Multiple suctions
It is connected between attached tower by pressure mouth.
Alternatively, system further includes equalizer tank, equalizer tank is connected with the pressure mouth of adsorption tower.Equalizer tank is preferably same with adsorption tower
Adsorbent is not loaded in the structure of sample, inside, and the dischargeable capacity after volume loads adsorbent with adsorption tower is identical.
A kind of medium temperature vacuum pressure swing absorption process, including absorption, constant pressure are along punching, inverse put and flushing and/or vacuum desorption
Etc. processes, comprising:
The product port of adsorption tower is opened, is connected to adsorption tower with product gas tank, inversely boosts to absorption setting pressure,
Adsorption tower is set to enter absorption process.This process is also referred to as filling eventually.
Absorption: being connected to the product port of adsorption tower with product gas tank, and is in the unstripped gas entrance of adsorption tower and opens
State；So that unstripped gas is entered adsorption tower by the unstripped gas entrance of adsorption tower, passes through the selective absorption of adsorbent in adsorption tower
Easy adsorbed gas is separated, difficult adsorbed gas is made to enter product gas tank from the product port of adsorption tower；The adsorption process duration can
With free regulation.
Constant pressure is along punching: being in close state the unstripped gas entrance of adsorption tower, is in the product port of adsorption tower and opens
State, and the suitable qi of chong channel ascending adversely entrance of adsorption tower is opened, make adsorption tower and product gas tank, be respectively at connected state along qi of chong channel ascending adversely tank；Make
Enter adsorption tower along qi of chong channel ascending adversely body；Under the propulsion along qi of chong channel ascending adversely body, the difficult adsorbed gas at the top of adsorption tower enters production from product port
Product gas tank；Make absorption tower pressure interior force constant in the process along punching.
Inverse put: opening the reverse gas outlet of adsorption tower, be connected to it with atmosphere or inverse put gas tank, along absorption opposite direction release
Gas in adsorption tower is depressurized to adsorption tower inversely identical as environmental pressure, exports easy adsorbed gas by reverse gas and enters
Inverse put gas tank.
Entering flushing and/or vacuum desorption after being depressured adsorption tower inverse put obtains the adsorbent in adsorption tower again
It is raw, and easy adsorbed gas component is made to release adsorption tower.Subsequent then flushing and/or vacuum desorption
It rinses: rinsing in process, so that the reverse gas of adsorption tower is exported and rinse gas entrance and open, make to rinse gas from adsorption tower
Top enters, and is exported and is flowed out by reverse gas, so that adsorbent is regenerated, and easy adsorbed gas component is gone out with air-flow is rinsed
Adsorption tower.
Very.Sky desorption: make the reverse gas port opening of adsorption tower, and be connected with 6 entrance of vacuum pump, made by vacuumizing
Gas so that adsorption tower is further inversely depressured, and is obtained along absorption opposite direction release at vacuum pump outlet in adsorption tower
To easy adsorbed gas, regenerate adsorbent.
After adsorption tower flushing and/or vacuum desorption, the product port of adsorption tower is opened, connects adsorption tower and product gas tank
It is logical, absorption setting pressure is inversely boosted to, adsorption tower is made to reenter absorption process.
When system setting includes at least multiple adsorption towers of adsorption tower A and adsorption tower B, or including multiple adsorption towers and multiple
When equalizer tank, the method also includes:
So that one of adsorption tower is inversely boosted to absorption setting pressure, sequentially enters absorption and constant pressure along rushing process；It is permanent
Under pressure condition, the propulsion of suitable qi of chong channel ascending adversely body is so that the difficult adsorbed gas at the top of adsorption tower enters product gas tank from product port；
It opens the pressure mouth of two adsorption towers or adsorption tower and equalizer tank and it is made to be interconnected, make to complete constant pressure along punching
Adsorption tower be in drop pressure process and be forward depressured, while another adsorption tower or equalizer tank being made to be in boost pressure work
Sequence is inversely boosted；
Make after the adsorption tower of drop pressure enters and rinses process and/or vacuum desorption process completion adsorbent reactivation,
Into boost pressure process；So that two adsorption towers or adsorption tower is opened and is connected to the pressure mouth of equalizer tank, makes to complete to adsorb
The regenerated adsorption tower of agent carries out reverse boost pressure, while another adsorption tower or equalizer tank being made to carry out forward drop pressure；
After adsorption tower boost pressure reaches predetermined pressure, the product port of adsorption tower is opened, adsorption tower and product gas are made
Tank connection, makes adsorption tower reenter absorption process.
Constant pressure along punching include high pressure along punching and low pressure along punching, the method also includes:
High pressure is along punching: entering high pressure after absorption process along process is rushed, the product port of adsorption tower is made to be in opening state
State, and the suitable qi of chong channel ascending adversely entrance of adsorption tower is opened, so that adsorption tower and high-voltage product tank, high pressure is kept connected state respectively along qi of chong channel ascending adversely tank
State；So that high pressure is entered adsorption tower along qi of chong channel ascending adversely body, obtains the satisfactory difficult adsorbed gas of purity in high-voltage product gas tank at this time；
Drop pressure: high pressure enters drop pressure process after journey along breaking through；Open adsorption tower A7's and adsorption tower B8
It presses mouth and makes its connection, so that one of adsorption tower is in drop pressure process and be forward depressured, and another adsorption tower
Or equalizer tank is in boost pressure process and is inversely boosted；
Low pressure is along punching: entering low pressure after drop pressure process along process is rushed, makes the product port and Shun Chong of adsorption tower
Gas entrance is opened, and keeps connected state respectively along qi of chong channel ascending adversely tank with low voltage product tank and low pressure；Low pressure enters adsorption tower along qi of chong channel ascending adversely, this
When in low voltage product gas tank obtain the satisfactory difficult adsorbed gas of purity；
Inverse put: entering inverse put process after low pressure is along punching, opens the reverse gas outlet of adsorption tower, make it with atmosphere or
Inverse put gas tank connection, the gas along absorption opposite direction release adsorption tower, is depressurized to adsorption tower inversely identical as environmental pressure, makes
Easy adsorbed gas enters inverse put gas tank by reverse gas outlet.
Adsorption tower after inverse put decompression goes successively to subsequent handling.
When two or more is arranged in adsorption tower, the adsorption tower in drop pressure and boost pressure is to correspond, that is, is had
As soon as adsorption tower is in drop pressure, there is an adsorption tower while being in boost pressure.
Easy adsorbed gas includes one of hydrogen sulfide, carbon dioxide, carbon monoxide, methane, vapor, oxygen or a variety of
Mixture.
Difficult adsorbed gas includes one of hydrogen, nitrogen, rare gas or a variety of mixtures.
It selects being easy to separate with product gas along qi of chong channel ascending adversely body and is not easy the gas being adsorbed by adsorbent, including nitrogen gas and water is steamed
Gas or argon gas.
Embodiment 1: synthetic-ammonia transformation gas medium temperature sulphur carbon takes off altogether.
Pressure-variable adsorption separation is carried out by raw material of synthetic-ammonia transformation gas, water-gas ratio is 1.2~1.4 in conversion gas, and pressure is
3.4MPa, butt raw gas pressure about 1.5MPa, ingredient are as shown in table 1:
1. conversion gas ingredient of table
| Component | CO2(%) | CO (%) | H2(%) | CH4(%) | N2(%) | Total sulfur (ppm) |
| Concentration | 28-36 | 0.3-0.5 | 51-65 | 4.0-7.8 | 2.0-4.0 | 1000 |
Conversion gas purification pressure swing adsorption system as shown in Fig. 2, comprising 4 adsorption tower A1-A4,4 equalizer tank T1-T4 with
And product gas holding vessel, reverse gas holding vessel, high pressure along qi of chong channel ascending adversely surge tank, low pressure along qi of chong channel ascending adversely surge tank and vacuum pump V.Equalizer tank
It is parallel relationship between adsorption tower.The design arrangement of pressure-swing absorber uses the above method, inside filled with molecular sieve and
Active carbon.Without filling, and only, at top, mouth, volume and volume phase after adsorption tower filling molecular sieve are pressed in setting to equalizer tank
Closely.Vapor is selected along qi of chong channel ascending adversely.
In adsorption system, adsorption tower, equalizer tank and hydrogen gas buffer temperature are 160 DEG C, and vapor surge tank temperature is 180
DEG C, pressure 1.55MPa；Adsorptive pressure is 1.5MPa, CO2The pressure of holding vessel is 0.15MPa.
After conversion gas enters adsorption tower by gaseous mixture entrance, moisture, carbon dioxide, carbon monoxide in gas, sulfur-bearing group
Point, methane and nitrogen be adsorbed agent removing, the hydrogen for being not easy to be adsorbed enters hydrogen gas buffer from product gas outlet.Each
Adsorption tower successively undergo absorption, high pressure Shun Chong, the equal pressure drop 1 of tower tank, the equal pressure drop 1 of tower tower, the equal pressure drop 2 of tower tank, the equal pressure drop 3 of tower tank,
The equal pressure drop 2 of tower tower, the equal pressure drop 4 of tower tank, vacuum desorption, tower tank press liter 4, tower tower to press liter 2, tower tank that liter 3, tower tank is pressed to press
Rising 2, tower tower presses liter 1, tower tank to press liter 1.Pressurising step；Each equalizer tank only carries out pressure and rises and equal voltage drop step.Each
The process flow of adsorption tower and equalizer tank is as shown in table 2.1-24 time span is all the same in table 2.
2. conversion gas of table purifies 8 tower process processes
Remarks: AD: absorption；HR: high pressure is along punching；EdA: the equal pressure drop 1 of tower tank；Ed1: the equal pressure drop 1 of tower tower；EdB: tower tank is pressed
Drop 2；EdC: the equal pressure drop 3 of tower tank；Ed2: the equal pressure drop 2 of tower tower；EdD: the equal pressure drop 4 of tower tank；BD: inverse put；VD: vacuum desorption；EpD:
Tower tank, which is pressed, rises 4；Ep2: tower tower, which is pressed, rises 2；EpC: tower tank, which is pressed, rises 3；EpB: tower tank, which is pressed, rises 2；Ep1: tower tower, which is pressed, rises 1；
EpA: tower tank, which is pressed, rises 1；PP: pressurising.
By taking adsorption tower A1 as an example, operating process of each adsorption tower in a circulation is described in detail.
(1) it adsorbs
Adsorption tower A1 has completed pressurising step at this time, and tower pressure interior force reaches adsorptive pressure.Sequencing valve 1A, 4A are opened, is become
Change gas from adsorption tower lower end enter, during flowing up, moisture, carbon dioxide, carbon monoxide, sulfur component, methane with
And nitrogen is adsorbed agent removing, minute quantity hydrogen is adsorbed, and remaining more pure hydrogen enters product gas from adsorption tower upper end
Holding vessel.With the progress of adsorption process, the adsorbent of adsorption tower lower part reaches saturation, the foreign gas in product gas outlet by
It is cumulative more.When hydrogen purity drops to a certain threshold value in product gas, adsorption process terminates.
(2) high pressure is along punching
After adsorption tower A1 completes adsorption step, sequencing valve 4A is closed, and 5A is opened.High-pressure steam enters absorption from lower end
Tower.Original residual gas drives substitution by vapor in tower, and flows out from adsorption tower upper end, into product gas holding vessel.When
When exporting hydrogen purity drops to a certain threshold value, high pressure terminates along breaking through journey.
(3) the equal pressure drop 1 of tower tank
High pressure is along after rushing step, and sequencing valve 1A, 5A closing, 2A, 2E are opened.Equalizer tank T1 pressure is lower than absorption at this time
Tower A1.Gas in A1 forward flows into T1, the reverse pressurising of T1, and A1 is forward bled off pressure, until A1 identical as the pressure in T1.
(4) the equal pressure drop 1 of tower tower
After equal 1 process of pressure drop of tower tank, sequencing valve 2E is closed, and 2C is opened.The pressure of adsorption tower A3 is lower than A1 at this time.A1
Interior gas forward flows into A3, the reverse pressurising of A3, and A1 is forward bled off pressure, until pressure is identical as A3 in A1.
(5) the equal pressure drop 2 of tower tank
After the equal pressure drop 1 of tower tower, sequencing valve 2C is closed, and 2F is opened.Equalizer tank T2 pressure is lower than adsorption tower A1.A1 is forward
It bleeds off pressure, the reverse pressurising of T2, until A1 identical as T2 pressure.
(6) the equal pressure drop 3 of tower tank
After the equal pressure drop 2 of tower tank, sequencing valve 2F, 2A closing, 3A, 3G are opened.Equalizer tank T3 pressure is lower than adsorption tower A1.
A1 is forward bled off pressure, the reverse pressurising of T3, until A1 identical as T3 pressure.
(7) the equal pressure drop 2 of tower tower
After the equal pressure drop 3 of tower tank, sequencing valve 3A, 3G closing, 2A, 2D are opened.Adsorption tower A4 pressure is lower than adsorption tower A1.
A1 is forward bled off pressure, the reverse pressurising of A4, until A1 identical as A4 pressure.
(8) the equal pressure drop 4 of tower tank
After the equal pressure drop 2 of tower tower, sequencing valve 2A, 2D closing, 3A, 3H are opened.Equalizer tank T4 pressure is lower than adsorption tower A1.
A1 is forward bled off pressure, the reverse pressurising of T4, until A1 identical as T4 pressure.
(9) inverse put
After equal 4 process of pressure drop of tower tank, sequencing valve 3A, 3H closing, 7A is opened.The pressure of reverse gas holding vessel is lower than suction
From lower end, outflow enters reverse gas holding vessel to gas in attached tower A1, A1, until A1 is identical as storage pressure tank.
(10) vacuum desorption
After inverse put process, sequencing valve 7A is closed, and 8A is opened, and the gas in adsorption tower A1 is pumped into reverse gas by vacuum pump
Holding vessel.
(11) tower tank, which is pressed, rises 4
After vacuum desorption, sequencing valve 8A is closed, and 3A, 3H are opened.Equalizer tank T4 pressure is higher than adsorption tower A1, and A1 is reverse
Pressurising, T4 are forward bled off pressure, until A1 identical as T4 pressure.
(12) tower tower, which is pressed, rises 2
After tower tank presses liter 4, sequencing valve 3A, 3H closing, 2A, 2B are opened.Adsorption tower A2 pressure is higher than adsorption tower A1,
The reverse pressurising of A1, A2 are forward bled off pressure, until A1 identical as A2 pressure.
(13) tower tank, which is pressed, rises 3
After tower tower presses liter 2, sequencing valve 2A, 2B closing, 3A, 3G are opened.Equalizer tank T3 pressure is higher than adsorption tower A1,
The reverse pressurising of A1, T3 are forward bled off pressure, until A1 identical as T3 pressure.
(14) tower tank, which is pressed, rises 2
After tower tank presses liter 3, sequencing valve 3A, 3G closing, 2A, 2F are opened.Equalizer tank T2 pressure is higher than adsorption tower A1,
The reverse pressurising of A1, T2 are forward bled off pressure, until A1 identical as T2 pressure.
(15) tower tower, which is pressed, rises 1
After tower tank presses liter 2, sequencing valve 2F is closed, and 2C is opened.Adsorption tower A3 pressure is higher than adsorption tower A1, and A1 is reverse
Pressurising, A3 are forward bled off pressure, until A1 identical as A3 pressure.
(16) tower tank, which is pressed, rises 1
After tower tower presses liter 1, sequencing valve 2C is closed, and 2E is opened.Equalizer tank T1 pressure is higher than adsorption tower A1, and A1 is reverse
Pressurising, T1 are forward bled off pressure, until A1 identical as T1 pressure.
(17) pressurising
After tower tank presses liter 1, sequencing valve 2A, 2E closing, 1A is opened, reverse to adsorption tower A1 by product gas holding vessel
Pressurising, until pressure reaches adsorptive pressure in A1, Plenum Process terminates.
A1 restores the state before adsorption step at this time, and a circulation terminates to start to recycle next time.Other adsorption towers A2-
The cyclic process of A4, equalizer tank T1-T4 are similar with A1, according to the corresponding sequencing valve of sequence switch shown in table 2, time each other
On mutually stagger.
Since separation carries out under mesophilic condition, can be added that vapor is suitable to rush step in pressure swing adsorption technique, thus
The content of hydrogen in reverse gas is reduced, hydrogen yield is promoted.The technical indicator of this technique and other purification processes is compared such as 3 institute of table
Show.
3. present invention process of table and the purification of other process shifts gas compare
Embodiment 2: the H of methanol steam reforming hydrogen manufacturing2/CO2Separation
Methane and vapor occur catalytic pyrolysis and water gas shift reation, become containing dioxy under certain temperature and pressure
Change the mixed gas of carbon, hydrogen and a small amount of carbon monoxide.Usual reaction temperature is 250-300 DEG C, pressure 1-5MPa.
For methanol steam reforming H2Purification 4 tower pressure swing adsorption systems as shown in figure 3, include 4 adsorption tower A1-A4,
Hydrogen storage tank, reverse gas holding vessel, for low pressure along qi of chong channel ascending adversely surge tank and vacuum pump V, the adsorbent filled is active carbon, is easily inhaled
Attached CO2And CO, it is not easy to adsorb H2；It is vapor along qi of chong channel ascending adversely.The process flow of adsorption tower is as shown in table 4, the unlatching of sequencing valve and pass
It closes similar to Example 1.
4. methanol recapitalization H of table2/CO2Separate four tower process processes
Remarks: AD: absorption；Ed1: the equal pressure drop 1 of tower tower；Ed2: the equal pressure drop 2 of tower tower；LR: low pressure is along punching；BD: inverse put；VD:
Vacuum desorption；Ep2: tower tower, which is pressed, rises 2；Ep1: tower tower, which is pressed, rises 1；PP: pressurising；ID: idle.
By taking adsorption tower A1 as an example:
(1) adsorb: Plenum Process is completed in adsorption tower at this time, reaches adsorptive pressure in tower.Sequencing valve 1A, 3A start
Adsorption process；
(2) the equal pressure drop 1 of tower tower: after adsorption process, sequencing valve 1A, 3A closing, 2A, 2C, which are opened, starts the equal pressure drop of tower tower
1；
(3) idle: sequencing valve 2A after the equal pressure drop 1 of tower tower, 2C are closed, and A1 is in idle condition；
(4) the equal pressure drop 2 of tower tower: idle state terminates, and opens sequencing valve 2A, and 2D starts the equal pressure drop 2 of tower tower；
(5) low pressure is along punching: after the equal pressure drop 2 of tower tower, closing 2A, 2D, opens 1A, 4A；
(6) inverse put: after low pressure is along punching, closing sequencing valve 1A, 4A, opens 5A and starts inverse put process；
(7) vacuum desorption: after inverse put, closing 5A, opens sequencing valve 6A, and vacuum pump starts to take out adsorption tower A1 true
It is empty；
(8) tower tower, which is pressed, rises 2: after vacuum desorption, closing sequencing valve 6A, opens 2A, 2B, adsorption tower A1 and A2 are equal
Pressure；
(9) idle: after tower tower presses liter 2, to close 2A, 2B, start idle state；
(10) tower tower, which is pressed, rises 1: idle state terminates, and opens sequencing valve 2A, 2C, adsorption tower A1 and A3 are pressed；
(11) pressurising: after tower tower presses liter 1, sequencing valve 2A, 2C are closed, opens 1A, product gas is inverse to adsorption tower A1
To pressurising.
It, can be under medium temperature directly to H using above-mentioned pressure-variable adsorption process2With CO2It is separated, gained H2Purity is higher than
99.99%, and CO concentration is lower than 0.4ppm, almost meets all application fields to H2Requirement, can be directly to proton exchange
Membrane cell gas supply, has vast potential for future development.
Embodiment 3:IGFC system moderate temperature desulphurization
In integral coal gasification fuel cell generation (IGFC), synthesis gas needs by deep desulfuration be solid oxygen
Compound fuel cell (SOFC) gas supply.Synthesis gas typical composition to be clean is as shown in table 1, and temperature is 200-300 DEG C, and pressure is general
For 3-6MPa.For SOFC operating temperature generally at 800 DEG C, the high-temperature tail gas of fuel cell carries out the utilization of energy by steam turbine.
The generating efficiency of system is mainly related to the rate of recovery of synthesis gas and gas heating energy consumption.Use technique proposed by the invention
Process directly can carry out desulfurizing and purifying to synthesis gas, trap a part of carbon dioxide, without sensible heat loss, while guarantee to close
At gas yield, system generating efficiency can be significantly improved compared to low temperature purification method.
Specific implementation method is as follows: purification system is made of 4 adsorption tower, 4 equalizer tank；Adsorbent is selected as total with sulphur carbon
The active carbon of de- function, to H2S、CO2With compared with high adsorption capacity, H2Adsorbance very little；It is elevated pressure nitrogen along punching and flushing gas
Gas, from the space division system of IGFC.PSA device is run according to process flow as shown in table 5.Product gas main component is
H2、CH4、N2、H2O、CO2,CO；H2S concentration can achieve 1ppm hereinafter, meeting SOFC requirement.
Table 5.IGFC system synthesis gas purifies 8 tower process processes
Remarks: AD: absorption；HR: high pressure is along punching；EdA: the equal pressure drop 1 of tower tank；Ed1: the equal pressure drop 1 of tower tower；EdB: tower tank is pressed
Drop 2；EdC: the equal pressure drop 3 of tower tank；Ed2: the equal pressure drop 2 of tower tower；EdD: the equal pressure drop 4 of tower tank；BD: inverse put；P: nitrogen rinses；EpD: tower
Tank, which is pressed, rises 4；Ep2: tower tower, which is pressed, rises 2；EpC: tower tank, which is pressed, rises 3；EpB: tower tank, which is pressed, rises 2；Ep1: tower tower, which is pressed, rises 1；
EpA: tower tank, which is pressed, rises 1；PP: pressurising.
Embodiment 4:PEMFC fuel C O deep purifying
Proton Exchange Membrane Fuel Cells (PEMFC) is higher to fuel hydrogen purity requirement, and wherein CO concentration should be lower than
0.4ppm.Using process flow proposed by the present invention, can at 100-200 DEG C to liquid fuel reformed syngas or detoxification after
Gasification synthesis gas carry out CO deep purifying, purified gas without heating, can be supplied directly to small-sized PEMFC.
Purification system by 2 adsorption tower groups at；Adsorbent is CO molecular sieve；It is nitrogen or vapor along qi of chong channel ascending adversely body, uses
The method of vacuum desorption.Process flow is as shown in table 6.
Table 6.CO advanced purification process process
Remarks: AD: absorption；HR: high pressure is along punching；VD: vacuum desorption.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
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| CN114588749A (en) * | 2022-03-16 | 2022-06-07 | 浙江天采云集科技股份有限公司 | Extracting H from synthetic ammonia purge gas2And NH3Pressure swing adsorption process of full temperature range simulated rotary moving bed |
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