CN111530241B - SO is separated and recovered from flue gas2With NOxApparatus and method of - Google Patents

SO is separated and recovered from flue gas2With NOxApparatus and method of Download PDF

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CN111530241B
CN111530241B CN202010285546.1A CN202010285546A CN111530241B CN 111530241 B CN111530241 B CN 111530241B CN 202010285546 A CN202010285546 A CN 202010285546A CN 111530241 B CN111530241 B CN 111530241B
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gas
stage
separation unit
membrane separation
flue gas
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CN111530241A (en
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李子宜
李俊
刘应书
章佳佳
杨雄
刘文海
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University of Science and Technology Beijing USTB
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    • 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
    • B01D53/22—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 diffusion
    • B01D53/225—Multiple stage diffusion
    • B01D53/226—Multiple stage diffusion in serial connexion
    • 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
    • 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
    • B01D53/22—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 diffusion
    • B01D53/225—Multiple stage diffusion
    • B01D53/227—Multiple stage diffusion in parallel connexion
    • 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
    • B01D53/22—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 diffusion
    • B01D2053/221—Devices
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/30—Sulfur compounds
    • B01D2257/302—Sulfur oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

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Abstract

The invention belongs to the technical field of flue gas pollutant recovery, and particularly relates to a method for separating and recovering SO from flue gas2With NOxThe device comprises: a first stage membrane separation unit for separating NO from flue gas2A gas; a second stage membrane separation unit for separating NO gas and SO from the flue gas2A gas; a first buffer tank; the flue gas analyzer group is used for analyzing gas components; the valve group is used for controlling the circulation of gas; a second buffer tank; a first gas collection tank; the first-stage membrane separation unit, the first buffer tank, the second-stage membrane separation unit, the second buffer tank and the first gas collecting tank are sequentially arranged on a main gas path of the device. The device aims at SO in current industrial flue gas2With NOxResource high value status and SO in desorption gas2/NOxThe technical requirement of effective separation can reduce energy waste, is economic and environment-friendly, and has popularization value.

Description

SO is separated and recovered from flue gas2With NOxApparatus and method of
Technical Field
The invention belongs to the technical field of flue gas pollutant recovery, and particularly relates to a method for separating and recovering SO from flue gas2With NOxThe device and the method separate and recycle SO from the desorption gas obtained by purifying the flue gas based on the adsorption method2With NOx。
Background
At present, the domestic energy application structure mainly comprises fossil fuels such as coal, petroleum and the like, and smoke generated after the fuels are combusted can cause serious pollution to the environment. SO in industrial flue gas2And NOxIs the main reason for air pollution and acid rain, but has high industrial utilization value. SO (SO)2Besides being used as basic raw material for producing sulfuric acid and fertilizer, the fertilizer is widely used for agricultural productsProcessing (soaking liquid, safety liquid), paper making industry (bleaching agent), petrochemical industry (refining agent), chemical industry (production of glue and gelatin), and the like. NOxThe product is used as an oxidant in rocket fuels and is often used for preparing industrial reagents such as nitric acid, nitrating agents, oxidants, catalysts, acrylate polymerization inhibitors and the like in industry. NO in flue gasxWith NO and NO2Contains a small amount of N as main component2O3，N2O and N2O5However, these nitrogen oxides are not stable and can be converted to NO by light, humidity or heat2Or NO. Therefore, in the process of adsorbing and purifying the multiple pollutants in the flue gas, the pollutant gas in the desorbed gas is mainly SO2、NO2And NO. SO in flue gas2With NOxHas high recovery value, but SO is generated in the process of purifying and recycling flue gas by an adsorption method2With NOxThe two gases coexist in desorption gas, the boiling points, the molecular sizes and the polarities of the two gases are relatively close, and the traditional rectification method or the temperature change/pressure change adsorption method has great difficulty.
The membrane separation is one of the mainstream gas separation technologies, and has wide application prospects in the preparation of industrial product gas, purification and comprehensive utilization of waste gas. Compared with the traditional separation methods such as distillation, extraction, recrystallization and the like, the membrane separation technology has the advantages of low energy consumption, low cost, low pollution, high efficiency and the like. The molecular sieve membrane is one of porous inorganic membranes, has high thermal stability and mechanical strength, has uniform pore channels, narrow pore size distribution and a cage-like structure close to the molecular size in the structure, and can selectively separate molecules with different kinetic diameters on the molecular scale. The common molecular sieve membranes at present are MFI, LTA, FAU, MOR, FER, AEI, DDR, T, CHA, RHO and the like, and compared with the MFI, FAU and MOR molecular sieve membranes of 10-membered ring or 12-membered ring channels which are widely researched and the molecular sieve membranes of 8-membered ring channels such as LTA, DDR, RHO, CHA and the like, the molecular sieve membranes can show more remarkable sieving effect on the separation of small molecular gases, thereby improving the separation coefficient. For SO2/NO2Separation of small molecular gas mixture, 8-membered ring molecular sieve membrane represented by CHA in many aspectsPresenting feasibility and applicability. SO (SO)2Has a kinetic diameter of
Figure BDA0002448371510000011
Smaller than the main pore diameter of the CHA molecular sieve membrane
Figure BDA0002448371510000021
And NO at low temperature2Will be converted to N substantially by bimolecular binding (dimerization)2O4Albeit NO2Kinetic diameter of (D) is more than SO2Small, but form N at low temperatures2O4Later kinetic diameter than SO2Large and it is a planar molecule with a minimum cross-sectional diameter of
Figure BDA0002448371510000022
Far larger than the main aperture of the molecular sieve membrane
Figure BDA0002448371510000023
And thus cannot easily pass through the molecular sieve membrane. In conclusion, the 8-membered ring molecular sieve membrane separator represented by CHA has reasonable pore diameter and can treat SO2/NO2A sieving effect is formed. For NO/SO2The separation of the small molecular gas mixture and the 8-membered ring molecular sieve membrane represented by RHO shows feasibility and applicability in many aspects. SO (SO)2Has a kinetic diameter of
Figure BDA0002448371510000024
Kinetic diameter of NO of
Figure BDA0002448371510000025
Main pore diameter of RHO molecular sieve membrane
Figure BDA0002448371510000026
Thus, NO can pass through the RHO molecular sieve membrane while SO2It cannot pass through the RHO molecular sieve membrane. In conclusion, the 8-membered ring molecular sieve membrane separator represented by RHO has reasonable pore diameter and can treat NO/SO2A sieving effect is formed.
At present, the method aims at removing hydrogen in natural gas and dioxygen in smokeThe separation and recovery of carbonized carbon and the like have relatively mature membrane separation processes, but for SO2/NOxThe membrane separation process has not been reported.
Disclosure of Invention
Aiming at the problems, the invention provides a method for separating and recovering SO from flue gas2With NOxThe apparatus and method of (1). The device aims at SO in current industrial flue gas2With NOxResource high value status and SO in desorption gas2/NOxThe technical requirement of effective separation can reduce energy waste, is economic and environment-friendly, and has popularization value. The CHA film with high silicon-aluminum ratio has stronger thermal stability and acid resistance, and can realize SO under severe conditions2And NO2Separating; the RHO film with low silicon-aluminum ratio can realize NO and SO2Separation of (4).
The invention is realized by the following technical scheme:
SO is separated and recovered from flue gas2With NOxThe apparatus of (a), the apparatus comprising:
a first stage membrane separation unit for separating NO from flue gas2A gas;
a second stage membrane separation unit for separating NO gas and SO from the flue gas2A gas;
a first buffer tank;
the flue gas analyzer group is used for analyzing gas components;
the valve group is used for controlling the circulation of gas;
a second buffer tank;
a first gas collection tank;
the first-stage membrane separation unit, the first buffer tank, the second-stage membrane separation unit, the second buffer tank and the first gas collecting tank are sequentially arranged on a main gas path of the device;
further, the flue gas analyzer group comprises:
the first flue gas analyzer is used for analyzing gas components in the first buffer tank;
the second flue gas analyzer is used for analyzing gas components in the second buffer tank;
the third flue gas analyzer is used for analyzing gas components in the first gas collecting tank;
the first flue gas analyzer is arranged on the first buffer tank;
the second flue gas analyzer is arranged on the second buffer tank;
the third flue gas analyzer is arranged on the first gas collecting tank. Further, the apparatus further comprises:
the first gas loop is used for returning the gas in the first buffer tank to the gas inlet of the first-stage membrane separation unit, so that the components in the gas are further sieved by the first-stage membrane separation unit;
a second gas loop for returning the gas in the second buffer tank to the gas inlet of the second stage membrane separation unit, so that the components in the gas are further sieved by the second stage membrane separation unit;
the first gas loop is a pipeline for communicating the first buffer tank with a gas inlet of the first-stage membrane separation unit;
the second gas loop is a pipeline which is communicated with the second buffer tank and the gas inlet of the second-stage membrane separation unit.
Further, the valve set includes:
the first valve is used for controlling the on-off of the first gas loop;
a second valve for controlling gas passing from the first buffer tank to the second stage membrane separation unit;
the third valve is used for controlling the on-off of the second gas loop;
a fourth valve for controlling the gas entering the first gas collection tank;
the first valve is arranged on the first gas circuit; the second valve is arranged between the first buffer tank and the second-stage membrane separation unit; the third valve is disposed on the second gas circuit; the fourth valve is arranged between the second buffer tank and the first gas collecting tank.
Further, the first valve is a one-way valve.
Further, the second valve is a one-way valve.
Further, the third valve is a one-way valve.
Further, the fourth valve is a one-way valve.
Further, the first gas collecting tank is used for collecting NO gas.
Furthermore, the first-stage membrane separation unit comprises a plurality of first-stage adsorption modules, a first-stage pressure gauge, a fifth valve, a fourth flue gas analyzer and a second gas collecting tank, wherein the first-stage pressure gauge, the fifth valve, the fourth flue gas analyzer and the second gas collecting tank are correspondingly arranged on the first-stage adsorption modules;
the first-stage adsorption module is provided with a first feeding end, a first residual end and a first permeation end;
the adjacent first-stage adsorption modules are communicated through interconnection of surplus ends and feeding ends;
the first permeation ends of the first-stage adsorption modules are connected in parallel and then connected with the second-stage membrane separation unit;
the last first residual end is connected with the fifth valve and the second gas collecting tank in sequence; and the fourth flue gas analyzer is arranged on the second gas collecting tank and is used for analyzing the gas components in the second gas collecting tank.
Further, the fifth valve is a one-way valve.
Further, the second gas collecting tank is used for collecting NO2A gas.
Further, the first pressure gauge is used to determine: when a certain first-stage adsorption module is blocked or a pipeline is blocked, a blocked place can be found according to the readings of the first-stage pressure gauges (when the first-stage adsorption module is blocked or the pipeline is blocked, the reading of the first-stage pressure gauge at the downstream of the blocked place is 0); in addition, the pressure of the first pressure gauge at the upstream of the device can also be used as the pressure of the flue gas entering the first-stage membrane separation unit.
Further, the first stage adsorption module comprises a first molecular sieve membrane and a first membrane separator;
the first molecular sieve membrane is placed in the first membrane separator.
Further, the first membrane separator is a space sealed by a rubber ring.
Furthermore, the number of the first-stage adsorption modules is m, and m is a positive integer not less than 2.
Further, the first molecular sieve membrane is of the type: AEI, CHA, LTA, MFI, SFW, RTH, KFI, ITE, ITW, CAN, EPI, MOR, FAU or FER; the CHA film is preferred, and the CHA film with high silicon-aluminum ratio has stronger thermal stability and acid resistance and can realize SO under severe conditions2/NO2And (5) separating.
Further, the second-stage membrane separation unit comprises a plurality of second-stage adsorption modules, and a second-stage pressure gauge, a sixth valve, a fifth flue gas analyzer and a third gas collecting tank which are correspondingly arranged on the second-stage adsorption modules;
the second-stage adsorption module is provided with a second feeding end, a second residual end and a second permeation end;
the adjacent second-stage adsorption modules are communicated with each other through a second residual end and a second feeding end;
second penetration ends on the second-stage adsorption modules are connected in parallel and then communicated with the second buffer tank;
the last second residual end, the sixth valve and a third gas collecting tank are connected in sequence; and the fifth flue gas analyzer is arranged on the third gas collecting tank and is used for analyzing the gas components in the third gas collecting tank.
Further, the sixth valve is a check valve.
Further, the third gas collecting tank is used for collecting SO2A gas.
Further, the second pressure gauge is used to determine: when a certain second-stage adsorption module is blocked or a pipeline is blocked, a blocked place can be found according to the readings of the second-stage pressure gauges (when the second-stage adsorption module is blocked or the pipeline is blocked, the reading of the second-stage pressure gauge at the downstream of the blocked place is 0); in addition, the pressure of the first second-stage pressure gauge at the upstream of the device can also be used as the pressure of the flue gas entering the second-stage membrane separation unit.
Further, the device also comprises a first permeation end pressure gauge for detecting the total pressure of the first permeation ends connected in parallel and a second permeation end pressure gauge for detecting the total pressure of the second permeation ends connected in parallel;
the first permeation end pressure gauge is arranged on the main path after the first permeation ends are connected in parallel;
the second permeation end pressure gauge is arranged on the main path after the second permeation ends are connected in parallel.
Further, the second stage adsorption module comprises a second molecular sieve membrane and a second membrane separator;
the second molecular sieve membrane is placed in the second membrane separator.
Further, the second membrane separator is a space sealed by a rubber ring.
Furthermore, the number of the second-stage adsorption modules is n, and n is a positive integer not less than 2.
Further, the second molecular sieve membrane is of the type: DDR, RHO, ERI, AFX, RTH, ITE, IHW, ITW, NSI, LEV, EDI, EPI, GIS, HEU, NAT, MOR, or FER; the RHO film is preferred, and the RHO film with low silicon-aluminum ratio can realize NO/SO2Separation of (4).
Further, the device also comprises a temperature controller and a thermometer, and the temperature controller and the thermometer are used for adjusting the temperature of the gas entering the device so as to optimize the effect of gas separation;
the temperature controller and the thermometer are arranged at the upstream of the first-stage membrane separation unit;
the temperature controller is an existing temperature control device.
Further, a mass flow meter, a blower, a pressure reducing valve, a vacuum pump and the like are arranged on each gas path of the device; the mass flow meter is used for controlling the flow of the gas; the vacuum pump is used for providing negative pressure for the permeation end of the first-stage membrane separation unit, so that the permeation pressure difference at two sides of the first-stage membrane separation unit is increased (the permeation quantity of gas can be increased, and the efficiency of the device is increased); the blower is used for providing positive pressure to the second feeding end, so that the osmotic pressure difference on two sides of the second-stage membrane separation unit can be increased; the pressure reducing valve is arranged between the first-stage membrane separation unit and the second-stage membrane separation unit and used for adjusting the pressure of gas entering the second-stage membrane separation unit.
Further, all the buffer tanks in the device function to reduce the unevenness of the flow of the permeated gas and serve as detection points for detecting the gas components by the flue gas analyzer.
Furthermore, the pipelines, the membrane separators (the first membrane separator and the second membrane separator) and the like in the device adopt corrosion-resistant materials such as stainless steel, quartz, silica gel, phenolic resin, fluoroplastic and the like to prevent SO2With NOxCorrosion is generated on the pipeline; the appearance type of the molecular sieve membrane can be a sheet membrane, a tubular membrane, a fiber tubular membrane and the like; the form of the membrane separator includes a plate frame type, a spiral wound type, a hollow fiber type, and the like.
Furthermore, inert gas is introduced into the device to serve as protective gas during shutdown maintenance, and the inert gas is selected from nitrogen, argon, helium, carbon dioxide and the like, so that the molecular sieve membrane in the membrane separation unit is prevented from being inactivated due to long-time standing.
Further, the first stage adsorption module further comprises:
the first gas sweeping end is used for introducing inert gas to sweep the permeation gas of the molecular sieve membrane, so that the permeation gas is rapidly discharged from the first permeation end, and the membrane separation efficiency is improved;
the first air sweeping ends of a plurality of (m) first-stage adsorption modules are connected in parallel and then communicated with an external air channel.
Further, the second stage adsorption module further comprises:
the second scavenging end is used for introducing inert gas to sweep the permeation gas of the molecular sieve membrane, so that the permeation gas is rapidly discharged from the first permeation end, and the membrane separation efficiency is improved;
and second scavenging ends of a plurality of (n) second-stage adsorption modules are connected in parallel and then are communicated with an external air passage.
Further, the inert gas is nitrogen, argon, helium or carbon dioxide.
Further, the flow rate of the inert gas is 0.01-1000L/min.
The invention also aims to provide a method for separating and recovering SO from flue gas2With NOxThe method adopts the device to separate and recover the flue gas, and comprises the following steps:
s1, leading the feed gas to a first-stage membrane separation unit after passing through a temperature controller, and separating NO from the first remaining end of the first-stage membrane separation unit2Gas, NO2Gas enters the second gas collecting tank to be collected;
s2, the permeation gas of the first-stage membrane separation unit enters the first buffer tank through the first permeation end, and NO detected by the smoke analyzer group (specifically the first smoke analyzer) is detected2When the volume concentration of the gas is not higher than 1%, conveying the gas to the second-stage membrane separation unit, otherwise returning the gas to the first feeding end of the first-stage membrane separation unit from the first gas loop;
s3, separating SO from the second residual end of the second-stage membrane separation unit2Gas, SO2Gas enters the third gas collecting tank to be collected; permeate gas enters the second buffer tank through the second permeate end; when the flue gas analyzer group (specifically, the second flue gas analyzer) detects SO2When the volume concentration of the gas is not higher than 1%, the NO gas separated from the second permeation end of the second-stage membrane separation unit is conveyed to the first gas collecting tank, and otherwise, the NO gas is returned to the second feeding end of the second-stage membrane separation unit through the second gas loop.
Further, when the screening efficiency of the first molecular sieve membrane and the second molecular sieve membrane is high, the gas does not need to be analyzed and the first gas loop and the second gas loop do not need to be opened; therefore, the S2 is replaced with: the first stage membrane separationThe permeate gas of the unit is directly conveyed to the second-stage membrane separation unit, and SO is separated from the second residual end2A gas;
the S3 is replaced by: and the permeation gas of the second-stage membrane separation unit is conveyed to the first gas collecting tank through the second permeation end to obtain NO gas.
Furthermore, the membrane separation process of the method is a two-stage membrane separation process, and membrane separation units (namely the first-stage membrane separation unit and the second-stage membrane separation unit) at different stages are sequentially connected; each stage of membrane separation unit is provided with a plurality of molecular sieves of the same type which are sequentially connected (namely, the first-stage adsorption modules are sequentially connected and the second-stage adsorption modules are sequentially connected), so that the separation performance of each stage of membrane separation unit is enhanced.
Further, the flow rate of the raw gas inlet in the method is as follows: 0.1-2000 ml/min; the temperature control range of the feed gas is-100 ℃ to 400 ℃;
the pressure differential between the first feed end and the first permeate end is in the range of: 0.01MPa to 5 MPa;
the pressure differential between the second feed end and the second permeate end ranges: 0.01MPa to 5 MPa.
Further, SO in the raw material gas2The volume concentration of (A) is 0.001-99%; NOxThe concentration of (A) is 0.001% -99%.
Further, said NOxIncluding NO and NO2NO concentration of 0.001% -99%, NO2The concentration of (A) is 0.001% -99%.
Further, the method adopts a membrane separation process, and the membrane separation process comprises the following two schemes:
(1) the raw material gas passes through each stage of membrane separation unit (a first stage membrane separation unit and a second stage membrane separation unit) in sequence, and the residual gas and the permeate gas of each stage of membrane separation unit are directly conveyed to corresponding gas collection tanks (a first gas collection tank, a second gas collection tank and a third gas collection tank) by pipelines;
(2) the permeated gas of each stage of membrane separation unit returns to a corresponding feed end through a corresponding circulating pipeline (a first gas loop and a second gas loop) to form a closed circulating flow, when the concentration detection of the gas reaches the standard (not higher than 1%), the permeated gas is conveyed to the next stage of membrane separation unit, and after the concentration detection of the permeated gas separated by the last stage of membrane separation unit reaches the standard, the permeated gas is conveyed to corresponding gas collecting tanks (a first gas collecting tank, a second gas collecting tank and a third gas collecting tank); the residual gas of each stage of membrane separation unit is conveyed to corresponding gas collecting tanks (a first gas collecting tank, a second gas collecting tank and a third gas collecting tank) through pipelines.
The invention has the following beneficial technical effects:
(1) the device aims at SO in the current industrial flue gas2With NOxResource high value status and SO in desorption gas2/NOxThe technical requirement of effective separation can reduce energy waste, is economic and environment-friendly, and has popularization value.
(2) The device is used for separating and recovering SO from the flue gas2With NOxWhile separating the recovered SO2The recovery rate is 70-95 percent, the recovery rate of NO is 70-95 percent, and NO is2The recovery rate is 70-95%.
(3) The design of the secondary membrane separation unit of the device can effectively separate and recycle three gases, and the gas resource circulation rate is improved.
(4) In the device, the first-stage membrane separation unit and the second-stage membrane separation unit are sequentially connected with the plurality of adsorption modules, and the sequentially connected adsorption modules can effectively improve the purity of the recovered gas.
(5) When the device is blocked, the pressure gauge arranged on the adsorption module can effectively detect the blocked part, so that the device is convenient to overhaul.
(6) Compared with the prior art, the device has the advantages of low production cost (the structure in the device is simple and easy to obtain) and use cost (only the molecular sieve membrane needs to be replaced), small occupied area and simple operation.
Drawings
FIG. 1 shows the separation and recovery of SO from flue gas in an embodiment of the present invention2With NOxThe structural diagram of the device is shown.
Description of reference numerals: 1-a temperature controller; 2-a thermometer; 3-a first-stage membrane separation unit, 31-a first-stage adsorption module, 311-a first feed end, 312-a first residual end, 313-a first permeation end, 32-a first-stage pressure gauge, 33-a fifth valve, 34-a fourth flue gas analyzer and 35-a second gas collection tank; 4-a second-stage membrane separation unit, 41-a second-stage adsorption module, 411-a second feed end, 412-a second residual end, 413-a second permeate end, 42-a second-stage pressure gauge, 43-a sixth valve, 44-a fifth flue gas analyzer, 45-a third gas collection tank; 5-a first buffer tank; 6-a first flue gas analyzer; 7-a second valve; 8-a second buffer tank; 9-a second flue gas analyzer; 10-a third valve; 11-a first valve; 12-a fourth valve; 13-a third flue gas analyzer; 14-a first gas collection tank; 15-first permeate side pressure gauge; 16-second permeate side pressure gauge.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
On the contrary, the invention is intended to cover alternatives, modifications, equivalents and alternatives which may be included within the spirit and scope of the invention as defined by the appended claims. Furthermore, in the following detailed description of the present invention, certain specific details are set forth in order to provide a better understanding of the present invention. It will be apparent to one skilled in the art that the present invention may be practiced without these specific details.
The embodiment provides a method for separating and recovering SO from flue gas2With NOxAs shown in fig. 1, the apparatus comprises:
a first stage membrane separation unit for separating NO from flue gas2A gas;
a second stage membrane separation unit for separating NO gas and SO from the flue gas2A gas;
a first buffer tank;
the flue gas analyzer group is used for analyzing gas components;
the valve group is used for controlling the circulation of gas;
a second buffer tank;
a first gas collection tank;
the first-stage membrane separation unit, the first buffer tank, the second-stage membrane separation unit, the second buffer tank and the first gas collecting tank are sequentially arranged on a main gas path of the device.
First gas loop second gas loop
In this embodiment, the flue gas analyzer group includes:
the first flue gas analyzer is used for analyzing gas components in the first buffer tank;
the second flue gas analyzer is used for analyzing gas components in the second buffer tank;
the third flue gas analyzer is used for analyzing gas components in the first gas collecting tank;
the first flue gas analyzer is arranged on the first buffer tank;
the second flue gas analyzer is arranged on the second buffer tank;
the third flue gas analyzer is arranged on the first gas collecting tank.
In this and other embodiments, the apparatus further comprises:
the first gas loop is used for returning the gas in the first buffer tank to the gas inlet of the first-stage membrane separation unit, so that the components in the gas are further sieved by the first-stage membrane separation unit;
a second gas loop for returning the gas in the second buffer tank to the gas inlet of the second stage membrane separation unit, so that the components in the gas are further sieved by the second stage membrane separation unit;
the first gas loop is a pipeline for communicating the first buffer tank with a gas inlet of the first-stage membrane separation unit;
the second gas loop is a pipeline which is communicated with the second buffer tank and the gas inlet of the second-stage membrane separation unit.
In this embodiment, the valve set includes:
the first valve is used for controlling the on-off of the first gas loop;
a second valve for controlling gas passing from the first buffer tank to the second stage membrane separation unit;
the third valve is used for controlling the on-off of the second gas loop;
a fourth valve for controlling the gas entering the first gas collection tank;
the first valve is arranged on the first gas circuit; the second valve is arranged between the first buffer tank and the second-stage membrane separation unit; the third valve is disposed on the second gas circuit; the fourth valve is arranged between the second buffer tank and the first gas collecting tank.
In this embodiment, the first valve, the second valve, the third valve and the fourth valve are all one-way valves.
In this embodiment, the first vapor collection canister is used to collect NO gas.
In this embodiment, the first-stage membrane separation unit includes a plurality of first-stage adsorption modules, and a first-stage pressure gauge, a fifth valve, a fourth flue gas analyzer, and a second gas collection tank, which are correspondingly disposed on the first-stage adsorption modules;
the first-stage adsorption module is provided with a first feeding end, a first residual end and a first permeation end;
the adjacent first-stage adsorption modules are communicated through interconnection of surplus ends and feeding ends;
the first permeation ends of the first-stage adsorption modules are connected in parallel and then connected with the second-stage membrane separation unit;
the last first residual end is connected with the fifth valve and the second gas collecting tank in sequence; and the fourth flue gas analyzer is arranged on the second gas collecting tank and is used for analyzing the gas components in the second gas collecting tank.
In this embodiment, the fifth valve is a check valve.
In this embodiment, the second vapor collection canister is used to collect NO2A gas.
In this embodiment, the first-stage pressure gauge is used to determine: when a certain first-stage adsorption module is blocked or a pipeline is blocked, a blocked place can be found according to the readings of the first-stage pressure gauges (when the first-stage adsorption module is blocked or the pipeline is blocked, the reading of the first-stage pressure gauge at the downstream of the blocked place is 0); in addition, the pressure of the first pressure gauge at the upstream of the device can also be used as the pressure of the flue gas entering the first-stage membrane separation unit.
In this embodiment, the first stage adsorption module comprises a first molecular sieve membrane and a first membrane separator;
the first molecular sieve membrane is placed in the first membrane separator.
In this embodiment, the first membrane separator is a sealed space with a rubber ring.
In this embodiment, the number of the first-stage adsorption modules is m, and m is a positive integer not less than 2.
In this embodiment, the types of the first molecular sieve membrane are: AEI, CHA, LTA, MFI, SFW, RTH, KFI, ITE, ITW, CAN, EPI, MOR, FAU or FER; the CHA film is preferred, and the CHA film with high silicon-aluminum ratio has stronger thermal stability and acid resistance and can realize SO under severe conditions2/NO2And (5) separating.
In this embodiment, the second-stage membrane separation unit includes a plurality of second-stage adsorption modules, and a second-stage pressure gauge, a sixth valve, a fifth flue gas analyzer, and a third gas collection tank, which are correspondingly disposed on the second-stage adsorption modules;
the second-stage adsorption module is provided with a second feeding end, a second residual end and a second permeation end;
the adjacent second-stage adsorption modules are communicated with each other through a second residual end and a second feeding end;
second penetration ends on the second-stage adsorption modules are connected in parallel and then communicated with the second buffer tank;
the last second residual end, the sixth valve and a third gas collecting tank are connected in sequence; and the fifth flue gas analyzer is arranged on the third gas collecting tank and is used for analyzing the gas components in the third gas collecting tank.
In this embodiment, the sixth valve is a check valve.
In this embodiment, the third vapor collection canister is used to collect SO2A gas.
In this embodiment, the second-stage pressure gauge is used to determine: when a certain second-stage adsorption module is blocked or a pipeline is blocked, a blocked place can be found according to the readings of the second-stage pressure gauges (when the second-stage adsorption module is blocked or the pipeline is blocked, the reading of the second-stage pressure gauge at the downstream of the blocked place is 0); in addition, the pressure of the first second-stage pressure gauge at the upstream of the device can also be used as the pressure of the flue gas entering the second-stage membrane separation unit.
In this embodiment, the apparatus further includes a first permeation end pressure gauge for detecting the total pressure after the first permeation ends are connected in parallel, and a second permeation end pressure gauge for detecting the total pressure after the second permeation ends are connected in parallel;
the first permeation end pressure gauge is arranged on the main path after the first permeation ends are connected in parallel;
the second permeation end pressure gauge is arranged on the main path after the second permeation ends are connected in parallel.
In this embodiment, the second stage adsorption module comprises a second molecular sieve membrane and a second membrane separator;
the second molecular sieve membrane is placed in the second membrane separator.
In this embodiment, the second membrane separator is a sealed space with a rubber ring.
In this embodiment, the number of the second-stage adsorption modules is n, and n is a positive integer not less than 2.
In this embodiment, the second molecular sieve membrane is of the type: DDR, RHO, ERI, AFX, RTH, ITE, IHW, ITW, NSI, LEV, EDI, EPI, GIS, HEU, NAT, MOR, or FER; the RHO film is preferred, and the RHO film with low silicon-aluminum ratio can realize NO/SO2Separation of (4).
In this embodiment, the apparatus further comprises a temperature controller and a thermometer for adjusting the temperature of the gas entering the apparatus to optimize the effect of the gas separation;
the temperature controller and the thermometer are arranged at the upstream of the first-stage membrane separation unit;
the temperature controller is an existing temperature control device.
In the present embodiment, a mass flow meter, a blower, a pressure reducing valve, a vacuum pump, and the like are provided in the gas path at various points of the apparatus; the mass flow meter is used for controlling the flow of the gas; the vacuum pump is used for providing negative pressure for the permeation end of the first-stage membrane separation unit, so that the permeation pressure difference at two sides of the first-stage membrane separation unit is increased (the permeation quantity of gas can be increased, and the efficiency of the device is increased); the blower is used for providing positive pressure to the second feeding end, so that the osmotic pressure difference on two sides of the second-stage membrane separation unit can be increased; the pressure reducing valve is arranged between the first-stage membrane separation unit and the second-stage membrane separation unit and used for adjusting the pressure of gas entering the second-stage membrane separation unit.
In this embodiment, all of the surge tanks in the apparatus function to reduce the non-uniformity of the permeate gas flow and serve as detection sites for the gas components detected by the flue gas analyzer.
In the embodiment, the pipeline, the membrane separator (the first membrane separator, the second membrane separator) and the like in the device are made of corrosion-resistant materials such as stainless steel, quartz, silica gel, phenolic resin, fluoroplastic and the like, SO that SO is prevented2With NOxCorrosion is generated on the pipeline; the appearance type of the molecular sieve membrane can be a sheet membrane, a tubular membrane, a fiber tubular membrane and the like; the form of the membrane separator includes a plate frame type, a spiral wound type, a hollow fiber type, and the like.
In the embodiment, inert gas is introduced into the device as protective gas during shutdown maintenance, and the inert gas is selected from nitrogen, argon, helium, carbon dioxide and the like, so as to prevent the molecular sieve membrane in the membrane separation unit from being inactivated due to long-time standing.
In this embodiment, the first stage adsorption module further includes:
the first gas sweeping end is used for introducing inert gas to sweep the permeation gas of the molecular sieve membrane, so that the permeation gas is rapidly discharged from the first permeation end, and the membrane separation efficiency is improved;
the first air sweeping ends of a plurality of (m) first-stage adsorption modules are connected in parallel and then communicated with an external air channel.
In this embodiment, the second stage adsorption module further includes:
the second scavenging end is used for introducing inert gas to sweep the permeation gas of the molecular sieve membrane, so that the permeation gas is rapidly discharged from the first permeation end, and the membrane separation efficiency is improved;
and second scavenging ends of a plurality of (n) second-stage adsorption modules are connected in parallel and then are communicated with an external air passage.
In this embodiment, the inert gas is nitrogen, argon, helium or carbon dioxide.
In this embodiment, the flow rate of the inert gas is 0.01 to 1000L/min.
The embodiment also provides a method for separating and recovering SO in flue gas2With NOxThe method adopts the device to separate and recover the flue gas, and comprises the following steps:
s1, leading the feed gas to a first-stage membrane separation unit after passing through a temperature controller, and separating NO from the first remaining end of the first-stage membrane separation unit2Gas, NO2Gas enters the second gas collecting tank to be collected;
s2, the permeation gas of the first stage membrane separation unit enters the first buffer tank through the first permeation end, and when the NO detected by the smoke analyzer group (first smoke analyzer)2When the volume concentration of the gas is not higher than 1%, the conveying gas enters the second-stage membrane separation unit, and otherwise returns to the first-stage membrane separation unit through the first gas loopA first feed end of the first stage membrane separation unit;
s3, separating SO from the second residual end of the second-stage membrane separation unit2Gas, SO2Gas enters the third gas collecting tank to be collected; permeate gas enters the second buffer tank through the second permeate end; when the flue gas analyzer group (specifically, the second flue gas analyzer) detects SO2When the volume concentration of the gas is not higher than 1%, the NO gas separated from the second permeation end of the second-stage membrane separation unit is conveyed to the first gas collecting tank, and otherwise, the NO gas is returned to the second feeding end of the second-stage membrane separation unit through the second gas loop.
In other embodiments, when the sieving efficiency of the first molecular sieve membrane and the second molecular sieve membrane is high, the gas does not need to be analyzed and the first gas loop and the second gas loop do not need to be opened; therefore, the S2 is replaced with: the permeate gas of the first stage membrane separation unit is directly conveyed to the second stage membrane separation unit, and SO is separated from the second residual end2A gas;
the S3 is replaced by: and the permeation gas of the second-stage membrane separation unit is conveyed to the first gas collecting tank through the second permeation end to obtain NO gas.
In this embodiment, the membrane separation process of the method is a two-stage membrane separation process, and membrane separation units of different stages (i.e., the first-stage membrane separation unit and the second-stage membrane separation unit) are connected in sequence. Each stage of membrane separation unit is provided with n molecular sieves of the same type which are sequentially connected (namely the first-stage adsorption module and the second-stage adsorption module), wherein the value of n is more than or equal to 2, so that the separation performance of each stage of membrane separation unit is enhanced.
In this example, the flow rates of the feed gas feed in the process were: 0.1-2000 ml/min; the temperature control range of the feed gas is-100 ℃ to 400 ℃;
the pressure differential between the first feed end and the first permeate end is in the range of: 0.01MPa to 5 MPa;
the pressure differential between the second feed end and the second permeate end ranges: 0.01MPa to 5 MPa.
In this example, SO is present in the feed gas2The volume concentration of (A) is 0.001-99%; NOxThe concentration of (A) is 0.001% -99%.
In this example, the NOxIncluding NO and NO2NO concentration of 0.001% -99%, NO2The concentration of (A) is 0.001% -99%.
In this embodiment, the method employs a membrane separation process, which includes the following two schemes:
(1) the raw material gas passes through each stage of membrane separation unit (a first stage membrane separation unit and a second stage membrane separation unit) in sequence, and the residual gas and the permeate gas of each stage of membrane separation unit are directly conveyed to corresponding gas collection tanks (a first gas collection tank, a second gas collection tank and a third gas collection tank) by pipelines;
(2) the permeated gas of each stage of membrane separation unit returns to a corresponding feed end through a corresponding circulating pipeline (a first gas loop and a second gas loop) to form a closed circulating flow, and is conveyed to the next stage of membrane separation unit when the concentration detection of the gas reaches the standard, and is conveyed to corresponding gas collecting tanks (a first gas collecting tank, a second gas collecting tank and a third gas collecting tank) after the concentration detection of the permeated gas separated by the last stage of membrane separation unit reaches the standard; the residual gas of each stage of membrane separation unit is conveyed to corresponding gas collecting tanks (a first gas collecting tank, a second gas collecting tank and a third gas collecting tank) through pipelines.
In this embodiment, the gas separation experiment is performed according to the apparatus and method described above, and the specific contents of the experiment are as follows:
SO in the same proportion2With NOxThe mixed gas is used as raw material gas, and SO is separated and recovered from the flue gas of the embodiment2With NOxMethod for separating and recovering SO2、NO2And NO, wherein the first molecular sieve membrane is a CHA molecular sieve membrane, and the second molecular sieve membrane is an RHO molecular sieve membrane, and the specific method comprises the following steps:
(1) the raw material gas with the flow rate of 20ml/min is conveyed to the first-stage membrane separation unit, the temperature of the temperature controller is adjusted to be 20 ℃, and the pressure on the two sides of the first-stage membrane separation unit and the second-stage membrane separation unitThe difference was adjusted to 0.15 MPa. Through the screening effect of m first-stage adsorption modules in the first-stage membrane separation unit, high-purity NO is separated from the first residual end of the last first-stage adsorption module2The gas is conveyed to the second gas collecting tank;
(2) the permeated gas of the first-stage membrane separation unit enters a first buffer tank and is subjected to gas concentration detection by adopting a first flue gas analyzer, and NO in the permeated gas is detected2When the volume concentration of the first-stage adsorption module is 0, the permeate gas is conveyed to a second-stage membrane separation unit, otherwise, the permeate gas returns to a first feeding end of the first-stage adsorption module through a first gas loop;
(3) in the second-stage membrane separation unit, high-purity SO is separated from the second residual end of the last second-stage adsorption module by the screening action of n second-stage adsorption modules2A gas. The permeating gas enters a second buffer tank and is subjected to gas concentration detection, and when SO in the permeating gas2Is 0, the high-purity NO gas separated from the second permeate side is delivered to the first gas-collecting tank, otherwise returned to the second feed side of the first second-stage adsorption module by the second gas loop.
The NO separated and recovered by the method is detected2Purity of about 95%, NO purity of about 95%, SO2Purity of about 95%, SO2、NO2The recovery rate of NO and the recovery rate of NO reach more than 90 percent.
The device can separate and recover high-purity SO2、NO2And NO, and one of the main core designs for higher recovery is the high separation performance of the alternative molecular sieves, exemplified below by the experimentally measured CHA molecular sieve separation (NO, SO)2)/NO2And RHO molecular sieve to NO/SO2Selectivity value of (a):
TABLE 1 CHA molecular sieve based separation data
Figure BDA0002448371510000151
TABLE 2 RHO molecular sieve based separation data
Figure BDA0002448371510000152
Figure BDA0002448371510000161
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present application has been described in detail with reference to the foregoing embodiments, it should be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. SO is separated and recovered from flue gas2With NOxThe apparatus of (a), wherein the apparatus comprises:
a first stage membrane separation unit for separating NO from flue gas2A gas;
a second stage membrane separation unit for separating NO gas and SO from the flue gas2A gas;
a first buffer tank;
the flue gas analyzer group is used for analyzing gas components;
the valve group is used for controlling the circulation of gas;
a second buffer tank;
a first gas collection tank;
the first-stage membrane separation unit, the first buffer tank, the second-stage membrane separation unit, the second buffer tank and the first gas collecting tank are sequentially arranged on a main gas path of the device;
the device further comprises:
the first gas loop is used for returning the gas in the first buffer tank to the gas inlet of the first-stage membrane separation unit, so that the components in the gas are further sieved by the first-stage membrane separation unit;
a second gas loop for returning the gas in the second buffer tank to the gas inlet of the second stage membrane separation unit, so that the components in the gas are further sieved by the second stage membrane separation unit;
the first gas loop is a pipeline for communicating the first buffer tank with a gas inlet of the first-stage membrane separation unit;
the second gas loop is a pipeline which is communicated with the second buffer tank and the gas inlet of the second-stage membrane separation unit.
2. The method for separating and recovering SO from flue gas according to claim 12With NOxThe device is characterized in that the first-stage membrane separation unit comprises a plurality of first-stage adsorption modules, a first-stage pressure gauge, a fifth valve, a fourth flue gas analyzer and a second gas collecting tank which are correspondingly arranged on the first-stage adsorption modules;
the first-stage adsorption module is provided with a first feeding end, a first residual end and a first permeation end;
the adjacent first-stage adsorption modules are communicated through interconnection of surplus ends and feeding ends;
the first permeation ends of the first-stage adsorption modules are connected in parallel and then connected with the second-stage membrane separation unit;
the last first residual end is connected with the fifth valve and the second gas collecting tank in sequence; and the fourth flue gas analyzer is arranged on the second gas collecting tank and is used for analyzing the gas components in the second gas collecting tank.
3. The method for separating and recovering SO from flue gas according to claim 22With NOxThe device is characterized in that the first-stage adsorption module comprises a first molecular sieve membrane and a first membrane separator;
the first molecular sieve membrane is placed in the first membrane separator.
4. A method according to claim 2 or 3SO is separated and recovered from flue gas2With NOxThe device is characterized in that the second-stage membrane separation unit comprises a plurality of second-stage adsorption modules, and a second-stage pressure gauge, a sixth valve, a fifth flue gas analyzer and a third gas collecting tank which are correspondingly arranged on the second-stage adsorption modules;
the second-stage adsorption module is provided with a second feeding end, a second residual end and a second permeation end;
the adjacent second-stage adsorption modules are communicated with each other through a second residual end and a second feeding end;
second penetration ends on the second-stage adsorption modules are connected in parallel and then communicated with the second buffer tank;
the last second residual end, the sixth valve and a third gas collecting tank are connected in sequence; and the fifth flue gas analyzer is arranged on the third gas collecting tank and is used for analyzing the gas components in the third gas collecting tank.
5. The method for separating and recovering SO from flue gas according to claim 42With NOxThe device of (2), characterized in that the second stage adsorption module comprises a second molecular sieve membrane and a second membrane separator;
the second molecular sieve membrane is placed in the second membrane separator.
6. The method for separating and recovering SO from flue gas according to claim 42With NOxThe device is characterized by further comprising a first permeation end pressure gauge for detecting the total pressure of the first permeation ends after being connected in parallel and a second permeation end pressure gauge for detecting the total pressure of the second permeation ends after being connected in parallel;
the first permeation end pressure gauge is arranged on the main path after the first permeation ends are connected in parallel;
the second permeation end pressure gauge is arranged on the main path after the second permeation ends are connected in parallel.
7. A cigarette according to claim 4Separating and recovering SO from gas2With NOxThe apparatus of (a), wherein the apparatus further comprises a temperature controller and a thermometer for adjusting the temperature of the gas entering the apparatus to optimize the effect of the gas separation;
the temperature controller and the thermometer are disposed upstream of the first-stage membrane separation unit.
8. Separating and recovering SO from flue gas as defined in any one of claims 4 to 72With NOxThe method for separating a device according to (1), characterized in that the method comprises the steps of:
s1, leading the feed gas to a first-stage membrane separation unit after passing through a temperature controller, and separating NO from the first remaining end of the first-stage membrane separation unit2Gas, NO2Gas enters the second gas collecting tank to be collected;
s2, the permeation gas of the first stage membrane separation unit enters the first buffer tank through the first permeation end, and NO detected by the first flue gas analyzer in the flue gas analyzer group2When the volume concentration of the gas is not higher than 1%, conveying the gas to the second-stage membrane separation unit, otherwise returning the gas to the first feeding end of the first-stage membrane separation unit from the first gas loop;
s3, separating SO from the second residual end of the second-stage membrane separation unit2Gas, SO2Gas enters the third gas collecting tank to be collected; permeate gas enters the second buffer tank through the second permeate end; when SO detected by a second flue gas analyzer in the flue gas analyzer group2When the volume concentration of the gas is not higher than 1%, the NO gas separated from the second permeation end of the second-stage membrane separation unit is conveyed to the first gas collecting tank, and otherwise, the NO gas is returned to the second feeding end of the second-stage membrane separation unit through a second gas loop.
9. Separation and recovery of SO from flue gas according to claim 82With NOxThe separation method of the apparatus in (1), wherein S2 is replaced with: the permeate gas of the first stage membrane separation unit is directlyIs conveyed to the second-stage membrane separation unit, and SO is separated from the second residual end2A gas;
the S3 is replaced by: and the permeation gas of the second-stage membrane separation unit is conveyed to the first gas collecting tank through the second permeation end to obtain NO gas.
10. Separation and recovery of SO from flue gas according to claim 82With NOxThe separation process of the apparatus according to (1), characterized in that the feed gas feed flow rate in the process is: 0.1-2000 ml/min; the temperature control range of the feed gas is-100 ℃ to 400 ℃;
the pressure differential between the first feed end and the first permeate end is in the range of: 0.01MPa to 5 MPa;
the pressure differential between the second feed end and the second permeate end ranges: 0.01MPa to 5 MPa.
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