WO2021220150A2 - Procédé d'élimination de formaldéhyde et de composés organiques volatils contenus dans des déchets de gaz industriels - Google Patents

Procédé d'élimination de formaldéhyde et de composés organiques volatils contenus dans des déchets de gaz industriels Download PDF

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Publication number
WO2021220150A2
WO2021220150A2 PCT/IB2021/053453 IB2021053453W WO2021220150A2 WO 2021220150 A2 WO2021220150 A2 WO 2021220150A2 IB 2021053453 W IB2021053453 W IB 2021053453W WO 2021220150 A2 WO2021220150 A2 WO 2021220150A2
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WO
WIPO (PCT)
Prior art keywords
formaldehyde
waste
gases
heat
absorber
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Application number
PCT/IB2021/053453
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English (en)
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WO2021220150A3 (fr
Inventor
Darko GORICANEC
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University of Maribor
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Publication date
Application filed by University of Maribor filed Critical University of Maribor
Publication of WO2021220150A2 publication Critical patent/WO2021220150A2/fr
Publication of WO2021220150A3 publication Critical patent/WO2021220150A3/fr

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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
    • B01D53/14—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 absorption
    • B01D53/1487—Removing organic compounds
    • 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
    • B01D53/005—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 heat treatment
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2252/00—Absorbents, i.e. solvents and liquid materials for gas absorption
    • B01D2252/10—Inorganic absorbents
    • B01D2252/103—Water
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2259/00—Type of treatment
    • B01D2259/65—Employing advanced heat integration, e.g. Pinch technology

Definitions

  • the subject of the invention relates to a method of removing formaldehyde and volatile organic compounds present in the waste process gases, generated in the metal oxide the process in the production of formaldehyde, or in other industrial processes.
  • heat which is used to produce heat or electricity is also released.
  • Patent WO2015/134470A1 describes the removal of formaldehyde produced by fuel combustion by catalytic oxidation in a catalyst mounted on the exhaust pipe of stationary or non-stationary internal combustion engines.
  • U.S. Pat. No. 4383123 relates to the production of an aqueous solution of formaldehyde, which is produced by a silver catalytic process, and this process differs significantly from the metal oxide process of formaldehyde production.
  • the purpose of the described process is the production of an aqueous solution of formaldehyde for the needs of the market, and not the removal of very small concentrations of formaldehyde from process gases.
  • Patent DE3221795A1 describes a process for absorbing formaldehyde with an aqueous solution of chemicals by circulating in an absorber, similar to that described in W02007/041831 .
  • Patent WO2016/132091 A1 deals with the process of formaldehyde production, where it provides for the absorption or desorption of CO from process gases.
  • the described technical solution does not refer to the removal of formaldehyde and volatile organic compounds from process waste gases generated in the metal oxide process of formaldehyde production.
  • U.S. Pat. No. 5272349 describes the removal of formaldehyde from wastewater generated in industrial processes, but does not describe the removal of formaldehyde from process waste gases.
  • the invention describes two processes for the removal of formaldehyde and volatile organic compounds from process waste gases generated by a metal oxide process for the production of formaldehyde.
  • the first process described in the invention represents an upgrade of the existing process for the catalytic removal of formaldehyde and volatile organic compounds from waste process gases generated in the metal oxide process for the production of formaldehyde.
  • the partially purified process gases are fed to a heat exchanger where they are cooled and then to an absorption device where formaldehyde is removed from the waste process gases by absorption in water. This significantly reduces emissions of formaldehyde compounds present in process waste gases into the environment.
  • the heat released during the catalytic removal of formaldehyde from process gases is used to produce steam, which can be used to produce heat or electricity produced by a single-stage radial discharge steam turbine.
  • the second process described in the invention is the co-combustion of formaldehyde and volatile organic compounds present in industrial process gas waste in a gas turbine.
  • the heat of the exhaust gases of the gas turbine is used to produce steam, which drives a single-stage steam turbine with a radial outlet, or the steam is used in whole or in part to produce heat.
  • the technical problem addressed in this patent application is the lack of a simplified method and cost effective method and&or apparatus for co-combustion of formaldehyde and volatile organic compounds present in industrial process gas waste in a gas turbine, hence the main object of disclosed invention is to provide a simplified method and cost effective apparatus for utilization of such a method by guided flow of volatile organic compounds from waste process gases generated in the metal oxide process for the production of formaldehyde.
  • the waste gas treatment process in the first embodiment represents an upgrade of the existing process for the catalytic removal of formaldehyde and volatile organic compounds from the waste process gases generated in the metal oxide formaldehyde production process.
  • Process waste gases from the metal oxide process of formaldehyde production contain a high content of formaldehyde and volatile organic compounds and should therefore not be discharged into the environment without cleaning.
  • Process waste gases leaving the existing exothermic catalytic process containing significantly lower concentrations of formaldehyde and volatile organic compounds are further cooled according to the invention and fed to an absorption device, where formaldehyde is absorbed in water by washing the process waste gases with water.
  • the waste process gases leaving the absorption device are then reheated to be more easily discharged through the chimney into the environment.
  • the concentration of formaldehyde in process waste gases discharged into the environment is significantly reduced.
  • the heat released from the existing catalytic removal of formaldehyde and volatile organic compounds from the process waste gases is used to produce steam, to be used to produce heat or electricity, which can be produced by a single-stage radial discharge steam turbine.
  • the process of cleaning the process waste gases according to the invention in second embodiment is the co-incineration of formaldehyde and volatile organic compounds present in the waste process gases generated in the metal oxide process for the production of formaldehyde.
  • the co-incineration of the process gas is carried out in a gas turbine by mixing the process gas with air with a static mixer before it is fed to the gas turbine compressor. From the compressor, a compressed mixture of air and waste process gases is led to the combustion chamber, where gaseous or liquid fuel is fed through the burners. At the high temperature generated in the combustion chamber, in addition to the added gaseous or liquid fuel, all organic substances that were present in the mixture of waste process gases and air also burn.
  • the hot gases leaving the combustion chamber drive the turbine and then lead to an evaporator where steam is produced, which drives a single-stage steam turbine with a radial outlet, or the steam is used in whole or in part to produce heat.
  • the method and apparatus according to the invention is a cost effective solution for simplified method and cost effective method and&or apparatus for co combustion of formaldehyde and volatile organic compounds present in industrial process gas waste in a gas turbine.
  • FIG. 1 shows a process diagram of the first embodiment of the invention of removing formaldehyde and volatile organic compounds from process waste gases generated by a metal oxide formaldehyde production process, with a designated existing and innovative part of the plant.
  • the figure shows and labels: existing process (1 ), process gas supply pipe (2), reactor (3), pipe connection to evaporator (4), evaporator (5), pipe connection for preheating of process gas (6), pipe connection to turbine (7), steam turbine with radial outlet (8), high pressure steam pipe (9), low pressure steam pipe (10), pipe connection to condenser (11), condenser (12), steam pipe (13), condensate pipe (14), cooling water supply pipe (15), process connection pipe gas (16), heat exchanger for preheating condensate (17), pipe for condensate supply (18), pipe connection for preheating condensate (19), pipe connection for waste heat recovery (20), heat exchanger for waste heat recovery (21), pipe connection to absorber (22), absorber (23), pipe connection to the water source (24), pipe connection
  • Figure 2 shows a process diagram of second embodiment of the invention of removing formaldehyde and volatile organic compounds from process waste gases generated by a metal oxide formaldehyde production process by co-incineration in a gas turbine (100).
  • Figure 2 shows and labels: gas turbine (100), compressor (101), combustion chamber (102), turbine (103), pipe connection for fuel supply (104), pipe connection for supply of process gases (105), pipe connection for air supply (106), static mixer (107), pipe connection to compressor (108), pipe connection to evaporator (109), evaporator for waste utilization heat exchanger (110), pipe connection to turbine (7), steam turbine with radial outlet (8), high- pressure steam production pipeline (9), low-pressure steam production pipeline (10), pipe connection to condenser (11), condenser (12), steam discharge pipeline (13), condensate discharge pipeline (14), a cooling water supply pipe (15), a condensate supply pipe (18) and a chimney (27) for discharging process waste gases into the environment.
  • the first embodiment according to the invention shown in Figure 1 represents a process for the additional purification of formaldehyde and volatile organic compounds from waste process gases generated in the metal oxide process for the production of formaldehyde.
  • Figure 1 shows the existing process (1) of exothermic catalytic removal of formaldehyde and volatile organic compounds from waste process gases generated by a metal oxide formaldehyde production process consisting of a reactor (3) and an evaporator (5) where high pressure steam is produced.
  • waste process gases generated in the metal oxide process of formaldehyde production are fed, where the waste process gases are heated first, and in the second part of the reactor (3), an exothermic catalytic reaction of organic substances with oxygen present in the waste process gases.
  • the hot reacted process gases leaving the reactor (3) are fed to the evaporator (5), where high-pressure steam is produced.
  • the process gases are partially cooled and conducted via a pipe connection for preheating the process gases (6) back to the reactor (3), where their heat is used to preheat the process gases entering the reactor via a heat exchanger installed at the beginning of the reactor (3).
  • Partially cooled process gases leaving the reactor (3) via a pipe connection for conducting process gases (16) are led to a heat exchanger for preheating condensate (17), where their heat preheats the condensate, which is fed to the evaporator via a pipe connection for preheating condensate (19).
  • the process gases leaving the heat exchanger for preheating the condensate (17) are led via a pipe connection for the use of waste heat (20) to the heat exchanger for the use of waste heat (21 ), where they are further cooled before being led to the absorber (23) via a pipe connection to the absorber (22).
  • formaldehyde is absorbed in the counter current in water, which is fed to the absorber (23) via a pipe connection to the water source (24), wherein a highly dilute aqueous formaldehyde solution, which can be used in the formalin production process itself.
  • the purified process gases are led via a pipe connection to the heat exchanger for the use of waste heat (26) to the heat exchanger for the use of waste heat (21 ), where they are heated before being discharged into the environment via the chimney (27).
  • the high-pressure steam produced in the evaporator (5) can be used in whole or in part for heat production, if required by the production process, whereby all or only part of the steam can be fed to a single-stage steam turbine with radial discharge (8).
  • Steam leaving a single-stage steam turbine with radial discharge (8) can be further used as medium pressure steam for heat production or can be piped to a condenser (12), where it condenses in a vacuum and drains as condensate via a condensate discharge line (14).
  • the condensate generated in the production of heat by condensing high-pressure steam, low-pressure steam or condensing steam in the condenser (12) is collected and returned to the heat exchanger to preheat the condensate (17) by means of a pump via the condensate supply line (18). Condensation of steam in the condenser (12) vacuum, where cooling water is supplied for cooling.
  • the low-pressure steam that can be used to heat the production process and the steam that leads to the condenser (12) are at different pressure levels.
  • the heat exchanger for preheating the condensate (17) may be discharged from the process scheme, with the waste process gases leaving the reactor (3) via a pipe connection to control the process gases (16), lead directly to the heat exchanger for the use of waste heat (21).
  • the first embodiment according to the invention shown in Figure 1 represents a process for the additional purification of formaldehyde and volatile organic compounds from waste process gases generated in the metal oxide process for the production of formaldehyde.
  • Figure 1 shows the existing process (1) of exothermic catalytic removal of formaldehyde and volatile organic compounds from waste process gases generated by a metal oxide formaldehyde production process consisting of a reactor (3) and an evaporator (5) where high pressure steam is produced.
  • waste process gases generated in the metal oxide process of formaldehyde production are fed in the first part of the reactor (3), where the waste process gases are heated, and in the second part of the reactor (3), an exothermic catalytic reaction of organic substances with oxygen present in the waste process gases.
  • the hot reacted process gases leaving the reactor (3) are fed to the evaporator (5), where high-pressure steam is produced.
  • the process gases are partially cooled and led through a pipe connection for preheating the waste process gases (6) back to the reactor (3), where through the heat exchanger installed on the first part of the reactor (3), their heat is used to preheat the waste process gases entering the reactor (3).
  • Partially cooled process gases leaving the reactor (3) via a pipe connection for conducting process gases (16) are led to a heat exchanger for preheating condensate (17), where their heat preheats the condensate, which is piped via a pipe connection for preheating condensate (19), which is fed to the evaporator (5).
  • the process gases leaving the heat exchanger for preheating the condensate (17) are led via a pipe connection (20) to the heat exchanger (21) for the use of waste heat, where they are further cooled before being led to the absorber (23) via a pipe connection (22).
  • formaldehyde is absorbed in the counter current in water, which is fed to the absorber (23) via a pipe connection to the water source (24), whereby a highly dilute aqueous formaldehyde solution, which can be used in the formalin production process itself.
  • the purified process gases are led via a pipe connection to the heat exchanger for the use of waste heat (26) to the heat exchanger (21) for the use of waste heat, where they are heated before being discharged into the environment via the chimney (27).
  • the high-pressure steam produced in the evaporator (5) can be used in whole or in part for heat production, if required by the production process, whereby all or only part of the steam can be fed to a single-stage steam turbine with radial discharge (8).
  • Steam leaving a single-stage steam turbine with radial discharge (8) can be further used as medium pressure steam for heat production or can be piped to a condenser (12), where it condenses in a vacuum and drains as condensate via a condensate discharge line (14).
  • the condensate generated in the production of heat by condensing high- pressure steam, low-pressure steam or condensing steam in the condenser (12) is collected and returned to the heat exchanger to preheat the condensate (17) by means of a pump via the condensate supply line (18).
  • the condensation of steam in the condenser (12) preferably takes place in a vacuum, where cooling water is supplied for cooling.
  • the low-pressure steam that can be used to heat the production process and the steam that leads to the condenser (12) are at different pressure levels.
  • the heat exchanger for preheating the condensate (17) can be released from the process scheme, whereby the waste process gases leaving the reactor (3) via a pipe connection to discharge the process gases (16), lead directly to the heat exchanger for the use of waste heat (21).
  • the second embodiment according to the invention is a process for purifying formaldehyde and volatile organic compounds present in waste process gases generated by a metal oxide formaldehyde production process by co-combustion in a gas turbine.
  • Figure 2 shows the second embodiment according to the invention, consisting of a gas turbine (100), which consists of a compressor (101 ) and a combustion chamber (102), to which gaseous or liquid fuel is supplied via a pipe connection for fuel supply (104), the exhaust gases leaving the combustion chamber (102) drive the turbine (103).
  • the air and process waste gases generated by the metal oxide formaldehyde production process are mixed in a static mixer (107) and fed to a compressor (101) which is an integral part of the gas turbine (100).
  • waste heat recovery evaporator 110
  • the heat of the exhaust gases is used to produce steam and is discharged into the environment when cooled.
  • the waste heat recovery evaporator (110) the produced high-pressure steam is discharged from the system for subsequent use, where all or part is used for heat production or, as in the first embodiment, all or part of the steam is led to a single-stage steam turbine with radial discharge (8).
  • the low-pressure steam leaving the turbine (103) can be used to produce heat within the needs of the production process, or it can be piped to the condenser (12), where it condenses in a vacuum.
  • Condensates generated during the production of heat by condensing high-pressure steam, low- pressure steam or by condensing steam in a condenser are discharged and collected for further use, being pumped back to the evaporator to use waste heat (110).
  • Steam condensation in the condenser (12) preferably takes place in a vacuum, where cooling water is supplied for cooling, leaving the condenser (12) via a pipeline.
  • the low-pressure steam discharged from the system for heat production and the steam supplied to the condenser (12) are at different pressure levels.
  • the first method - Figure 1 represents an upgrade of the existing process of catalytic removal of formaldehyde and volatile organic compounds from waste process gases generated in the metal oxide process of formaldehyde production, which comprises the following processes:
  • - heat production can be carried out by extracting all or part of the high-pressure steam through the high-pressure steam pipeline 9 or the low-pressure steam pipeline (10) during the electricity production process.
  • the second method - Figure 2 represents the removal of formaldehyde and volatile organic compounds present in waste process gases generated in the metal oxide process of formaldehyde production, by co-incineration in a gas turbine (100), which comprises the following processes:
  • the first process according to the invention shown in Figure 1 represents an upgrade of the existing process of catalytic removal of formaldehyde and volatile organic compounds from waste process gases generated by a metal oxide formaldehyde production process, where formaldehyde emissions to the environment can be reduced by six times.
  • the second process according to the invention shown in Figure 2 represents the co-incineration of formaldehyde and volatile organic compounds present in the waste process gases generated by the metal oxide formaldehyde production process in a gas turbine, where formaldehyde and volatile organic compounds are practically completely removed from the process waste.
  • Both of the described processes are exothermic, where the released energy can be used to produce electricity and/or heat.
  • gas turbine 100 [0053] compressor 101 ,
  • combustion chamber 102 [0054] combustion chamber 102
  • PTL1 W02007/041831
  • PTL2 WO2015/134470A1
  • PTL3 US4383123
  • PTL4 DE3221795A1
  • PTL5 US5272349

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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)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Treating Waste Gases (AREA)

Abstract

Le premier procédé selon l'invention représenté sur la Figure 1 représente une mise à niveau du processus existant d'élimination catalytique de formaldéhyde et de composés organiques volatils à partir de gaz de traitement de déchets générés par un procédé de production de formaldéhyde d'oxyde métallique, les émissions de formaldéhyde dans l'environnement pouvant être réduites de six fois. Le second procédé selon l'invention représenté sur la Figure 2 représente la co-incinération de formaldéhyde et de composés organiques volatils présents dans les gaz de traitement de déchets générés par le procédé de production de formaldéhyde d'oxyde métallique dans une turbine à gaz, dans lequel le formaldéhyde et les composés organiques volatils sont pratiquement complètement éliminés des déchets de traitement. Les deux procédés selon la présente invention sont exothermiques, l'énergie libérée pouvant être utilisée pour produire de l'électricité et/ou de la chaleur.
PCT/IB2021/053453 2020-04-28 2021-04-27 Procédé d'élimination de formaldéhyde et de composés organiques volatils contenus dans des déchets de gaz industriels WO2021220150A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
SI202000074 2020-04-28
SIP-202000074 2020-04-28

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WO2021220150A2 true WO2021220150A2 (fr) 2021-11-04
WO2021220150A3 WO2021220150A3 (fr) 2021-12-23

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PCT/IB2021/053453 WO2021220150A2 (fr) 2020-04-28 2021-04-27 Procédé d'élimination de formaldéhyde et de composés organiques volatils contenus dans des déchets de gaz industriels

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Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60101401A (ja) * 1983-11-07 1985-06-05 三菱瓦斯化学株式会社 ホルムアルデヒド生成ガスの廃熱回収法
ES2103193B1 (es) * 1995-05-16 1998-04-01 Patentes Novedades Sa Procedimiento para la preparacion en continuo de soluciones acuosas de formaldehido.
AT516530B1 (de) * 2014-11-20 2018-02-15 Johnson Matthey Plc Verfahren und Vorrichtung zur Herstellung einer wässrigen Lösung von Formaldehyd
CN105617846A (zh) * 2016-03-17 2016-06-01 北京汉清节能技术有限公司 低浓度甲醛废气氧化处理工艺及专用设备
GB201716132D0 (en) * 2017-10-03 2017-11-15 Johnson Matthey Plc Emissions control system
CN108689817A (zh) * 2018-08-01 2018-10-23 江苏道尔顿石化科技有限公司 一种铁钼法生产甲醛联产ufc的装置和方法

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