• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    A mixture of sulfuric acid and hydrochloric acid essentially free from dissolved sulfur dioxide to be used in a chlorine dioxide reactor is produced by reacting chlorine and sulfur dioxide in at least two reaction zones. In the bottom of a primary reaction zone the total amount of sulfur dioxide needed for the mixed acid production is introduced in an aqueous mixture of sulfuric and hydrochloric acid containing dissolved chlorine and gaseous chlorine. The sulfur dioxide reacts with chlorine in the aqueous phase to produce sulfuric acid and hydrochloric acid. The mixed acid produced in the primary reaction zone contains dissolved quantities of sulfur dioxide and is forwarded to a secondary reaction zone. Chlorine is introduced into the lower part of the secondary reaction zone. The amount introduced can be the total amount of chlorine to be used in the production of the mixed acid for the chlorine dioxide reactor, or it can be a part of that amount, the balance being introduced in the primary reaction zone. The amount should be large enough for a gaseous chlorine phase to leave the secondary reaction zone. The produced mixed acid is withdrawn from the lower part, and preferably the bottom of the secondary reaction zone. At least a part of the mixed acid is introduced into a chlorine dioxide reactor.
    公开号:SU1627080A3
    申请号:SU864027009
    申请日:1986-03-03
    公开日:1991-02-07
    发明作者:Маргарета Холмстрем Улла-Кари；Мартин Сандгрен Лаге；Гертруд Норелл Мария；Альф Аксегорд Петер
    申请人:Эка Новель Аб (Фирма)；
    IPC主号:
    专利说明:

    The invention relates to a method for producing chlorine dioxide, used in particular as a bleach in the pulp and paper industry.
    The aim of the invention is to increase the efficiency of the process by reducing the consumption of sulfuric acid.
    The drawing is a flow chart of the method.
    Example 1. To the reactor 1 to produce chlorine dioxide, a solution is fed containing 550 g / l NaClS, 4.2 g / l Na2 Cr20; and 97.8 g / l of NaCI, as well as a solution of a mixture of sulfuric and hydrochloric acids, obtained in the subsequent stages of the technological process, with a total concentration of 12 n., containing 17.5% of hydrochloric acid and
    23.5% sulfuric acid. Sulfuric acid in the amount of 23 g / h is also fed to the reactor. A pressure of 235 mm Hg is maintained in the reactor. and a temperature of 78 ° C.
    The gaseous mixture formed in the reactor, containing, g / l: chlorine dioxide 90, chlorine 59, air 12, water vapor 557, is continuously removed from the reactor and sent to a condenser for cooling to 43 ° C. The sodium sulfate precipitate formed in the reactor is removed as a slurry from the bottom of the reactor and filtered. .
    The mixture of gas and liquid formed after the condenser is directed to the lower part of the absorber 2, into the upper part of which water is supplied at a rate of 11 tt / h.
    At the outlet in the lower part of the absorber, an aqueous solution is obtained containing 8 g / l of chlorine dioxide and 1.2 g / l of chlorine.
    The remaining unabsorbed gaseous mixture containing chlorine (45 g / h) and air (12 g / h) is fed to the reactor 3, which is a packed column divided into upper and lower reaction zones, and the height of the upper zone in this reactor is 22% of the total height of the reactor. The air-chlorine mixture is introduced into the lower reaction zone, and sulfur dioxide in the amount of 41 g / h is fed to the reactor in the lower part of the upper reaction zone. The reactor 3 is equipped with a tail tower 4, in the upper part of which water is supplied (178 g / h) at a temperature of less than 20 ° C. Non-propulsion gases in the reactor enter the tail tower, and the aqueous solution of the mixture of acids formed as a result of their absorption is returned to the reactor.
    In the lower reaction zone, part of the chlorine dissolves in the aqueous acid solution and reacts with the residual amount of sulfur dioxide contained in this solution, and part of the chlorine in gaseous form enters the upper reaction zone, where it reacts with the sulfur dioxide fed into this zone.
    The resulting mixture of acids containing 17.5 wt.% HCI, 23.5% H2SO4 and 0.03% SO2 is removed from the bottom of the reactor 3 and is divided in a ratio of 1:50 into two streams. A smaller part with a concentration of 12 n. to the reactor 1 to produce chlorine dioxide, the large is recirculated to the upper part of the reactor 3 through a heat exchanger for cooling.
    The results of the other experiments, carried out analogously to example 1, but with different ratios of acid solution flows, are given in the table.
    Example 6. An aqueous solution of chlorine dioxide is prepared analogously to Example 1. Unabsorbed chlorine is reacted with sulfur dioxide in two reactors, with the entire amount of sulfur dioxide being fed to the first one along the air-chlorine mixture, and chlorine to the second. The mixture of acids formed in the first reactor is fed to irrigation in the upper part of the second reactor. The mixture of acids with a concentration of 12 N formed in the second reactor. containing,%: HCI 17,5; HaSO 23.5, SO2 0.03, is returned to the head of the process in the reactor to produce chlorine dioxide and fed for irrigation to the first reactor.
    An example (known). An aqueous solution of chlorine dioxide is obtained similarly
    Example 1. A gaseous mixture from the absorber containing 45 g / h CI2 and 12 g / h of air is fed to the lower part of the reactor 3 to the stage of obtaining an acid mixture, where it is mixed with 28 g / h of sulfur dioxide, which corresponds to a 30% excess of chlorine .
    Water is delivered to the top of the tail tower at a rate of 124 g / h. The resulting mixture of acids contains,%: HCl 17.5;
    H2S04 23.5 and SO 0.03. A portion of the acidic solution is sent to the reactor to produce sulfur dioxide, to which 61 g / h of sulfuric acid is additionally fed.
    The gas coming out of the tail tower and
    containing 14 g / h of CI2 and 12 g / h of air, is taken up with 14% sodium hydroxide solution to give a 7% solution of NaCIO (NaOH consumption of 31 g / h).
    Thus, the proposed method
    allows for 32-38 g / h to reduce the consumption of sulfuric acid compared with the known, in addition, does not require additional operations for the purification of gases from the reactor from chlorine using caustic soda solution.
    权利要求:
    Claims (2)
    [1]
    1. A method for producing chlorine dioxide,
    including the interaction of chlorate and sodium chloride in a solution of a mixture of sulfuric and hydrochloric acids with a concentration of 2.0-4.8 n. at 50-100 ° C and under vacuum, removal of sodium sulphate precipitate formed from the reaction zone, water absorption of the reaction gaseous mixture containing chlorine dioxide, chlorine and water vapor to form chlorine dioxide solution, supply of unabsorbed chlorine to
    the stage of interaction with sulfur dioxide in an aqueous medium to obtain a mixture of sulfuric and hydrochloric acids recycled to the head of the process, the absorption of gases from this stage by water and the supply
    the resulting solution at the stage of interaction, characterized in that, in order to increase the efficiency of the process by reducing the consumption of sulfuric acid, the interaction of chlorine with sulfur dioxide
    Q is carried out in a reactor divided into upper and lower reaction zones, with sulfur dioxide being fed into the lower part of the upper zone, while chlorine is fed into the lower zone in an amount ensuring its excess
    at the outlet of this zone, and the solution of the mixture of acids leaving the lower zone is divided into two streams in a mass ratio of 1: (5-50), with a smaller part of the stream with a concentration of 8-13 n. sent to the stage of interaction of the initial reagents, and
    large - for irrigation of the upper reaction zone.
    [2]
    2. A method according to claim 1, characterized in that the reaction of chlorine with sulfur dioxide in an aqueous medium is carried out in two reactors with flow into the first along the gas
    reactor total sulfur dioxide, and chlorine - in the second reactor, irrigated with the solution obtained in the first reactor, with a mixture of acids sent from the bottom of the second reactor to the irrigation of the first reactor and to the stage of interaction of the initial reactants.
    H90
    CW2 / Cli
    / s
    NQCL03
    HzSUJ
    NaCt
    v
    Cl
    T
    HzSOt + HCl NgZo + NSh
    类似技术:
    公开号 | 公开日 | 专利标题
    AU603252B2|1990-11-08|Process for production of chlorine dioxide
    USRE31236E|1983-05-10|Method of removing sulfur dioxide from combustion exhaust gas
    US3653812A|1972-04-04|Process for removal of sulfur dioxide from gas streams
    SU1627080A3|1991-02-07|Method of obtaining of chlorine dioxide
    US4098639A|1978-07-04|Process for reducing the requirement of fresh chemicals without increasing emissions in the pulping of cellulosic material
    US2317443A|1943-04-27|Process for making chlorine dioxide and for separating the same from chlorine
    CA1333519C|1994-12-20|Process for the production of chlorine dioxide
    US4629545A|1986-12-16|Electrodialytic water splitter and process for removal of SO2 from gases containing same and for recovery of SO2 and NaOH
    US3971844A|1976-07-27|Method for removing sodium sulfate from aqueous solutions
    US3341288A|1967-09-12|Production of chlorine dioxide
    US2481240A|1949-09-06|Method for producing chlorine dioxide
    US4216195A|1980-08-05|Production of chlorine dioxide having low chlorine content
    US4203959A|1980-05-20|Process for the preparation of nitrous oxide
    US3965242A|1976-06-22|Method for desulfurizing exhaust gas by alkali sulphite-gypsum process
    US4241041A|1980-12-23|Methods for the recovery of sulfur components from flue gas and recycle sodium sulfite by reduction-smelting and carbonating to strip hydrogen sulfide
    US3864457A|1975-02-04|Process for the production of chlorine dioxide
    CA1076306A|1980-04-29|Process for reducing the requirement of fresh chemicals without increasing emissions in the pulping of cellulose material with alkaline sodium- and sulfur-containing sulfate pulping liquor
    US2922735A|1960-01-26|Method of producing pulping liquor
    EP0560316B1|1999-10-20|Method for producing alkaline metal hydroxide
    US3402992A|1968-09-24|Method for recovering chemicals from waste liquor obtained during the production of cellulose
    FI79078B|1989-07-31|FOERFARANDE FOER FRAMSTAELLNING AV KLORDIOXID.
    CA1170816A|1984-07-17|Production of mixed acid feed for chlorine dioxidegeneration
    US2845329A|1958-07-29|Process for making sodium carbonate and acetylene
    US3669625A|1972-06-13|Production of barium hydroxide
    US3134639A|1964-05-26|Treatment of alkali metal sulfates
    同族专利:
    公开号 | 公开日
    AU573073B2|1988-05-26|
    SE452756B|1987-12-14|
    PT82116B|1988-01-22|
    US4678654A|1987-07-07|
    FI860872A0|1986-02-28|
    BR8600877A|1986-11-11|
    CH671393A5|1989-08-31|
    NO166931B|1991-06-10|
    FI83208C|1991-06-10|
    AT396458B|1993-09-27|
    SE8501046D0|1985-03-04|
    PT82116A|1986-03-01|
    NZ215317A|1988-06-30|
    SE8501046L|1986-09-05|
    JPH0776081B2|1995-08-16|
    AU5415186A|1986-09-11|
    FI83208B|1991-02-28|
    FR2578238B1|1990-08-03|
    ATA53886A|1993-01-15|
    CA1227619A|1987-10-06|
    FR2578238A1|1986-09-05|
    FI860872A|1986-09-05|
    NO166931C|1991-09-18|
    JPS61205602A|1986-09-11|
    NO860794L|1986-09-05|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    RU2527513C2|2009-06-16|2014-09-10|Акцо Нобель Н.В.|Method of chlorine dioxide production|US3864456A|1964-08-13|1975-02-04|Electric Reduction Co|Manufacture of chlorine dioxide, chlorine and anhydrous sodium sulphate|
    US3714040A|1970-10-16|1973-01-30|Stauffer Chemical Co|Process of regenerating carbon beds|
    US4086329A|1974-12-13|1978-04-25|Erco Industries Limited|Integrated chlorine dioxide producing system|
    US4206193A|1978-12-18|1980-06-03|Hooker Chemicals & Plastics Corp.|Versatile process for generating chlorine dioxide|
    CA1171238A|1980-11-17|1984-07-24|Maurice C.J. Fredette|Chlorine dioxide production using mixed acid feed|
    SE442523B|1981-06-22|1986-01-13|Mo Och Domsjoe Ab|PROCEDURE FOR PREVENTING EMISSIONS OF SULFUR INHALING GASES IN THE PREPARATION OF CHEMICAL CELLULOSAMASSA|
    CA1170816A|1981-11-05|1984-07-17|Maurice C.J. Fredette|Production of mixed acid feed for chlorine dioxidegeneration|
    US4393036A|1981-11-10|1983-07-12|Erco Industries Limited|Production of mixed sulfuric and hydrochloric acid feed and chlorine dioxide generation therewith|
    WO1983001940A1|1981-12-02|1983-06-09|Olson, Erik|Method for the manufacture of chlorine dioxide|
    GB2121769A|1982-06-16|1984-01-04|Roneo Alcatel Ltd|Sheet feed mechanism|SE464193B|1988-10-20|1991-03-18|Eka Nobel Ab|PROCEDURE FOR PREPARATION OF CHLORIDE Dioxide|
    SE9002262D0|1990-06-27|1990-06-27|Eka Nobel Ab|PROCEDURE FOR THE PREPARATION OF CHLOROXIDE|
    US5833865A|1993-06-16|1998-11-10|Sumitomo Chemical Company, Limited|Sedimentation type solid-liquid separator|
    CA2125792C|1993-06-16|2005-01-18|Takuo Harato|Sedimentation type solid-liquid separator|
    FR2742350B1|1995-12-15|1998-02-13|Givin Stephane Jules|STATIC DECANTER WITH CENTRAL SLUDGE RECOVERY JUICE FORCING SYSTEM AND MULTIPLE PRODUCT INJECTION|
    US5792441A|1996-10-11|1998-08-11|Pulp And Paper Research Institute Of Canada|Fixed-resin bed technologies for the treatment of the chlorine dioxide generator effluent and feeds stream|
    US6322768B1|1998-09-29|2001-11-27|International Paper Company|Recovery of chlorine dioxide from gas streams|
    US8123843B2|2007-10-17|2012-02-28|Dow Global Technologies Llc|Rich gas absorption apparatus and method|
    WO2018029500A1|2016-08-08|2018-02-15|Rhodia Poliamida E Especialidades S.A.|New components to clarify sugar cane juice in a process for producing crystal or raw sugar|
    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    SE8501046A|SE452756B|1985-03-04|1985-03-04|PROCEDURE FOR THE PREPARATION OF CHLORIDE Dioxide|
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