• 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 machine-controlled chlorine dioxide generating process which produces a gaseous mixture of chlorine dioxide and chlorine is described. Efficiency determinations are made from gas analysis and adjustment made as required. The gas analysis may be used in combination with actual production rate and required production rate machine determinations, possibly along with reaction medium analysis, to adjust operating parameters as required to attain optimum production rate and chemical usage.
    公开号:SU1080739A3
    申请号:SU792814347
    申请日:1979-09-18
    公开日:1984-03-15
    发明作者:Свинделлз Ричард；Коули Джеральд
    申请人:Эрко Индастриз Лимитед (Фирма)；
    IPC主号:
    专利说明:

    00
    about
    &0; O The invention relates to process control methods and can be used in the chemical industry to produce chlorine dioxide when chlorine dioxide and chlorine are formed by reducing sodium chlorate with added chloride ions in the absence of reducing chlorine agents. A known method of controlling a chemical process by measuring the redox potential and density of the medium and determining the composition of the reaction mass C1 by their value. Closest to the proposed technical entity is a method for monitoring the process of producing chlorine dioxide by measuring the concentration of chlorine dioxide in the gas stream after the generator and determining the efficiency of the process 2. Known methods are not inherently high accuracy control. The chlorine dioxide production reaction can be represented by the equation NotceOj + Nwce + ff.j50 - ceo tf / 2CP + H20tH, 2S04 (A parallel reaction also occurs during which chlorine dioxide is not formed, represented by the equation No (C OjtSNa N 4-3H, SO - 3Ce2 3H O + 3Mof 50 Thus, the efficiency of the process is determined by the degree of the reaction according to equation (1), which transforms the reaction that proceeds according to equation (2). Any decrease in the efficiency of this process means that smaller amounts of chlorate sodium is converted to the desired end product dioxide chlorine. Since sodium chlorate and silver salts are expensive raw materials, it is desirable to keep the efficiency of the process as high as possible all the time. A number of factors can influence this efficiency, mainly the concentration of the catalyst and, to a lesser extent, the molar the ratio of chlorate ions to chloride ions in the reaction medium and the temperature of the reaction medium. The process efficiency is determined by the method of manual control, which guarantees the operation of the plant at the desired level of efficiency this reduction is compensated by the addition of additional amounts of catalyst, usually silver salts, to this generator. Two types of determinations can be made, one of which is based on measuring the amounts of chlorate consumed and the chlorine dioxide formed. in percent, meaning the percent of one mole of chlorate, which chemically reacts according to equation (1), to form chlorine dioxide. This determination of efficiency is rarely carried out, if necessary, the mass balance of the system, and the amount of chlorate and chlorine dioxide produced is measured during a certain time interval, and the required determinations are made on the basis of these quantities. Another definition with manual control is based on measurements of gram-atom percent chlorine dioxide (g-at.% C102) in the flow formed. G-at.%. CU is determined from the equation G-at% CY-C1 B C102,400 (3) i at.% TlU2-C1 b ClOj-Cl b C1 - by measuring at.% Chlorine in the form of a dems gas stream that is present in this stream in as chlorine dioxide and chlorine. The G-at.% COO value is an exact reproduction of chemical efficiency, and 100% efficiency is achieved when the G-at.% ClOj 50 value. This value is a true definition of the effectiveness of the process described, since chlorine is formed along with chlorine dioxide and present in the resulting gas stream, unlike chlorine dioxide formation processes, when chlorine is reduced directly in the work area to form chloride ions and G-at.% is a true indicator of efficiency. The determination of the efficiency of the process as G – at.% CU is carried out more simply / than the determination of efficiency based on the measurement of chlorate consumed and the formation of chlorate dioxide. The use of which requires the formation of a sample of the produced gas and the wet chemical angshiz of this sample in order to determine the content of the two chlorides and chlorine. However, the determination of G-at.% C102 is carried out at intervals of time over a wide range, usually ranging from a small offset interval to. The gas flow generated is in the region of high temperature and below atmospheric pressure, and great skill of the operator is required to select a typical sample for analysis. The need for highly skilled operator work and the problem of selecting a typical sample result in a detectable performance indicator Gat.% SOUD may be inaccurate. In addition, the differences in efficiency values between the periodically performed determinations are not compensated. As a result, the overall efficiency of the chlorine dioxide production process over a long period is usually below the optimum, which leads to a lower overall yield of chlorine dioxide and to a higher consumption of chemical reagents and catalysts than the optimum.
    In large volume chlorine dioxide generators, this process is less sensitive to changes in conditions, as well. it is to a change in the molar ratio of chloride to chlorate, the concentration of catalyst in the reaction medium to temperature, than in smaller volume generators producing the same volume of dioxyl chloride. In order to save costs on the manufacture of chlorine dioxide generators, which are often constructed from titanium, smaller generators are used that are more sensitive to changes in process parameters. In order to achieve higher process efficiency and increased chlorine dioxide yield, and therefore, to achieve a reduction in the cost of raw materials in the form of sodium chlorate and catalyst, it is necessary to provide a continuous and fast measurement of efficiency so that all changes in efficiency can be compensated. The aim of the invention is to increase the accuracy of the control. The goal is achieved. As a control method by measuring the chlorine dioxide concentration in the gas stream after the generator and determining the process efficiency, the chlorine concentration in the gas stream after the generator is additionally measured by measured mm chlorine dioxide and chlorine dioxide concentrations determine the molar ratio of chlorine dioxide to chlorine, and from this ratio, the efficiency of the process is calculated using the equation,. 6R 2 + 5R where and is the molar ratio of chlorine dioxide to chlorine. At the same time, gas samples for measuring the concentration of chlorine and chlorine dioxide from the gas stream with a pressure below atmospheric and returned after analysis to the gas new npTok. The proposed method provides a continuous determination of the efficiency of the process by analyzing the formation efficiency (E. If the ratio of chlorine dioxide to chlorine in the resulting gas stream,
    gas flow in such a way that the process parameters can be closely monitored.  Thus, eliminating the possibility of errors occurring in the system of chemical analysis of a sample of a gas stream produced by the manual control method, as well as difficulties resulting from periodic measurements by the manual control method, and an overall improvement in efficiency, increased chlorine dioxide yield and reduced consumption of chemicals and catalyst.  According to the proposed method, a sample of the formed gas stream containing chlorine dioxide and chlorine is analyzed using analytical instruments, preferably chromatographic analysis.  which results in the formation of two separate signals, one of which is an indication of the amount of dioxide. chlorine present in the sample, and the other - an indicator of the amount of chlorine present in the sample.  . These signals are automatically converted into a signal that is indicative of the molar ratio of chlorine dioxide to chlorine present in the sample.  According to this signal, the calculation is; chemical efficiency is lost.  This efficiency can be visualized so that the operator can easily detect a decrease in efficiency, which he can usually compensate by adding additional amounts of catalyst to the reaction medium or by changing other parameters.  In addition, the process efficiency can be compared with previous definitions using electronometric devices, and any change is compensated for by detecting the catalyst supply valve signal or adjusting the supply valve of another chemical reagent.   In addition, the invention provided for an automatic control of the chlorine dioxide production method, which includes an automatically controlled analysis and comparison, not only to maintain the efficiency of the process at optimal levels, but also to achieve the desired product production rates and the desired chlorine dioxide solution.  Chemical efficiency of the dioxide production process; chlorine is determined by the ratio of whether 100% is formed.  to give the chlorate of iatri from the generator 5 to R, and if the amount of sodium chlorate consumed in the reaction occurring by equation (1) is given as y, then from equations (1) and (2) for each mole of consumed sodium chlorate.  y / 2 + 3 (1-y) It follows that bH, E, 2 + 5R 100 Therefore, if the molar ratio of chlorine dioxide to chlorine in the resulting gas mixture is determined, the chemical efficiency of the process can be calculated by the equation ( 4 The invention can be applied to any method of producing chlorine dioxide, using which chlorate is reduced by the added chloride ion, which is the only reducing agent, and the reducing agents of chlorine are practically absent.  In addition, although the invention is preferably used to control the processes for producing chlorine dioxide, in which a gas mixture containing chlorine dioxide, chlorine and vaporized water vapor is formed, in which the pressure in the generator is kept below atmospheric, it can also be used for carrying out processes in which atmospheric pressure is maintained in a generator and injecting diluent gas is used, as well as for producing chlorine dioxide, when hydrogen chloride provides: like It has chloride as a reducing agent — sodium chlorate, as well as acidity.  FIG. 1 shows the principle of the implementation of the proposed method; in fig. 2 is a flowchart illustrating the automatic monitoring of the chlorine dioxide production unit; in fig. H - schematic of the control system.  The method is carried out as follows.  In generator 1, a gas mixture containing chlorine dioxide, chlorine and water vapor, directed along the flow line 2, is formed from the aqueous acid reaction mixture.  The sodium chlorate, sodium chloride, and sulfuric acid are fed to the vessel of generator 1 along lines 3.4 and 5.  In the reaction medium, a total acidity of about 2-4.8, preferably 2-4.4, is maintained, and anhydrous neutral sodium sulfate precipitates from this reaction mixture, which 1st is removed along the b line unresolved or periodically.  Generator 1 is periodically supplied with a silver salt through line 7, which is the source of the catalyst in generator 1, which is required to support the effectiveness of the chlorine dioxide production process at the desired level.  Any other suitable catalyst may be used.  It can be completely eliminated if a reduced effect is tolerated as a result of this elimination (efficiency of the process or if the process for producing chlorine dioxide is sufficiently effective.  The gas flow through line 2 is cooled in the condenser 8 with external cooling, causing the main mass to condense, and the condensed water and the remaining gas phase are fed to the chlorine dioxide absorption column in which chlorine dioxide, along with some chlorine, dissolves in the water supplied through line 9, forming a stream of chlorine dioxide solution leaving through line 10, which can be used in bleaching pulp operations, and a stream of chlorine gas leaving through line 11, which This can then be processed in a known manner.  Samples of the vapor phase are taken at very close intervals from line 12, running to the Cooling Condenser 8, and sent through line 13 to the gas exchanger / 1 Injector 14, which is a gas-liquid chromatograph.  Each sample after analysis is returned to main line 12 via line 15, in which a small water ejector 16 is installed or, correspondingly, vacuum generating means for withdrawing the sample through the gas analyzer 14 by creating a higher superatmospheric pressure than that created in line 12.  This device provides assay samples that are easily taken from the vapor phase maintained at high temperature and at a pressure below atmospheric, and eliminates the need for the operator to take a typical sample.  The gas analyzer 14 analyzes the incoming gas stream sample and, via line 17, is connected to detector 18, which detects pressure peaks in line 17 corresponding to chlorine dioxide and sample chlorine, measures the height of each such peak above the zero line, which is (height) equivalent to the dioxide concentration chlorine and chlorine in the sample, and transmits two separate pneumatic or other signals depending on the shape of the detector 18 and in accordance with the analyzed quantities of chlorine dioxide and chlorine in the gas sample and the HU investigator, in accordance with t he these gases present in line 1 Any convenient operation for data analyzer 14 and the detector 18 can cope with, the functions described may be Utilized to give the required output signals.  Pneumatic signals from lines 19 and 20 are supplied from detector 18 to a counting device with a 21 molar ratio, in which these signals are converted into a signal characterizing the ratio of molar amounts of chlorine dioxide and chlorine in line 13.  The conversion of the absolute values of chlorine and chlorine dioxide and measured by detector 18 to their molar ratio is very important in that this conversion excludes deviations of any instrument zero point and peak heights that may be caused by changes in the characteristics of the analyzer characteristics of the absorbent chromatograph, as well as changes in temperature and pressure in the chromatograph.  The molar ratio signal in line 22 is then converted to an efficiency, characterized by a molar ratio signal, in the metering device 23 of efficiency.  The calculating solution of the efficiency device 23 may have any accepted form for performing efficiency calculations based on equation (4).  The performance indicator in line 24 is then recorded by the recorder 25 of any desired shape, such as a pen.  The efficiency value thus obtained is the chemical efficiency of the conversion of chlorate to chlorine dioxide in generator 1 at the time of sampling the gas sample.  As the individual caM samples are sampled by the recorder 25, the corresponding effective value is recorded.  ti process.  The operator can detect a downward trend in the efficiency of the process according to the recording by the scribe.  In this case, the catalyst is fed through line 7 to the generator in order to restore efficiency to the desired level.  Along with this, a recording device 25 with output line 26 is provided, the signal in which is triggered when the recording efficiency drops to a pre-specified value, which leads the operator to add a catalyst.  In the case where the chlorine dioxide production process takes place without catalyst input, the operator can change other operating parameters, such as a flow of reagents to restore the desired process efficiency.  In addition to or with visual observations of a determined efficiency, the recording device 25 can activate the automatic supply of catalyst and / or other raw materials to the generator, compensating for an undesirable decrease in efficiency, with the result that the monitoring of efficiency is fully automatic and does not require any operator intervention.  Sometimes, when higher chlorine quality is required, it is desirable to perform the operation specifically with lower efficiency.  Efficiency can be determined by maintaining the process and individual chlorine and chlorine dioxide outputs at desired levels.  The individual signals in lines 19 and 20 can be independently recorded by the recorder 25 as signals indicated by lines 27 and 28, respectively, so that the calibration of the recorded performance indicators can be carried out by independent calculation based on the measured parameters for chlorine dioxide and chlorine.  A system can be used to determine the efficiency of the process at wide intervals of time, for example, a day or two, in order to determine long-term changes in efficiency instead of monitoring manually the values of G-at at the same time at wide intervals of time. % Su.  However, the main advantage of this scheme is its ability to continuously monitor the efficiency of the process in the chlorine dioxide generator by taking samples as often as possible, for example, every 3-5 minutes.  In this counting control system, a whole series of measurements is carried out continuously and automatically, these measurements are used to determine system parameters, such as chlorine dioxide efficacy and its production rate, and also when the installation is completely shut down or stopped in the event of an emergency condition. these determinable parameters are used to make the adjustment.  According to the diagram (FIG. 2) the efficiency of the chlorine dioxide production process and the rate of formation are controlled and regulated through a variety of automatic operations.  Generator off-gas is automatically analyzed in analyzer 29, where chlorine, chlorine and air dioxide concentrations are determined, process efficiency is calculated on the basis of these data in computing unit 30, the calculated efficiency is compared with current data in comparison unit 31, and catalyst consumption is observed in block 32, so that an additional amount of catalyst can be introduced if it is necessary to restore efficiency to the desired level.  The calculated efficiency is compared with the flow rate data in order to ensure that the detectable decrease in efficiency is not caused by the incorrect consumption of one of the chemicals.  If a detectable decrease in efficiency is the result of such an incorrect flow rate, the introduction of the catalyst should have very little or no effect.  Only in the case when the determined flow rates are correct, the readings of the catalyst consumption, determined by e1 "1e in block 32, indicate the need to compensate for the efficiency by adding a catalyst.  Gas analysis and efficiency calculations can be carried out using performance monitoring systems (F1). 1), or with the help of some other adopted automatic continuous monitoring system.  The concentration of the chlorine dioxide solution that is formed during the production of chlorine dioxide is analyzed in analyzer 33, and the flow rate of the cooled water into the absorber of the chlorine dioxide column is measured with a sensor 34.  This data is used to calculate the actual production rate of the product in the computing unit 35.  Chlorine dioxide, chlorine and air concentrations are detected in analyzer 29 and are also used to calculate the rate of formation of the product in computing unit 35 by comparing chlorine dioxide to air and chlorine to air ratios.  This last calculation is also used to double control the calculation, based on data from an analysis of chlorine dioxide solution concentration and a chilled water flow rate.  The content of chlorine dioxide solution in the storage tank of the final chlorine dioxide solution obtained is continuously determined by analyzer 36 and, on the basis of this definition, an indication is given of the required production rate of the product, as well as an indication about shutting down the installation due to a possible emergency condition if the detected values exceed the specified maximum level.  The actual product formation rate, as determined by the computing unit 35, is compared with the required product formation rate in the comparison unit 37, and the readings of these values are given on the indicator 38.  This comparison is carried out to determine whether the chlorine dioxide formation rate is required or not.  Node 39 provides for manual data entry for comparing product production rates in comparison unit 37 so as to enable the production rate to be adjusted according to external factors.   The flow rates of chemicals and other flowables, as well as the pressure and temperature in the installation, are continuously monitored by sensors 40.  The flow rate data is used when comparing the flow rate and process efficiency in the comparison unit 31 to determine whether or not catalyst control is required in response to a decrease in efficiency.  The various operating parameters of the installation, which are the actual monitoring data of the installation, are compared in comparison block 41 with the control data required to achieve the formation rate of the product, corresponding to the control indications of the required formation rate compared in the formation rate comparison block 37 .  Separate sample concentrations of the solution formed in the generator can vary as a result of changes in the concentration of the starting materials and the loss of chemical reagents in the generator due to, for example, leakage and entrainment with solid by-products, such changes resulting either to too high or too low. the concentration of samples in the solution, and therefore the exact overall material balance cannot be directly determined, and a comparison of the theoretical concentration of the generator liquid solution with the actual concentration of this solution.  The actual concentration of samples in the generator solution can be automatically or periodically manually analyzed in the analyzer 42.  The actual data of the liquid analysis is compared in block 43 of the comparison with the theoretical concentration of the generator liquid solution calculated in the computing unit 44 by the operating parameters of the installation.  This comparison of the efficiency of the process and the rate of formation of the product is carried out to determine the differences.  The existence of differences indicates a divergence of the concentrations of individual samples resulting from one or several reasons.  These divergences are not applied to the reference resistance in comparison unit 41, compensated by a corresponding change in flow rates.  When these distributions exceed the pre-determined limits and show an undesired condition of the installation, a signal is displayed on the indicator 45.  The analysis of the generator solution can be excluded, although it is desirable to carry it out for the purpose of the additional information that is provided by this analysis.  Comparing the parameters of the actual control and the required control in the comparison unit 41 provides one of three possibilities, one of which is the regulation of the control parameter 46 to the required product formation rates.  A second possibility is created in response to the requirement to turn off the installation with a detector 47 when there is a possibility of an emergency condition as a result of exceeding the maximum formation of chlorine dioxide solution.  In the emergency state of the installation, the flow rate of the chemicals is set to zero, and the flow rate of the cooled water is reduced.  Such vacuum and reaction temperature conditions are maintained that allow for the rapid resumption of chlorine dioxide production as soon as the flow rates of the reactants are again established. A third possibility is a complete blocking shutdown by switch 48 caused by the formation of an erroneous signal.  An erroneous signal may be formed as a result of undesirably low or high temperatures of the generator, high condenser-cooler temperature, low heating steam pressure and low air pressure in the instruments.  When this unit is turned off, the purge system is turned on to clean the flow lines of gaseous and liquid substances.  Along with using the efficiency calculation in the computing unit 30 and calculating the product formation rate in the computing unit 35, periodic comparison of the efficiency and product formation rate in the comparison unit 50 can be made, which is recorded on the indicator 51, and this observed reading is the rate of product formation, which is expressed as a percentage of efficiency and serves as a functional parameter reflecting the overall characteristics of the chlorine dioxide production process.  The analysis, the chlorine dioxide solution concentration in the analyzer 33, the generator solution analysis in the analyzer 42 and / or in the computing unit 44 and the flow rate analysis of the sensor 40 can be performed periodically or continuously to calculate the approximate overall mass balance of the chlorine dioxide production process in the computing unit 52, and this calculated mass balance gives indications on indicator 53.  The various indications recorded on the indicators 54,51 and 53 can be accumulated in any suitable manner for continuous, periodic or interleaved reproduction by means of a visual reproducing device such as a cathode tube and / or for continuous, intermittent or alternate printing by any suitable for the purpose of printing device.  The set of input signals of the analog installation 54 is obtained through the input analog block -55 of the installation.  These inputs are respectively an acid consumption signal 56, a sodium chlorate solution consumption signal 57, a generator liquid level signal 58, a generator solution density signal 59, a heater water vapor consumption signal 60, a sodium chloride solution consumption signal 61, an air consumption signal 62, signal 63 of the pressure in the generator, signal 64 of the chlorine dioxide solution level in the storage tank, gas analysis signal 65 of the outgoing gas stream, signal 66 of the concentration of chlorine dioxide solution and analysis signal 67 generator solution.  These analog input signals are transmitted to a central processing unit 68, controlled by a real-time clock 69.  The central processing unit 68 consists of a plurality of software-controlled integrating circuits for performing the calculations (FIG. 2).  These analog input signals are processed in the central processing unit 68, providing signals sent to the set point control module 70, which individually controls the flow control valves so that the desired process efficiency and speed is achieved.  product development, or installation, is turned off when there is a possibility of an emergency condition in response to a signal 64, reflecting a high level of product in the storage tank of the product.  The individual outputs of the setpoint control module 70 are acid consumption signals 71, sodium chlorate solution consumption signal 72, sodium chloride solution consumption signal 73, heating water vapor consumption signal 74, water consumption signal 75 that absorbs chlorine dioxide, signal 76 air flow, signal 77 pressure generators, signal 78 water flow used in the generator.  The data entry unit 79 allows the operator to enter the desired process parameters and analysis data manually in the central processing unit 68 in order to eliminate and / or supplement the analog signals, and / or modify the software control of the central processing unit 68.  output unit 80 provides data printing and output via line 81 and visual reproduction, for example, in a cathode tube connected via line 82, so that visually reproducible and printed readings of current and previous characteristics are stored.  Digital information input unit 83 receives digital signals, corresponding to undesirable conditions of the process for obtaining chlorine dioxide, which require the complete disconnection of the installation and revision of requirements.  These digital signals corresponding to the installation shutdown requirements are the low air pressure signal 84 in the instruments, the low water vapor pressure signal 85, the low and high temperature of the generator gas signals 86 and 87, the high temperature gas signal 88 in the cooling condenser.  Repeated signals are created by re-activating the water vapor and source chemical buttons along lines 89 and 90.  These digital signals are fed to a central processing unit 68, where they are processed, giving signals to a digital output unit 91, which produces a plurality of individual signals.  The individual digital signals are on (off) signals supplied to the acid consumption solenoid valve through line 92, sodium chlorate solution consumption solenoid valve through line 93, sodium chloride consumption solenoid valve through line 94, water vapor flow solenoid valve through line 95, purge flow solenoid valve through line 96, into motors through line 97, and external alarm signals through line 98.  As a result of strict control of the efficiency of chlorine dioxide formation and the rate of its formation in response to both the solution concentration and the need for the product according to the proposed method, the uneven operation of the installation is minimized and optimum consumption of chemical reagents is achieved.  Since a properly concentrated chlorine dioxide solution is provided, a better control of the plant operations is possible.  bleaching to obtain better quality wood pulp and with an economical bleaching consumption.  The need for labor during the operation of such an installation is significantly reduced, since it is only necessary to carry out chemical analysis and visual verification of indications only from time to time.
    69
    SS
    BB
    83
    79
    权利要求:
    Claims (2)
    [1]
    1. METHOD FOR MONITORING THE PROCESS OF PRODUCING CHLORINE DIOXIDE by measuring the concentration of chlorine dioxide in the gas stream after the generator and determining the process efficiency indicator, which is different from the fact that, in order to increase the accuracy of control, there is an additional source of electricity. The concentration of chlorine in the gas stream after the generator is determined, the molar ratio of chlorine dioxide to chlorine is determined from the measured concentrations of chlorine and chlorine dioxide, and the process efficiency is calculated from this ratio by the equation y = 2 + 5R ' 100% where B is the molar ratio of chlorine dioxide to chlorine . '
    [2]
    2. The method according to claim 1, including the fact that gas samples for measuring the concentration of chlorine and chlorine dioxide are taken from the gas stream with a pressure below atmospheric and returned after analysis to the gas stream.
    c, 1080 739 A
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    同族专利:
    公开号 | 公开日
    CA1123099A|1982-05-04|
    SE446857B|1986-10-13|
    PL218386A1|1980-05-19|
    BR7905894A|1980-05-20|
    CA1121025A|1982-03-30|
    FR2447886B1|1983-01-14|
    SE7907665L|1980-03-20|
    US4251224A|1981-02-17|
    SE8505718L|1985-12-03|
    SE459336B|1989-06-26|
    FI68037C|1985-07-10|
    FR2450229B1|1984-06-01|
    JPS5542296A|1980-03-25|
    FR2450229A1|1980-09-26|
    US4251503A|1981-02-17|
    SE8505718D0|1985-12-03|
    FI792866A|1980-03-20|
    FR2447886A1|1980-08-29|
    FI68037B|1985-03-29|
    CS229626B2|1984-06-18|
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    优先权:
    申请号 | 申请日 | 专利标题
    GB7837336|1978-09-19|
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