WO2019039759A1 - Procédé de production de mono-iodobenzène et mono-iodobenzène produit à partir de celui-ci - Google Patents

Procédé de production de mono-iodobenzène et mono-iodobenzène produit à partir de celui-ci Download PDF

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WO2019039759A1
WO2019039759A1 PCT/KR2018/008646 KR2018008646W WO2019039759A1 WO 2019039759 A1 WO2019039759 A1 WO 2019039759A1 KR 2018008646 W KR2018008646 W KR 2018008646W WO 2019039759 A1 WO2019039759 A1 WO 2019039759A1
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iodine
carbon
iodobenzene
activated carbon
mono
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PCT/KR2018/008646
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English (en)
Korean (ko)
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이용진
함병경
강정국
김태형
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에스케이케미칼 주식회사
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Publication of WO2019039759A1 publication Critical patent/WO2019039759A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/23—Preparation of halogenated hydrocarbons by dehalogenation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/013—Preparation of halogenated hydrocarbons by addition of halogens
    • C07C17/02—Preparation of halogenated hydrocarbons by addition of halogens to unsaturated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/389—Separation; Purification; Stabilisation; Use of additives by adsorption on solids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/38—Separation; Purification; Stabilisation; Use of additives
    • C07C17/42—Use of additives, e.g. for stabilisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C25/00—Compounds containing at least one halogen atom bound to a six-membered aromatic ring
    • C07C25/02—Monocyclic aromatic halogenated hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/584—Recycling of catalysts

Definitions

  • the present invention relates to a process for the preparation of mono-iodobenzene and mono-iodobenzene prepared therefrom. More specifically, it is possible to selectively recover gaseous iodine which is lost in the regeneration of the catalyst used in the reaction, and to recover mono-iodine, which improves process efficiency by recovering iodine and regenerated catalyst, Benzene and mono-iodobenzene prepared therefrom.
  • Exhaust gas discharged during regeneration of the poisoned catalyst in the heterogeneous catalytic converter is usually neutralized with caustic soda through a scrubber.
  • the halogens are counteracted with caustic soda and present as salts in aqueous solution.
  • acid treatment is required, and a large amount of wastewater is generated.
  • the exhaust gas discharged during the catalyst regeneration contains a large amount of C0 / C0 2 generated by burning of the hydrocarbon material present in within the coke coming from the poisoning of the catalyst.
  • a large amount of C0 / C0 2 is also in the scrubber and banung caust ic soda and produce a NaHC0 3, NaHC0 3 high solubility in water is present in a saturated state in the aqueous solution.
  • a neutralization treatment using an acid for recovering a halogen element is performed, a large amount of acid is also consumed in the neutralization of NaHCO 3 , and thus a large amount of wastewater is generated.
  • a chemical process involving the reaction of a substance containing a halogen element it is necessary to recover or separate halogens released in exchange for wastewater in relation to the relatively high price of halogen element and air / soil contamination.
  • the recovery and separation techniques of halogens which are known until now, Can, in addition there is a limited number of drink group of a halogen element present in a low concentration of the liquid phase within several hundred p pm.
  • Halogen recovery and separation techniques of known gaseous state are methods of neutralization using caust ic soda, which generate large amounts of wastewater.
  • the method of recovering halogen elements in the gaseous state which has been known so far, is limited to the separation of air containing low-concentration halogen elements, not the recovery of halogen elements from the waste gas.
  • the present invention relates to a process for the production of mono-iodobenzene which can selectively recover gaseous iodine which is lost during the regeneration of the catalyst used in the reaction, and which proceeds by using recovered iodine and regenerated catalyst,
  • the method is intended to provide three days.
  • the present invention also provides mono-iodobenzene prepared from the process for producing mono-iodobenzene.
  • the present inventors have found that, by using the above-described method for producing mono-iodobenzene, it is possible to adsorb an iodine gas in a relatively high amount of activated carbon among gaseous impurities generated in the regeneration process of an inactive catalyst, Iodine and carbon oxides, iodine can be selectively desorbed and recovered, thereby being reused in the initial reaction of mono-iodobenzene synthesis.
  • the mono-iodobenzene synthesis reaction process is carried out using the regenerated catalyst and recovered iodine It is possible to realize high efficiency in the process because it can proceed again.
  • the zeolite catalyst is a zeolite catalyst for use in a trans-iodination reaction from a reaction product comprising multi-iodinated benzene and benzene, wherein the catalyst is a catalyst in which the molar ratio of Si / Al is 5 to 100, 50% is ion exchanged with an alkali metal or an alkaline earth metal.
  • 'multi-iodinated benzene' refers to benzene in which at least one hydrogen of benzene such as mono-iodobenzene, di-iodobenzene, and tri-iodobenzene is substituted with iodine.
  • trans-iodide counter-attack refers to a reaction involving intramolecular movement (isomerization) or intermolecular movement of iodine atoms contained in a molecule, and polyphenyl sulfide iodo benzene (MIB) and p-di-iodo benzene (p-DIB), which are used as raw materials for the synthesis of poly (phenylene sulfide) And can be very usefully used for manufacturing.
  • MIB polyphenyl sulfide iodo benzene
  • p-DIB p-di-iodo benzene
  • p-DIB which is the main raw material of PPS, from benzene and iodine
  • the oxyiodination reaction and the trans-iodination reaction must be combined and include the same process as proposed in the countermeasure scheme shown in FIG. 1 .
  • p-DIB is prepared from benzene and iodine via an oxiodidation counter mass, and benzene and MIB are recovered to the oxy-iodinated semi-annular phase through distillation among the produced sub- (M-di-iodo benzene, m-DIB), o-di-iodobenzene benzene, o-DIB) and tri-iodo benzene (TIB) are separated by crystallization and then sent to the trans-iodobarbital period and then converted to MIB and sent to the oxyiodide hector .
  • M-di-iodo benzene, m-DIB o-di-iodobenzene benzene
  • TIB tri-iodo benzene
  • the oxo-iodination reaction and the trans-iodination reaction in particular the trans-iodination reaction using m-DIB, o-DIB ⁇ TIB, which are by-products of the oxyiodination reaction.
  • the loss of aromatics iodide compounds in these two antagonists has a critical impact on economic viability. Therefore, it is necessary to study the oxiodination reaction and the trans iodination reaction which can minimize the loss of iodine.
  • the catalyst suitable for this reaction the cation exchange zeolite catalyst according to the above embodiment can be used.
  • the zeolite catalyst can be used to prepare MIB and P-DIB through the trans-iodobenzene, preferably MIB.
  • the zeolite catalyst increases the selectivity to mono-iodobenzene in the trans-iodination reaction and alleviates the deactivation of the catalyst even when it is used for a long time, thereby improving the lifetime of the catalyst.
  • the Si / Al molar ratio of the zeolite catalyst may be suitably in the range of 5 to 15.
  • a Si / Al molar ratio in the range of 5 to 15 is advantageous for maintaining a high trans ionization reaction activity of the catalyst.
  • the alkali metal or alkaline earth metal used for the cation exchange may be selected without limitation of its constitution, but preferably it can be exchanged with sodium (Na) or potassium (K).
  • the degree of the cation exchange can be determined depending on the type of the alkali metal or alkaline earth metal cation to be exchanged within the range of 2% to 50% of the total ion exchange capacity.
  • the total ion exchange capacity 10% to 50% is preferable.
  • the trans-iodination reaction proceeds using a cation-exchanged catalyst within the above range, the degree of selectivity of mono-iodobenzene is high and the phenomenon of catalyst deactivation is small. This When the ion exchange capacity of the cation component is less than 2%, the catalytic activity effect can not be obtained. When the ion exchange capacity exceeds 50%, the acid site of the catalyst is excessively reduced and the activity of the trans- have.
  • the specific conditions and methods for the cation exchange reaction using the alkali metal or alkaline earth metal can be used without any limitation in the extent known to be applicable to the ion exchange reaction of the zeolite catalyst.
  • the catalyst which can be used for preparing the cation-exchange zeolite can be selected from cation exchange from any one selected from the group consisting of Y, BEA, and ZSM-5 agents by cation exchange with an alkali metal or an alkaline earth metal have.
  • Catalysts used in the preparation of cation-exchange zeolites are characterized by acid strength and pore structure as solid-phase acid catalysts. The strong acidity of the zeolite catalyst occurs when ammonium ions are exchanged and then fired to convert to hydrogen ions.
  • Typical zeolite catalysts include Y, BEA, ZSM-5, and Mordeni te.
  • zeolite catalyst such as HY, HBEA or HZSM- Can be used.
  • the addition of benzene to the reactant mullite-iodide benzene has a positive effect on the selectivity of the MIB and the inactivation of the catalyst. In particular, it plays a decisive role in reducing the rate of deactivation of the catalyst.
  • the effect of reducing the deactivation rate of the catalyst and the selectivity of the MIB was observed to be larger as the amount of benzene contained in the reactant increased.
  • the molar ratio of benzene / multi-iodide benzene is 2: 1 or more.
  • the molar ratio of the multi-iodinated benzene is 3: 1 or more.
  • the molar ratio of benzene / multi-iodide benzene is preferably 25: 1 or less.
  • the remaining process conditions except for the selection of the catalyst and the reactant are not particularly limited, but the trans-iodination reaction may be considered to have a greater importance of the reaction temperature than the other reaction products.
  • the initial selectivity of MIB may decrease if the temperature of the catalyst is excessively high. In this case, the initial selectivity of the MIB may be lowered.
  • the trans-iodination reaction of the present invention is carried out at a degree of silver of 120 ° C to 250 ° C for maintaining the selectivity and catalytic activity of the MIB, and the reaction at a temperature of 160 ° C to 200 ° C desirable.
  • the repulsive pressure is also an important parameter in terms of catalyst deactivation as well as the reaction temperature. It is desirable to keep the reaction pressure below a certain pressure. That is, it is highly desirable that the benzene contained in the water is kept at a pressure lower than a pressure that can exist in a gas phase, not a liquid phase. If the pressure is higher than this range, the deactivation of the catalyst may proceed more rapidly. Therefore, it is desirable to maintain the atmospheric pressure of about atmospheric pressure within the range of 120 ° C to 250 ° C, In view of prevention of deactivation of the catalyst which maintains the unreasonable pressure at 10 atm or less, which is a possible pressure.
  • the activity of antimony and the selectivity of MIB decrease after a lapse of a certain period of time.
  • the deactivated zeolite catalyst can be reused by calcining it at a temperature of 400 ° C to 650 ° C under oxygen or air atmosphere.
  • a gaseous iodine and a carbon oxide together with nitrogen are generated due to the combustion of a multibenzene ring compound, that is, a coke material, in which an iodine compound present in the catalyst repellant and an iodine ring present in the catalyst pore are connected to each other.
  • a multibenzene ring compound that is, a coke material, in which an iodine compound present in the catalyst repellant and an iodine ring present in the catalyst pore are connected to each other.
  • the gaseous impurities may comprise from 0.1 vol% to 10 vol% iodine gas, from 15 vol% to 24 vol% carbon oxide gas, and from 70 vol% to 80 vol% nitrogen gas.
  • iodine and carbon oxides can be adsorbed in an amount of 80 to 90 parts by weight based on 100 parts by weight of the activated carbon. That is, in the case of nitrogen which occupies the majority of the gaseous fugitives, the ratio of the adsorbed nitrogen to the activated carbon is very small, while the iodine and carbon oxides in the gaseous fugace are mostly adsorbed on the activated carbon.
  • activated carbon selectively has high adsorption power against iodine and carbon oxides, and it is possible to effectively recover an iodine compound that is easily lost in a gaseous state by the adsorption force of the activated carbon.
  • the content of the carbon oxide adsorbed on the activated carbon relative to 100 parts by weight of iodine adsorbed on the activated carbon is 25 parts by weight or less, or 1 part by weight To 25 parts by weight. That is, when adsorbed by the activated carbon, iodine can be adsorbed at a high content through the highest adsorption force on the activated carbon. It can be confirmed from the fact that iodine occupying 0.1 to 10 volume% in the gaseous sludge shows a larger amount than carbon oxide in the amount of adsorption in the final active carbon.
  • the carbon oxide is a compound formed by chemical bonding of carbon and oxygen, and may include, for example, carbon monoxide or carbon dioxide.
  • the carbon oxide is selectively desorbed from the activated carbon, And iodine is controlled to a temperature range capable of maintaining the state of being adsorbed on activated carbon.
  • the example of the temperature raising method of the activated carbon is not limited to a wide range. For example, a method of heating the activated carbon column by heated nitrogen or external tracing can be used.
  • the iodine content desorbed from the activated carbon is less than 100 ppm, or 0.1 ppm to 50 ppm, or 1 ppm to 20 ppm Lt; / RTI > It is considered that some iodine is desorbed from activated carbon even at a temperature of 184 ° C before the boiling point of iodine is due to the sublimation property of iodine.
  • the rate of iodine desorption according to the following formula 1 is less than 1 3 ⁇ 4, or 0.01% to 0.5%, or 0.05% to 0.2% when the temperature of the activated carbon is raised from 20 ° C to 90 ° C to desorb the carbon oxide .
  • Iodine desorption (%) desorbed iodine content (ppm) I adsorbed on activated carbon Chromium iodide content (ppm) x 100.
  • the total iodine content (p pm ) adsorbed on the activated carbon means the iodine ion content measured on the basis of 10000 g of the NaOH aqueous solution in which all the iodine adsorbed on the activated carbon has been collected, and the desorbed iodine content Means the iodine ion content measured on the basis of 1000 g of the aqueous NaOH solution desorbed from the step of desorbing carbon oxides by raising the temperature of the above-mentioned activated carbon from 20 ° C to 90 ° C.
  • the carbon oxide desorption rate according to the following formula 2 may be 95% or more, or 90% to 100%.
  • Carbon Oxide Desorption Rate (%) Desorbed Carbon Oxide Content (ppm) I Total Carbon Oxide Content Absorbed in Activated Carbon (ppm) X 100.
  • the total carbon oxide content (ppm) adsorbed on the activated carbon means the NaHCO 3 content measured on the basis of 1000 g of the NaOH aqueous solution in which all the carbon oxides adsorbed on the activated carbon have been collected, and the desorbed carbon oxide
  • the content (ppm) means the content of NaHCO 3 measured based on 1000 g of the aqueous NaOH solution desorbed from the step of desorbing the carbon oxide by raising the activated carbon from 20 ° C to 90 ° C.
  • the carbon oxide content desorbed from the activated carbon may be 1000 ppm or more, or 1000 ppm to 2000 ppm. Accordingly, in the step of raising the temperature from 20 ° C to 90 ° C to desorb the carbon oxide, the majority of the carbon oxides can be desorbed from the activated carbon and separated with high selectivity. Thus, in the step of raising the temperature of the activated carbon from 20 ° C to 90 ° C, the desorption rate of iodine and carbon oxide adsorbed on the activated carbon shows a remarkable difference.
  • iodine is adsorbed on the activated carbon, Most of the oxides can be desorbed from the activated carbon to separate iodine and carbon oxides.
  • the reason why the sublimable iodine is not desorbed even at 90 is that in order to desorb iodine adsorbed on the activated carbon, And it seems that it requires thermal energy higher than 90 ° C.
  • iodine and carbon oxides can be easily separated from the gaseous impurities in which iodine and carbon oxides are mixed only by a simple heating step, and only iodine can be recovered while satisfying the high yield and selectivity.
  • the method may further include neutralizing the desorbed carbon oxide after desorbing the carbon oxide by raising the activated carbon from 20 ° C to 90 ° C.
  • the neutralization of the carbon oxide may be an alkali solution, for example, a sodium hydroxide solution.
  • the activated carbon is heated from 20 ° C to 90 ° C Iodine adsorbed on the activated carbon can be selectively desorbed through the step of desorbing the carbon oxide.
  • the method for raising the temperature of the activated carbon are not particularly limited, and for example, a method of heating the active carbon column with heated nitrogen or external tracing may be used.
  • the iodine desorbed from the activated carbon may be 4000 ppm or more, or 4000 ppm to 7000 ppm. Accordingly, in the step of desorbing iodine by raising the temperature of the activated carbon from 90 ° C to 450 ° C, the majority of iodine can be desorbed from the activated carbon and separated with high selectivity.
  • the iodine desorption rate according to the following formula 3 may be 70% or more, or m> 10 or 70% to 80% in the step of desorbing iodine by raising the temperature of the activated carbon from 90 ° C to 450 ° C. have.
  • Iodine desorption (%) desorbed iodine content (ppm) I total iodine adsorbed on activated carbon (ppm) X 100.
  • the total iodine content (ppm) adsorbed on the activated carbon is The iodine content (ppm) of the desorbed iodine is measured by removing the iodine from 90 ° C to 450 ° C by removing the iodine from the activated carbon, Means the iodine ion content measured on the basis of 10000 g of the aqueous NaOH solution in which the desorbed iodine is captured in the step.
  • the carbon oxide content desorbed from the activated carbon may be less than 0.1 ppm. Accordingly, in the step of desorbing iodine by raising the temperature of the activated carbon from 90 ° C to 450 ° C, it can be confirmed that carbon oxides are hardly separated and discharged.
  • the desorption rate of carbon oxide by the following formula (4) is less than 1%, 0% to 0.5%, or 0% to 0.2% Lt; / RTI >
  • Carbon Oxide Desorption Rate (%) Desorbed Carbon Oxide Content (ppm) I Total Carbon Oxide Content Absorbed in Activated Carbon (ppm) X 100.
  • the total carbon oxide content (ppm) adsorbed on the activated carbon means the NaHCO 3 content measured on the basis of 1000 g of the NaOH aqueous solution in which all the carbon oxides adsorbed on the activated carbon have been collected, and the desorbed carbon oxide The content (ppm) was measured on the basis of 1000 g of NaOH aqueous solution in which carbon oxide desorbed in the step of desorbing iodine by raising the activated carbon from 90 ° C to 450 ° C
  • the step of desorbing iodine by raising the temperature of the activated carbon from 90 ° C to 450 ° C may be followed by a step of neutralizing desorbed iodine with an alkali solution.
  • an alkali solution is a sodium hydroxide solution.
  • the desorbed iodine can be directly transferred to the reactor in which the initial reaction proceeds, or transferred to an iodine storage tank and stored.
  • iodine has a high purity through the above-mentioned two-step heating process, iodine can be directly applied to the reaction without a separate purification process.
  • the method may further include neutralizing the desorbed iodine with an alkali solution before recovering desorbed iodine, if necessary.
  • An example of the alkali solution is a sodium hydroxide solution.
  • the step of recovering the desorbed iodine may further include a step of reacting the recovered iodine with benzene to produce multi-iodinated benzene. Oxy iodide, which synthesizes benzene iodide with benzene and iodine as a starting material, proceeds slowly, so it can usually be carried out in liquid phase using nitric acid, acetic acid, hydrogen peroxide and silver sulfide as oxidizing agents.
  • the multi-iodinated benzene obtained in the step of reacting the recovered iodine with benzene to produce multi-iodinated benzene may be used as a reactant for the step of preparing the mono-iodobenzene of step 1 described above.
  • the mono-iodobenzene obtained by the process for producing mono-iodobenzene of the above embodiment can be provided.
  • the process for preparing mono-iodobenzene may include all of the above-mentioned embodiments.
  • the mono-iodobenzene may be prepared by a process for preparing mono-iodobenzene of the above- .
  • Figure 1 is a simplified illustration of the countercyclical behavior of the trans-iodinated counterpart according to one embodiment of the present invention.
  • the Na-exchanged zeolite catalysts of Synthesis Examples 1 and 2 were prepared by ion exchange using 0.05N NaCl.
  • the ion-exchanged water in an amount more than 60 ° C taking a 0.05N NaCl in distilled water to And washed.
  • the above procedure was repeated once and then dried in an oven at 110 ° C.
  • the ion-exchanged catalyst was calcined at 550 ° C in an air atmosphere to prepare a Na-exchanged zeolite catalyst.
  • the K exchanger of Synthesis Examples 3 and 4 was prepared by ion exchange with a light catalyst of 0.05N KNO 3 .
  • a powdery catalyst was pressed into a press and used in the form of granules of 300 to 800 p in size.
  • Han Woonggi used a 3/4 "diameter stainless steel tubular barn, Fifty grams of the catalyst in the form of granules was added to the reaction chamber and reacted.
  • the catalyst was pretreated at 200 ° C for 2 hours while flowing dry air at a flow rate of 200 ml / min.
  • the feed rate of the reaction was 50 ml / h.
  • the multi-iodinated benzene includes m-DIB and o-DIB as main components and partially contains MIB, p-DIB, and TIB. Respectively.
  • the multi-iodinated benzene and benzene were used in a weight ratio of 3: 7 (the ratio of benzene / multi-iodide benzene was 16.5: 1) in the reaction product.
  • feed multi-iodinated benzene
  • feed refers to residual components of MIB and p-DIB separated out from products produced by benzoin and iodine oxyiodide reaction.
  • 50 g of the catalysts of Synthesis Examples 1 to 4 were reacted at 250 ° C and 1 atm under a pressure of 50 ml / hr. After a certain period of reaction, the poisoned catalyst was obtained.
  • the reactor in which the target monomer of the above production example was placed was heated at 500 ° C by a furnace outside the semi-wool machine, and air diluted with nitrogen was injected into the reactor to burn the target material. Thereafter, a gas mixture of iodine (about 0.3 volume 0, carbon monoxide (CO) / carbon dioxide (CO 2 ) (about 24 vol 3 ⁇ 4), water vapor (about 0.7 vol%), and nitrogen And then adsorbed on the activated carbon in the activated carbon column.
  • iodine about 0.3 volume 0, carbon monoxide (CO) / carbon dioxide (CO 2 ) (about 24 vol 3 ⁇ 4)
  • water vapor about 0.7 vol%
  • the carbon monoxide (CO) or carbon dioxide (CO 2 ) gas generated while raising the temperature of the activated carbon column from the upper to the 90 ° C was treated with a scrubber located at the rear end of the activated carbon column, 25 ° C, concentration: 2%, volume: 1000 ml).
  • the amount (ppm) of desorbed iodine adsorbed on the activated carbon by the temperature rise of the activated carbon was measured in the target-repelling step of the above embodiment, and the results are shown in Table 2 below.
  • the desorbed iodine content was measured by ion chromatography (IC) analysis on 1000 g of desorbed iodine-containing NaOH aqueous solution.
  • the desorption rate of iodine according to the change of the activated carbon temperature was calculated through the following equation, and it is shown in Table 2 below.
  • Iodine desorption (%) Desorbed iodine content (ppm) I Total iodine adsorbed on activated carbon (ppm) 100.
  • 350 (12 hours) refers to the period of temperature maintained for 12 hours immediately after reaching 350 ° C.
  • iodine ion content in desorbed iodine-captured NaOH aqueous solution As shown in Table 2 above, in the above example, the iodine gas and the carbon oxide gas generated in the regeneration step of the adsorbent are adsorbed using activated carbon , Desorption can be performed by heating the activated carbon through heat treatment.
  • iodine is not desorbed in the 50 to 80 ° C section where most of the carbon oxides are desorbed (see Table 3 below), and most of the iodine is desorbed in the section of 80 ° C or more, particularly 90 ° C to 380 ° C It can be confirmed that iodine and carbon oxides can be desorbed selectively.
  • Experimental Example 3 Determination of carbon oxide desorption content / desorption rate
  • Ppm in which the carbon oxide adsorbed on the activated carbon, for example, carbon monoxide (CO) or carbon dioxide (CO 2 ) is desorbed by the temperature rising section of the activated carbon
  • IC electrochromatography
  • 350 (12 hours) refers to the period of temperature maintained for 12 hours immediately after reaching 350 ° C.
  • oxides of carbon has been most desorbed at 50 ⁇ 80 ° C range, 80 - can be confirmed that the 90 "full is complete desorption in the C interval.
  • desorption of the carbon oxides is completed in 50 - 90 ° C range, 90 It can be seen that the carbon oxides are no longer desorbed in the range of ° C to 380 ° C. Since the desorption rates of iodine and carbon oxides adsorbed on activated carbon are different depending on the rising and falling sections, It can be confirmed that selective detachment is possible.

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Abstract

La présente invention porte sur un procédé de production de mono-iodobenzène ainsi que du mono-iodobenzène produit à partir de celui-ci, le procédé permet de récupérer de manière sélective l'iode à l'état gazeux perdu lors de la régénération d'un catalyseur utilisé dans une réaction, et permet d'atteindre une efficacité de traitement améliorée en facilitant la mise en oeuvre de la réaction par l'iode récupéré et le catalyseur régénéré.
PCT/KR2018/008646 2017-08-23 2018-07-30 Procédé de production de mono-iodobenzène et mono-iodobenzène produit à partir de celui-ci WO2019039759A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
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