KR20140032191A - Method of manufacturing para-phenylenediamine - Google Patents

Method of manufacturing para-phenylenediamine Download PDF

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KR20140032191A
KR20140032191A KR1020120098793A KR20120098793A KR20140032191A KR 20140032191 A KR20140032191 A KR 20140032191A KR 1020120098793 A KR1020120098793 A KR 1020120098793A KR 20120098793 A KR20120098793 A KR 20120098793A KR 20140032191 A KR20140032191 A KR 20140032191A
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paranitroaniline
para
paranitrochlorobenzene
paraphenylenediamine
amination
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KR1020120098793A
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KR101906168B1 (en
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이효진
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코오롱인더스트리 주식회사
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/30—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds
    • C07C209/32—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups
    • C07C209/36—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of nitrogen-to-oxygen or nitrogen-to-nitrogen bonds by reduction of nitro groups by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C211/00—Compounds containing amino groups bound to a carbon skeleton
    • C07C211/43—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/44—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring
    • C07C211/49—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton
    • C07C211/50—Compounds containing amino groups bound to a carbon skeleton having amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton having amino groups bound to only one six-membered aromatic ring having at least two amino groups bound to the carbon skeleton with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton
    • C07C211/51—Phenylenediamines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2523/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00
    • C07C2523/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group C07C2521/00 of noble metals

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to a method for manufacturing para-phenylenediamine, comprising the steps of: manufacturing para-nitrochlorobenzene by nitrifying chlorobenzene using nitric acid and sulfuric acid; manufacturing para-nitroaniline by aminating the manufactured para-nitrochlorobenzene; and reducing the manufactured para-nitroaniline. The present invention minimizes the pollution of a precious metal catalyst used in the reduction of para-nitroaniline because neutralizing and washing processes before the amination of para-nitrochlorobenzene and/or neutralizing and washing processes before the reduction of para-nitroaniline are conducted so that the content of sulfur ions remaining in the para-nitroaniline can be less than or equal to 1,000 ppm, thereby keeping reaction conditions and production yield unchanged even during the reuse of the precious metal catalyst. Therefore, the present invention can reduce production costs owing to the reuse of the precious metal.

Description

파라페닐렌디아민의 제조방법{Method of manufacturing para-phenylenediamine}Method of manufacturing para-phenylenediamine

본 발명은 아라미드 섬유 제조용 모노머 등으로 유용한 파라페닐렌디아민의 제조방법에 관한 것으로서, 보다 구체적으로는 파라니트로아닐린의 환원공정에 사용되는 귀금속 촉매의 오염을 최소화하여 재사용이 가능하게 함으로써 제조비용을 크게 절감할 수 있는 파라페닐렌디아민의 제조방법에 관한 것이다.
The present invention relates to a method for preparing paraphenylenediamine, which is useful as a monomer for preparing aramid fibers, and more particularly, to minimize the contamination of the noble metal catalyst used in the reduction process of paranitroaniline, thereby making it possible to reuse it. It relates to a method for producing paraphenylenediamine which can be reduced.

파라페닐렌디아민은 화장품 원료, 산화방지제, 연료 첨가제 및 염료합성 원료로 사용되고 있다. 특히, 고강도, 고탄성 및 고내열성 특성을 갖는 아라미드 섬유의 중합 원료로 사용하고 있다. Paraphenylenediamine is used as a cosmetic raw material, antioxidant, fuel additive, and dye synthesis raw material. In particular, it is used as a polymerization raw material of aramid fiber which has high strength, high elasticity, and high heat resistance property.

이와 같은 파라페닐렌디아민은 다양한 방법에 의해 제조할 수 있다. 특히, 수첨법을 이용한 파라니트로아닐린의 제조방법이 널리 사용되고 있다. 이러한 수첨법은 금속 촉매를 사용하여 파라니트로아닐린에 수소 기체를 첨가시켜 수소화 반응을 수행한다. 이러한 수소화 반응은 용매 하에서 수행되는데, 출발 물질인 파라니트로아닐린을 녹일 수 있는 알콜과 같은 극성용매를 통상적으로 사용한다.Such paraphenylenediamine can be manufactured by various methods. In particular, the manufacturing method of paranitroaniline using the hydrogenation method is widely used. This hydrogenation method uses a metal catalyst to add hydrogen gas to paranitroaniline to perform the hydrogenation reaction. This hydrogenation reaction is carried out under a solvent, usually using a polar solvent such as an alcohol capable of dissolving the starting material paranitroaniline.

파라니트로아닐린은 알콜에 대한 용해도가 낮아 반응초기에는 슬러리상으로 진행하다가 반응이 진행되어 파라페닐렌디아민이 생성되면서 알콜에 용해된다.Paranitroaniline has low solubility in alcohol, and proceeds to a slurry phase at the beginning of the reaction, and the reaction proceeds to produce paraphenylenediamine, which is dissolved in alcohol.

그러나, 이러한 극성용매를 사용할 경우, 수소화 반응 완료 후 생성된 물과 상기 극성용매를 분리 및 회수하기 위해 별도의 증류설비를 설치함으로써 초기 투자비용을 증가시킨다. 특히, 아라미드 섬유의 중합 원료로 사용될 경우, 상술한 방법에 의해 제조된 파라페닐렌디아민은 순도가 떨어지고 이로부터 제조된 아라미드 섬유는 업계에서 요구하는 수준의 인장 강도를 나타내지 못하였다.However, when using such a polar solvent, the initial investment cost is increased by installing a separate distillation unit to separate and recover the water and the polar solvent produced after the completion of the hydrogenation reaction. In particular, when used as a raw material for the polymerization of aramid fibers, the paraphenylenediamine prepared by the above-described method is inferior in purity and the aramid fibers produced therefrom did not exhibit the level of tensile strength required by the industry.

이를 해결하고자 탄화수소계 용매에 물과 계면활성제를 첨가한 후 레이니 니켈(Raney-Ni) 촉매를 이용하여 수소화 반응시키는 방법이 제안되었다. In order to solve this problem, a method of adding a water and a surfactant to a hydrocarbon solvent and then performing a hydrogenation reaction using a Raney-Ni catalyst has been proposed.

그러나, 이러한 방법은 반응완료 후에 반응물을 포함하는 물과 탄화수소 용매를 분리하는 유수분리 공정이 필요하기 때문에 생산속도가 떨어지는 문제가 있다. 또한, 이러한 방법은 고가의 계면활성제를 사용하고 반응완료 후 별도로 계면활성제 회수 공정을 수행함에 따라 경제성이 떨어지는 문제가 있다. 또한, 이러한 방법은 활성 및 활성의 지속성이 떨어지는 레이니 니켈을 이용함에 따라 반응시간이 길고 수율 및 순도가 떨어지는 문제가 있다.However, this method has a problem in that the production rate is lowered because the oil and water separation process for separating the water and the hydrocarbon solvent including the reactants after completion of the reaction is required. In addition, such a method has a problem in that the economical efficiency is lowered by using an expensive surfactant and performing a separate surfactant recovery process after completion of the reaction. In addition, this method has a problem in that the reaction time is long and the yield and purity are lowered by using Raney nickel having low activity and sustainability.

이와 같은 문제들을 해결하기 위한 또 다른 종래기술로서 대한민국 특허출원 제10-2010-71017호에서는 탄화수소 용매하에서 귀금속 촉매를 이용하여 파라니트로아닐린에 수소 기체를 반응시켜 수소화하는 공정을 통해 파라페닐렌디아민을 제조하는 방법을 게재하고 있다.As another conventional technology for solving such problems, Korean Patent Application No. 10-2010-71017 discloses a paraphenylenediamine by a process of hydrogenating paranitroaniline by hydrogen gas using a noble metal catalyst in a hydrocarbon solvent. We publish method to make.

상기와 같이 귀금속 촉매를 이용하여 파라니트로아닐린을 탄화수소 용매하에서 수소화시키는 상기 종래 방법은 물이나 계면활성제를 사용하지 않고 탄화수소 용매만을 사용하기 때문에 탄화수소 용매의 회수가 용이하고 또한 귀금속 촉매를 사용하므로 반응속도가 향상되어 생산수율이 높은 장점은 있으나, 상기 귀금속 촉매가 고가이므로 생산원가가 높은 문제가 있었다.As described above, the conventional method of hydrogenating paranitroaniline under a hydrocarbon solvent using a noble metal catalyst is easy to recover the hydrocarbon solvent because only a hydrocarbon solvent is used without using water or a surfactant. Although there is an advantage that the production yield is high, but the precious metal catalyst is expensive, there was a problem of high production cost.

따라서, 상기 종래방법과 같이 파라니트로아닐린의 환원공정에 귀금속촉매를 사용하는 경우, 생산원가 절감을 위해서는 상기 환원공정에 한번 사용한 귀금속 촉매를 다시 재사용하는 것이 매우 중요하였다.Therefore, when using the noble metal catalyst in the reduction process of paranitroaniline as in the conventional method, it was very important to reuse the noble metal catalyst once used in the reduction process in order to reduce the production cost.

그러나, 상기의 종래방법은 파라니트로아닐린내 잔류 황산이온의 함량이 높아 환원공정에 사용되는 귀금속 촉매가 상기 잔류 황산이온에 의해 쉽게 오염되어 상기 귀금속 촉매를 재사용할 경우 반응속도 및 생산수율이 크게 저하되었다. 이로 인해 상기의 종래방법에서는 귀금속 촉매를 재사용할 수 없어 결국 생산원가를 절감할 수 없었다.
However, the conventional method has a high content of residual sulfate ions in paranitroaniline, so that the noble metal catalyst used in the reduction process is easily contaminated by the residual sulfate ion, and the reaction rate and production yield greatly decrease when the precious metal catalyst is reused. It became. For this reason, in the conventional method, the precious metal catalyst cannot be reused, and thus, the production cost cannot be reduced.

본 발명의 과제는 귀금속 촉매를 사용하여 파라니트로아닐린을 환원시켜 파라페닐렌디아민을 제조할 때, 상기 귀금속 촉매가 파라니트로아닐린내 잔류 황산이온에 의해 오염되는 것을 방지하여 귀금속 촉매의 재사용시에도 반응속도 및 생산수율이 저하되지 않도록 하는 방법을 제공하는 것이다.An object of the present invention is to reduce the paranitroaniline by using a noble metal catalyst to produce paraphenylenediamine, to prevent the noble metal catalyst from being contaminated by residual sulfate ions in paranitroaniline, even when the precious metal catalyst is reused It is to provide a method for preventing the speed and production yield from being lowered.

본 발명의 또 다른 과제는 파라페닐렌디아민 제조시 사용되는 귀금속 촉매를 재사용할 수 있어서 생산원가를 절감할 수 있는 방법을 제공하는 것이다.
Still another object of the present invention is to provide a method for reducing production costs by reusing a noble metal catalyst used in preparing paraphenylenediamine.

이와 같은 과제를 해결하기 위해서 본 발명은(ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조할 때, 파라니트로클로로벤젠을 아미노화 시키기 이전에 중화 및 수세하는 공정 및/또는 파라니트로아닐린을 환원시키기 이전에 중화 및 수세하는 공정을 실시하여 상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm, 바람직하기로는 200ppm 이하가 되도록 한다.
In order to solve the above problems, the present invention provides a process for preparing paranitrochlorobenzene by nitrifying chlorobenzene using nitric acid and sulfuric acid, and (ii) paranitroaniline by amination of paranitrochlorobenzene. In the preparation of paraphenyllin diamine through the step of preparing and (iii) reducing the prepared paranitroaniline, the process of neutralizing and washing water prior to amination of paranitrochlorobenzene and / or paranitroaniline Neutralization and washing with water are carried out prior to the reduction so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm, preferably 200 ppm or less.

본 발명은 파라페닐렌디아민 제조에 사용되는 파라니트릴로아닐닌내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 관리함으로서, 파라니트로아닐린의 환원공정에 사용되는 귀금속 촉매의 오염을 최소화하여 귀금속 촉매 재사용시에도 반응조건 및 생산수율이 그대로 유지되도록 한다. 그로 인해 본 발명은 상기 귀금속 촉매의 재사용으로 제조비용을 절감할 수 있다.
The present invention is managed so that the residual sulfate ion content in the paranitrilo ananiline used for the production of paraphenylenediamine is less than 1,000ppm, minimizing the contamination of the precious metal catalyst used in the reduction process of paranitroaniline, even when reusing the precious metal catalyst The reaction conditions and production yields are maintained as they are. Therefore, the present invention can reduce the manufacturing cost by reusing the noble metal catalyst.

이하, 본 발명을 상세하게 살펴본다.Hereinafter, the present invention will be described in detail.

본 발명의 제1구현예로서 (ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조할 때, 상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 상기 파라니트로클로로벤젠을 아미노화 시키기 이전에 중화 및 수세 한다.As a first embodiment of the present invention (i) nitration of chlorobenzene using nitric acid and sulfuric acid to produce paranitrochlorobenzene, (ii) amination of the paranitrochlorobenzene prepared to prepare paranitroaniline And (iii) reducing the prepared paranitroaniline to prepare paraphenylindiamine, thereby aminating the paranitrochlorobenzene so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm or less. Neutralize and flush before.

본 발명의 제2구현예로서 (ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조할 때, 상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 상기 파라니트로클로로벤젠을 아미노화 시키기 이전에 중화 및 수세하고 계속해서 상기 파라니트로아닐린을 환원 시키기 이전에 중화 및 수세 한다.In a second embodiment of the present invention, (i) nitrifying chlorobenzene using nitric acid and sulfuric acid to prepare paranitrochlorobenzene, and (ii) amination of the prepared paranitrochlorobenzene to prepare paranitroaniline. And (iii) reducing the prepared paranitroaniline to prepare paraphenylindiamine, thereby aminating the paranitrochlorobenzene so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm or less. Neutralize and wash before, and then neutralize and wash before reducing the paranitroaniline.

본 발명의 제3구현예로서 (ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조할 때, 상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 상기 파라니트로아닐린을 환원 시키기 이전에 중화 및 수세 한다.In a third embodiment of the present invention, (i) nitrifying chlorobenzene using nitric acid and sulfuric acid to prepare paranitrochlorobenzene, and (ii) amination of the prepared paranitrochlorobenzene to prepare paranitroaniline. And (iii) reducing the prepared paranitroaniline before preparing the paraphenylindiamine, before reducing the paranitroaniline so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm or less. Neutralize and flush.

이때, 상기 파라니트릴아닐린내 잔류 황산이온 함량은 1,000ppm 이하, 보다 바람직하기로는 200ppm 이하로 상기 중화 및 수세공정을 실시한다.At this time, the residual sulfate ion content in the paranitrile aniline is carried out the neutralization and washing process to 1,000ppm or less, more preferably 200ppm or less.

상기 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 일례로서, 파라니트로클로로벤젠을 암모니아와 반응시키는 방법등이 사용될 수 있다.As an example of preparing paranitroaniline by amination of paranitrochlorobenzene, a method of reacting paranitrochlorobenzene with ammonia may be used.

상기 파라니트로아닐린을 환원시켜 파라페닐렌디아민을 제조하는 구현일례로서 탄화수소 용매하에서 귀금속 촉매를 이용하여 상기 파라니트로아닐린과 수소기체를 반응시켜 수소화시키는 방법이 바람직하다.As an embodiment of reducing paranitroaniline to produce paraphenylenediamine, a method of hydrogenating the paranitroaniline and a hydrogen gas by using a noble metal catalyst in a hydrocarbon solvent is preferred.

중화처리시에는 중화제로 NaOH, Mg(OH)2, Ca(OH)2 등이 사용될 수 있다.In the neutralization treatment, NaOH, Mg (OH) 2 , Ca (OH) 2, etc. may be used as the neutralizing agent.

상기 귀금속 촉매로는 파라듐(Pd), 로듈(Rh), 루테늄(Ru), 백금(Pt) 등이 사용될 수 있다.As the noble metal catalyst, palladium (Pd), rodules (Rh), ruthenium (Ru), platinum (Pt), and the like may be used.

상기 탄화수소 용매로 사용될 탄화수소는 n-펜테인(n-pentane), n-헥세인(n-hexane), n-헵테인(n-heptane), n-옥테인(n-octane), n-노네인(n-nonane), 데케인(decane), 사이클로펜테인(cyclopentane), 사이클로헥세인(cyclohexane), 사이클로헵테인(cycloheptane), 메틸-사이클로헥세인(methyl-cyclohexane), 2-에틸헥세인(2-ethylhexane), 2-메틸펜테인(2-methylpentane), 아이소펜테인(isopentane), 아이소헥세인(isohexane), 아이소헵테인(isoheptane), 및 아이소옥테인(isooctane) 중 적어도 하나일 수 있다.Hydrocarbons to be used as the hydrocarbon solvent are n-pentane, n-hexane, n-heptane, n-octane, n-octane, n-nonne Phosphorus (n-nonane), decane (cyclone), cyclopentane (cyclopentane), cyclohexane (cyclohexane), cycloheptane (cycloheptane), methyl-cyclohexane, 2-ethylhexane (2-ethylhexane, 2-methylpentane, isopentane, isohexane, isoheptane, and isooctane can be at least one of have.

이하, 실시예 및 비교실시예를 통해 본 발명을 보다 구체적으로 살펴본다.Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

그러나 하기의 실시예들은 본 발명의 이해를 돕기 위한 것일 뿐 이것에 의해 본 발명의 권리범위가 제한되어서는 안된다.However, the following examples are only intended to help the understanding of the present invention by which the scope of the present invention should not be limited.

실시예Example 1 One

먼저, 클로로벤젠에 황산과 질산을 반응시켜 파라니트로클로로벤젠을 제조한 다음, 제조된 파라니트로클로로벤젠을 1%농도의 가성소오다 용액으로 중화시킨 후 계속해서 물로 수세하였다.First, paranitrochlorobenzene was prepared by reacting chlorobenzene with sulfuric acid and nitric acid, and then neutralized the prepared paranitrochlorobenzene with a 1% concentration of caustic soda solution, followed by washing with water.

다음으로, 중화 및 수세처리된 상기 파라니트로클로로벤젠에 암모니아를 반응시켜 파라니트로아닐린을 제조하였다.Next, paranitroaniline was prepared by reacting ammonia in the neutralized and washed water with paranitrochlorobenzene.

제조된 파라니트로아닐린내 잔류 황산이온 함량은 200ppm 이였다.The residual sulfate ion content in the prepared paranitroaniline was 200 ppm.

다음으로, 냉각기와 온도계가 부착된 2ℓ의 압력반응기에 용매로 100 중량부의 n-헥세인을 넣고 교반하면서 상기 용매 대비 50 중량부의 파라니트로아닐린을 넣은 후, 0.25 중량부의 5% Pd/C 촉매를 사용하여 140℃의 반응온도 및 20바의 수소압력 하에서 수소화 반응을 수행하여 파라페닐렌디아민을 제조하였다. Next, 100 parts by weight of n-hexane was added to a 2 L pressure reactor equipped with a cooler and a thermometer while 50 parts by weight of paranitroaniline was added to the solvent while stirring, followed by 0.25 parts by weight of 5% Pd / C catalyst. Paraphenylenediamine was prepared by performing a hydrogenation reaction under a reaction temperature of 140 ° C. and a hydrogen pressure of 20 bar.

상기 파라페닐렌디아민의 수율은 표 1과 같았다.The yield of the paraphenylenediamine was as shown in Table 1.

실시예Example 2 2

파라니트로아닐린의 수소화반응에 사용되는 Pd/C 촉매로서 실시예 1에서 사용된 Pd/C 촉매를 회수하여 재사용한 것을 제외하고는 실시예 1과 동일한 방법으로 파라페닐렌디아민을 제조하였다.Paraphenylenediamine was prepared in the same manner as in Example 1 except that the Pd / C catalyst used in Example 1 was recovered and reused as a Pd / C catalyst used for hydrogenation of paranitroaniline.

상기 파라페닐렌디아민의 수율은 표1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

실시예Example 3 3

먼저, 클로로벤젠에 황산과 질산을 반응시켜 파라니트로클로로벤젠을 제조한 다음, 제조된 파라니트로클로로벤젠을 1%농도의 가성소오다 용액으로 중화시킨 후 계속해서 물로 수세하였다.First, paranitrochlorobenzene was prepared by reacting chlorobenzene with sulfuric acid and nitric acid, and then neutralized the prepared paranitrochlorobenzene with a 1% concentration of caustic soda solution, followed by washing with water.

다음으로, 중화 및 수세처리된 상기 파라니트로클로로벤젠에 암모니아를 반응시켜 파라니트로아닐린을 제조한 다음 제조된 파라니트로클로로벤젠을 10% 농도의 가성소오다 용액으로 중화시킨 후 계속해서 물로 수세하였다.Next, the paranitrochlorobenzene neutralized and washed with ammonia was reacted to prepare paranitroaniline, and the prepared paranitrochlorobenzene was neutralized with a caustic soda solution at a concentration of 10%, and subsequently washed with water.

제조된 파라니트로아닐린내 잔류 황산이온 함량은 120ppm 이였다.The residual sulfate ion content in the prepared paranitroaniline was 120 ppm.

다음으로, 냉각기와 온도계가 부착된 2ℓ의 압력반응기에 용매로 100 중량부의 n-헥세인을 넣고 교반하면서 상기 용매 대비 50 중량부의 파라니트로아닐린을 넣은 후, 0.25 중량부의 5% Pd/C 촉매를 사용하여 140℃의 반응온도 및 20바의 수소압력 하에서 수소화 반응을 수행하여 파라페닐렌디아민을 제조하였다. Next, 100 parts by weight of n-hexane was added to a 2 L pressure reactor equipped with a cooler and a thermometer while 50 parts by weight of paranitroaniline was added to the solvent while stirring, followed by 0.25 parts by weight of 5% Pd / C catalyst. Paraphenylenediamine was prepared by performing a hydrogenation reaction under a reaction temperature of 140 ° C. and a hydrogen pressure of 20 bar.

상기 파라페닐렌디아민의 수율은 표 1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

실시예Example 4 4

파라니트로아닐린의 수소화반응에 사용되는 Pd/C 촉매로서 실시예 3에서 사용된 Pd/C 촉매를 회수하여 재사용한 것을 제외하고는 실시예 3과 동일한 방법으로 파라페닐렌디아민을 제조하였다.Paraphenylenediamine was prepared in the same manner as in Example 3, except that the Pd / C catalyst used in Example 3 was recovered and reused as a Pd / C catalyst used for hydrogenation of paranitroaniline.

상기 파라페닐렌디아민의 수율은 표1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

실시예Example 5 5

먼저, 클로로벤젠에 황산과 질산을 반응시켜 파라니트로클로로벤젠을 제조하였다.First, paranitrochlorobenzene was prepared by reacting chlorobenzene with sulfuric acid and nitric acid.

다음으로, 제조된 파라니트로클로로벤젠에 암모니아를 반응시켜 파라니트로아닐린을 제조한 다음 제조된 파라니트로클로로벤젠을 10% 농도의 가성소오다 용액으로 중화시킨 후 계속해서 물로 수세하였다.Next, paranitroaniline was prepared by reacting the prepared paranitrochlorobenzene with ammonia, and the prepared paranitrochlorobenzene was neutralized with a caustic soda solution at a concentration of 10%, followed by washing with water.

제조된 파라니트로아닐린내 잔류 황산이온 함량은 120ppm 이였다.The residual sulfate ion content in the prepared paranitroaniline was 120 ppm.

다음으로, 냉각기와 온도계가 부착된 2ℓ의 압력반응기에 용매로 100 중량부의 n-헥세인을 넣고 교반하면서 상기 용매 대비 50 중량부의 파라니트로아닐린을 넣은 후, 0.25 중량부의 5% Pd/C 촉매를 사용하여 140℃의 반응온도 및 20바의 수소압력 하에서 수소화 반응을 수행하여 파라페닐렌디아민을 제조하였다. Next, 100 parts by weight of n-hexane was added to a 2 L pressure reactor equipped with a cooler and a thermometer while 50 parts by weight of paranitroaniline was added to the solvent while stirring, followed by 0.25 parts by weight of 5% Pd / C catalyst. Paraphenylenediamine was prepared by performing a hydrogenation reaction under a reaction temperature of 140 ° C. and a hydrogen pressure of 20 bar.

상기 파라페닐렌디아민의 수율은 표 1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

실시예Example 6 6

파라니트로아닐린의 수소화반응에 사용되는 Pd/C 촉매로서 실시예 5에서 사용된 Pd/C 촉매를 회수하여 재사용한 것을 제외하고는 실시예 3과 동일한 방법으로 파라페닐렌디아민을 제조하였다.Paraphenylenediamine was prepared in the same manner as in Example 3, except that the Pd / C catalyst used in Example 5 was recovered and reused as a Pd / C catalyst used for hydrogenation of paranitroaniline.

상기 파라페닐렌디아민의 수율은 표1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

비교실시예Comparative Example 1 One

제조된 파라니트로클로로벤젠을 암모니아와 반응시켜 파라니트로아닐린을 제조하기 이전에 중화 및 수세하지 않은 것을 제외하고는 실시예 1과 동일한 방법으로 파라페닐렌디아민을 제조하였다.Paraphenylenediamine was prepared in the same manner as in Example 1 except that the prepared paranitrochlorobenzene was not neutralized and washed with water before reacting with ammonia to prepare paranitroaniline.

이때 파라니트로아닐린내 잔류 황산이온 함량은 2,000ppm 이였다.In this case, the residual sulfate ion content in paranitroaniline was 2,000 ppm.

상기 파라페닐렌디아민의 수율은 표 1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

비교실시예Comparative Example 2 2

파라니트로아닐린의 수소화반응에 사용되는 Pd/C 촉매로서 비교실시예 1에서 사용된 Pd/C 촉매를 회수하여 재사용한 것을 제외하고는 비교실시예 1과 동일한 방법으로 파라페닐렌디아민을 제조하였다.Paraphenylenediamine was prepared in the same manner as in Comparative Example 1 except that the Pd / C catalyst used in Comparative Example 1 was recovered and reused as a Pd / C catalyst used for hydrogenation of paranitroaniline.

상기 파라페닐렌디아민의 수율은 표1과 같았다.
The yield of the paraphenylenediamine was as shown in Table 1.

구분division 수율(%)yield(%) 비고Remarks 실시예 1Example 1 97.697.6 새로운 Pd/C 촉매사용Use of new Pd / C catalyst 실시예 2Example 2 97.597.5 재활용 Pd/C 촉매 사용Use of recycled Pd / C catalyst 실시예 3Example 3 98.898.8 새로운Pd/C 촉매New Pd / C Catalyst 실시예 4Example 4 98.698.6 재활용 Pd/C 촉매 사용Use of recycled Pd / C catalyst 실시예 5Example 5 97.897.8 새로운 Pd/C 촉매사용Use of new Pd / C catalyst 실시예 6Example 6 97.797.7 재활용 Pd/C 촉매 사용Use of recycled Pd / C catalyst 비교실시예 1Comparative Example 1 96.596.5 새로운Pd/C 촉매New Pd / C Catalyst 비교실시예 2Comparative Example 2 10.310.3 재활용 Pd/C 촉매 사용Use of recycled Pd / C catalyst

실시예 2 및 실시예 4의 경우 각각 실시예 1에서 사용한 Pd/C 촉매 및 실시예 3에서 사용한 Pd/C 촉매를 재사용하였음에도 실시예 1 및 실시예 3과 비교시 수율차이가 미미하였다.In case of Example 2 and Example 4, the yield difference was small compared with Example 1 and Example 3 even though the Pd / C catalyst used in Example 1 and the Pd / C catalyst used in Example 3 were reused.

그러나 비교실시예 2의 경우에 비교실시예 1에서 사용한 Pd/C 촉매를 재사용한 결과 비교실시예 1에 비해 수율이 현저하게 저하되었다.
However, in the case of Comparative Example 2, as a result of reusing the Pd / C catalyst used in Comparative Example 1, the yield was significantly lower than that of Comparative Example 1.

Claims (8)

(ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조함에 있어서,
상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 상기 파라니트로클로로벤젠을 아미노화 시키기 이전에 중화 및 수세하는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.(Iii) nitrifying chlorobenzene with nitric acid and sulfuric acid to produce paranitrochlorobenzene, (ii) amination of paranitrochlorobenzene, to prepare paranitroaniline, and (iii) In preparing paraphenylindiamine by the steps of reducing paranitroaniline,
A method of producing paraphenylenediamine, characterized in that the neutralization and washing before the paranitrochlorobenzene amination so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm or less. 제1항에 있어서, 상기 파라니트로아닐린을 환원 시키기 이전에 중화 및 수세하는 공정을 더 포함하는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.The method for preparing paraphenylenediamine according to claim 1, further comprising neutralizing and washing with water before reducing the paranitroaniline. 제1항에 있어서, 파라니트로아닐린내 잔류 황산이온 함량이 200ppm 이하인 것을 특징으로 하는 파라페닐렌디아민의 제조방법.The method for producing paraphenylenediamine according to claim 1, wherein the residual sulfate ion content in paranitroaniline is 200 ppm or less. 제1항에 있어서, 상기 파라니트로클로로벤젠을 암모니아와 반응시켜 아미노화 시키는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.The method for producing paraphenylenediamine according to claim 1, wherein the paranitrochlorobenzene is reacted with ammonia for amination. 제1항에 있어서, 용매 하에서 귀금속 촉매를 이용하여 상기 파라니트로아닐린과 수소기체를 반응시켜 수소화하는 공정으로 상기 파라니트로아닐린을 환원시키는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.The method for producing paraphenylenediamine according to claim 1, wherein the paranitroaniline is reduced by reacting the paranitroaniline with a hydrogen gas using a noble metal catalyst in a solvent to hydrogenate the paranitroaniline. (ⅰ) 질산과 황산을 사용하여 클로로벤젠을 니트로화시켜 파라니트로클로로벤젠을 제조하는 단계, (ⅱ) 제조된 파라니트로클로로벤젠을 아미노화시켜 파라니트로아닐린을 제조하는 단계 및 (ⅲ) 제조된 파라니트로아닐린을 환원시키는 단계들을 거쳐 파라페닐린디아민을 제조함에 있어서,
상기 파라니트로아닐린내 잔류 황산이온 함량이 1,000ppm 이하가 되도록 상기 파라니트로아닐린을 환원 시키기 이전에 중화 및 수세하는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.(Iii) nitrifying chlorobenzene with nitric acid and sulfuric acid to produce paranitrochlorobenzene, (ii) amination of paranitrochlorobenzene, to prepare paranitroaniline, and (iii) In preparing paraphenylindiamine by the steps of reducing paranitroaniline,
Method for producing paraphenylenediamine characterized in that the neutralization and washing before the reduction of the paranitroaniline so that the residual sulfate ion content in the paranitroaniline is 1,000 ppm or less. 제6항에 있어서, 파라니트로아닐린내 잔류 황산이온 함량이 200ppm 이하인 것을 특징으로 하는 파라페닐렌디아민의 제조방법.The method for producing paraphenylenediamine according to claim 6, wherein the residual sulfate ion content in paranitroaniline is 200 ppm or less. 제6항에 있어서, 상기 파라니트로클로로벤젠을 암모니아와 반응시켜 아미노화 시키는 것을 특징으로 하는 파라페닐렌디아민의 제조방법.
The method for producing paraphenylenediamine according to claim 6, wherein the paranitrochlorobenzene is reacted with ammonia for amination.
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