JPH0526540B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a method for purifying vinyl compounds, and more specifically, the present invention relates to a method for purifying vinyl compounds, and more specifically, an adsorbent containing monovalent and/or zero-valent copper and/or silver supported on a carrier is used to purify a vinyl compound containing an acetylene compound. The present invention relates to a method for purifying a vinyl compound, which comprises contacting with a mixture of vinyl compounds and adsorbing and removing the acetylene compound. (Prior art) A generally known method for purifying and removing trace amounts of acetylene compounds contained in vinyl compounds is, for example, as shown in Japanese Patent Application Laid-Open No. 58-210852. One example is a method of selectively hydrogenating and purifying an acetylene compound by bringing the compound into contact with a catalyst in the presence of hydrogen. It is known that an acetylenic compound reacts with copper and/or silver to form copper acetylenide and/or silver acetylenide (for example, "Fieser Modern Organic Chemistry" Maruzen 2nd edition p264). (Problems to be solved by the invention) However, these techniques have the following problems. First, in the method of selectively hydrogenating and purifying and removing vinyl compounds, the hydrogenation reaction of vinyl compounds is unavoidable, and alkyl compounds are produced as side reaction products.
If the contamination of such by-product alkyl compounds is undesirable, further purification such as distillation separation is required, which is not economical. Next, in the method of purifying and removing copper or silver acetylenide, the copper or silver acetylenide produced in this way is unstable and sometimes explosive, so there are problems in handling, and the produced precipitate must be separated. The process becomes complicated. As a result of extensive research into such purification methods, the present inventors have discovered a method that can easily and safely remove acetylene compounds from a mixture of vinyl compounds without producing by-products of alkyl compounds. I was able to accomplish this. (Means for Solving the Problems) The present invention involves bringing a mixture of vinyl compounds containing an acetylene compound into contact with an adsorbent containing monovalent to zero-valent copper and/or silver supported on a carrier, and This is a purification method characterized by removing an acetylene compound by adsorbing it onto the adsorbent. The acetylene compound described in the present invention has the general formula
Represented by RC≡CH, R is hydrogen or carbon number 10
For example, CH≡CH, CH ₃ C
≡CH, C ₂ H ₅ C≡CH, C ₃ H ₇ C≡CH,
(CH ₃ ) ₂ CHC≡CH, C ₄ H ₉ C≡CH, C ₅ H ₁₁ C≡
CH, C ₆ H ₁₃ C≡CH, C ₇ H ₁₅ C≡CH, C ₈ H ₁₇ C≡
CH, C ₉ H ₁₉ C≡CH, C ₁₀ H ₂₁ C≡CH, CH ₂ =CHC
Examples include ≡CH and C ₆ H ₅ C≡CH. Further, there is no particular problem even if the substituent R contains a nitrogen atom and/or an oxygen atom. For example, HC≡CCOOCH ₃ ,
HC≡CCH ₂ OH, HC≡CCH ₂ COOH, HC≡
_CCH2N ( _CH3 ) ₂ , HC≡CCH( _CH3 )NHCH
( _CH3 ) ₂ , HC≡CCH(OH) _CH3 , HC≡CCH
(OH) _{C6H5 ,}

[Formula] Examples include HC≡CCONH ₂ and HC≡CCOOH. Furthermore, the vinyl compound in the present invention refers to one having one or more vinyl groups, for example,
CH ₂ = CH ₂ , CH ₃ CH = CH ₂ , CH ₃ CH ₂ CH =
CH ₂ , (CH ₃ ) ₂ CHCH=CH ₂ , C ₃ H ₇ CH=CH ₂ ,
CH ₃ CH=CHCH ₃ , C ₂ H ₅ CH=CHCH ₃ ,
C ₄ H ₉ CH=CH ₂ , C ₃ H ₇ CH=CHCH ₃ , C ₂ H ₅ CH
＝CHC ₂ H ₅ , (CH ₃ ) ₂ CHCH＝CHCH ₃ ,
(CH ₃ ) ₂ CHCH ₂ CH=CH ₂ , (CH ₃ ) ₃ CCH=CH ₂ ,

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

【formula】

[Formula] CH ₂ =C=CH ₂ , CH ₂ =C=CHCH ₃ , CH ₂ =CHCH=CH ₂ , CH ₂
=CH( _CH3 )CH= _CH2 ,

[Formula] etc. The mixture of vinyl compounds refers to one containing at least one of the vinyl compounds. The adsorbent containing monovalent or zero-valent copper and/or silver supported on a carrier that can be used in the present invention is a carrier containing at least one of an inorganic acid salt, an organic acid salt, or an oxide of copper and/or silver. It is prepared by supporting the compound and reducing it using a suitable reducing agent. As the carrier, various metal oxides, activated carbon, etc. can be used, but alumina, silica, activated carbon, etc. are particularly preferred. As for the composition, the ratio of copper and/or silver to the carrier is 1 to 48 wt%, preferably 5
A range of ~30wt% can be selected. There are no particular restrictions on the method for preparing the adsorbent, and any commonly used supporting method may be used as appropriate. For example, it can be prepared by the following method. After impregnating an alumina carrier with a predetermined amount of a solution of an acid or water-soluble salt such as copper chloride, copper nitrate, copper acetate, or copper sulfate, the copper salt is dissolved in air or an inert gas containing oxygen. Heat to high temperature. This copper oxide is then reduced to monovalent or metallic copper by a dry or wet method using a suitable reducing agent such as hydrogen, hydrazine, formaldehyde, or sodium formate. There are no strict limitations on the reaction conditions when carrying out the method of the present invention, but the reaction is generally carried out under the following conditions. Reaction temperature is -10~150℃, preferably 0~100℃
You can choose the range. If the reaction temperature is high, polymerization of the vinyl compound will proceed, which is not preferable. When a mixture of vinyl compounds containing an acetylene compound exists as a gas at the reaction temperature, the space velocity (gas flow rate/amount of catalyst) can be selected in the range of 1000 to 100000 Hr ^-1 , preferably 4000 to 50000 Hr ^-1 . . If the mixture is present as a liquid at the reaction temperature, the LHSV is 0.1 to 80 Hr ^-1 , preferably 1 to 80 Hr -1.
You can choose within the range of 30Hr ^-1 . Although there is no particular limitation on the content of the acetylene compound in the mixture of vinyl compounds used in the present invention, it is possible to remove the acetylene compound even if the concentration is in the range of 10 ^-4 to 10 wt%. The reaction type in carrying out the method of the present invention is preferably a fixed bed reaction, and either a flowing-down type or an overflow type can be adopted, but the method is not limited thereto. (Effects of the Invention) By the method described above, the acetylene compound contained in the mixture of vinyl compounds can be easily and safely removed without producing by-products of alkyl compounds. (Example) Examples of the present invention will be shown below, but the present invention is not limited thereto. Preparation of Adsorbent Preparation of Adsorbent (A) 290 g of copper nitrate trihydrate was dissolved in 318 g of water, 318 g of γ-alumina was added thereto, and the mixture was evaporated and concentrated on a water bath.
The obtained copper salt-supported material was calcined in air at 600°C for 3 hours, and then reduced under a hydrogen stream at 200°C for 2 hours to obtain copper-supported alumina adsorbent A. Preparation of adsorbent (B) 12 g of silver nitrate was dissolved in 32 g of water, 32 g of γ-alumina was added thereto, and the mixture was evaporated and concentrated on a water bath. The obtained silver salt-supported material was calcined in air at 600°C for 3 hours, and then subjected to reduction treatment at 200°C for 2 hours under a hydrogen stream to obtain silver-supported alumina adsorbent B. Preparation of adsorbent (C) A column with an inner diameter of 8 mm was filled with 30 ml of activated carbon that had been dried at 150°C for 3 hours, and 40 ml of ethanol in which 6 g of cuprous chloride had been dissolved was flowed into the column. Thereafter, a reduction treatment was performed at 200° C. for 2 hours in a hydrogen stream to obtain a copper-supported activated carbon adsorbent C. Example 1 30 ml of adsorbent A was packed into a column with an inner diameter of 8 mm, and a 1,3-butadiene mixture containing 1000 ppm of ethyl acetylene and 1000 ppm of vinyl acetylene was passed through the column at room temperature and under a gauge pressure of 10 kg/cm ² at LHSV 5 hr ^-1 . did. After flowing the solution for 1 hour, samples were taken and compositional analysis was performed, but these acetylene compounds were not detected. Example 2 Adsorbents B and C were also tested in the same manner as in Example 1, and after passing through them for 1 hour, they were sampled and analyzed for composition, and no acetylene compound was detected. Example 3 Same as Example 1, take 30 ml of adsorbent A and make the inner diameter 8 mm.
was packed into a column. A gas containing 100 ppm of acetylene in ethylene was flowed at room temperature and normal pressure at SV.5000 hr ^-1 . When the composition was analyzed after flowing for 1 hour, acetylene was not detected. Example 4 A gas containing 100 ppm of methylacetylene in propylene was treated in the same manner as in Example 3.
When the composition was analyzed after flowing for 1 hour, no methylacetylene was detected. Example 5 A styrene mixture containing 50 ppm of phenylacetylene in styrene was treated in the same manner as in Example 1. However, the pressure was normal pressure and LHSV was 10hr ^-1 .
After flowing the solution for 1 hour, it was sampled and analyzed for composition, and no phenylacetylene was detected.

Claims (1)

[Claims] 1. A mixture of vinyl compounds containing an acetylene compound is brought into contact with an adsorbent containing monovalent or zero-valent copper and/or silver supported on a carrier, and the acetylene compound in the mixture is adsorbed onto the adsorbent and removed. A refining method characterized by: