JPS61192343A - Regeneration of adsorbent - Google Patents

Abstract

PURPOSE:To enable the reutilization of an adsorbent, by performing the hydrotreating of a copper and/or silver-containing adsorbent, which was contacted with an acetylene compound, at room temp. or more. CONSTITUTION:An adsorbent is prepared by a method wherein at least one inorg. acid salt, org. acid salt or oxide of copper and/or silver is supported by a carrier and reduced to monovalent and/or zero-valent copper and/or silver by using a proper reducing agent and used to remove a minute amount of the acetylene compound contained in a vinyl compound to refine said vinyl compound. The used adsorbent can be regenerated by treating the same at room temp. or more in the presence of hydrogen to separate the adsorbed acetylene compound by hydrogenation.

Description

DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a method for regenerating an adsorbent.
(Relates to a method in which an adsorbent containing zero-valent copper and/or silver is brought into contact with an acetylene compound, and then the adsorbent is regenerated by hydrogen treatment at a temperature higher than room temperature.

(Prior Art) Contacting an acetylene compound with copper and/or silver is not recommended because the acetylenides of copper and/or silver produced are unstable and sometimes explosive. I was avoiding it.

(Problems to be Solved by the Invention) The present inventors have discovered a method for purifying and removing trace amounts of acetylene compounds contained in vinyl compounds using an adsorbent in which copper and/or silver compounds are supported on a carrier. , had previously applied for a patent application, but at that time, there was no known method for regenerating the used adsorbent, and there was a need for an appropriate regeneration method.

(Means for Solving All Problems) As a result of intensive research on such a regeneration method, the present inventors discovered that an acetylene compound containing an adsorbent containing monovalent and/or zero-valent copper and/or silver supported on a carrier If the hydrogen treatment is performed at a temperature higher than room temperature after contacting with K,
We have discovered that the adsorbent can be reused.

That is, the present invention provides K that is supported on a carrier and adsorbed on an adsorbent containing fc monovalent and/or zero valent iron and /f or silver, and then the acetylene compound is removed from the adsorbent and regenerated.
This is a method for regenerating an adsorbent, which involves treating the adsorbent at a temperature above room temperature in the presence of hydrogen.

The acetylene compound in the present invention has the general formula R-C3C
Represented by H, R refers to hydrogen or a hydrocarbon having up to 10 carbon atoms, for example, CH3CH1CH, CmiCH%C
,H,C3CH,C3H? C: CH, (CH3)IC
HC3CH, C,H,C3CH,C,H,,C3CH,
C,H,,CmiCH.

C,H,,C”E CH,C,H,,C3CH%C9H
,,C3CH, C1oHt+ CmiCH% CH,=
Examples include CH-C3CH, C, HIl-CE CH, and the like. Further, there is no particular problem even if the substituent R contains a nitrogen atom and/or an oxygen atom. For example, HC3C-
C00CH,,ICmiC-CH,OH,HCmiC・CH
,C0OH,HCmiC-CHt-N(CHs)t,
Examples include HCmiC-CH(CHm)miC-C0OH.

The adsorbent that can be used in the present invention is prepared by supporting at least one of inorganic #IR salts, organic acid salts, or oxides of copper and/or refined silver on a carrier, and using an appropriate reducing agent to prepare monovalent and / or reduced to zero-valent copper and/or sawdust.

As the carrier, various metal oxides and activated carbon can be used in equal parts, but alumina, silica, activated carbon, etc. are particularly preferred.
”-I. In the composition, copper and/or copper to the carrier
The ratio of -i silver can be selected in the range of 1 to 48% by weight, preferably 5 to 30% by weight.

There are no particular restrictions on the method for preparing the adsorbent, and any commonly used supporting method may be used as appropriate. As an example, vI4 can be produced by the following method. Copper chloride on alumina carrier,
After impregnating a predetermined amount of a solution of acid or water-soluble salts such as steel nitrate, copper acetate, or copper sulfate, the copper salt is heated at high temperature in air or in an inert gas containing oxygen. Then,
This w4 oxide is reduced to monovalent or metallic steel by a dry or wet method using a suitable reducing agent such as hydrogen, hydrazine, formaldehyde, or sodium formate.

Although there are no strict limitations on the regeneration conditions under which the entire method of the present invention is carried out, it is generally carried out under the following conditions.

Regeneration temperature is 20-300C, preferably 50-200C
You can choose from a range of Regeneration pressure is 0-30 kg
/cIIG, preferably in the range of 0 to 1oky/cIIG. The required hydrogen flow rate can be selected in a molar ratio of 0.001 to 100, preferably 0.1 to 10, relative to the supported copper and/or silver. The hydrogen used in the present invention may be pure or diluted with an inert gas, such as nitrogen. Furthermore, it is preferable to clean or purge the inside of the system with an inert gas in advance during regeneration.

When carrying out the method of the present invention, a fixed bed reaction is preferable, and the reactor can be either an external heating type or an internal heating type, but is not limited thereto.

(Effects of the Invention) By the method described above, the adsorbent can be easily and safely regenerated and reused. This is probably because the adsorbed acetylene compound was hydrogenated, desorbed, and regenerated.

(Example) Hereinafter, typical examples of the method of the present invention will be shown and more specifically explained. However, these are merely examples, and it goes without saying that the present invention is not limited thereto.

(Preparation method of adsorbent) Adsorbent A Copper nitrate trihydrate 29 Of' was dissolved in 318 f of water, 51 Bff of r-alumina was added thereto, and the mixture was evaporated and concentrated in a water bath. The obtained copper salt supported material was calcined in the air at 600 C for 5 hours, and then subjected to reduction treatment at 200 C for 2 hours under a hydrogen stream to obtain a supported alumina adsorbent Al1-.

Adsorbent B 12t of silver nitrate was dissolved in 52f of water, 52f of r-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.

Adsorbent C A column of activated carbon 30 mm dried for 5 hours at 150 C was packed into a column having a total internal diameter of 8 mm, and 40 mm of ethanol in which 62 mm cuprous chloride was dissolved was flowed. After that, 20 hours in a hydrogen stream.
A DC reduction treatment was performed for 2 hours to obtain a copper-supported activated carbon adsorbent c'l.

Example 1 Adsorbent), 'ft30d, υ, inner diameter 8, packed in an IIO column, containing ethyl acetylene 1000p%'i,
The 5-butadiene mixture was passed through at LH8V 5 Hr-'' at room temperature and under a gauge pressure of 1 kg/cIit. After passing for 1 hour, the system was purged with nitrogen, and then
Regeneration treatment was performed by passing hydrogen at 0OC for 2 hours at 1zoo-/= of hydrogen. Cool to room temperature and add ethyl acetylene containing 1.3-
After passing the butadiene mixture, sampling and composition analysis were performed, and no acetylene compound was detected. Even when the same operation sound was repeated 10 times, the ability of the adsorbent to adsorb ethyl acetylene did not decrease.

Example 2 Adsorbents B and C were also tested in the same manner as in Example 1, and the ability of the adsorbents to adsorb ethyl acetylene was examined, and no decrease in activity was observed.

Example 3 A tr styrene mixture containing 500μ of phenylacetylene in styrene was subjected to the same pressure as in Example 1 and the liquid passage/regeneration treatment was repeated. However, the pressure is normal pressure, and LH8V is 1
0 Hr-”.Even after playing more than 10 times,
Phenylacetylene adsorption capacity did not decrease.

Claims (1)

[Claims] Monovalent and/or zero-valent copper supported on a carrier and/or
or an acetylene compound adsorbed on a silver-containing adsorbent,
A method for regenerating an adsorbent, which comprises treating the adsorbent in the presence of hydrogen at a temperature higher than room temperature when removing and regenerating the adsorbent.