CN101348236B

CN101348236B - Method for recovering iodine from alkyl iodides catalyst

Info

Publication number: CN101348236B
Application number: CN2008101432026A
Authority: CN
Inventors: 胡汉忠; 吴飞
Original assignee: Hunan Lijie Biochemical Co Ltd
Current assignee: Hunan Crown Bio Chemical Technology Co Ltd
Priority date: 2008-09-12
Filing date: 2008-09-12
Publication date: 2010-06-30
Anticipated expiration: 2028-09-12
Also published as: CN101348236A

Abstract

The invention provides an industrial method for recovering iodine element in iodoalkane catalysts in the process of synthesizing alkylphenols by the aromatization of alkyl cyclohexenone. The method utilizes the steps of neutralization, separation, acidification and oxidation to recover iodine element in iodoalkane catalysts, which not only lowers manufacturing cost but also relieves the corrosion of iodide on equipment in production process, so that the method has obvious economic meaning.

Description

The recovery method of iodine element in the alkane iodide catalyzer

Technical field

The present invention relates to the plain industrial method that reclaims of iodine in a kind of alkane iodide catalyzer.

Background technology

Iodine is grey black or plate crystal or the block black-and-blue, that metalluster is arranged, and is distributed widely in atmospheric sphere, hydrosphere and the litre geosphere with trace, belongs to one of rare iodine element.Iodine is called as bioelement, wisdom element, is the indispensable element of human body and plant-growth, is the raw material of creating inorganic or organic iodide, also is the good catalyzer of many chemical reactions.Product is widely used in all conglomeraties such as food, medicine, industry, agricultural, national defence hard-core technology.

At present, owing to developing rapidly of industries such as relevant medicine, sterilizing agent, film development, and from elderly population increase and developing country's growth of requirement.The whole world iodine sought-after.Though China's iodine resource is positioned at prostatitis, the world, because the limitation that falls behind and develop relatively of Technology.The output of China's iodine can not satisfy domestic demand, still needs a large amount of import iodine products every year.The supply and demand anxiety of world market iodine is influenced by it at present, and the price of domestic market iodine continues to raise up.

In process, need use and contain the catalyzer of iodine compound as aromizing with alkyl cyclohexene ketone aromizing synthesis of alkyl phenol.Because the rare property of iodine, and high value.Therefore, industrial iodine is reclaimed has important economic implications and social effect.

In the United States Patent (USP) 4086282, people such as Freddy Wattimena have proposed to use methyl iodide as catalyzer, utilize the method for homogeneous gas-phase method cracking alkyl cyclohexene ketone.This reaction conditions is a synthesis under normal pressure, if reach transformation efficiency more than 99%, selectivity is more than 90%, and catalyst consumption need increase production cost greater than 1.5%.And this patent do not have and can reclaim catalyzer, not only wastes rare elements iodine element, and causes environmental pollution and to the pollution of equipment.

Among the Chinese patent CN1583697A, the method that Liu Chunshan has proposed a liquid-solid two-phase catalyzer prepares alkylphenol with the cracking of alkyl cyclohexene ketone.Wherein catalyzer comprises methyl iodide and aluminium sesquioxide load chromic oxide.Although transformation efficiency is 100%, selectivity only is 92.8%.And the reaction must in inert atmosphere, carry out, increased production cost of products, and the biphase catalyzer be not easy to control, the catalyzer methyl iodide is not reclaimed.

Summary of the invention

The objective of the invention is the iodine element in the alkane iodide catalyzer that reclaims is in the past reclaimed research, thereby put forward the periodic utilization ratio, alleviate halogen-containing materials the pollution of environment and the corrosion of minimizing chemical industry equipment.

This patent the inventor think, in the catalytic aromatization of organic iodide, organic iodide can resolve into compounds such as hydrogen iodide.So, the inventor herein is according to the process characteristic with 3-methyl cyclohexanol ketenes aromizing synthesis of alkyl phenol, provide the recovery method of iodine element in a kind of alkane iodide catalyzer: with the hydrogen iodide that produces in the weakly alkaline aqueous solution and in the alkyl cyclohexene ketone aromizing synthesis of alkyl phenol process, the water sepn that will contain salt compounded of iodine then, oxidizer is carried out oxidation and is got water-fast iodine element, carry out filtering separation at last, obtain the plain product of iodine.

Concrete removal process is described below: 1) add a certain amount of weak base aqueous solution in surge tank, the weak base of being mentioned comprises yellow soda ash, salt of wormwood, sodium bicarbonate, saleratus etc., preferably selects yellow soda ash for use; In the aqueous solution, weakly alkaline concentration is controlled between 1-20%, is advisable between 5-10%; Weakly alkaline consumption be controlled at the iodide add-on 100-300% between, between 120%-200%, be advisable; 2) after the reaction product cooling, pass through the buck layer, iodide and buck in the reaction product are reacted, iodide are rested in the buck with the mode of bubbling; 3) after the static layering, buck is told; 4) buck is poured in the enamel reaction still, under agitation condition, added oxygenant; Selected oxygenant comprises iron trichloride, sulfuric acid, perhaps hydrogen peroxide, and it is good wherein selecting hydrogen peroxide for use; The consumption of oxygenant and the mol ratio of iodide between 0.75-1.5:1, preferred 0.95-1.05:1; 5) will react the plain filtration of the iodine that produces, promptly get product.

Facts have proved that reclaim iodine element in the production process by method of the present invention, the rate of recovery is greater than 80%.Greatly reduce production cost and environmental pollution, and iodide are to the problems such as corrosion of later separation equipment.

Embodiment

The following examples have been explained this invention, but the technical scheme of this invention and application in other respects are not construed as limiting.

Embodiment 1:

The recovery of iodine element in the methyl iodide catalyzer

The sodium carbonate solution that adds 200 kilogram 20% in the surge tank of 1000L, the mixture of alkane cyclonene and methyl iodide injects cracking still through volume pump, reacts under 550 ℃ and 2atm condition.Reacted product is after condensation, and through a stainless steel tube bubbling that immerses in the sodium carbonate solution, the methane of generation is the bubbling emptying after water seal.After treating that surge tank is filled material, material is imported in the similar surge tank of another one.The former static about 4 hours, lower floor's moisture content is told, detecting iodine content is 3%.Drop in 1000 liters of enamel stills telling 500 kilograms of the aqueous solution that cumulative contains iodine 3%, to acid, be added dropwise to 13.4 kilogram of 30% hydrogen peroxide with the hydrochloric acid adjust pH, react 1 hour, filter, get 14 kilograms of thick iodine, content is 90%.

Embodiment 2:

Method is with embodiment 1, and just oxygenant changes 64 kilogram 30% ferric chloride aqueous solutions into, gets 13.5 kilograms of thick iodine, and content is 88%.

Embodiment 3:

Method is with embodiment 1, and just oxygenant changes 12 kilograms of vitriol oils into, gets 12.5 kilograms of thick iodine, and content is 90%.

Embodiment 4:

Method just changes methyl iodide into iodoethane with embodiment 1, gets 12 kilograms of thick iodine, content 90%.

Embodiment 5:

Method changes 200 kilogram 20% sodium carbonate solution into 300 kilogram 10% sodium hydrogen carbonate solution with embodiment 1, gets 13 kilograms of thick iodine, and content is 88%.

Embodiment 6:

Method just changes 200 kilogram 20% sodium carbonate solution into 300 kilogram 15% solution of potassium carbonate with embodiment 1, and 13.4 kilogram of 30% hydrogen peroxide changes 20 kilogram of 30% hydrogen peroxide into and get 14.5 kilograms of thick iodine, and content is 91%.

Embodiment 7:

Method just changes 200 kilogram 20% sodium carbonate solution into 150 kilogram 15% potassium bicarbonate solution with embodiment 1, gets 12.5 kilograms of thick iodine, and content is 90%.

Claims

1. the recovery method of iodine element in the alkane iodide catalyzer, it is characterized in that: with the hydrogen iodide that produces in the weakly alkaline aqueous solution and in the alkyl cyclohexene ketone aromizing synthesis of alkyl phenol process, the water sepn that will contain salt compounded of iodine then, oxidizer is carried out oxidation and is got water-fast iodine element, carry out filtering separation at last, obtain the plain product of iodine; Wherein, described weak base is water-soluble yellow soda ash or salt of wormwood, sodium bicarbonate, saleratus; The quality of weak base in reaction is the 100%-300% of iodine quality; Added oxygenant is iron trichloride or hydrogen peroxide; The amount of the oxygenant that is added and the mol ratio of salt compounded of iodine are 0.95-1.05: 1.

2. recovery method according to claim 1 is characterized in that described alkane iodide catalyzer is methyl iodide or iodoethane.