CN102247841A - Method for recovering catalyst rhodium from industrial waste liquid of carbonyl synthesis of acetic anhydride - Google Patents

Abstract

The invention is a method for recovering catalyst rhodium from industrial waste liquid of carbonyl synthesis of acetic anhydride. The invention is characterized in that the method comprises the following steps: (1) waste liquid incineration and cineration, (2) melt oxidation transformation, water washing, (3) preparation of aqueous rhodium salt solution, (4) zinc powder displacement, (5) pickling for zinc powder removal. The content of the recovered rhodium is not less than 78%, and the recovery rate is not less than 98%. The invention provides a method for recovering catalyst rhodium from industrial waste liquid of carbonyl synthesis of acetic anhydride, which has high recovery rate, simple process, and low cost. The content of the recovered rhodium is not less than 78%, which not only meets the process requirements for the carbonyl synthesis of acetic anhydride, but also greatly reduces recovery cost; the recovery rate of rhodium is not less than 98%, and the method provides genuine goods at a fair price, and is convenient for a fair shake.

Description

From carbonyl synthesis of acetic acid acid anhydride industrial wastes, reclaim the method for catalyst rhodium

Technical field

The present invention is a kind of method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride industrial wastes.Belong to the regeneration of catalyst.

Background technology

Metal rhodium is as the catalyst of carbongl group synthesis reaction, have good, the active high characteristics of selectivity, plurality of advantages such as when especially using with complexing agent or co-catalyst, synthetic reaction can be carried out smoothly under lower pressure, produce and be stablized, the taking-up product is convenient.Therefore, though prices are rather stiff, still obtained classical rhodium catalyst.

But the recycling of rhodium catalyst is difficult, and the method that reclaims catalyst at present roughly has the precipitation method, extraction, burning method etc.Wherein the precipitation method rate of recovery is low, extraction complex process, cost height.

Summary of the invention

The objective of the invention is to avoid above-mentioned weak point of the prior art, and a kind of rate of recovery height, simple, the lower-cost method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride waste liquid of technology are provided.

Purpose of the present invention can reach by following measure:

The method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride industrial wastes of the present invention is characterized in that comprising the steps:

1.. liquid waste incineration, ashing

Accurately measure the carbonyl synthesis of acetic acid acid anhydride tower still waste liquid of rhodium-containing 10～20ppm, sending into incinerator burns,, burn back gained weight of material and be waste liquid 30%～35% of the weight that feeds intake, will burn back gained material again and transfer in the ashing furnace, 750 ℃ of control temperature, room temperature is reduced in constant temperature ashing 6 hours, obtains the ashing material, its weight is waste liquid 1.2%～4.5% of the weight that feeds intake, and is equipped with to use transition;

2.. melt oxidation makes the transition, washing

With sodium peroxide and NaOH mixture is oxidant, and its part by weight is Na ₂O ₂: NaOH=1: 3, an amount of oxidant is added step 1. in the material after the ashing, under 800～900 ℃ of temperature, melt oxidation 2～4 hours, reduce to room temperature for the oxide of rhodium transition, then, it dropped in the washing still, under 70～80 ℃ of temperature, washed 30 minutes, standby;

3.. the preparation of rhodium salt solution

The oxide of the rhodium that 2. accurate metrology steps prepares adds an amount of technical hydrochloric acid, under ℃ temperature of control pH＜2,80～90, slowly drips 10% NaClO ₃The aqueous solution, making the oxygenate conversion of rhodium is rhodium salt solution, purchases and uses instead;

4.. zinc dust precipitation

The rhodium salt solution that 3. step prepares adds flocculant, stirs, and staticly settles, and gets supernatant liquid filtering, filter residue reclaims raw material as rhodium and recycles, and filtrate is dropped in the displacement still, stirs down, slowly adds zinc dust precipitation, control pH＞4 are the displacement terminal point, and standing demix filters, and filter cake is equipped with pickling;

5. zinc powder is removed in pickling

With 1: 1 hydrochloric acid the rhodium powder is carried out pickling, remove zinc powder, obtain reclaiming the rhodium powder, rhodium content 〉=78%, the rate of recovery reaches 98%.

The method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride industrial wastes of the present invention has following good effect compared to existing technology:

1. a kind of rate of recovery height, simple, the lower-cost method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride industrial wastes of technology are provided.

2. reclaim rhodium content 〉=78%, can reach the carbonyl synthesis process of acetic anhydride requirement, can reduce cost recovery significantly.And if any demand, further purify, obtain 99%～99.9% rhodium powder, be easy.

3. the rhodium rate of recovery 〉=98%.

4. genuine goods at a fair price are convenient to fair deal.

The specific embodiment

The present invention will now be further detailed embodiment:

Embodiment 1

From carbonyl synthesis of acetic acid acid anhydride waste liquid, reclaim catalyst rhodium according to following steps

1.. liquid waste incineration, ashing

Accurately measure the carbonyl synthesis of acetic acid acid anhydride synthesis unit acetic anhydride tower still waste liquid of rhodium-containing 20ppm, 1000 kilograms, be loaded in the burning dish, send into incinerator and burn,, burn 400 kilograms of back gained weight of material.To burn back gained material again and transfer in the ashing furnace, 750 ℃ of control temperature, room temperature is reduced in constant temperature ashing 6 hours, obtains 4 kilograms in ashing material, is equipped with to use transition;

2.. melt oxidation makes the transition, washing

With sodium peroxide and NaOH mixture is oxidant, and its part by weight is Na ₂O ₂: NaOH=1: 3, with Na ₂O ₂The oxidant that 5 kilograms and NaOH15 kilogram mix adds step 1. in the material after the ashing, and under 800～900 ℃ of temperature, melt oxidation 2～4 hours is reduced to room temperature, then, it is dropped in washing still, under 70～80 ℃ of temperature, washes 30 minutes, and is standby;

3.. the preparation of rhodium salt solution

In the oxide of the rhodium that 2. step prepares, add an amount of technical hydrochloric acid, under ℃ temperature of control pH＜2,80～90, slowly drip 10% NaClO ₃About 4 kilograms of the aqueous solution, making the oxygenate conversion of rhodium is rhodium salt solution, purchases and uses instead;

4.. zinc dust precipitation

The rhodium salt solution that 3. step prepares adds flocculant, stirs, and staticly settles, and gets supernatant liquid filtering, filter residue reclaims raw material as rhodium and recycles, and filtrate is dropped in the displacement still, stirs down, slowly adds zinc dust precipitation, control pH＞4 are the displacement terminal point, and standing demix filters, and filter cake is equipped with pickling;

5. zinc powder is removed in pickling

With 1: 1 hydrochloric acid the rhodium powder is carried out pickling, remove zinc powder, obtain reclaiming 0.025128 kilogram in rhodium powder, rhodium content 78%, the rate of recovery reaches 98.12%.

Claims (1)

1. a method that reclaims catalyst rhodium from carbonyl synthesis of acetic acid acid anhydride industrial wastes is characterized in that comprising the steps:

1.. liquid waste incineration, ashing

Accurately measure the carbonyl synthesis of acetic acid acid anhydride tower still waste liquid of rhodium-containing 10～20ppm, sending into incinerator burns,, burn back gained weight of material and be waste liquid 30%～35% of the weight that feeds intake, will burn back gained material again and transfer in the ashing furnace, 750 ℃ of control temperature, room temperature is reduced in constant temperature ashing 6 hours, obtains the ashing material, its weight is waste liquid 1.2%～4.5% of the weight that feeds intake, and is equipped with to use transition;

2.. melt oxidation makes the transition, washing

With sodium peroxide and NaOH mixture is oxidant, and its part by weight is Na ₂O ₂: NaOH=1: 3, an amount of oxidant is added step 1. in the material after the ashing, under 800～900 ℃ of temperature, melt oxidation 2～4 hours, reduce to room temperature for the oxide of rhodium transition, then, it dropped in the washing still, under 70～80 ℃ of temperature, washed 30 minutes, standby;

3.. the preparation of rhodium salt solution

The oxide of the rhodium that 2. accurate metrology steps prepares adds an amount of technical hydrochloric acid, under ℃ temperature of control pH＜2,80～90, slowly drips 10% NaClO ₃The aqueous solution, making the oxygenate conversion of rhodium is rhodium salt solution, purchases and uses instead;

4.. zinc dust precipitation

The rhodium salt solution that 3. step prepares adds flocculant, stirs, and staticly settles, and gets supernatant liquid filtering, filter residue reclaims raw material as rhodium and recycles, and filtrate is dropped in the displacement still, stirs down, slowly adds zinc dust precipitation, control pH＞4 are the displacement terminal point, and standing demix filters, and filter cake is equipped with pickling;

5. zinc powder is removed in pickling

With 1: 1 hydrochloric acid the rhodium powder is carried out pickling, remove zinc powder, obtain reclaiming the rhodium powder, rhodium content 〉=78%, the rate of recovery 〉=98%.