CN1081085C

CN1081085C - Method for applying regenerated circulation of fluid-bed catalytic hydrogenation catalyst

Info

Publication number: CN1081085C
Application number: CN96118414A
Authority: CN
Inventors: 李宽义; 陈绪标
Original assignee: Individual
Current assignee: Individual
Priority date: 1996-11-15
Filing date: 1996-11-15
Publication date: 2002-03-20
Anticipated expiration: 2016-11-15
Also published as: CN1182640A

Abstract

The present invention relates to a using method for regeneration and circulation of fluid-bed catalytic hydrogenation catalysts, which is used for recovering, regenerating and cyclically using copper-chromium hydrogenation catalysts. A mixed liquid after fluid-bed catalytic hydrogenation reaction is centrifugally separated, and a filter cake is the recovered catalyst; the filter cake is regenerated by alkali recovering liquid and a regenerated catalyst is obtained through centrifugation and washing; a finished product of the regenerated catalyst is obtained through drying, pulverization and activation; thus, the catalyst is repeatedly and cyclically used. The method has the advantages of more than 80% of regeneration rate, resource saving and small pollution.

Description

Regeneration and recycling method of fluid bed catalytic hydrogenation catalyst

A regeneration and recycling method of a fluid bed catalytic hydrogenation catalyst is used for recovering, regenerating and recycling a copper-chromium hydrogenation catalyst, and belongs to a catalyst regeneration method.

The copper-chromium hydrogenation catalyst is widely used for fluid bed catalytic hydrogenation and is an important hydrogenation catalyst. Such as furfuryl alcohol production by furfural fluidized bed catalytic hydrogenation.

The copper-chromium hydrogenation catalyst is generally prepared by using ammonium chromate, copper nitrate, calcium nitrate and the like as raw materials to prepare an aqueous solution according to a certain proportion, and then dropwise adding ammonia water for complexation. However, the catalyst for catalytic hydrogenation in a fluidized bed has no good regeneration method so far, and is generally used once, so that huge resource waste is caused, and serious environmental pollution is caused.

Therefore, the invention aims to provide a regeneration recycling method of a fluid bed catalytic hydrogenation catalyst, which has the advantages of simple process, high regeneration rate, recycling of the catalyst and no abandon except natural loss. Saving resources, reducing pollution, prolonging the service life of the equipment and improving the utilization rate of the equipment.

The invention achieves the aim through the following specific technical measures, the mixed liquid after the hydrogenation reaction of the fluidized bed is centrifugally separated, the filter cake is the recovered catalyst, the filter cake is regenerated by alkaline regenerated liquid, the regenerated catalyst is obtained by centrifugal separation and water washing, and the finished regenerated catalyst is obtained by drying, crushing and activating. The features of the process are detailed below in conjunction with the treatment procedures, process flows, and examples.

The method is simple, convenient and reliable and mainly comprises the following four steps.

The first step is as follows: catalyst recovery

The second step is that: regeneration of recovered catalyst

The third step: regenerated catalyst separation

The fourth step: regeneration catalyst finishing

The method comprises the following treatment steps:

the finished regenerated catalyst is completely equivalent to a newly prepared catalyst (activity, appearance and the like), can be independently recycled, can also be matched with the newly prepared catalyst in any proportion for use, and has the same effect as the newly prepared catalyst, thereby realizing the regeneration recycling method of the fluid bed catalytic hydrogenation catalyst.

FIG. 1 is a process flow chart of the method:

from the above processing steps and process flows, the characteristics of the method can be seen:

(1) the mixed liquid after hydrogenation is directly discharged into a centrifuge through a liquid discharging device of a hydrogenation system, and the catalyst is recovered throughcentrifugal separation. The discharge and storage of the product liquid are not influenced, the work of the next working section is not influenced, and the recovery rate of the catalyst can reach more than 98 percent. The regenerated medicine of the recovered catalyst is cheap and easy to obtain, has no toxicity or pollution, is easy to control, has stable and reliable performance, and has the regeneration rate of over 95 percent. The whole process is simple, safe and reliable.

(2) In the whole process flow, all the devices except the centrifuge for newly adding the recovered catalyst are the same as the devices for preparing the newly prepared catalyst, so the devices can be commonly used. Thus greatly saving the equipment investment.

(3) The total consumption of the catalyst is greatly reduced to below 1/5 due to the regeneration and recycling of the catalyst, so that the economic benefit of enterprises is greatly improved, and meanwhile, the raw material resources are greatly saved and the pollution is reduced. Because of the recovery of the catalyst, the solid (including tar) in the product liquid entering the next working section is separated, thereby bringing great convenience to the operation of the following working sections, prolonging the service life of the equipment, improving the utilization rate and the labor efficiency of the equipment and reducing the labor intensity.

Example (b):

directly discharging the mixed liquid after the hydrogenation reaction of the fluidized bed into a centrifugal machine through a discharge device for centrifugal separation, and recovering the catalyst. 30kg (containing 10 percent of water) of filter cake in a centrifuge is put into a 500l reaction kettle containing 400kg of water, alkaline regeneration liquid (prepared by ammonia, sodium carbonate and the like) is dripped under stirring tokeep the pH value at about 7.5, the temperature is raised to 70 ℃, the stirring is continued for 1.5 hours, the centrifugation and the water washing are carried out, and the filter cake is washed by water until the using liquid is neutral. And drying the filter cake at 110 ℃ for 12 hours, crushing and activating to obtain 23.8kg of finished regenerated catalyst. The performance of various indexes of the catalyst is equivalent to that of a newly prepared catalyst, and the recycling effect is good.

Claims

1. A method for regenerating and recycling a copper-chromium catalyst for catalytic hydrogenation of a fluidized bed is characterized by comprising the following steps: the mixed liquid after the hydrogenation reaction of the fluidized bed is discharged from the tower, is depressurized and directly discharged into a centrifugal machine for centrifugal separation, the liquid phase part is treated in the next working section of the original product, the filter cake is the recovered catalyst, the recovered catalyst is stirred in a reaction kettle by 4-20 times of water under normal pressure, alkaline regeneration liquid prepared by ammonia or sodium carbonate and the like is dripped to keep the pH value above 7, the mixture is stirred for 1-2 hours at the temperature of 50-90 ℃, the temperature is reduced, the centrifugal separation and the washing are carried out until the mother liquid is neutral, and the filter cake is dried, crushed and activated to obtain the finished catalyst for recycling.

2. The method for regenerating and recycling the copper-chromium catalyst for catalytic hydrogenation of the fluid bed according to claim 1, which is characterized in that: and (2) centrifugally separating the mixed solution after the hydrogenation reaction of the fluidized bed to obtain a recovered catalyst and a product solution, wherein the product solution is used for the next working section to be refined, adding an alkaline regeneration solution prepared by ammonia or sodium carbonate into the recovered catalyst to keep the pH value above 7, activating at the temperature of 50-90 ℃ for 1-2 hours to obtain an activated mixture, centrifugally separating and washing the mixture to obtain a regenerated catalyst, precipitating and neutralizing the mother solution, then discharging, drying, crushing and activating the regenerated catalyst to obtain a finished catalyst, and recycling the finished catalyst.