KR101620570B1 - A System for Recovering Palladium Catalyst in Polyketone Polymerisation - Google Patents

Abstract

The present invention relates to a basic process technology to collect palladium, a noble metal, in waste matters discharged from a polyketone polymerization process and, more specifically, relates to a configuration of a device developed to easily collect the noble metal palladium from waste matters discharged in real time. Palladium obtained by filtrating solid state waste matters in real time and existing in a liquid state can be obtained using an ion exchange resin; and at the same time, easily separate solid state waste matters.

Description

[0001] The present invention relates to an apparatus for recovering a polyketone catalyst,

The present invention relates to a process for recovering noble metal palladium from wastes discharged from a polyketone polymerization process, and a device for easily recovering noble metal palladium from wastes discharged in real time.

The polyketone polymerization process is a batch slurry process using methanol as a solvent, and since excessive methanol is used, recovery of waste methanol using a fractional distillation apparatus is essential.

       The basic constitution of the polyketone polymerization solvent is methanol containing about 20,000 ppm of water. Waste methanol generated after the polymerization contains, in addition to the catalyst part composed of the Group VIII metal ion / bidentate phosphine ligand / acid, a low molecular weight polyketone oligomer, Polyketone fine particles, and the like. Components other than methanol and water are not vaporized in the fractional distillation apparatus for the purification of methanol and are accumulated in the lower part of the apparatus and transferred to a heavy end tank for disposal.

The solution classified as a heavy end is kept in a state of more than 60 degrees Celsius when discharged from the fractionation distillation apparatus, but when it is cooled to room temperature, a part of it is precipitated and is present as a solid state. The precipitated solids and liquid components are shown in Table 1 below.

Sample classification Elemental Content (ppm) Amount Generated (g) Remaining amount of Pd (g) Pd remaining ratio MeOH content (ppm) P Fe Pd
solid Heavy End Black 1,109.0 431.9 156.1 389 0.061 17% N / A Heavy End Powder 395.1 127.9 1,211.0 193 0.234 65% N / A Liquid HE Solvent 35.1 7.8 4.2 15,190 0.064 18% 12.29

The Heavy End Black / Heavy End Powder can be obtained by using a filter having a pore size of 10 μm or less. When the total amount of palladium discharged into the heavy end Of the total. On the other hand, palladium present in liquid form can not be recovered by physical methods and should be recovered using chemical methods such as ion exchange resins.

The process waste storage tank has a cylindrical shape in order to reduce the cost, and there is a problem that it is difficult to recover the solid material which has precipitated and settles at the bottom of the tank.

Korean Patent No. 10-1307935 Korean Patent No. 10-0652072 Korean Patent No. 10-0663260 Korea Patent Publication No. 2010-0019805

The present invention relates to a method for separating and purifying solid wastes by real-time filtration of solid wastes as described above, combining two apparatuses for obtaining palladium present in a liquid phase using an ion exchange resin, .

The present invention made for this purpose

The slurry discharged from the bottom of the heavy end tank is supplied to a continuous centrifugal centrifugal separator to separate real-time heavy-end sediment and the liquid phase is recovered to the heavy end tank.

The recovered liquid phase serves to agitate the heavy end sediment that sits on the floor with the structure (Figure 1) installed on the bottom end of the heavy end reservoir.

Examples of measures for improving the filtering workability of sediments immersed in the bottom include a stirrer, air bubbling, or return of heavy end solution. The use of the stirrer is costly, and the addition of a physical stirrer is excluded since agitation of the apparatus is unnecessary.

After the heavy end solution has passed through the Sentry Fuse high / liquid separation unit, the solution is passed through the liquid filter palladium recovery unit through the additional filter and then transferred to the wastewater treatment plant.

As described above, according to the present invention, in recovering noble metal palladium from wastes generated in a polyketone solvent recovery apparatus, separation of solid / liquid phase in real time is performed to form a basic process of recovering palladium.

The solid phase of the heavy end solution is recovered by drying and recovering the palladium through the specialist of precious metals. If the liquid waste is recovered through the liquid precious metal recoverer before the wastewater treatment, it can recover more than 99% of the palladium present in the waste, have.

Transportation problems are the most serious problem for the use of precious metal recovery companies. To solve these problems, it is most urgent to concentrate or reduce them.

Since the wastes of the present polyketone solvent recovery apparatus maintains a slurry state at room temperature, it is possible to obtain a solid phase through a filter / Sentry fuse high / liquid separator, and the liquid phase after the filter can be treated in real time through a liquid recoverer to obtain process stability and palladium recovery It is in solving transportation problems.

1 is a schematic view of a Pd precious metal recovery apparatus of the present invention.
2 is a schematic view of a heavy-end tank including an air bubbling device that serves to stir the heavy-end sediment in the heavy-end tank of the present invention.

The composition of the apparatus for recovering palladium as a noble metal in the polyketone catalyst after the polyketone polymerization process of the present invention is as follows.

An apparatus for recovering noble metal palladium in a heavy end waste generated from a refining apparatus for a polyketone polymerization solvent, comprising: a heavy end tank; A slurry pump for transferring a slurry to a discharge port located at a lower end of the heavy end tank; A Centrifuge solid-liquid separator for separating the slurry transferred through the slurry pump into a solid phase and a liquid phase; A heavy end sludge obtaining device for recovering the suspended solid matter discharged through the centrifugal separator; A three-way valve for recovering the liquid phase passed through the centrifugal separator and transferring the liquid phase to a heavy end tank or transferring the liquid phase to a filter; A filter for filtering the liquid phase through the three-way valve; And a palladium recovery device for recovering palladium from the liquid through the filter.

Specifically, the heavy end tank may include an air bubbling device at an inner bottom edge thereof. The slurry pump is preferably a diaphragm pump. The slurry pump is preferably a diaphragm pump. The slurry pump is preferably a diaphragm pump.

In addition, the heavy end tank may be provided with a cooling jacket.

The process flow of the present invention is as follows. As shown in FIG. 2, an air line is inserted into the bottom of the heavy end storage tank (1) of FIG. 1, and the air line is pierced in the center of the tank in the circular air line, And moves the float to the discharge port 3 located at the lower center of the float. This is to prevent immersion / sticking of the suspension in the solution at the edge of the tank. The slurry coming out from the discharge port 3 is conveyed through the slurry pump 4 and the suspended solid matter 6 discharged through the centrifugal separator 5 is sent to the precious metal recovery company through the drying operation. The liquid phase which has passed through the centrifugal separator 5 is recovered to the tank 1 by the 3-way valve 7 and some of the liquid phase passes through the liquid phase palladium recovery device 9 through the filter 8 Only palladium is adsorbed on the column and then transferred to the wastewater treatment plant 10. The adjustment of the three-way valve 7 can be adjusted in accordance with the capacity of the liquid palladium recovery device 9 or the remaining amount of the slurry in the tank 1.

The solution flowing into the heavy end tank (1) flows into a clear liquid phase of about 60 degrees Celsius or more, and solid matters are precipitated upon cooling to below about 30 degrees Celsius. Therefore, it is preferable to stop the operation of the slurry pump 4 and maintain only the air bubbling when the temperature in the tank rises to 30 degrees or more. It is also preferable to provide a cooling jacket in the tank 1 in order to accelerate the precipitation of suspended matters.

It is preferable that the centripetal solid / liquid separation device 5 has a resolution of 10 um. A relatively inexpensive filter method may be applied. However, if the filter cartridge is filled with floating matters, an excessive loss may occur when the cartridge is replaced, and the filter cartridge may not be reused, which may lead to additional cost burden .

The slurry pump 4 is preferably a diaphragm pump using air pressure as an energy source. The slurry mixed with the solid / liquid phase has a possibility that the transporting ability is lowered due to the accumulation of the solid content. However, since the slurry has a low solid content and a high floating property, it is unnecessary to use a pump using an electric motor.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the scope of the present invention is not limited thereto.

Comparative Example

1, a 10um filter housing device was constructed in place of the Sentry fuse solid-liquid separator 5, and an air line in the tank, a three-way valve 7, a filter 8, a liquid recovery device (9) was omitted, and the filter operation was performed for one month. The obtained slurry was dried to obtain a total of 54 kg of a solid suspended matter, and the liquid solution was discarded. As a result of ICP (Inductively Coupled Plasma) analysis of the obtained slurry, the Pd content was about 2050 ppm and the ICP of the discarded liquid solution was 4.1 ppm.

After the completion of the operation for one month, the inside of the heavy end tank was observed. As a result, it was confirmed that the excessive amount of suspended solid matter could not be discharged to the bottom of the tank. As a result, about 90 kg of solid suspended matter remained in the tank.

The replacement period of the filter cartridge was 30 minutes, and the loss of solid-state suspended matter due to the replacement of the filter each time was about 5%.

Example

The apparatus shown in Fig. 1 was constructed and operated for one month. The slurry was dried through a Sentry fugue solid / liquid separator 5 to obtain a total of 148 kg of solid suspended solids. The liquid phase solution was found to have 0.06 g of Pd adhered to the column in the liquid recoverer via a liquid recoverer. As a result of ICP (Inductively Coupled Plasma) analysis of the obtained slurry, the Pd content was about 2015 ppm, and the Pd content of the discarded liquid solution was 0.5 ppm as a result of ICP.

Solid phase Liquid recovery machine Pd system (kg) Yield (kg) Pd content (ppm) Pd present amount (kg) Pd content Comparative Example 54.21 2050 0.11 - 0.11 Example 148.33 2015 0.30 0.06 0.36

As shown in Table 2, when the palladium noble metal is recovered through the embodiment of the present invention, not only the high Pd recovery effect is obtained in the recovered solid sludge, but also the Pd precious metal can be recovered through the liquid recoverer.

1. Heavy-end tank 2. Air bubbling device
3. Outlet 4. Slurry pump
5. Centrifugal solid-liquid separator 6. Solid suspended solids
7. Three Way Valve 8. Filter
9. Liquid palladium recovery system 10. Wastewater treatment system

Claims (6)

An apparatus for recovering noble metal palladium in heavy-end waste generated from a refining apparatus for a polyketone polymerization solvent,
Heavy end tank;
A slurry pump for transferring a slurry to a discharge port located at a lower end of the heavy end tank;
A Centrifuge solid-liquid separator for separating the slurry transferred through the slurry pump into a solid phase and a liquid phase;
A heavy end sludge obtaining device for recovering suspended solid matter discharged through the centrifugal separator;
A three-way valve for recovering the liquid phase passed through the centrifugal separator and transferring the liquid phase to a heavy end tank or transferring the liquid phase to a filter;
A filter for filtering the liquid phase through the three-way valve; And
And a palladium recovery device for recovering palladium from the liquid through the filter,
Wherein the slurry pump stops the operation when the temperature inside the heavy end tank rises to 30 DEG C or higher. The method according to claim 1,
Wherein the heavy end tank includes an air bubbling device at an inner bottom edge thereof. The method according to claim 1,
Wherein the air gap of the filter is 10um or less. delete The method according to claim 1,
Wherein the slurry pump is a diaphragm pump. The method according to claim 1,
Wherein the heavy end tank is provided with a cooling jacket.

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