JPS6279848A - Method for reactivation of oxide catalyst for removing arsenic in hydrocarbon - Google Patents

Abstract

PURPOSE:To easily reactivate a deactivated catalyst by passing air or a gaseous mixture composed of air and gaseous nitrogen onto an oxide catalyst consisting of deactivated manganese oxide and/or copper oxide. CONSTITUTION:This invention relates to a method for reactivation of the oxide catalyst consisting of the manganese oxide and/or copper oxide for removing the arsenic in hydrocarbon, in which valves 8, 9 are closed, then a regenerating gas outlet 7 and a supply valve 11 for gaseous nitrogen for purging are closed to introduce the gaseous nitrogen into a reactor 3 and to purge the gas; thereafter a supply valve 10 for air for regeneration is opened to incorporate the air into the gaseous nitrogen and the regeneration of the catalyst is executed at a prescribed temp. for a prescribed period. The deactiveted oxide catalyst is thus easily reactivated.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to a method for reactivating an oxide catalyst such as mancan oxide and/or copper erythrium oxide, which is a hydrocarbon membrane arsenic catalyst that has lost its activity. be.

[Conventional technology and its problems]

The present inventors first discovered manganese oxide (Mn02) and/or
Or copper oxide (CuO) L! It has been discovered that the catalyst 1.1 has an excellent ability to remove trace amounts of arsenic compounds, especially alumines (AsH3, CH3AaHg, etc.) contained in hydrocarbons such as LPG, and using this oxide catalyst, it has been found that proposed a method for removing arsenic from
No. 7627 J0 During production, these oxide catalysts are used to remove arsenication of hydrocarbons by firing the produced manganese or steel oxides or by treating them with peroxides such as hydrogen peroxide. It gives it activity as a tact.

On the other hand, catalysts that have been used for arsenication of hydrocarbons and those that have been deactivated due to long-term storage are either disposed of or disposed of because there is no known method for regenerating or reactivating them. This deactivated catalyst is used as a raw material to produce a new catalyst at great cost, resulting in waste.

[Purpose of the invention]

The present invention can easily regenerate acid and arsenic catalysts made of manganese oxide and/or copper oxide, which are commonly used for hydrocarbon dearsenization, and which have been deactivated by use in arsenication of hydrocarbons or by long-term storage. The purpose is to provide a complete method of activation.

[Structure of the invention]

The present invention is directed to deactivated manganese oxide and/or oxidized steel! Nitrogen or V
A method for reactivating the catalyst, characterized in that a mixed gas of air and nitrogen gas is passed through the catalyst, and the present inventors have developed a method for reactivating the catalyst, which is characterized by passing a mixed gas of air and nitrogen gas. The inventors have discovered that by treating the arsenic oxide catalyst with air or a mixed gas of air and nitrogen gas, the deactivated oxide catalyst can be easily reactivated, leading to the present invention.

The reactivation treatment conditions for the deactivated acid-1 arsenic catalyst of the present invention vary depending on the type of catalyst and the degree of deactivation, but the treatment conditions vary depending on the type of catalyst and the degree of deactivation, but at a temperature within the range of room temperature to several hundred degrees Celsius, air or air and nitrogen are used. Dregs mixed in any proportion? It is preferable to deactivate the catalyst and allow it to flow over the 7'c catalyst at a rate of 10 to 500 Nm31#/m3 catalyst.

Next V? Embodiments of the present invention will be explained based on FIG.

The first factor is the removal of arsenic impurities contained in LPG by passing the LPG through a reactor filled with a catalyst containing manganese oxide, copper oxide, or a mixture of manganese oxide and cupric oxide in any proportion; It also shows a flowchart of a method for regenerating a deactivated catalyst, in which reference numeral 1 indicates a process gas (L
PG ) inlet to the reactor, 2 is the process gas reactor outlet, 3 is the reactor, 4 is inside the reactor @ monitoring equipment, 5
is a regeneration air inlet, 6 is a nitrogen gas inlet for regeneration and purging, 7 is a regeneration gas or purge gas outlet, 8 is a process gas supply valve, 9 is a process gas block valve, 10 is a regeneration air supply valve, 11 is for regeneration or purge nitrogen gas supply valve; 12 is a regeneration air flow meter; 15ii is a regeneration or purge nitrogen gas flow meter;

First, completely charge the catalyst into the reactor 5, open the valve on the regeneration gas output lower piping, and then open the purge nitrogen gas supply valve 11 to supply nitrogen into the purge nitrogen gas into the reactor. When gas is injected into the reactor to purge all of the air in the reactor, the temperature in the reactor is set to 45.
Raise the temperature to C. After the purge is completed, close the square on the piping of the regeneration gas output lower and the purge nitrogen gas supply valve 11', then fully open the process gas supply 9P8 and the process gas block valve 9, and completely supply LPG from the LPG reactor port 1. Then, the arsenization reaction of LPG is started.

Then, for a certain period of time I, PI:) L7) Dearsenization and unreacted reaction are performed, and if the catalyst is deactivated, valves 8 and 9 are closed, and then the tank on the pipe of the regeneration gas output lower and the purge nitrogen are removed. Close the gas supply valve 11, introduce nitrogen gas into the reactor, and after purging the LPG i verge in the reactor and LPG, open the regeneration air supply valve 10 and mix air into the nitrogen scum. Then, the catalyst is regenerated at a predetermined temperature for a predetermined period of time. When regenerating the catalyst, that is, after purging LPG from the de-IC device, the valve 11 of the regeneration nitrogen gas inlet 6 may be closed and only air can be fully supplied, or during the regeneration period, the regeneration nitrogen gas The supply of fii' may be gradually reduced, the amount of regeneration air introduced may be gradually increased, and at the end of regeneration only air may be sent for regeneration.

Next, all examples of the present invention will be described.

Example 1 Using an apparatus as shown in FIG. 1, a reactor filled with manganese oxide tapelets of 5 m3f (4 fins) with a diameter of 6 nodules and a height of 4 fins was placed at a pressure of 1 &5'rJ/cm'G and a temperature of 4.
At 5°C, 92 mol of propylene fluoride, 6 mol of probuff, 1 mol of a C2 fraction consisting of ethylene and ethane, and 1 mol % of a C4 fraction such as butane and pumediene were added to a gas '4.
000 to 9/h passed through the reactor. Figure 2 shows the changes in A8H3 at the inlet and outlet of the reactor.

As can be seen from Figure 2, the amount of AsH3 at the reactor outlet gradually increased from the 5th month after the start of the reaction, and by the 7th month, the amount of AsH3 at the reactor outlet rose to 8 PPB. Therefore, the reaction completely stopped at this point, and the C! , After purging with LPG 1 nitrogen gas, 25℃
11l100N of mixed gas of nitrogen gas and air for 10 hours.
The catalyst was regenerated by passing through the reactor at a rate of 1/h.

While regenerating the catalyst, the amount of air mixed into the nitrogen gas was gradually increased, and the mixing ratio of nitrogen gas and air was fully controlled so that the air ratio reached 100% at 10 hours.

After regenerating the catalyst, the air in the reactor was purged, and the arsenic removal of the C3LPG fraction was restarted under the same conditions as before through the C3PLG fraction. Figure 3 shows the concentration of AsH3 at the reactor inlet and outlet before and after the catalyst regeneration period.

As can be seen from Fig. 5, O after regeneration of the catalyst,
The arsenic removal ability from LPG has been restored to the same level as that of the new catalyst.

In addition, when regenerating the catalyst, only air is used as the regeneration gas after purging the C and LPG in the reactor with nitrogen gas.
In case c, the catalyst could be regenerated in about 12 hours.

Example 2 A reactor filled with the same manganese oxide catalyst 1.5- as used in Example 1 was placed at a pressure of 16.5 ky/iG and a temperature of 45
03LPG of the same composition as used in Example 1 at 90°C.
0 at a rate of 9/hour. C at the inlet and outlet of the reactor, LPG K-containing ASH,
The same situation is shown in Figure 4. As can be seen from FIG. 4, the concentration of ASH3 at the reactor outlet gradually increased from the 15th month after the start of the reaction, and reached AsH3n Hoso20 PPB in the C3LPG at the reactor outlet at the 16th month. At this point, the reaction is stopped and the C, LP in the reactor is
After purging G with nitrogen gas, the catalyst was regenerated at 15° C. for 15 hours. During regeneration, the amount of air mixed into the nitrogen gas is gradually increased, and the 15:00 time period is 9 air 100%.
While controlling the regeneration gas to 180 Nm
It passed at a rate of '/hour.

Figure 5 shows the activity of the catalyst before and after regeneration.

It can be seen from FIG. 5 that after reactivation, the activity of the catalyst returned to its initial activity.

[Brief explanation of drawings]

FIG. 1 is a flow diagram showing an example of an apparatus for carrying out the method fc of the present invention, FIG. 2 is a diagram showing the amount of change in ASH3 at the inlet and outlet of the reactor in Example 1, and FIG. 3 Figure 4 shows the change in AsH content at the reactor inlet and outlet before and after catalyst regeneration in Example 1, and Figure 5 shows the change in A8H content at the reactor inlet and outlet in Example 2. 1 is a diagram showing changes in AsH3 content at the inlet and outlet of the reactor before and after catalyst regeneration in Example 2. FIG. 1. Input of process gas to reactor, 2. Outlet of process gas to reactor, 5. Reactor, 5. Air inlet for regeneration, 6. Inlet of nitrogen gas for regeneration and purging, 7.・
Regeneration gas or gas outlet

Claims (1)

[Claims] 1. A method for reactivating a catalyst, which comprises flowing air or a mixed gas of air and nitrogen gas over an oxide catalyst for dearsenizing hydrocarbons made of manganese oxide and/or copper oxide that has lost its activity. .