JPS5822066B2 - Method for thermal decomposition of oil sand bits - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for pyrolyzing oil sand bitumen to produce a large amount of gas and light oil useful as fuel.

Oil sands are oil-containing sands or sandstones that are produced in large quantities in Canada and Venezuela, and with the depletion of petroleum resources, they have come to attract attention as a source of fuel oil in place of crude oil.

The object of the present invention is to further obtain fuel gas and light oil using bitumen, which is the residue after sand is removed from this oil sand, as a raw material.

Up to now, the method for thermally decomposing oil sand bitumen has been to heat it to a temperature of 600° C. or higher, and to collect the gas generated and distilled light oil at this temperature.

As a result of extensive research in order to more efficiently thermally decompose oil sand bitumen and obtain fuel gas and light oil with even higher yields, the inventor added iron hydroxide as a catalyst during thermal decomposition. It was discovered that the decomposition temperature could be significantly lowered by doing this, and the present invention was completed based on this finding.

That is, the present invention provides a method for thermally decomposing oil sand bitumen in the presence of at least 1.5 parts by weight of iron hydroxide per 100 parts by weight of oil sand bitumen.
The present invention provides a method characterized by heating to 0 to 500°C.

As raw material for the process of the invention, the residue after sand removal from the oil sands is used.

This is commonly known as oil sand bitumen.

Further, the iron hydroxides used as catalysts in the method of the present invention include Fe(OH)3, Fe(OH)2 and Fed(O
H) may be used.

These iron hydroxides have not been recognized to be effective as decomposition catalysts.

These iron hydroxides have very specific catalytic activity and are completely ineffective against heavy oils other than oil santobitunon, such as Kafji vacuum distillation residue and Kuwait vacuum distillation residue. be.

In addition, for the thermal decomposition of oil sand bitumen, substances conventionally known as catalysts for the thermal decomposition of various heavy oils, such as silica-alumina, zeolite, iron powder, ferrous oxide, iron sesquioxide, Iron oxide, iron sulfide, calcium oxide, etc. have no effect.

In the method of the present invention, oil sand bitumen 10
At least 1.5 parts by weight per 0 parts by weight, preferably from 3 to 0 parts by weight
10 parts by weight of iron hydroxide are added in powder form.

If this amount is less than 1.5 parts by weight, sufficient catalytic action will not be exhibited.

However, even if more than 10 parts by weight is added, no increase in the effect is observed, so there is no point.

According to method J of the present invention, oil sand bitumen is heated and melted, a predetermined amount of iron hydroxide powder is added thereto, stirred to disperse it well, and then heated to 400 to 500 degrees Celsius at a rate of 50 to 500 degrees Celsius per minute. Raise the temperature.

The faster the temperature increase rate at this time, the lower the decomposition temperature is, and the more efficiently the decomposition reaction can proceed.

This temperature increase rate can be lowered to about 3° C. per minute if desired, but in this case it is necessary to perform the heating under an inert gas atmosphere to suppress the oxidation reaction.

In the method of the present invention, no change in the amount of coke produced in the final product is observed due to the addition of a catalyst, and only an increase in the yield of fuel gas and light oil at a lower temperature is observed compared to the case without the addition of a catalyst. Therefore, it is considered that the low temperature promotes the splitting of naphthenic hydrocarbons present in relatively large amounts in oil sand bitumen, thereby improving the yield.

As described above, according to the method of the present invention, oil sand bitumen can be thermally decomposed efficiently and the yield of useful fuel gas and light oil can be increased, so it is suitable as a means for effectively utilizing oil sand. be.

Next, the present invention will be explained in more detail with reference to Examples.

Example 1 Oil sand bitumen collected in the Cold Lake region of Canada was preliminarily distilled under reduced pressure to remove components having a boiling point of 400° C. or less in terms of normal pressure.

This was used as a sample for decomposition.

A three-necked flask with an internal volume of 500 TLl was equipped with a stirrer, and 400 g of the sample was placed in it, followed by iron hydroxide (F).
e (OH) 3) 40'? added.

While flowing nitrogen gas at a rate of 00 ml per minute to prevent oxidation, it was heated in an electric furnace at a temperature increase rate of 3° C./min to 400° C., and held at this temperature for 1 hour.

After the time elapsed, the flask was immediately removed from the electric furnace and cooled.

The cracked oil produced during this heat treatment process was collected in an ice-cooled trap.

Table 1 shows the amounts of cracked oil and gas and the yield of residual pitch-like substances when heated to 400°C and held for 30 minutes, and treated at 420°C and 440°C for 60 minutes in the same manner as above. .

Furthermore, the amounts of cracked oil and gas and the yield of pitch-like substances when heat-treated in the same manner as above without adding iron hydroxide are also listed in Table 1.

Note that the amount of iron hydroxide added was 5 wt%, but Table 1
There was almost no difference.

Comparative Example 1 Using the same sample and method as in Example 1, a sample was treated by adding 10% by weight of a substance other than iron hydroxide to the sample.

Table 2 shows the yields of cracked oil, gas, and pitch-like substances at this time.

The silica-alumina (13%) and zeolite used here are industrial catalysts for catalytic cracking.

Example 2 Using the same sample as in Example 1, the weight loss rate was measured using a thermobalance in order to investigate decomposition due to temperature increase rate.

A quartz cell was used as the sample container, and a sample of 30±27n was placed in it.
9 in a helium stream (200 ml/ml).

The results are shown in Table 3. Note that the amount of iron hydroxide added was 10% by weight.

As shown in Table 3, by adding iron hydroxide to oil sand bitumen, the weight loss after 30 minutes at 500℃,
That is, although the coke yield is almost the same as in the case without additives, a decrease in the decomposition temperature is observed.

The decrease becomes larger as the temperature increase rate increases.

Comparative Example 2 A vacuum distillation residue of Khafji crude oil was used as a sample, and 10% by weight of iron hydroxide was added thereto in the same manner as in Example 1, followed by heat treatment at 420° C. for 60 minutes.

Table 4 shows the yield of the product at this time.

Furthermore, we also investigated the residual oil from vacuum distillation of crude oil produced in Kuwait.

As seen in this table, almost no effect was observed due to the addition of iron hydroxide.

Claims (1)

[Claims] 1. At least 1 part per 100 parts by weight of oil sand bitumen in thermally decomposing oil sand bitumen.
．． A method characterized by heating to 400 to 500°C in the presence of 5 parts by weight of iron hydroxide. 2. The method according to claim 1, wherein the temperature is raised to a predetermined temperature at a rate of 50 to 500°C per minute.