JP4382552B2 - Processing method of plastic decomposition oil - Google Patents

Description

  The present invention produces a naphtha fraction and a kerosene oil fraction that are processed into a petroleum base material, a petrochemical feedstock, and a kerosene oil by treating the plastic cracked oil produced by pyrolysis of waste plastics with the petroleum fraction in the petroleum refining process. On how to do.

  In general, there is a strong demand for naphtha fractions, kerosene and light oil fractions, which are gasoline base materials and petrochemical materials produced from crude oil. As this raw material, petroleum fractions obtained from crude oil such as straight-run naphtha, vacuum naphtha, pyrolysis naphtha, straight-run kerosene, vacuum kerosene, pyrolysis kerosene, straight-run gas oil, vacuum gas oil, and pyrolysis gas oil are used. .

Plastic cracked oil is an oil produced by cracking plastic separated from waste or the like. The raw material plastic is not particularly limited, and examples thereof include polyolefins such as polyethylene and polypropylene, styrene resins such as polystyrene, polyamide resins, polyvinyl chloride, polyvinylidene chloride, and polycarbonate. Usually, discarded plastic is used as a raw material. Such a thermal decomposition reaction of plastic is known.
JP-A-11-061148 JP 09-235563 A JP 08-245108

This plastic cracked oil is generally used for boiler fuel and the like, and since it has many impurities, it is not used as a gasoline base material, kerosene oil, or petrochemical raw material. Among waste plastics, polyamide resins, polyurethanes, ABS resins and NBR contain nitrogen, and polyvinyl chloride (PVC), polyvinylidene chloride (PVDC) and polyethylene chloride contain chlorine. For this reason, a relatively large amount of impurities such as chlorine and nitrogen remain in the plastic cracked oil, and it has been proposed to hydrotreat the plastic cracked oil to remove this.
JP 09-049883

  However, if the plastic cracked oil is used as it is, it cannot be substantially hydrorefined. This is because when the plastic cracked oil is heated for hydrorefining and introduced into the catalyst bed, carbon precipitates (coking) on the surface of the catalyst and cannot be operated for a long time. Or, since the coking is performed on the catalyst, the activity of the catalyst is rapidly reduced.

  The present invention solves such problems in the hydrorefining of plastic cracked oil, and uses the plastic cracked oil as a gasoline base material, petrochemical feedstock, and kerosene as a naphtha fraction and kerosene oil fraction. It is the purpose.

  The present invention relates to a method for treating plastic light oil by mixing a plastic-decomposed light oil obtained by fractionating a plastic-decomposed oil produced by thermal decomposition of waste plastic and a petroleum fraction, and treating the mixture in a petroleum refining process, The cracked light oil is a plastic cracked light oil treatment method having a specific gravity of 0.88 or less and a 90% distillation temperature of 100 ° C to 300 ° C.

  The plastic cracked light oil preferably has a specific gravity of 0.80 to 0.88 and a 90% distillation temperature of 150 ° C to 270 ° C, or an initial boiling point of less than 100 ° C.

  The 90% distillation temperature of the petroleum fraction is 100 ° C to 500 ° C higher than the 90% distillation temperature of the plastic cracked light oil, and moreover, 250 ° C to more than the 90% distillation temperature of the plastic cracked light oil. It is preferably 450 ° C. and the 10% distillation temperature of the petroleum fraction is 50 ° C. to 200 ° C. higher than the 90% distillation temperature of the plastic cracked light oil.

  The petroleum refining step preferably includes at least one step of hydrorefining, hydrocracking and catalytic cracking.

  The present invention is a plastic cracked light oil having a specific property, which is mixed with a petroleum fraction and processed in a petroleum refining process, and can be processed without causing problems such as coking. Impurities such as chlorine and nitrogen can be reduced by hydrorefining treatment. Therefore, a plastic-decomposed light oil with a small impurity content can be obtained, and can be used as a gasoline base material, petrochemical raw material, and kerosene oil.

[Plastic decomposition light oil]
The plastic cracked light oil is fractionated from the plastic cracked oil and has a specific gravity of 0.88 or less and a 90% distillation temperature of 100 ° C. to 300 ° C., preferably a specific gravity of 0.80 to 0.00. It is preferable that the 88 and 90% distillation temperature is 150 ° C. to 270 ° C., or the initial boiling point is less than 100 ° C. Particularly preferably, the initial boiling point is 50 ° C. or lower, the 50% distillation temperature is 80 ° C. to 240 ° C., and the 90% distillation temperature is 150 ° C. to 270 ° C.

  The properties of the plastic decomposed light oil include a sulfur content of 300 ppm or less, particularly 100 ppm or less, a nitrogen content of 100-1500 ppm, particularly 300-1000 ppm, a chlorine content of 100 ppm or less, a total acid value of 0.01 mgKOH / g or more, In particular, 0.05 to 0.2 mgKOH / g, bromine value is 1.5 gBr2 / 100 g or more, particularly 10 to 300 gBr2 / 100 g, diene value is 0.3 g / 100 g or more, particularly 1 to 5 g / 100 g. Is preferred. In addition, when an impurity etc. remove | deviates from this range, the plastic decomposition oil or the plastic decomposition light oil after fractionation can also be processed beforehand by removal processes, such as adsorption removal of an impurity.

The mixing ratio of the plastic cracked light oil is preferably 1 to 50% by volume, particularly 2 to 25% by volume, and more preferably 5 to 20% by volume with respect to the entire processing target. When it exceeds this range, coking and / or corrosion occurs, and the treatment becomes difficult.

[Oil fraction]
The distillation property of petroleum fractions is that 90% distillation temperature is preferably 130 ° C to 600 ° C, particularly 300 ° C to 600 ° C, and is 100 ° C to 500 ° C higher than 90% distillation temperature of plastic cracked light oil, Is preferably higher by 200 ° C to 400 ° C. If 90% distillation temperature of the plastic cracked light oil is higher than this, a metal content, residual carbon multi no longer the catalyst is poisoned, the process and / or caulking becomes difficult to occur because It is not preferable.

  The 10% distillation temperature of the petroleum fraction is preferably 150 ° C. to 450 ° C., particularly 240 ° C. to 370 ° C., 50 ° C. to 200 ° C. higher than the 90% distillation temperature of the plastic cracked light oil, particularly 100 ° C. to It is preferably 150 ° C higher. When the 10% distillation temperature of the petroleum fraction is higher than this, it is not preferable because a high temperature is required for the treatment, and the plastic-decomposed light oil is excessively decomposed and can be obtained only as a gas component.

  The petroleum fraction is not particularly limited as long as it is a fraction made of hydrocarbons obtained from crude oil. For example, straight-run naphtha, vacuum naphtha, pyrolysis naphtha, straight-run kerosene, vacuum kerosene, pyrolysis kerosene, Examples include straight-run gas oil, vacuum gas oil, pyrolysis gas oil, residual oil, and vacuum residue. In particular, the 10% distillation temperature is preferably 150 ° C. to 450 ° C., and straight-run gas oil, vacuum gas oil, and pyrolysis gas oil are preferably used. Further, the total metal content is preferably 10 ppm or less, particularly 3 ppm or less.

[Oil refinery process]
The oil refining process in which the plastic cracked light oil and the petroleum fraction are mixed and processed includes at least one of hydrotreating, hydrocracking and catalytic cracking, and the hydrotreating process is particularly preferable. . Thereby, the sulfur content, nitrogen content, etc. of the petroleum fraction are reduced, and the nitrogen content, chlorine content, etc. of the plastic-decomposed light oil are reduced. Petroleum fraction with a sulfur content of 0.5% or more, especially 1% or more, is mixed with light plastic oil, and the sulfur content is 0.2% or less, particularly 0.1% or less by hydrorefining. Such a purification step is preferred.

  In hydrorefining, treated oil is brought into contact with a hydrorefining catalyst in the presence of hydrogen. As the hydrorefining catalyst, a catalyst in which at least one of molybdenum, nickel, cobalt, and phosphorus is supported on an inorganic porous carrier such as alumina, and particularly at least one of molybdenum and nickel or cobalt is preferably used. Preferred reaction conditions are: reaction temperature: 250 to 430 ° C., reaction pressure: 1 to 15 MPa, LHSV: 0.1 to 30 h−1, H2 / Oil (hydrogen / oil ratio): 20 to 1500 L / L.

  After hydrorefining, it is divided into naphtha fractions, kerosene fractions, diesel oil fractions, etc., and is converted into products such as naphtha, petrol, kerosene, diesel oil for petrification as it is or through other petroleum refining processes. . In particular, as naphtha for petrochemicals and gasoline base materials, sulfur content is 10 ppm or less, particularly 2 ppm or less, nitrogen content is 10 ppm or less, particularly 2 ppm or less, chlorine content is 10 ppm or less, particularly 1 ppm or less, total acid value is 0.01 mgKOH / g or less, diene The value can be 0.2 g / 100 g or less, particularly 0.1 / 100 g or less.

  EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not interpreted limitedly by this Example. In this example, the density is JIS K 2249, the sulfur content is JIS K 2541 (ultraviolet fluorescence method), the nitrogen content is JIS K 2609 (chemiluminescence method), the chlorine content is coulometric titration, and the total acid value is The bromine number was measured according to JIS K 2501, the bromine number was measured according to JIS K 2605, the diene value was measured according to UOP 326-65, and the distillation properties were measured according to JIS K 2254.

  Table 1 summarizes the properties of plastic cracked oil and hydrocarbon oil. Plastic cracked oil is obtained by fractionating plastic cracked raw material oil obtained from the Containers and Packaging Plastic Oil Company Association. The hydrocarbon oil is a mixed oil of a heavy gas oil fraction obtained by atmospheric distillation of Middle Eastern crude oil and a vacuum gas oil fraction obtained by distillation of residual oil under reduced pressure.

  The hydrocarbon oil of Table 1 and the plastic decomposition oil were mix | blended in the ratio shown in Table 2, and mixed raw material oil was prepared. This mixed feedstock was hydrorefined under the following conditions.

  In a fixed bed flow reactor having a vertical length of 1160 mm and an inner diameter of 19 mm, about 100 ml of 3φ alumina balls, 60 ml (49.2 g) of hydrorefining catalyst (ART HOP473), 3φ About 25 ml of alumina balls were filled, and mixed raw material oil and hydrogen were introduced from the upper end. The reaction conditions were hydrorefining under the conditions of temperature: 350 ° C., pressure 8.0 MPa, LHSV: 2h−1, H2 / Oil: 230 L / L. The used HOP473 manufactured by ART contains 11 wt% molybdenum, 3 wt% nickel, and 2 wt% phosphorus using alumina as a metal as a carrier.

As a result, it was possible to operate without increasing the differential pressure until the end of the experiment. Inside the reactor, coking did not occur and oil was flowing. And if the specific gravity of the plastic cracked oil exceeds 0.88, when a 90% distillation temperature exceeds 300 ° C., the coking is generated inside the poisoning and / or reactor of the catalyst, hydrotreating process difficult It becomes. Table 3 shows the properties of the entire refined oil obtained and the properties of each fraction obtained by fractionating the entire refined oil.

  The present invention uses a plastic cracked light oil having specific properties and mixes with a hydrocarbon oil in petroleum refining to perform petroleum refining processing such as hydrorefining. Since impurities such as chlorine and nitrogen can be reduced without difficulty, the refined naphtha fraction and kerosene / light oil fraction can be used as a gasoline base material, petrochemical raw material, kerosene and light oil.

Claims (5)

A plastic-decomposed light oil treatment method in which a plastic-decomposed light oil obtained by fractionating a plastic-decomposed oil produced by thermal decomposition of waste plastic and a petroleum fraction are mixed and processed in an oil refining process, wherein the plastic-decomposed light oil is , total acid number 0.01 mg / g or more, bromine number 1.5gBr ₂ / 100g or more, diene value 0.3 g / 100 g or more, a specific gravity of 0.88 or less and 90% distillation temperature of 100 ° C. to 300 ℃ der I, the mixing ratio of the plastic cracked light oil is 1 to 20% by volume based on the total processed, the petroleum refining process plastic cracked light oil treatment method is a hydrotreating process. The plastic cracked light oil has a sulfur content of 300 ppm or less, a nitrogen content of 100 to 1500 ppm, a chlorine content of 100 ppm or less, a specific gravity of 0.80 to 0.88, and a 90% distillation temperature of 150 ° C. to 270 ° C. The plastic decomposition light oil processing method of Claim 1.   The method for treating plastic light oil according to claim 1, wherein the plastic light oil has an initial boiling point of less than 100 ° C.   The method for treating a plastic cracked light oil according to claim 1, wherein a 90% distillation temperature of the petroleum fraction is 100 ° C to 500 ° C higher than a 90% distillation temperature of the plastic cracked light oil.   The 90% distillation temperature of the petroleum fraction is 250 ° C to 450 ° C higher than the 90% distillation temperature of the plastic cracked light oil, and the 10% distillation temperature of the petroleum fraction is that of the plastic cracked light oil. The method for treating a plastic cracked light oil according to claim 1, which is higher by 50 to 200 ° C than the 90% distillation temperature.