JPH08337782A - Conversion of heavy oil into light oil - Google Patents

Abstract

PURPOSE: To convert a heavy oil into a light oil in high economy and safety, reutilizing waste plastics without necessitating expensive hydrogen and catalyst by mixing a heavy oil with waste plastics and heat-treating the mixture at a specific temperature in a non-oxidizing atmosphere. CONSTITUTION: (A) A heavy oil consisting of a petroleum-based heavy oil or a coal-based heavy oil is mixed with (B) waste plastics and the mixture is heat-treated at 350-460 deg.C (especially 380-450 deg.C) in (C) a non-oxidizing atmosphere such as nitrogen, argon, helium or hydrocarbon gas. The mixing ratio of the component A to the component B is preferably 0.1-1.0 pt. wt. of the component B based on 1 pt.wt. of the component A and the heat-treatment is carried out under a pressure between atmospheric pressure and 50 atm for 10-40 min.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for lightening heavy oil, and more particularly to a method for lightening heavy oil using waste plastics. INDUSTRIAL APPLICABILITY The present invention is useful in a petroleum refining industry, a coke manufacturing industry, a waste oil processing industry, a waste processing industry and the like.

[0002]

2. Description of the Related Art At present, a general and typical lightening method or reforming method for heavy oil or the like is a so-called hydrocracking method. The method comprises naphtha as a raw material,
Catalysts such as silica-alumina, platinum, nickel, tungsten for light gas oil, heavy gas oil, vacuum gas oil, coker gas oil, cracked circulating oil, solvent deasphalting oil, atmospheric residual oil, vacuum residual oil, solvent deasphalting asphalt, etc. Etc., under a hydrogen atmosphere, at a temperature of 350 to 450 ° C., 30 to 200 kg /
It is processed under a pressure of cm ² G. Typical processes include the Isomax method, the H-oil method, the uni-cracking JHC method, etc., which are widely used as petroleum refining equipment. However, in this method, expensive hydrogen and a catalyst are used, and the reaction is carried out under severe conditions of high temperature and high pressure, so that the economy is poor. Further, in terms of ensuring safety, there is a problem that it requires skill in driving technology.

[0003]

The present invention does not require expensive hydrogen and a catalyst, is not only economical and safe, but is also a novel method for lightening heavy oil by recycling waste plastics. Is provided.

[0004]

According to the present invention, one or more heavy oils selected from petroleum heavy oils and coal heavy oils and waste plastics are mixed under a non-oxidizing atmosphere at 350. ~
It is a method for lightening heavy oil, characterized in that it is heat-treated at a temperature of 460 ° C.

In the present invention, under the above-mentioned conditions, the heavy oil is decomposed and the carbon-carbon bond is cleaved to generate reactive radicals, and at the same time, the waste plastics are decomposed to generate highly reactive hydrogen. Is supplied. As a result, the reactive radicals generated from the heavy oil are combined with the produced hydrogen to achieve the lightening of the heavy oil, and further heavy oil such as coking is suppressed. It is.

The waste plastics used in the present invention include plastics contained in general waste or so-called shredder dust produced from industrial wastes such as automobiles and home electric appliances. Generally, for example polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyamide, polyurethane, polycarbonate,
Epoxy resin, phenol resin, acrylic resin, polyimide resin, acrylonitrile-butadiene-styrene (ABS) resin, etc., and further acrylonitrile-butadiene rubber (NBR), styrene-butadiene rubber (S
BR), isoprene rubber (IR), butylene / butadiene rubber, chloroprene rubber, silicone rubber, butadiene rubber, acrylic rubber, natural rubber and the like. The waste plastics may contain other organic substances such as paints and adhesives. In the shredder dust, in addition to the above plastics, metals such as iron, aluminum and copper (for example, wiring), glass, pigment,
Includes inorganic substances such as sand and soil. In the method of the present invention, these metals and inorganic substances can be used as they are without being removed in advance.

The heavy petroleum oil used in the present invention is not particularly limited. For example, fuel oil such as heavy oil A and heavy oil C, residual oil obtained in the petroleum refining process, natural tar, oil shale oil, tar sand. Examples include system oils. There is also no particular limitation on heavy coal-based oil, for example, coal tar by-produced during coke production, anthracene oil,
Naphthalene oil, creosote oil or the like, coal liquefied oil, low temperature carbonized tar or the like is used. Of the petroleum heavy oil and the coal heavy oil, A heavy oil and C heavy oil are preferably used. Further, waste oils containing the above-mentioned petroleum-based and coal-based heavy oils, for example, used lubricating oil, used cleaning oil, etc., can also be used.

The mixing ratio of one or more heavy oils selected from petroleum heavy oils and coal heavy oils to waste plastics is
Preferably 0.1 to 1.0 parts by weight of waste plastics, particularly preferably 0.4 to 0.7 parts by weight, relative to 1 part by weight of heavy oil.
Parts by weight. If the amount is less than the above lower limit, the lightening of heavy oil is insufficient and coking occurs. If the amount exceeds the above upper limit, no significant improvement in lightening effect is observed.

Mixing of one or more heavy oils selected from petroleum heavy oils and coal heavy oils with waste plastics is carried out, for example, as follows. First, waste plastics are crushed in advance so that the weight of particles having a particle size of 1 mm or less is preferably 80% by weight or more, and this is mixed with the above heavy oil in a predetermined weight ratio. It is then preferred to swell the mixture. The swelling of the mixture is preferably 100
It is carried out by holding at a temperature of ~ 200 ° C, preferably for 10 to 60 minutes. More preferably, the heavy oil may be preheated to 250 ° C. or higher, mixed with waste plastics, and then kept at a temperature of 100 to 200 ° C. for 10 to 30 minutes to swell the waste plastics.

Next, the mixture of heavy oil and waste plastics produced as described above is subjected to dechlorination treatment, if desired. The mixture is dechlorinated by heating to 150-350 ° C, preferably 250-350 ° C. If it is less than the above range, dechlorination proceeds slowly, and if it exceeds the above range, coking occurs, which is not preferable. The mixture is heated in the preferred range mentioned above in order to ensure good dechlorination and to limit coking.

During heating in the above dechlorination treatment, the pressure is preferably normal pressure to autogenous pressure, and the upper limit thereof is preferably 10 kg / cm ² . If it is less than the above range, the evaporation of oil in the mixture is remarkable, and if it exceeds 10 kg / cm ² , the pressure resistance of the apparatus must be increased, which is not economically preferable.

The chlorine contained in the waste plastics is
Usually, hydrogen chloride gas is liberated by the above heat treatment. Therefore, for example, in a conventional gas-liquid separation device, hydrogen chloride gas and entrained hydrocarbon gas are separated, cooled,
Recovered as hydrochloric acid and condensed oil, respectively.

The mixture is then heated under a non-oxidizing atmosphere, preferably at least one gas selected from the group consisting of nitrogen, argon, helium and hydrocarbon gases. The heating is carried out at a temperature of 350 to 460 ° C, preferably 380 to 450 ° C, particularly preferably 420 to 430 ° C. If the heating temperature exceeds the upper limit, coking tends to occur, and if the heating temperature is lower than the lower limit, the heavy oil and the waste plastics are insufficiently decomposed, and the lightening cannot be sufficiently performed. Further, the pressure during the heating is preferably atmospheric pressure to autogenous pressure, and the upper limit thereof is preferably 50 atmospheric pressure. If the pressure exceeds the upper limit or less than the lower limit, the cost of the apparatus is increased, which is not preferable from the economical viewpoint, and is also not preferable from the viewpoint of operation. The heat treatment is preferably carried out for 10 to 40 minutes, particularly preferably 15 to 20 minutes. If the heating time is less than the above lower limit, decomposition of heavy oil and waste plastics is insufficient, and if the heating time exceeds the above range, no remarkable effect is expected,
It is not preferable because coking may occur.

No catalyst addition is required in the process of the present invention. However, the addition of a catalyst is not excluded at all, and can be added to accelerate decomposition or reaction during heat treatment. For example, an iron-based cracking catalyst is added according to the type of heavy oil to be used, or a silica-alumina-based catalyst, a transition metal-based catalyst, a noble metal catalyst, a metal compound to adjust the properties of the recovered light oil or gas. A catalyst, a natural mineral, etc. can be added.

After the above heat treatment, the solids are preferably separated from the mixture and the light oil is recovered. In particular, when waste plastics having a relatively high content of metals and inorganic substances such as shredder dust are used, the mixture is treated with a solids separator such as a filter or a centrifuge to obtain a mixture in the mixture. It is preferable to remove solids such as contained metals.

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[0017]

【Example】

[0018]

Example 1 A small pressure reaction tube made of stainless steel of 200 cc was pulverized in advance so that 100 mesh or less was 80% by weight or more. 6.25 g of polypropylene, 6.25 g of polyethylene, 6.25 g of polystyrene and polyvinyl chloride 6 0.25 g and A heavy oil 75 g were charged. Then, under a nitrogen atmosphere, the mixture was heated at 350 ° C. for about 10 minutes without stirring to perform dechlorination treatment to obtain 97 g of a dechlorinated product and 3 g of gas. At this time, the pressure is 10k when the temperature reaches 350 ° C.
The pressure was g / cm ² G, and thereafter, the pressure became a maximum of 24 kg / cm ² G due to generation of decomposition gas and the like. Next, 97 g of the obtained dechlorinated product was charged into a 500 cc autoclave made of stainless steel, and the temperature was about 15 at 450 ° C. under a nitrogen atmosphere.
Heat treatment was performed for 150 minutes with stirring at 150 rpm to obtain 82 g of decomposed oil, 12 g of decomposed gas, and 3 g of solid matter. The maximum pressure during the heat treatment was 40 kg / cm ² G. The chlorine content in the obtained cracked oil was 50 ppm by weight, and the chlorine content in the solid was 0.47% by weight.

Distillation curves and viscosity-temperature curves of cracked oil (indicated by ◯ in the figure) and heavy oil A used as a raw material (indicated by ● in the figure) are shown in FIGS. 1 and 2, respectively. From these figures, it was found that the obtained cracked oil was lighter than the heavy oil A used as the raw material.

[0020]

Example 2 A 500 cc stainless autoclave was charged with 34 g of shredder dust having a composition shown in Table 1 below and 66 g of A heavy oil, which had been pulverized in advance so that 100 mesh or less was 80% by weight or more. The chlorine content of the shredder dust used was 3% by weight on a dry basis, the water content was 30% by weight, and the bulk specific gravity was about 0.14 g /
It was cc. Then, the mixture is placed under a nitrogen atmosphere for 4 hours.
After heat treatment at 50 ° C. for about 20 minutes while stirring at 150 rpm, the mixture was cooled and then centrifuged to obtain 62 g of cracked oil and 18 g of a solid matter. The decomposition gas generated by the heat treatment was 20 g. The maximum pressure during the heat treatment was 35 kg / cm ² G. The chlorine content in the obtained cracked oil was 60 ppm by weight, and the chlorine content in the solid was 3.54% by weight.

FIG. 3 shows the viscosity-temperature curves of cracked oil (indicated by a circle in the figure) and heavy oil A used as a raw material (indicated by a ● in the figure). From FIG. 3, it was found that the obtained cracked oil was lighter than the heavy oil A used as a raw material.

[0022]

[Table 1] Table 1 Shredder dust ────────────────────────────── Composition content ──────── ─────────────────────── Polyurethane 47% by weight (dry base) Hard plastics 17 〃 Rubber 10 〃 Metals (wiring etc.) 3 〃 Glass 7 〃 Other inorganic substances 16 〃 ───────────────────────────────

[0023]

INDUSTRIAL APPLICABILITY The present invention provides a novel method for lightening heavy oil, which does not require expensive hydrogen and a catalyst and is not only economical and safe but also reuses waste plastics.

[Brief description of drawings]

FIG. 1 is a distillation curve of cracked oil obtained in Example 1 and heavy oil A used as a raw material.

FIG. 2 is a viscosity-temperature curve of cracked oil obtained in Example 1 and heavy oil A used as a raw material.

FIG. 3 is a viscosity-temperature curve of cracked oil obtained in Example 2 and heavy oil A used as a raw material.

[Explanation of symbols]

 ●: Indicates heavy oil A. ◯: Degraded oil is shown.

Claims (6)

[Claims] 1. Mixing one or more heavy oils selected from petroleum heavy oils and coal heavy oils with waste plastics,
A method for lightening heavy oil, which comprises heat-treating at a temperature of 350 to 460 ° C. in a non-oxidizing atmosphere. 2. The method according to claim 1, wherein the heat treatment temperature is 380 to 450 ° C. 3. The method according to claim 1, wherein the heat treatment is carried out under a pressure of atmospheric pressure to 50 atmospheric pressure. 4. The method according to claim 1, wherein the heat treatment is carried out for 10 to 40 minutes. 5. The method according to claim 1, wherein the non-oxidizing atmosphere is an atmosphere of at least one gas selected from the group consisting of nitrogen, argon, helium and hydrocarbon gas. 6. The mixing ratio of one or more heavy oils selected from petroleum heavy oils and coal heavy oils to waste plastics is such that 1 part by weight of the heavy oil is 0 waste plastics. .1
~ 1.0 parts by weight. The method according to any one of claims 1 to 5.