Method for extracting and dechlorinating waste plastic oil and / or waste tire oil

Abstract

The invention relates to a method for extracting and dechlorinating waste plastic oil and / or waste tire oil, the waste plastic oil and / or the waste tire oil are / is contacted with an extraction agent in an extraction tower for extraction reaction, the extraction agent is a reaction reagent and an optional extraction reagent, a low-chlorine material extracted from the tower top of the extraction tower is subjected to alkali washing to obtain a low-chlorine product, and the low-chlorine product is subjected to dechlorination. The chlorine content of the low-chlorine product is not greater than 50mu g / g, and after the high-chlorine material extracted from the bottom of the extraction tower is regenerated, part of the high-chlorine material is used as a circulating extraction agent to return to the extraction tower. According to the invention, waste plastic oil and waste tire oil converted by various processes can be treated, chlorine impurities in the waste plastic oil and the waste tire oil can be effectively removed, and high-quality raw materials are provided for subsequent deep processing processes.

Description

Technical Field

[0001] The present invention relates to the technical field of dechlorination of hydrocarbon oil raw materials, and particularly relates to a method for extracting and dechlorinating waste plastic oil and / or waste tire oil. Background Art

[0002] With the continuous development of the urbanization process in China, the urban population has been increasing year by year, the living standards of the people have been continuously improved, and the output of urban domestic waste has also been increasing. At present, the main methods for treating urban waste include landfill, incineration, etc. Whether it is incineration or landfill, there are a series of subsequent environmental protection problems.

[0003] Chemical conversion methods can convert plastic waste into industrial raw materials or fuel oil with utilization value, which can not only eliminate environmental pollution, but also realize the sustainable development and utilization of resources, and is an effective way to control "white pollution". At present, the waste plastic refining industry has spread all over the country, and some enterprises have built small-scale pyrolysis demonstration devices, but the problem of high-value utilization of waste plastic pyrolysis products remains to be effectively solved.

[0004] The waste plastic oil and waste tire oil converted by various processes are quite different from traditional petroleum-based oil products, with high impurity content, especially the chlorine content, which is much higher than that in crude oil. Processing raw materials with high chlorine content using hydrogenation, catalytic and other devices in refineries will seriously corrode the devices, bringing great troubles and safety hazards to subsequent processing.

[0005] Oil dechlorination technology includes two categories. One is to remove inorganic chlorine by using a solid adsorbent to adsorb hydrogen chloride in the oil, and the other is to remove organic chlorine. Usually, the method of removing organic chlorine can be to convert organic chlorine into inorganic chlorine by hydrogenation and then remove it with an adsorbent. However, when the chlorine content in the raw material is too high, it will bring great safety hazards to high-temperature and high-pressure hydrogenation devices. Therefore, the removal of organic chlorine is the difficulty of oil dechlorination.

[0006] CN102127464A discloses a method for removing organic chlorine from hydrocarbon oil. A demulsifier, an alkaline compound, a phase transfer agent, water injection and hydrocarbon oil are mixed, and under the action of heat and / or electric field, oil-water separation is carried out, and organic chlorides are converted into inorganic chlorides and removed with the water phase to achieve the purpose of dechlorination. The method of the present invention is applicable to conventional crude oil, heavy crude oil and distillate oil containing organic chlorine.

[0007] CN105885935A discloses a method for removing organic chlorides from wastewater, which includes making the wastewater enter tangentially in a circulating manner to form a swirl and then rise; changing it into an upflow to fully fluidize the solid reducing agent or the solid reducing agent particles loaded with a catalyst in the reactor, so that the wastewater and the solid reducing agent or the solid reducing agent particles loaded with a catalyst are in full contact for reaction; after the upflow passes through the main reaction zone, gradually reducing the upward flow velocity of the upflow; the upflow enters the precipitation separation zone, the fluid is approximately laminar flow, and the reacted solid reducing agent or the solid reducing agent particles loaded with a catalyst effectively settle to remove the organic chlorides in the wastewater. The present invention also provides a device for removing organic chlorides from wastewater. This device is suitable for the mixing reaction of high-density metal particles and wastewater, without scaling, blocking, can operate continuously, the dosage of the reducing agent is adjustable, and the operation and management are simple.

[0008] CN104726134A discloses a method for producing high-quality gasoline and diesel from chlorinated plastic oil. This method involves injecting chlorinated plastic oil into a high-temperature dechlorination tower equipped with activated alumina for high-temperature dechlorination. A small amount of NaOH aqueous solution is sprayed at the top of the high-temperature dechlorination tower. The dechlorinated plastic oil enters a catalytic distillation tower equipped with a molecular sieve / alumina catalyst for reaction and rectification; after catalytic distillation, the plastic oil enters a hydrofining tower under pressure. The fractionated oil after hydrofining is subjected to atmospheric distillation and cut into gasoline and diesel according to the distillation temperature. The heavy oil at the bottom of the tower is mixed with the raw material chlorinated plastic oil for re-reaction. The dechlorination catalyst and sulfide catalyst used in the present invention are prepared by selecting a suitable method according to the composition and properties of the plastic oil.

[0009] CN104560414A discloses a hydrotreating method for chlorinated catering waste oil. The catering waste oil enters the hydrogenation reactor from the upper part of the hydrogenation reactor, and hydrogen enters the hydrogenation reactor from the lower part of the hydrogenation reactor. Under the hydrogenation reaction conditions, the catering waste oil and hydrogen flow countercurrently through the bed layer containing the hydrogenation catalyst in the hydrogenation reactor; between the bed layers of the hydrogenation reactor, the catering waste oil is divided into multiple strands and enters the hydrogenation reactor. The effluent from the top of the hydrogenation reactor directly enters the dechlorination reactor; it passes through the bed layer filled with a dechlorinating agent under the dechlorination reaction conditions; the effluent from the bottom of the hydrogenation reactor and the effluent from the dechlorination reactor enter a separation system for gas-liquid separation to obtain the hydrorefined oil of the catering waste oil. By using the method provided by the present invention, the problem of chloride ion corrosion in the separation system of the hydrogenation device during the hydrogenation process of catering waste oil can be effectively solved, and at the same time, the axial temperature difference of the catalyst bed layer can be reduced, and the overall utilization rate of the hydrogenation catalyst can be improved. Summary of the Invention

[0010] The present invention is to solve the technical problems of poor dechlorination effect and high dechlorination cost when processing raw materials of waste plastic oil and / or waste tire oil in the prior art.

[0011] The method for extracting and dechlorinating waste plastic oil and / or waste tire oil provided by the present invention includes: the waste plastic oil and / or waste tire oil, as hydrocarbon raw materials, enter the extraction tower from the lower part of the extraction tower, contact with the extractant fed from the upper part of the extraction tower, and carry out an extraction reaction under certain conditions. The extractant is a reaction reagent and an optional extraction reagent. The reaction reagent is an organic amine compound, and the extraction reagent is an alcohol organic solvent;

[0012] The low-chlorine material drawn from the top of the extraction tower is alkali-washed to obtain a low-chlorine product, and the chlorine content of the low-chlorine product is not more than 50 μg / g. The high-chlorine material drawn from the bottom of the extraction tower is regenerated, and part of it is returned to the upper part of the extraction tower as a circulating extractant.

[0013] In one embodiment of the present invention, the waste plastic oil is a hydrocarbon material obtained by one or several conversion methods such as thermal cracking, catalytic cracking, and dissolution liquefaction of waste plastics; the distillation range of the waste plastic oil is 30-600 °C, more than 50% of the fractions of the waste plastic oil are less than 350 °C, and the chlorine content is 100-100000 μg / g. In the composition of the waste plastic oil, the volume fraction of olefins is 5-80%, preferably 5-60%, the volume fraction of aromatics is less than 90%, preferably 2-60%, and the volume fraction of paraffins is less than 90%, preferably 5-60%.

[0014] In the present invention, the waste plastics are one or several of waste plastics in fresh domestic waste, waste plastics in industrial and agricultural production, and waste plastics in aged garbage, and the types of waste plastics are one or more selected from PE, PP, PS, and PVC.

[0015] In one embodiment of the present invention, the waste tire oil is a hydrocarbon material obtained by one or several conversion methods such as thermal cracking, catalytic cracking, and dissolution liquefaction of waste tires; the distillation range of the waste tire oil is 30-700 °C, more than 50% of the fractions of the waste tire oil are less than 350 °C, and the chlorine content is 100-100000 μg / g. In the composition of the waste tire oil, the volume fraction of olefins is 5-80%, preferably 5-60%, the volume fraction of aromatics is less than 90%, preferably 2-60%, and the volume fraction of paraffins is less than 90%, preferably 5-60%.

[0016] In the present invention, the waste tires are various waste tires made of natural rubber and / or synthetic rubber.

[0017] In the present invention, the thermal cracking reaction refers to the reaction in which hydrocarbon molecules, including waste plastics and waste tires, decompose into smaller molecules under high-temperature conditions and in an air-free environment. In the present invention, the catalytic cracking reaction refers to the reaction in which hydrocarbon molecules, including waste plastics and waste tires, decompose into smaller molecules under high-temperature conditions in the presence of a catalyst. In the present invention, the dissolution and liquefaction reaction refers to the reaction in which waste plastics and waste tires are converted from a solid state to a liquid state in the presence of solvent oil and / or organic solvents.

[0018] In the present invention, the hydrocarbon raw material entering the extraction column is the whole fraction of waste plastic oil and / or waste tire oil, or any fraction after cutting. In addition, the extraction dechlorination method of the present invention can be used in any combination with other dechlorination methods, and the other dechlorination methods are not limited to existing dechlorination technologies such as hydrodechlorination and adsorption dechlorination.

[0019] In one embodiment of the present invention, the waste plastic oil and / or waste tire oil are cut to obtain a light fraction and a heavy fraction, and the cutting point is 100°C to 300°C, preferably 150°C to 250°C, and the obtained light fraction enters the extraction column for reaction.

[0020] In one embodiment of the present invention, the heavy fraction obtained after cutting is subjected to hydrodechlorination treatment.

[0021] In one embodiment of the present invention, after the waste plastic oil and / or waste tire oil are subjected to extraction dechlorination, the obtained low-chlorine product is subjected to hydrorefining.

[0022] In one embodiment of the present invention, the extraction reagent is one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, glycerol, and diglycerol.

[0023] In one embodiment of the present invention, the reaction reagent is one or more selected from ethanolamine, diethanolamine, triethanolamine, ethylenediamine, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, diethylamine, aniline, and triethylamine, and preferably ethanolamine.

[0024] In the present invention, the extraction agent, which is the reaction reagent and optionally the extraction reagent, means that the extraction agent is only the reaction reagent, or the extraction agent is a mixture of the reaction reagent and the extraction reagent.

[0025] In one embodiment of the present invention, the extraction column is any one or a combination of a spray column, a packed column, a sieve plate column, and a rotary column.

[0026] In one embodiment of the present invention, the extraction reaction conditions are as follows: the top pressure of the tower is 0.01 to 5 MPa, the extraction reaction temperature is 100°C to 350°C, and the mass ratio of the extractant to the hydrocarbon raw material is 0.1 to 10:1. Preferably, the extraction reaction conditions are: the top pressure of the tower is 0.05 to 3 MPa, the extraction reaction temperature is 100°C to 300°C, and the mass ratio of the extractant to the hydrocarbon raw material is 0.3 to 5:1.

[0027] In one embodiment of the present invention, the caustic solution used for caustic washing is an aqueous solution selected from one or more of NaOH, KOH, NH3, and ethanolamine, and the mass concentration is 1 to 50%. The present invention uses the method of caustic washing to remove the generated HCl in the reaction.

[0028] In an alternative embodiment of the present invention, a water washing step is carried out after the caustic washing step to obtain a low-chlorine product after water washing.

[0029] In one embodiment of the present invention, the high-chlorine material at the bottom of the extraction tower is regenerated by a method of fractional distillation and optional adsorption dechlorination. The adsorption dechlorination uses an adsorbent to remove HCl to reduce the chlorine content in the circulating extractant.

[0030] In one embodiment of the present invention, the chlorine content in the circulating extractant is controlled, and the chlorine content in the circulating extractant is 0 to 15% by mass, preferably 0 to 5% by mass.

[0031] Features of the present invention:

[0032] (1) The present invention can process waste plastic oil and waste tire oil transformed by various processes, effectively remove their chlorine impurities, and provide high-quality raw materials for subsequent deep processing processes, such as the hydrogenation and catalytic processes for producing vehicle fuels and chemical raw materials.

[0033] (2) The extraction dechlorination method provided by the present invention, on the one hand, solves the problem of low dechlorination rate when using adsorption dechlorination to treat high-chlorine raw materials, and on the other hand, solves the problems of high cost and potential safety hazards caused by chlorine ion corrosion when directly using hydrogenation dechlorination for high-chlorine raw materials.

[0034] (3) The present invention can completely remove the organic chlorine in the high-chlorine raw materials through combination with the hydrogenation process, improving the product value. Brief Description of the Drawings

[0035] Figure 1 is a schematic diagram of one embodiment of the method for extracting and dechlorinating waste plastic oil and / or waste tire oil provided by the present invention.

[0036] Figure 2 is a schematic diagram of one embodiment of the method for extracting and dechlorinating waste plastic oil and / or waste tire oil provided by the present invention. Detailed Embodiments

[0037] The present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereby.

[0038] Figure 1 It is a schematic diagram of one of the embodiments of the method for extracting and dechlorinating waste plastic oil and / or waste tire oil provided by the present invention. As Figure 1 shown, the waste plastic oil obtained from the waste plastic pyrolysis device 1 enters the extraction tower 3 from the lower part of the extraction tower 3 through the pipeline 2, contacts the extractant fed from the upper part of the extraction tower 3, and undergoes an extraction reaction under certain conditions. The low-chlorine material drawn from the top of the extraction tower enters the caustic scrubbing tower 5 through the pipeline 4 for caustic scrubbing to remove the generated HCl. The low-chlorine product obtained after caustic scrubbing is drawn out through the pipeline 6. The chlorine content of the low-chlorine product is not more than 50 μg / g. The high-chlorine material at the bottom of the extraction tower 3 enters the regeneration unit 8 through the pipeline 7. After regeneration, part of the high-chlorine material is returned to the upper part of the extraction tower 3 as a circulating extractant through the pipeline 9.

[0039] Figure 2 It is a schematic diagram of one of the embodiments of the method for extracting and dechlorinating waste plastic oil and / or waste tire oil provided by the present invention. As Figure 2 shown, the waste plastic oil obtained from the waste plastic pyrolysis device 1 enters the fractionating tower 10 for cutting. The obtained light fraction enters the extraction tower 3 from the lower part of the extraction tower 3 through the pipeline 2, contacts the extractant fed from the upper part of the extraction tower 3, and undergoes an extraction reaction under certain conditions. The low-chlorine material drawn from the top of the extraction tower enters the caustic scrubbing tower 5 through the pipeline 4 for caustic scrubbing to remove the generated HCl. The low-chlorine product obtained after caustic scrubbing is drawn out through the pipeline 6. The high-chlorine material at the bottom of the extraction tower 3 enters the regeneration unit 8 through the pipeline 7. After regeneration, part of the high-chlorine material is returned to the upper part of the extraction tower 3 as a circulating extractant through the pipeline 9. The heavy fraction obtained by cutting in the fractionating tower 10 enters the hydrogenation unit 12 through the pipeline 11 for hydrodechlorination. The heavy fraction after hydrodechlorination is drawn out through the pipeline 13, mixed with the low-chlorine product drawn out through the pipeline 6, and low-chlorine hydrocarbon oil is obtained and drawn out through the pipeline 14.

[0040] The present invention will be further described below in conjunction with the embodiments, but the present invention is not limited thereby.

[0041] In the embodiment, the chlorine content in the liquid material is measured by the coulometric method. The specific method is the method of "Determination of Total Chlorine Content in Crude Oil by Coulometry" (RIPP 64-90) in "Analysis Methods in Petrochemical Industry" (RIPP Test Methods). The instrument used is a microcoulometric analyzer, and the sample is the liquid material.

[0042] The commercial brand number of the hydrogenation catalyst used in the embodiment is RSA-100, and all are produced by Sinopec Catalyst Changling Co., Ltd.

[0043] The HCl adsorbent used in the examples and comparative examples is the dechlorination agent RDY-100, which is produced by Jinan Ruidong Industry Co., Ltd.

[0044] The hydrocarbon raw materials used include:

[0045] Hydrocarbon raw material 1: waste plastic oil, chlorine content 3700 μg / g, distillation range 97-481 °C;

[0046] Hydrocarbon raw material 2: waste plastic oil, chlorine content 109.3 μg / g, distillation range 122-431 °C;

[0047] Hydrocarbon raw material 3: waste tire pyrolysis oil, chlorine content 127 μg / g, distillation range 27-546 °C.

[0048] The lye used in the caustic scrubber is: NaOH solution, mass concentration 15%.

[0049] Example 1

[0050] In this example, the hydrocarbon raw material 1 used is waste plastic oil. The hydrocarbon raw material 1 enters the extraction tower from the lower part of the extraction tower and contacts the extractant fed from the upper part of the extraction tower. Under certain conditions, an extraction reaction is carried out. The low-chlorine material drawn from the top of the extraction tower is the low-chlorine product after caustic scrubbing. The high-chlorine material drawn from the bottom of the extraction tower is fractionated in the regeneration unit, and part of it is returned to the upper part of the extraction tower as a circulating extractant. The extractant used, the process conditions of the extraction tower, and the chlorine content of the low-chlorine product are listed in Table 1. The solvent ratio in Table 1 is the mass ratio of the extractant to the hydrocarbon raw material, and the same applies hereinafter.

[0051] Example 2

[0052] In this example, the hydrocarbon raw material 2 used is waste plastic oil. The hydrocarbon raw material 2 enters the extraction tower from the lower part of the extraction tower and contacts the extractant fed from the upper part of the extraction tower. Under certain conditions, an extraction reaction is carried out. The low-chlorine material drawn from the top of the extraction tower is the low-chlorine product after caustic scrubbing. The high-chlorine material drawn from the bottom of the extraction tower is fractionated in the regeneration unit, and part of it is returned to the upper part of the extraction tower as a circulating extractant. The extractant used, the process conditions of the extraction tower, and the chlorine content of the low-chlorine product are listed in Table 1.

[0053] Table 1

[0054]

[0055]

[0056] Example 3

[0057] The hydrocarbon raw material 1 used in this embodiment is waste plastic oil. The hydrocarbon raw material 1 enters the extraction tower from the lower part of the extraction tower, contacts with the extractant fed from the upper part of the extraction tower, and undergoes an extraction reaction under certain conditions. The low-chlorine material drawn from the top of the extraction tower is the low-chlorine product after alkali washing. The high-chlorine material drawn from the bottom of the extraction tower is regenerated in the regeneration unit. After being regenerated in the solvent regeneration tower, the solvent at the top of the tower is adsorbed by HCl in the adsorption tower and then returned to the upper part of the extraction tower as a circulating extractant. The extractant used, the process conditions of the extraction tower, the process conditions of the solvent regeneration tower, the process conditions of the adsorption tower, and the chlorine content of the low-chlorine product are listed in Table 2.

[0058] Example 4

[0059] The hydrocarbon raw material 3 used in this embodiment is waste tire pyrolysis oil. The hydrocarbon raw material 3 enters the extraction tower from the lower part of the extraction tower, contacts with the extractant fed from the upper part of the extraction tower, and undergoes an extraction reaction under certain conditions. The low-chlorine material drawn from the top of the extraction tower is the low-chlorine product after alkali washing. The high-chlorine material drawn from the bottom of the extraction tower is regenerated in the regeneration unit. After being regenerated in the solvent regeneration tower, the solvent at the top of the tower is adsorbed by HCl in the adsorption tower and then returned to the upper part of the extraction tower as a circulating extractant. The extractant used, the process conditions of the extraction tower, the process conditions of the solvent regeneration tower, the process conditions of the adsorption tower, and the chlorine content of the low-chlorine product are listed in Table 2.

[0060] Table 2

[0061]

[0062]

[0063] Example 5

[0064] The hydrocarbon raw material 1 used in this embodiment is waste plastic oil. The hydrocarbon raw material 1 enters the extraction tower from the lower part of the extraction tower, contacts with the extractant fed from the upper part of the extraction tower, and undergoes an extraction reaction under certain conditions. The low-chlorine material drawn from the top of the extraction tower is the low-chlorine product after alkali washing and water washing. The low-chlorine product then enters the hydrogenation unit for hydrorefining to obtain the low-chlorine product after hydrogenation. The high-chlorine material drawn from the bottom of the extraction tower is fractionated in the regeneration unit, and part of it is returned to the upper part of the extraction tower as a circulating extractant.

[0065] The extractant used, the process conditions of the extraction tower, the process conditions of the hydrogenation unit, and the chlorine content of the low-chlorine product are listed in Table 3.

[0066] Example 6

[0067] The hydrocarbon raw material 1 used in this embodiment is waste plastic oil. The hydrocarbon raw material 1 enters the extraction tower from the lower part of the extraction tower and contacts the extractant fed from the upper part of the extraction tower, and an extraction reaction is carried out under certain conditions. The low-chlorine material drawn from the top of the extraction tower is washed with alkali and then with water to obtain a low-chlorine product. The low-chlorine product then enters the hydrogenation unit for hydrorefining to obtain a low-chlorine product after hydrogenation; the high-chlorine material drawn from the bottom of the extraction tower is fractionated in the regeneration unit, and part of it is returned to the upper part of the extraction tower as a circulating extractant.

[0068] The extractant used, the process conditions of the extraction tower, the process conditions of the hydrogenation unit, and the chlorine content of the low-chlorine product are listed in Table 3.

[0069] Table 3

[0070]

[0071]

[0072] Example 7

[0073] The hydrocarbon raw material 1 used in this embodiment is waste plastic oil. The hydrocarbon raw material 1 enters the fractionating tower for cutting, and the obtained light fraction enters the extraction tower from the lower part of the extraction tower and contacts the extractant fed from the upper part of the extraction tower, and an extraction reaction is carried out under certain conditions. The low-chlorine material drawn from the top of the extraction tower is washed with alkali to obtain a low-chlorine product. After regeneration, part of the high-chlorine material at the bottom of the extraction tower is returned to the upper part of the extraction tower as a circulating extractant. The heavy fraction obtained by cutting in the fractionating tower enters the hydrogenation unit for hydrodechlorination, and after hydrodechlorination, the heavy fraction is mixed with the low-chlorine product to obtain low-chlorine hydrocarbon oil.

[0074] The distillation range of the light fraction, the extractant used, the process conditions of the extraction tower, the process conditions of the hydrogenation unit, and the chlorine content of the low-chlorine hydrocarbon oil are listed in Table 4.

[0075] Example 8

[0076] The hydrocarbon raw material 1 used in this embodiment is waste plastic oil. The hydrocarbon raw material 1 enters the fractionating tower for cutting, and the obtained light fraction enters the extraction tower from the lower part of the extraction tower and contacts the extractant fed from the upper part of the extraction tower, and an extraction reaction is carried out under certain conditions. The low-chlorine material drawn from the top of the extraction tower is washed with alkali to obtain a low-chlorine product. After regeneration, part of the high-chlorine material at the bottom of the extraction tower is returned to the upper part of the extraction tower as a circulating extractant. The heavy fraction obtained by cutting in the fractionating tower enters the hydrogenation unit for hydrodechlorination, and after hydrodechlorination, the heavy fraction is mixed with the low-chlorine product to obtain low-chlorine hydrocarbon oil.

[0077] The distillation range of the light fraction, the extractant used, the process conditions of the extraction tower, the process conditions of the hydrogenation unit, and the chlorine content of the low-chlorine hydrocarbon oil are listed in Table 4.

[0078] Table 4

[0079] Item Example 9 Example 10 Hydrocarbon feedstock Hydrocarbon feedstock 1 Hydrocarbon feedstock 1 Cut point, °C 198 198 Chlorine content of light fraction, μg / g 13300 13300 Distillation range of light fraction, °C 30～198 30～198 Chlorine content of heavy fraction, μg / g 558 558 Extractant Extraction reagent - Ethylene glycol Reaction reagent Ethanolamine Ethylenediamine Concentration of reaction reagent, mass % 100 10 Process conditions of extraction column Temperature, °C 150 150 Pressure, MPa 0.1 3.0 Solvent ratio (mass ratio) 1:1 2:1 Chlorine content of recycled extractant, μg / g 100 100 Process conditions of hydrogenation unit Hydrogenation catalyst RSA-100 RSA-100 Reaction pressure, MPa 8.0 8.0 <![CDATA[Liquid hourly space velocity, h -1 > 3 3 Reaction temperature, °C 400 400 <![CDATA[Hydrogen-oil ratio, Nm 3 / m 3 > 500 500 Chlorine content of low-chlorine hydrocarbon oil, μg / g 32 35

Claims

1. A method for extracting and dechlorinating waste plastic oil and / or waste tire oil, characterized in that Waste plastic oil and / or waste tire oil, as hydrocarbon raw materials, enter the extraction column from the lower part of the extraction column and contact with the extractant fed from the upper part of the extraction column to carry out an extraction reaction under certain conditions. The extractant is a reaction reagent and an optional extraction reagent. The reaction reagent is an organic amine compound, and the extraction reagent is an alcohol organic solvent; The low-chlorine material withdrawn from the top of the extraction column is washed with alkali to obtain a low-chlorine product. The chlorine content of the low-chlorine product is not more than 50 μg / g. After the high-chlorine material withdrawn from the bottom of the extraction column is regenerated, part of it is returned to the upper part of the extraction column as a circulating extractant.

2. The method according to claim 1, wherein The waste plastic oil is a hydrocarbon material obtained by one or more conversion methods such as thermal cracking, catalytic cracking, and dissolution liquefaction of waste plastics; the distillation range of the waste plastic oil is 30 - 600 °C, more than 50% of the fractions in the waste plastic oil are less than 350 °C, and the chlorine content is 100 - 100000 μg / g; The waste tire oil is a hydrocarbon material obtained by one or more conversion methods such as thermal cracking, catalytic cracking, and dissolution liquefaction of waste tires; the distillation range of the waste tire oil is 30 - 700 °C, more than 50% of the fractions in the waste tire oil are less than 350 °C, and the chlorine content is 100 - 100000 μg / g.

3. The method according to claim 1, wherein The extraction reagent is one or more selected from ethylene glycol, diethylene glycol, triethylene glycol, glycerol, and diglycerol.

4. The method according to claim 1, wherein The reaction reagent is one or more selected from ethanolamine, diethanolamine, triethanolamine, ethylenediamine, methylamine, ethylamine, propylamine, dimethylamine, trimethylamine, diethylamine, aniline, and triethylamine, preferably ethanolamine.

5. The method according to claim 1, wherein The extraction column is any one or a combination of a spray column, a packed column, a sieve plate column, and a rotating column.

6. The method according to claim 1, wherein Extraction reaction conditions: the top pressure is 0.01 - 5 MPa, the extraction reaction temperature is 100 °C - 350 °C, and the mass ratio of the extractant to the hydrocarbon raw material is 0.1 - 10:1; Preferred extraction reaction conditions: the top pressure is 0.05 - 3 MPa, the extraction reaction temperature is 100 °C - 300 °C, and the mass ratio of the extractant to the hydrocarbon raw material is 0.3 - 5:

1.

7. The method according to claim 1, wherein The alkali solution used for the alkali washing is an aqueous solution of one or more selected from NaOH, KOH, NH3, and ethanolamine, and the mass concentration is 1 - 50%.

8. The method according to claim 1, characterized in that, The high-chlorine material at the bottom of the extraction column is regenerated by a method of fractional distillation and optional adsorption dechlorination; The chlorine content in the circulating extractant is 0 - 15% by mass.

9. The method according to claim 1, characterized in that, The waste plastic oil and / or waste tire oil are cut to obtain a light fraction and a heavy fraction. The cutting point is 100 °C - 300 °C, preferably 150 °C - 250 °C, and the obtained light fraction enters the extraction column for reaction.

10. The method according to claim 9, characterized in that The obtained heavy fraction is subjected to hydrodechlorination treatment.

11. The method according to claim 1, wherein After the waste plastic oil and / or waste tire oil are subjected to extraction dechlorination, the obtained low-chlorine product is subjected to hydrorefining.

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