A method for dechlorinating waste plastic oil and / or waste tire oil

Abstract

The present invention relates to a method for dechlorinating waste plastic oil and / or waste tire oil, comprising: waste plastic oil and / or waste tire oil enters a hydrogenation reactor and contacts with a hydrogenation catalyst for reaction, the obtained reaction effluent enters a high-pressure gas stripping tower, the gas phase material at the top of the high-pressure gas stripping tower enters a dechlorination reactor for adsorption dechlorination, the obtained dechlorinated material enters a cold high-pressure separator for gas-liquid separation, the liquid phase material separated by the cold high-pressure separator is used as a refined plastic oil light fraction out of a device, the liquid phase material obtained at the bottom of the high-pressure gas stripping tower is used as a refined plastic oil heavy fraction out of a device, and the chlorine content of the refined plastic oil light fraction and the refined plastic oil heavy fraction is less than 0.5μg / g. The present invention can greatly improve the penetration chlorine capacity of the dechlorinating agent, reduce the processing cost of high-chlorine raw materials, and effectively solve the problem of hydrogen chloride corrosion to the device.

Description

Technical Field

[0001] The invention relates to the technical field of hydrocarbon raw material processing, and in particular to a method for dechlorinating waste plastic oil and / or waste tire oil. Background Art

[0002] With the continuous development of urbanization in my country, the urban population has increased year by year, the people's living standards have continued to improve, and the output of urban domestic waste has also continued to increase. At present, the main methods of urban waste treatment include landfill and incineration. Both incineration and landfill have a series of subsequent environmental protection problems.

[0003] Chemical conversion methods can transform plastic waste into valuable industrial raw materials or fuel oil, which can not only eliminate environmental pollution, but also achieve sustainable development and utilization of resources, and is an effective way to control "white pollution". At present, the waste plastic refining industry has blossomed in China, and some companies have built small-scale pyrolysis demonstration devices, but the high-value utilization of waste plastic pyrolysis products has yet to be effectively solved.

[0004] Waste plastic oil, waste tire oil and traditional petroleum-based oil converted through various processes are quite different. They contain high impurities, especially chlorine, which can cause corrosion to subsequent processing equipment, causing great troubles and safety hazards to subsequent processing.

[0005] One part of the existing technology for dechlorination of oil products is in the field of reforming pre-hydrogenation technology. The reaction raw material is naphtha, which has a low boiling point and is usually in a gas phase under reaction conditions. Hydrogenation converts the organic chlorine contained in the raw material into hydrogen chloride. A dechlorination reactor is set after the reactor to adsorb hydrogen chloride, thereby achieving the purpose of dechlorination.

[0006] CN103980938A discloses a method for producing clean fuel from chlorine-containing plastic oil, wherein the chlorine-containing plastic oil is injected into a catalytic distillation tower equipped with a molecular sieve / alumina catalyst for reaction and rectification; after catalytic cracking, the chlorine-containing plastic oil enters a low-pressure liquid phase hydrogenation tower through heat exchange for hydrogenation and dechlorination, and the catalyst used is a loaded metal catalyst; the distillate oil after liquid phase hydrogenation enters a water washing tower, the lower water phase at the bottom of the tower is circulated, and the upper distillate oil phase after water washing enters a hydrorefining tower through pressurization, and the catalyst used for hydrorefining is a sulfide catalyst, and the monoolefin compounds are removed by monoolefin hydrogenation saturation reaction, and desulfurization, nitrogen removal, and colloid removal are used to produce a gasoline and diesel mixed oil with no odor and high quality, and then gasoline and diesel distillate oil are obtained by distillation, and the heavy oil at the bottom of the tower is mixed with the raw material chlorine-containing plastic oil for re-reaction. The method removes organic chlorine by hydrogenation-water washing.

[0007] CN104726134A discloses a method for producing high-quality gasoline and diesel from chlorine-containing plastic oil, the method is to inject chlorine-containing plastic oil into a high-temperature dechlorination tower equipped with active aluminum oxide for high-temperature dechlorination, spray a small amount of NaOH aqueous solution on the top of the high-temperature dechlorination tower, and 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 hydrorefining tower under pressure, and the distillate oil after hydrorefining is distilled at normal pressure, cut into gasoline and diesel according to the distillation temperature, and the heavy oil at the bottom of the tower is mixed with the raw material chlorine-containing 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 performance of the plastic oil.

[0008] CN106318462A discloses a reaction system for hydrodechlorination of chlorine-containing diesel, and provides a method for hydrodechlorination of chlorine-containing diesel using the system, wherein chlorine-containing diesel and hydrogen are sequentially introduced into a hydrogenation reactor and a dechlorination tank connected in series, and are contacted and reacted with a hydrorefining catalyst bed of the hydrogenation reactor, and a hydrodemetallizing agent bed and a dechlorinating agent bed of the dechlorination tank; according to the flow direction of chlorine-containing diesel and hydrogen, the hydrogenation reactor is loaded with a hydrorefining catalyst; and the dechlorination tank is sequentially loaded with a hydrodemetallizing agent, a dechlorinating agent I and a dechlorinating agent II. In the method, ammonium chloride is generated in the chlorine-containing diesel in the hydrogenation reactor, and the iron-containing impurities and ammonium chloride from the hydrogenation reactor are removed by grading and loading the hydrodemetallizing agent and the dechlorinating agent in the dechlorination tank. Compared with the prior art, the advantages of the present invention are: first, the iron-containing impurities are uniformly deposited in the hydrodemetallizing agent, and the long-term operation of the dechlorinating agent is maintained. Secondly, the graded loading of the two dechlorinating agents improves the utilization rate of the dechlorinating agents, prolongs the life of the dechlorinating agents, and reduces the cost of the dechlorinating agents.

[0009] CN104560414A discloses a method for hydrogenating chlorinated restaurant waste oil. Restaurant 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, restaurant waste oil and hydrogen countercurrently pass through a bed containing a hydrogenation catalyst in the hydrogenation reactor; between the beds of the hydrogenation reactor, restaurant waste oil is divided into multiple strands and enters the hydrogenation reactor, and the effluent from the top of the hydrogenation reactor directly enters the dechlorination reactor; under the reaction conditions of dechlorination, the bed containing a dechlorinating agent is passed; the effluent from the bottom of the hydrogenation reactor and the effluent from the dechlorination reactor enter the separation system for gas-liquid separation to obtain restaurant waste oil hydrogenated refined oil. The method provided by the present invention can effectively solve the problem of chloride ion corrosiveness of the separation system of the hydrogenation device during the hydrogenation of restaurant waste oil, while reducing the axial temperature difference of the catalyst bed and improving the overall utilization rate of the hydrogenation catalyst.

[0010] The existing technology mainly focuses on how to remove chlorine from high-chlorine raw materials. The methods used are alkali solution, molecular sieve or water washing to remove inorganic chlorine, and hydrogenation and adsorption dechlorination to remove organic chlorine. The developed dechlorinating agent is mainly for dechlorination under gas phase conditions, and the chlorine capacity is large. However, for gas-liquid mixed phase or pure liquid phase materials, the penetration chlorine capacity of the dechlorinating agent is greatly reduced due to diffusion and other reasons, resulting in a significant increase in the consumption of dechlorinating agents and a significant increase in dechlorination costs. Summary of the invention

[0011] The invention aims to solve the problems of high dechlorination processing cost and easy corrosion of the device by hydrogen chloride when processing waste plastic oil and / or waste tire oil raw materials in the prior art.

[0012] The first aspect of the present invention provides a method for dechlorinating waste plastic oil and / or waste tire oil, comprising: in the presence of hydrogen, the waste plastic oil and / or waste tire oil enters a hydrogenation reactor to contact with a hydrogenation catalyst, and reacts under hydrogenation reaction conditions, wherein the hydrogenation catalyst loaded in the hydrogenation reactor is a waste hydrogenation catalyst and / or a fresh hydrogenation catalyst, the obtained reaction effluent enters a high-pressure gas stripping tower, the gaseous material at the top of the high-pressure gas stripping tower enters a dechlorination reactor to contact with a dechlorinating agent for adsorption dechlorination, the obtained dechlorinated material enters a cold high-pressure separator for gas-liquid separation, the liquid phase material separated by the cold high-pressure separator is used as a refined plastic oil light fraction out of a device, and the liquid phase material obtained at the bottom of the high-pressure gas stripping tower is used as a refined plastic oil heavy fraction out of a device, and the chlorine content of the refined plastic oil light fraction and the refined plastic oil heavy fraction is less than 0.5 μg / g.

[0013] In one embodiment of the present invention, the waste plastic oil is a hydrocarbon material obtained by converting waste plastics through one or more conversion methods of thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution liquefaction; the distillation range of the waste plastic oil is 30-700°C, and the chlorine content is less than 10000 μg / g. The composition of the waste plastic oil includes a volume fraction of olefins of 5-80%, preferably 5-60%, a volume fraction of aromatics of less than 90%, preferably 2-60%, and a volume fraction of paraffins of less than 90%, preferably 5-60%.

[0014] In the present invention, the waste plastic is one or more of waste plastic in fresh domestic waste, waste plastic in industrial and agricultural production, and waste plastic in aged waste, and the type of waste plastic is 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 converting waste tires through one or more conversion methods of thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution liquefaction; the distillation range of the waste tire oil is 30-700°C, and the chlorine content is less than 10000μg / g. The composition of the waste tire oil includes a volume fraction of olefins of 5-80%, preferably 5-60%, a volume fraction of aromatics of less than 90%, preferably 2-60%, and a volume fraction of paraffins of 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 and thermal pyrolysis reaction refer to the reaction in which hydrocarbon molecules, including waste plastics and waste tires, are decomposed into smaller molecules under high temperature conditions in an airtight condition. According to the reaction temperature, the reaction temperature less than or equal to 600°C is called thermal cracking reaction, and the reaction temperature greater than 600°C is called thermal pyrolysis reaction.

[0018] In the present invention, the catalytic cracking and catalytic cracking reaction refer to the reaction in which hydrocarbon molecules including waste plastics and waste tires are decomposed into smaller molecules under high temperature conditions and in the presence of a catalyst. According to the different reaction products, the reaction with low-carbon olefins (ethylene, propylene, butene) as the target product is called catalytic cracking reaction, and the reaction with motor gasoline as the target product is called catalytic cracking reaction.

[0019] In the present invention, the dissolution-liquefaction reaction refers to the reaction in which waste plastics and waste tires are converted from solid to liquid in the presence of solvent oil and / or organic solvent.

[0020] In one embodiment of the present invention, the hydrogenation reactor is loaded with waste hydrogenation catalyst and / or fresh hydrogenation catalyst, and waste plastic oil and / or waste tire oil are subjected to hydrogenation reaction through the hydrogenation reactor to convert organic chloride into hydrogen chloride gas.

[0021] In one embodiment of the present invention, the hydrogenation reaction conditions are: hydrogen partial pressure 0.5-20.0 MPa, reaction temperature 60-500°C, liquid hourly volume space velocity 0.1-30 h -1 , Hydrogen oil volume ratio 5~1000Nm 3 / m 3 Preferably, the hydrogenation reaction conditions are: hydrogen partial pressure 1-12 MPa, reaction temperature 100-450°C, liquid hourly volume space velocity 0.2-20 h -1 , Hydrogen oil volume ratio 5~800Nm 3 / m 3 .

[0022] In one embodiment of the present invention, the waste hydrogenation catalyst is one or more selected from the protective agent and the catalyst at the end of use of any fixed-bed hydrogenation process unit in the field of hydrocarbon oil processing, as well as the protective agent and the catalyst after regeneration; the fresh hydrogenation catalyst is the protective agent and / or catalyst selected from any fixed-bed hydrogenation process unit in the field of hydrocarbon oil processing, and is a hydrogenation catalyst other than the waste hydrogenation catalyst.

[0023] In one embodiment of the present invention, the equivalent diameter of the spent hydrogenation catalyst and / or the fresh hydrogenation catalyst is 0.5 to 16 mm, preferably 1 to 10 mm. The present invention has no restrictions on the shape of the spent hydrogenation catalyst and / or the fresh hydrogenation catalyst, for example, the shape includes spherical, and various anisotropic shapes such as strip clover, butterfly, Raschig ring, honeycomb, etc.

[0024] In one embodiment of the present invention, the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, a hydrogenation active metal oxide content of 0 to 50 weight%, a carbon content of 0 to 50 weight%, and a sulfur content of 0 to 40 weight%, wherein the hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals; preferably, based on the total weight of the waste hydrogenation catalyst, the carbon content is 0 to 30 weight%, and the sulfur content is 0 to 30 weight%.

[0025] In one embodiment of the present invention, the spent hydrogenation catalyst comprises, based on the total weight of the spent hydrogenation catalyst, a hydrogenation active metal oxide content of 1 to 40 weight % and a carbon content of less than or equal to 20 weight %.

[0026] In one embodiment of the present invention, the fresh hydrogenation catalyst comprises, based on the total weight of the fresh hydrogenation catalyst, a hydrogenation active metal oxide content of 1 to 50 weight%, a carbon content of 0 to 20 weight%, a sulfur content of 0 to 20 weight%, and the hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals; preferably, the content of the hydrogenation active metal oxide is 2 to 40 weight%.

[0027] In one embodiment of the present invention, the operating conditions of the high-pressure stripping tower are: pressure 0.5-20.0 MPa, tower top temperature 100-300°C, tower bottom temperature 200-500°C. Preferably, the operating conditions of the high-pressure stripping tower are: pressure 1.0-12.0 MPa, tower top temperature 150-250°C, tower bottom temperature 250-350°C.

[0028] Preferably, stripping gas is introduced into the bottom of the high-pressure stripping tower, wherein the stripping gas is selected from one or more of hydrogen, nitrogen and water vapor, and the mass fraction of the stripping gas feed to the total amount of the high-pressure stripping tower feed is 0.1% to 15%.

[0029] The inventor of the present invention has found through in-depth research that in the process of dechlorination by adsorption of dechlorination agent, when hydrogen chloride gas is in the gas phase, the adsorption efficiency is high, and the chlorine capacity can reach 35%. When the material is gas and liquid, the liquid covers the adsorbent, resulting in a decrease in the efficiency of the dechlorination agent, and the chlorine capacity is about 10-15%. In addition, if the mixed material is cooled and separated, and then dechlorinated, hydrogen chloride and condensed water vapor will cause serious dew point corrosion during the cooling process of the material. In order to solve the above problems, the present invention adopts a technical solution combining high-pressure gas stripping and high-temperature fractionation to separate the gas and liquid phases of the material at a higher temperature. Due to the gas stripping process, the hydrogen chloride contained in the liquid phase is fully separated and transferred to the gas phase. Then the gas phase material is introduced into the dechlorination reactor and contacted with the dechlorination agent, and adsorption dechlorination is carried out under gas phase conditions, so that hydrogen chloride is removed in the gas phase, with high efficiency, and the chlorine capacity of the dechlorination agent is greatly improved. The present invention can effectively reduce the amount of dechlorination agent used, reduce processing costs, and also avoid the risk of dew point corrosion.

[0030] In one embodiment of the present invention, the dechlorinating agent comprises at least one Group IA metal compound and / or at least one Group IIA metal compound, optionally one or more metal oxides selected from Cu, Fe, Zn, and a carrier and / or a binder;

[0031] The carrier and / or binder is selected from one or more of silicon oxide, aluminum oxide, silicon oxide-aluminum oxide, zirconium oxide and clay. The clay is selected from one or more of kaolin, illite, montmorillonite and bentonite; the kaolin includes halloysite.

[0032] In the present invention, "optional" means selectable, and the optional one or several metal oxides selected from Cu, Fe, and Zn means that the one or several metal oxides selected from Cu, Fe, and Zn are optional components of the dechlorinating agent.

[0033] In the present invention, in a preferred case, the dechlorinating agent is a high temperature dechlorinating agent and / or a medium temperature dechlorinating agent. The present invention has no limitation on the high temperature dechlorinating agent and the medium temperature dechlorinating agent, and conventional high temperature dechlorinating agents and medium temperature dechlorinating agents can realize the present invention. It is further preferred that the high temperature dechlorinating agent and / or the medium temperature dechlorinating agent have a larger chlorine capacity.

[0034] In one embodiment of the present invention, the operating conditions of the dechlorination reactor are: pressure 3-15.0 MPa, reaction temperature 150-350°C, liquid hourly volume space velocity: 0.1-10 h -1 The liquid hourly volume space velocity can be obtained by dividing the volume of the feed amount of the dechlorination reactor at normal temperature and pressure by the volume of the dechlorination agent.

[0035] In one embodiment of the present invention, the dechlorinated material obtained from the dechlorination reactor is cooled and then enters a cold high-pressure separator for gas-liquid separation. The gas phase logistics obtained from the cold high-pressure separator is circulated to the inlet of the hydrogenation reactor as circulating hydrogen, and the other path is used as gas stripping gas to enter the bottom of the high-pressure gas stripping tower. The liquid phase material obtained by the cold high-pressure separator is separated as a light fraction of refined plastic oil and discharged from the device, and the liquid phase material obtained at the bottom of the high-pressure gas stripping tower is separated as a heavy fraction of refined plastic oil and discharged from the device, and the chlorine content of the light fraction of refined plastic oil and the heavy fraction of refined plastic oil are both less than 0.5μg / g.

[0036] In one embodiment of the present invention, the liquid phase material separated by the cold high-pressure separator enters the cold low-pressure separator for further gas-liquid separation, and the liquid phase material obtained by the cold low-pressure separator is used as a light fraction of refined plastic oil and discharged from the device.

[0037] Features of the present invention:

[0038] 1. The present invention can process waste plastic oil and waste tire oil converted from various processes and effectively remove chlorine impurities. It can provide high-quality raw materials for subsequent deep processing processes (such as the production of automotive fuel, hydrogenation of chemical raw materials, and catalytic processes) and extend the operating cycle of the overall processing process.

[0039] 2. In order to solve the problem that the penetration capacity of chlorine of the dechlorinating agent is greatly reduced under the condition of gas-liquid mixed phase, the present invention adopts a high-pressure gas stripping tower, and the hydrogen chloride generated by the reaction is enriched in the gas phase of the high-pressure gas stripping tower by a combination of gas stripping and fractionation, and then the gas phase material of the high-pressure gas stripping tower is introduced into the dechlorination reactor to contact the dechlorinating agent. In the dechlorination reactor of the present invention, adsorption dechlorination is carried out under gas phase conditions, which greatly improves the penetration capacity of chlorine of the dechlorinating agent, saves a large amount of dechlorinating agent, thereby reducing the processing cost of high-chlorine raw materials, and effectively solves the problem of corrosion of hydrogen chloride to the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 It is a schematic diagram of one embodiment of the method for dechlorinating waste plastic oil and / or waste tire oil provided by the present invention. DETAILED DESCRIPTION

[0041] The present invention will be further described below in conjunction with the accompanying drawings, but the present invention is not limited thereby.

[0042] Figure 1 Schematic diagram of one embodiment of the method for dechlorinating waste plastic oil and / or waste tire oil provided by the present invention, such as Figure 1As shown, the waste plastic oil and / or waste tire oil from pipeline 1 is pressurized by feed pump 2, enters heat exchanger 4 from pipeline 3 and exchanges heat with the reaction product, and then enters heating furnace 6 through pipeline system 5 together with new hydrogen from pipeline 27 and circulating hydrogen from pipeline 26 for heating. The heated mixed hydrogen material enters hydrogenation reactor 8 through pipeline 7 to contact with hydrogenation catalyst, and converts organic chlorine into hydrogen chloride under hydrogenation reaction conditions. The reaction effluent obtained from the hydrogenation reactor enters heat exchanger 4 through pipeline 9 to exchange heat with the reaction raw materials, and then enters high-pressure stripping tower 11 through pipeline 10 to separate the gas-liquid mixed material. The gaseous material at the top of the high-pressure gas stripping tower enters the dechlorination reactor 14 through pipeline 13 and contacts with the dechlorinating agent for adsorption dechlorination. The dechlorinated product enters the cold high-pressure separator 18 for gas-liquid separation after being cooled by water cooling 16 and air cooling 17 through pipeline 15. The separated gaseous material enters the circulating hydrogen compressor 25 for pressure increase through pipeline 24, a part of which is recycled through pipeline 26, and the other part enters the bottom of the high-pressure gas stripping tower through pipeline 28 for use as gas stripping gas. A part of the liquid material obtained by the cold high-pressure separator is circulated back to the upper part of the high-pressure gas stripping tower 11 through pipeline 20, and the other part enters the cold low-pressure separator 21 through pipeline 19 for further gas-liquid separation. The gaseous material obtained by the cold low-pressure separator is discharged through pipeline 23, and the liquid material obtained by the cold low-pressure separator is the light fraction of refined plastic oil and is discharged from the device through pipeline 21. The liquid material at the bottom of the high-pressure gas stripping tower is the heavy fraction of refined plastic oil and is discharged from the device through pipeline 22 as a product or subsequent processing raw material. The chlorine contents in the obtained light fraction of refined plastic oil and the heavy fraction of refined plastic oil are both less than 0.5 μg / g.

[0043] The present invention will be further described below in conjunction with embodiments, but the present invention is not limited thereto.

[0044] In the embodiment, the chlorine content in the liquid material is determined by the coulometric method, and the specific method is the method of "Coulometric Determination of Total Chlorine Content in Crude Oil" (RIPP 64-90) in "Petrochemical Analysis Method" (RIPP Test Method). The instrument used is a microcoulometric analyzer, and the sample is a liquid material.

[0045] The dechlorinating agent used in the examples and comparative examples is industrial dechlorinating agent RDY-100, produced by Jinan Ruidong Industrial Co., Ltd.

[0046] The waste hydrogenation catalyst used in the embodiment is the final stage catalyst A of distillate oil hydrogenation protective agent, the carrier is alumina, clover, equivalent diameter 3.6mm, and the composition includes: 12% by weight of molybdenum oxide, 3.0% by weight of cobalt oxide, 3% by weight of carbon content, and 4% by weight of sulfur content;

[0047] The fresh hydrogenation catalysts used in the examples are distillate hydrogenation catalysts RSA-100 and RS-2100, both produced by Sinopec Catalyst Changling Branch;

[0048] The raw materials used for hydrogenation pretreatment include:

[0049] Raw material 1: waste plastic oil, chlorine content 2980μg / g, distillation range 118~480℃;

[0050] Raw material 2: waste plastic oil, chlorine content 246μg / g, distillation range 102~365℃;

[0051] Raw material 3: waste tire pyrolysis oil, chlorine content 127μg / g, distillation range 27~546℃.

[0052] Embodiment 1 to Embodiment 4

[0053] In the presence of hydrogen, the waste plastic oil and / or waste tire oil raw materials enter the hydrogenation reactor and contact with the hydrogenation catalyst to react, converting the organic chloride into hydrogen chloride, and the reaction effluent enters the high-pressure gas stripping tower. The gaseous material at the top of the high-pressure gas stripping tower enters the dechlorination reactor and contacts with the dechlorinating agent for adsorption dechlorination. After adsorption dechlorination, the material is cooled and enters the cold high-pressure separator for gas-liquid separation. The gaseous material obtained by the cold high-pressure separator enters the circulating hydrogen compressor. The liquid material obtained by the cold high-pressure separator is used as a refined plastic oil light fraction product and exits the device. The liquid material at the bottom of the high-pressure gas stripping tower is used as a refined plastic oil heavy fraction product and exits the device.

[0054] Specific raw materials, catalyst loading conditions, hydrogenation reaction conditions and reaction results are listed in Table 1. As can be seen from Table 1, the chlorine content in the obtained refined plastic oil light fraction and the refined plastic oil heavy fraction is less than 0.5 μg / g.

[0055] Table 1

[0056]

[0057]

[0058] Example 5

[0059] Raw material 2 enters the hydrogenation reactor in the presence of hydrogen and contacts with the hydrogenation catalyst to react, converting the organic chloride into hydrogen chloride. The reaction effluent enters the high-pressure gas stripping tower. The gaseous material at the top of the high-pressure gas stripping tower enters the dechlorination reactor and contacts with the dechlorinating agent for adsorption dechlorination. After adsorption dechlorination, the material enters the cold high-pressure separator for gas-liquid separation after cooling. The gaseous material obtained by the cold high-pressure separator enters the circulating hydrogen compressor. The liquid material obtained by the cold high-pressure separator is used as a light fraction product of refined plastic oil and is discharged from the device. The liquid material at the bottom of the high-pressure gas stripping tower is used as a heavy fraction product of refined plastic oil and is discharged from the device.

[0060] The specific raw materials, catalyst loading conditions, hydrogenation reaction conditions and reaction results are listed in Table 2. As can be seen from Table 2, the chlorine content of the light fraction of refined plastic oil obtained at the initial stage of the reaction is less than 0.5 μg / g. When the reaction is carried out for 600 hours, the chlorine content of the light fraction of refined plastic oil is greater than 1 μg / g, indicating that the dechlorinating agent has penetrated at this time.

[0061] Comparative Example 1

[0062] In the presence of hydrogen, raw material 2 enters the hydrogenation reactor and contacts with the hydrogenation catalyst to react and convert the organic chloride into hydrogen chloride. The material at the outlet of the hydrogenation reactor does not enter the gas stripping tower, but directly enters the dechlorination reactor for contact dechlorination. After dechlorination, the material enters the cold high separation for gas-liquid separation to obtain a low-chlorine liquid phase product.

[0063] Specific raw materials, catalyst loading conditions, hydrogenation reaction conditions and reaction results are listed in Table 2. As can be seen from Table 2, the chlorine content of the low-chlorine liquid phase product obtained in the initial stage is less than 0.5 μg / g. When the operation reaches 200 hours, the chlorine content of the low-chlorine liquid phase product obtained is greater than 1 μg / g, indicating that the dechlorination agent has penetrated at this time.

[0064] From the comparison between Comparative Example 1 and Example 5, when the same amount of dechlorinating agent is loaded, the penetration time of the dechlorinating agent in Example 5 is extended by 3 times, indicating that the corresponding dechlorinating agent's penetration chlorine capacity is also increased by 3 times, and the dechlorination efficiency is greatly improved.

[0065] Table 2

[0066]

[0067]

Claims

1. A method for dechlorinating waste plastic oil and / or waste tire oil, comprising: in the presence of hydrogen, the waste plastic oil and / or waste tire oil enters a hydrogenation reactor to contact with a hydrogenation catalyst, and reacts under hydrogenation reaction conditions, wherein the hydrogenation catalyst loaded in the hydrogenation reactor is a waste hydrogenation catalyst and / or a fresh hydrogenation catalyst, the resulting reaction effluent enters a high-pressure gas stripping tower, the gaseous material at the top of the high-pressure gas stripping tower enters a dechlorination reactor to contact with a dechlorinating agent, and performs adsorption dechlorination under gas phase conditions, the resulting dechlorinated material enters a cold high-pressure separator for gas-liquid separation, the liquid phase material separated by the cold high-pressure separator is used as a refined plastic oil light fraction and discharged from a device, and the liquid phase material obtained at the bottom of the high-pressure gas stripping tower is used as a refined plastic oil heavy fraction and discharged from a device, and the chlorine content of the refined plastic oil light fraction and the refined plastic oil heavy fraction is less than 0.5 μg / g; The operating conditions of the high-pressure gas stripping tower are: pressure 0.5~20.0MPa, tower top temperature 100~300℃, tower bottom temperature 200~500℃; gas stripping gas is introduced into the bottom of the high-pressure gas stripping tower, and the gas stripping gas is selected from one or more of hydrogen, nitrogen, and water vapor, and the mass fraction of the gas stripping gas feed amount to the total amount of the high-pressure gas stripping tower feed is 0.1%~15%.

2. The method according to claim 1, characterized in that The waste plastic oil is a hydrocarbon material obtained by converting waste plastics through one or more conversion methods including thermal cracking, thermal pyrolysis, and dissolution liquefaction; the distillation range of the waste plastic oil is 30-700° C., and the chlorine content is less than 10,000 μg / g and greater than 0 μg / g.

3. The method according to claim 1, characterized in that The waste plastic oil is a hydrocarbon material obtained by converting waste plastics through one or more conversion methods such as catalytic cracking and catalytic cracking.

4. The method according to claim 2 or 3, characterized in that: The waste plastics are one or more of the waste plastics in fresh domestic waste, waste plastics in industrial and agricultural production, and waste plastics in aged waste.

5. The method according to claim 1, characterized in that The waste tire oil is a hydrocarbon material obtained by converting waste tires through one or more conversion methods including thermal cracking, thermal pyrolysis, and dissolution liquefaction; the distillation range of the waste tire oil is 30-700° C., and the chlorine content is less than 10000 μg / g and greater than 0 μg / g.

6. The method according to claim 1, characterized in that The waste tire oil is a hydrocarbon material obtained by converting waste tires through catalytic cracking or one or more conversion methods of catalytic cracking.

7. The method according to claim 1, characterized in that The waste hydrogenation catalyst is one or more selected from the protective agent and catalyst at the end of use of any fixed bed hydrogenation process unit in the hydrocarbon oil processing field, as well as the regenerated protective agent and regenerated catalyst.

8. The method according to claim 7, characterized in that The waste hydrogenation catalyst includes, based on the total weight of the waste hydrogenation catalyst, a hydrogenation active metal oxide content of 0 to 50 weight%, a carbon content of 0 to 50 weight%, a sulfur content of 0 to 40 weight%, and the hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals.

9. The method according to claim 8, characterized in that Based on the total weight of the waste hydrogenation catalyst, the carbon content is 0-30 weight %, and the sulfur content is 0-30 weight %.

10. The method according to claim 8, characterized in that Based on the total weight of the waste hydrogenation catalyst, the content of the hydrogenation active metal oxide is 1 to 40 weight %, and the carbon content is less than or equal to 20 weight %.

11. The method according to claim 1, characterized in that: The fresh hydrogenation catalyst includes, based on the total weight of the fresh hydrogenation catalyst, a hydrogenation active metal oxide content of 1 to 50 weight percent, a carbon content of 0 to 20 weight percent, and a sulfur content of 0 to 20 weight percent. The hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals.

12. The method according to claim 1, characterized in that The fresh hydrogenation catalyst includes, based on the total weight of the fresh hydrogenation catalyst, a hydrogenation active metal oxide content of 2 to 40 weight percent.

13. The method according to claim 1, characterized in that The hydrogenation reaction conditions are: hydrogen partial pressure 0.5~20.0MPa, reaction temperature 60~500℃, liquid hourly volume space velocity 0.1~30h -1 、Hydrogen oil volume ratio 5~1000Nm 3 / m 3 .

14. The method according to claim 1, characterized in that The hydrogenation reaction conditions are: hydrogen partial pressure 1-12 MPa, reaction temperature 100-450°C, liquid hourly volume space velocity 0.2-20 h -1 , Hydrogen oil volume ratio 5~800Nm 3 / m 3 .

15. The method according to claim 1, characterized in that The operating conditions of the high-pressure gas stripping tower are: pressure 1.0~12.0MPa, tower top temperature 150~250℃, tower bottom temperature 250~350℃.

16. The method according to claim 1, characterized in that The gas phase stream obtained from the cold high-pressure separator is circulated to the inlet of the hydrogenation reactor as circulating hydrogen on one side, and enters the bottom of the high-pressure gas stripping tower as stripping gas on the other side; The liquid phase material separated by the cold high-pressure separator enters the cold low-pressure separator for further gas-liquid separation, and the liquid phase material obtained by the cold low-pressure separator is used as a light fraction of refined plastic oil and discharged from the device.

17. The method according to claim 1, characterized in that The dechlorinating agent contains at least one Group IA metal compound and / or at least one Group IIA metal compound, optionally one or more metal oxides selected from Cu, Fe, Zn, and a carrier and / or a binder; The carrier and / or binder is selected from one or more of silicon oxide, aluminum oxide, silicon oxide-aluminum oxide, zirconium oxide and clay.

18. The method according to claim 1 or 17, characterized in that The dechlorinating agent is a high-temperature dechlorinating agent and / or a medium-temperature dechlorinating agent.

19. The method according to claim 1, characterized in that The operating conditions of the dechlorination reactor are: pressure 3~15.0MPa, reaction temperature 150~350℃, liquid hourly volume space velocity: 0.1~10h -1 .

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