CN114437776A - A method and system for preparing pyrolysis raw material from waste plastic oil and/or waste tire oil - Google Patents

Abstract

The present invention relates to a method and system for preparing pyrolysis raw materials from waste plastic oil and/or waste tire oil. In the decontamination reaction, the obtained reaction effluent enters the hydrotreating reactor, and is contacted with the hydrotreating catalyst for reaction. After the reaction effluent is separated, gas-phase material and liquid-phase material are obtained, and all or part of the obtained liquid-phase material is prepared by steam cracking. Raw material for ethylene cracking. The invention can effectively remove impurities in waste plastic oil and/or waste tire oil, provide high-quality cracking raw materials for the process of preparing ethylene by steam cracking, and has low cost and long operation period.

Description

A method and system for preparing pyrolysis raw material from waste plastic oil and/or waste tire oil

technical field

The present invention relates to the technical field of hydrocarbon raw material processing, in particular to a method and system for preparing pyrolysis raw materials from waste plastic oil and/or waste tire oil.

Background technique

With the continuous development of my country's urbanization process, the urban population is increasing year by year, the people's living standards are constantly improving, and the output of urban domestic waste is also increasing. At present, urban waste treatment methods mainly include landfill and incineration. Whether it is incineration or landfill, there are a series of subsequent environmental problems.

The chemical conversion method can convert plastic waste into valuable industrial raw materials or fuel oil, which can not only eliminate environmental pollution, but also realize the sustainable development and utilization of resources, which is an effective way to control "white pollution". At present, the waste plastic refining industry has blossomed everywhere in China, and some enterprises have built small-scale pyrolysis demonstration plants, but the problem of high-value utilization of waste plastic pyrolysis products has yet to be effectively solved.

The waste plastic oil, waste tire oil and traditional petroleum-based oil products transformed by various processes are quite different, and the content of impurities is high, especially the high content of silicon, which brings great trouble to the subsequent processing. At present, there are few researches on the deep processing of waste plastic oil and waste tire oil. Many researches focus on the influence of chlorine impurities in waste plastic oil on the post-processing of waste plastic oil, and they do not realize that waste plastic oil also contains Other impurities, such as silicon impurities, metal impurities, and these impurities have a serious impact on the subsequent processing technology.

CN104611060A discloses a method for producing clean fuel oil by utilizing waste plastics and high aromatic components. After the high aromatic component is mixed with the waste plastic oil, it first passes through the thermal cracking reaction zone, which adopts a combination of gradual temperature rise and constant temperature operation; the pyrolysis gas is obtained and then enters the catalytic reaction zone, where it contacts with the catalyst for catalytic reaction. , the obtained reaction effluent is subjected to gas-liquid separation to obtain gas products and liquid-phase oil products.

CN104726134A discloses a method for producing high-quality gasoline and diesel oil from chlorine-containing plastic oil. It is characterized by injecting chlorine-containing plastic oil into a high-temperature dechlorination tower equipped with active aluminum oxide for high-temperature dechlorination, and spraying a small amount of NaOH aqueous solution on the top of the high-temperature dechlorination tower, and the plastic oil after dechlorination enters into a high-temperature dechlorination tower equipped with molecular sieve/oxidant. The reaction and rectification are carried out in the catalytic distillation tower of aluminum catalyst; after the catalytic distillation, the plastic oil is pressurized into the hydrotreating tower, and the distillate oil after hydrotreating is distilled under normal pressure, and is cut into gasoline and diesel oil according to the distillation temperature. The heavy oil is mixed with the raw chlorinated plastic oil for re-reaction. The dechlorination catalyst and sulfide catalyst used in the present invention are prepared by selecting appropriate methods according to the composition and performance of the plastic oil.

CN102942951A discloses a method for preparing clean diesel fuel by hydrogenation of plastic oil, which includes the following steps: a. plastic oil and hydrogen are mixed into a pre-hydrogenation reactor equipped with a hydrogenation protection catalyst for chemical reaction; b. The effluent enters the hot high pressure separator for separation and stripping, and the effluent at the bottom of the hot high pressure separator and the gas at the top of the cold high pressure separator enter the main hydrogenation reactor for chemical reaction; c. The effluent of the main hydrogenation reactor enters The cold high pressure separator conducts gas-liquid separation, and the bottom effluent of the cold high pressure separator enters the cold low pressure separator and mixes with the light oil extracted from the middle of the cold high pressure separator, and then enters the fractionation tower for separation, and sulfur can be extracted from the side line of the fractionation tower. Clean diesel fraction with content less than 5μg/g and cetane number higher than 50.

CN102226103A discloses a method for producing gasoline and diesel by utilizing plastic oil. It is characterized by the process of producing high-quality gasoline and diesel with plastic oil as the raw material, followed by hydro-refining. It is characterized in that, firstly, the plastic oil is distilled to obtain fractions less than 300°C and fractions greater than 300°C, and then the fractions less than 300°C are distilled in sulfide. Hydrorefining reaction on catalyst, removing monoolefin compound through monoolefin hydrogenation saturation reaction, and desulfurization, nitrogen removal, and gum removal to produce odorless, high-quality gasoline and diesel mixed oil, and then distillation to obtain gasoline and diesel fractions Oil. Distilled fractions greater than 300°C should undergo reactive distillation and then hydrorefined or mixed with plastic oil for re-reaction. The sulfide catalyst used in the present invention is prepared by a liquid phase method by selecting a suitable carrier according to the composition and performance of the cracked plastic oil.

The prior art mainly focuses on the dechlorination and refining process of waste plastic oil, and it has not been realized that the silicon-containing compound in the waste plastic oil will cause serious poisoning to the above-mentioned hydrogenation catalyst of the prior art and the catalyst of other subsequent processes. As a result, the operation cycle of the subsequent processing process is short, or in fact the industrialized operation cannot be realized at all.

SUMMARY OF THE INVENTION

The present invention is to solve the problem of short processing cycle when processing waste plastic oil and/or waste tire oil raw materials in the prior art, and aims to provide a method and system for preparing pyrolysis raw materials from waste plastic oil and/or waste tire oil.

A first aspect of the present invention provides a method for preparing pyrolysis raw material from waste plastic oil and/or waste tire oil, comprising:

(1) decontamination unit, waste plastic oil and/or waste tire oil, in the presence of hydrogen, enter the decontamination reactor and contact with the waste hydrogenation catalyst, and carry out decontamination reaction under the decontamination reaction conditions, and in the obtained reaction effluent The silicon content of the liquid phase material is less than 1μg/g, and the metal content is less than 5μg/g;

(2) hydrotreating unit, the reaction effluent obtained in step (1) enters the hydrotreating reactor, contacts with the hydrotreating catalyst, and carries out the hydrotreating reaction under the hydrotreating reaction conditions, and after the reaction effluent is separated, A gas phase material and a liquid phase material are obtained, and all or part of the obtained liquid phase material is a cracking material for preparing ethylene by steam cracking.

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

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

In one embodiment of the present invention, the waste tire oil is a hydrocarbon material obtained from waste tires by one or more conversion methods in thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution liquefaction; The distillation range is 30～700℃, the silicon content is less than 10000μg/g, the chlorine content is less than 10000μg/g, and the metal content is less than 10000μg/g. The composition of the waste tire oil includes that the volume fraction of olefins is 5-80%, preferably 5-60%, the volume fraction of aromatic hydrocarbons is less than 90%, preferably 2-60%, and the volume fraction of paraffins is less than 90%, preferably 5-60% %.

In the present invention, the waste tires are various waste tires prepared from natural rubber and/or synthetic rubber.

In the present invention, the thermal cracking and thermal cracking reaction refer to the reaction in which hydrocarbon molecules, including waste plastics and waste tires, are decomposed into smaller molecules under the condition of isolating air under high temperature conditions. Depending on 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 cracking reaction.

In the present invention, the catalytic cracking and catalytic cracking reaction refer to a 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 light olefins (ethylene, propylene, butene) as the target product is called catalytic cracking reaction, and the reaction with vehicle gasoline as the target product is called catalytic cracking reaction.

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

In one embodiment of the present invention, the decontamination reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. The fixed bed hydrogenation reactor and/or the moving bed reactor are filled with waste hydrogenation catalysts, and waste plastic oil and/or waste tire oil are fed through at least one fixed bed hydrogenation reactor and/or at least one moving bed. The hydrogen reactor is used for desiliconization, dechlorination, demetallization and other decontamination reactions.

In one embodiment of the present invention, the decontamination reactors are two or more fixed-bed hydrogenation reactors connected in parallel, each reactor is filled with waste hydrogenation catalyst, and waste plastic oil and/or waste tire oil pass through it At least one fixed-bed hydrogenation reactor is used for decontamination reaction. When the waste hydrogenation catalyst in the fixed-bed hydrogenation reactor is saturated with silicon or metal, the waste plastic oil and/or waste tire oil are switched to other fixed beds. Hydrogenation reactor.

In one embodiment of the present invention, when the silicon content of the liquid phase material in the reaction effluent is greater than or equal to 1 μg/g or the metal content is greater than or equal to 5 μg/g, it is considered that the waste hydrogenation catalyst in the decontamination reactor is saturated with silicon or metal saturation.

In one embodiment of the present invention, the spent hydrogenation catalyst is selected from the protective agent used to the final stage of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, the catalyst in the final stage, and the protective agent after regeneration, after regeneration one or more of the catalysts.

In an embodiment of the present invention, the equivalent diameter of the spent hydrogenation catalyst is 0.5-16 mm, and in a preferred case, 1-10 mm. The present invention does not have any limitation on the shape of the spent hydrogenation catalyst, for example, its shape includes spherical shape, and various anomalous shapes such as strip clover, butterfly shape, Raschig ring, and honeycomb shape.

In one embodiment of the present invention, the waste hydrogenation catalyst includes, based on the total weight of the waste hydrogenation catalyst, the content of hydrogenation active metal oxides is 0-50 wt %, and the carbon content is 0-50 wt % , the sulfur content is 0 to 40% by weight, and the hydrogenation active metal is selected from one or more metals of Group VIII and Group VIB.

In one embodiment of the present invention, the waste hydrogenation catalyst includes, based on the total weight of the waste hydrogenation catalyst, molybdenum oxide and/or tungsten oxide in an amount of 0 to 50% by weight, nickel oxide and/or cobalt oxide The content of carbon is 0-40% by weight, the carbon content is 0-30% by weight, and the sulfur content is 0-30% by weight.

In an embodiment of the present invention, the waste hydrogenation catalyst includes, based on the total weight of the waste hydrogenation catalyst, the content of hydrogenation active metal oxides is 1-40 wt%, and the carbon content is less than or equal to 20 wt% , the hydrogenation active metal is selected from one or more metals of Group VIII and Group VIB.

In one embodiment of the present invention, multiple waste hydrogenation catalysts are packed in layers, and along the direction of material flow, the equivalent diameter of the waste hydrogenation catalysts gradually decreases, the pore diameter gradually decreases, and the active metal content gradually increases.

In an embodiment of the present invention, the decontamination reactor is also filled with a dechlorination agent, and the packing volume ratio of the dechlorination agent to the spent catalyst is 1-80:20-99. The waste hydrogenation catalyst and dechlorination agent are uniformly mixed and packed or packed in layers.

In one embodiment of the present invention, the waste hydrogenation catalyst and the dechlorination agent are loaded in layers, and the dechlorination agent is loaded downstream of the waste hydrogenation catalyst according to the flow direction.

In an embodiment of the present invention, there are one or more dechlorinating agents, and when there are multiple dechlorinating agents, they can be loaded in a gradation and combination, or mixed and loaded.

In one embodiment of the present invention, the hydrogenation reactor is at least one moving bed hydrogenation reactor, and the waste hydrogenation catalyst and dechlorination agent are loaded in the moving bed hydrogenation reactor. The waste hydrogenation catalyst and dechlorination agent are mechanically mixed in a certain proportion.

In one embodiment of the present invention, the dechlorination agent comprises at least one Group IA metal compound and/or at least one Group IIA metal compound, optionally one or more selected from Cu, Fe, Zn Metal oxides, and supports and/or binders;

The carrier and/or binder is selected from one or more of silica, alumina, silica-alumina, zirconia, and clay. The clay is selected from one or more of kaolin, illite, montmorillonite, and bentonite; the kaolin includes halloysite.

In the present invention, the meaning of "optional" is optional, and the optional one or more metal oxides selected from Cu, Fe, Zn refers to, selected from Cu, Fe, Zn One or more metal oxides of . are optional components of the dechlorination agent.

In the present invention, in a preferred case, the dechlorination agent is a high temperature dechlorination agent and/or a medium temperature dechlorination agent. The present invention does not have any 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. Further preferred are high-temperature dechlorinating agents and/or medium-temperature dechlorinating agents with larger chlorine capacity.

In one embodiment of the present invention, the chlorine content in the liquid-phase material in the reaction effluent of step (1) is less than 0.5 μg/g.

In an embodiment of the present invention, the de-impurification reaction conditions are: hydrogen partial pressure 0.5-20.0MPa, reaction temperature 60-500°C, volume space velocity 0.1-30h ^-1 , hydrogen-oil volume ratio 5-1000Nm ³ / m ³ .

The preferred de-impurification reaction conditions are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-450°C, volume space velocity of 0.2-20 h ^-1 , and hydrogen-to-oil volume ratio of 5-800 Nm ³ /m ³ .

In the hydrorefining unit of step (2) of the present invention, the reaction effluent obtained from the decontamination unit in step (1) directly enters the hydrorefining reactor, and is contacted and reacted with the hydrorefining catalyst under the conditions of the hydrorefining reaction to remove In addition to impurities such as sulfur and nitrogen, olefins are hydrogenated and saturated.

In one embodiment of the present invention, the hydrotreating reaction conditions are: hydrogen partial pressure 1.0-20.0 MPa, reaction temperature 250-430°C, volume space velocity 0.5-20h ^-1 , hydrogen-oil volume ratio 50-1000Nm ³ /m ³ ;

The preferred hydrorefining reaction conditions are: hydrogen partial pressure 1.0-12 MPa, reaction temperature 280-400°C, volume space velocity 0.5-15 h ^-1 , and hydrogen-to-oil volume ratio 100-800 Nm ³ /m ³ .

In one embodiment of the present invention, the hydrotreating catalyst includes a hydrogenation metal active component and a carrier, and based on the total weight of the hydrotreating catalyst, in terms of oxides, the content of the hydrogenation metal active component 5 to 50% by weight.

In a preferred case, the hydrogenation metal active component is at least one metal element selected from group VIB and at least one metal element selected from group VIII, and the metal element of group VIB is molybdenum and/or tungsten , the Group VIII metal element is cobalt and/or nickel; based on the total weight of the hydrorefining catalyst, in terms of oxides, the content of the Group VIB metal element is 4-40% by weight, preferably 8-40% by weight. 35% by weight, the content of the Group VIII metal element is 1-10% by weight, preferably 2-5% by weight.

After separation of the reaction effluent obtained from the hydrorefining reactor, gas-phase material and liquid-phase material are obtained. In one embodiment of the present invention, the olefin content in the obtained liquid-phase material is ≤2% by mass, and the sulfur content is <50 μg/g , the nitrogen content is <50μg/g, the silicon content is <1μg/g, the chlorine content is <0.5μg/g, and the metal content is <1μg/g. The obtained liquid phase material is low in sulfur, low in nitrogen and low in olefin, all or part of which can be the cracking raw material for preparing ethylene by steam cracking.

Another aspect of the present invention provides a system for any of the above methods, comprising a decontamination unit and a hydrofinishing unit, wherein the decontamination unit is provided with a decontamination reactor filled with spent hydrogenation catalysts, and the decontamination reactor is provided with at least One waste plastic oil and/or waste tire oil inlet, at least one reaction effluent outlet, the waste hydrogenation catalyst is a protective agent and a catalyst selected from any fixed bed hydrogenation process unit used to the end of the hydrocarbon oil processing field, And one or more of the regenerated protective agent and the regenerated catalyst;

The reaction effluent outlet of the decontamination unit is communicated with the feed inlet of the hydrotreating unit. The hydrotreating unit is provided with a hydrotreating reactor filled with a hydrotreating catalyst, and the reaction effluent outlet of the hydrotreating reactor is connected with the inlet of the separation unit. In communication, the separation unit is provided with at least one gas-phase material outlet and at least one liquid-phase material outlet.

In one embodiment of the present invention, the decontamination reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor.

In one embodiment of the present invention, the decontamination reactors are two or more fixed-bed hydrogenation reactors connected in parallel, each fixed-bed hydrogenation reactor is filled with waste and used hydrogenation catalysts, and each fixed-bed hydrogenation reactor is provided with At least one waste plastic oil and/or waste tire oil inlet, at least one reaction effluent outlet.

Features of the present invention:

1. The present invention can process waste plastic oil and waste tire oil transformed by various processes, and after being processed by the decontamination unit and the hydrorefining unit, it can provide high-quality cracking raw materials for the process of steam cracking to prepare ethylene.

2. The present invention effectively removes impurities in waste plastic oil and waste tire oil in the decontamination unit, especially silicon impurities, chlorine impurities and metal impurities, and avoids the influence of these impurities on the hydrorefining catalyst in the hydrorefining unit, Thereby extending the overall operating cycle.

3. The present invention uses waste and old hydrogenation catalyst, which has low cost and good impurity removal effect. And in a preferred embodiment of the present invention, a moving bed or two fixed-bed reactors switched in parallel and alternately are used for pretreatment, so as to achieve the purpose of long-term deep desiliconization, demetallization and dechlorination.

Description of drawings

FIG. 1 is a schematic diagram of one embodiment of the method for preparing pyrolysis feedstock from waste plastic oil and/or waste tire oil provided by the present invention.

Detailed ways

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

Fig. 1 is a schematic diagram of one embodiment of the method for preparing pyrolysis raw materials from waste plastic oil and/or waste tire oil provided by the present invention. As shown in Fig. 1, the waste plastic oil and/or waste tire oil from pipeline 1 passes through a feed pump 2 After the pressure increase, from the pipeline 3, together with the new hydrogen from the pipeline 17 and the circulating hydrogen from the pipeline 16, it enters the heating furnace 4 for heating, and the heated mixed hydrogen material enters the decontamination unit through the pipeline 5, and the decontamination unit is provided with two The fixed-bed hydrogenation reactors 8 and 9 are connected in parallel. The fixed-bed hydrogenation reactor 8 is provided with a catalyst bed A, which is filled with waste hydrogenation catalysts in gradation, and a catalyst bed B is provided in the fixed-bed hydrogenation reactor 9. Gradient loading of spent hydrogenation catalysts. In one of the embodiments, the mixed hydrogen material enters the fixed-bed hydrogenation reactor 8 through the pipeline 6, contacts with the waste hydrogenation catalyst packed in gradation, and conducts the de-impurification reaction under the condition of de-impurification reaction. The bed hydrogenation reactor 9 is used as a backup. When the waste hydrogenation catalyst in the fixed bed hydrogenation reactor 8 is saturated with silicon or metal, the hydrogen mixed material enters the fixed bed hydrogenation reactor 9 through the pipeline 7 for reaction, and the fixed bed hydrogenation reactor 8 is cut out. The reaction system, and then the spent hydrogenation catalyst in the catalyst bed A is replaced.

The reaction effluent obtained from the decontamination unit enters the hydrotreating reactor 12 through the pipelines 10 and 11, and is contacted with the hydrotreating catalyst for reaction, and the reaction effluent enters the high-pressure separator 14 through the pipeline 13 for gas-liquid separation, and the obtained liquid-phase material It is drawn out through line 18, and the obtained gas-phase material is boosted by circulating hydrogen compressor 15 and returned to the inlet of heating furnace 4 through line 16.

The present invention is further described below in conjunction with the examples, but the present invention is not limited in any way.

In the embodiment, the silicon content in the hydrocarbon material is determined by the method of "Determination of Silicon Content in Gasoline and Related Products by Single Wavelength Dispersive X-ray Fluorescence" (SH/T 0993-2019).

In the embodiment, the chlorine content in the liquid material is measured by the Coulomb method, and the concrete method is the method of "Measurement of Total Chlorine Content in Crude Oil by Electricity Method" (RIPP 64-90) in "Petrochemical Analysis Method" (RIPP Test Method) to measure. The instrument used is a microcoulomb analyzer, and the sample is a liquid material.

The dechlorinating agent used in Examples and Comparative Examples is an industrial implementation dechlorinating agent RDY-100, produced by Jinan Ruidong Industrial Co., Ltd.

The catalyst D in the final stage of reforming and pre-hydrogenation used in the embodiment has an alumina carrier, a butterfly shape, and an equivalent diameter of 1.6 mm. The composition includes: 18 wt% tungsten oxide, 2 wt% nickel oxide, 0.04 wt% cobalt oxide, carbon dioxide The content is 5.0% by weight, and the sulfur content is 6% by weight;

The gasoline hydrogenation final catalyst E carrier used in the examples is alumina, butterfly-shaped, and has an equivalent diameter of 1.6 mm. %;

The diesel hydrotreating final stage catalyst F used in the example, the carrier is alumina, butterfly shape, the equivalent diameter is 1.6mm, and the composition includes: molybdenum oxide 26 weight %, nickel oxide 4.0 weight %, carbon content 20 weight %, sulfur content 15% by weight;

The final stage hydrogenation catalyst G used in the embodiment is the final stage catalyst of residual oil hydrogenation protection agent, the carrier is alumina, Raschig ring, the equivalent diameter is 6.0mm, and the composition includes: molybdenum oxide 2 wt%, nickel oxide 0.5 wt%, The carbon content is 40% by weight, and the sulfur content is 5% by weight;

The hydrorefining catalyst H used in the examples has an alumina carrier, a butterfly shape, an equivalent diameter of 1.6 mm, and the composition includes: molybdenum oxide 26 wt % and nickel oxide 4.0 wt %.

The properties of the raw materials used are shown in Table 1, wherein the raw material I is waste plastic oil, J is the ratio of waste plastic oil to waste tire oil, which is 80:20 weight, and raw material K is that the ratio of waste plastic oil and waste tire oil is 40:60 weight.

Table 1

Example 1 to Example 5

After the waste plastic oil and/or waste tire oil is mixed with hydrogen, it enters the decontamination reactor and contacts with the waste hydrogenation catalyst, and the decontamination reaction is carried out under the decontamination reaction conditions. The catalyst loading, reaction conditions and reaction results of the decontamination unit Included in Table 2. It can be seen from Table 2 that the silicon content of the liquid phase material in the reaction effluent obtained from the decontamination unit is less than 1 μg/g, the chlorine content is less than 0.5 μg/g, and the metal content is less than 5 μg/g.

The reaction effluent obtained from the decontamination unit enters the hydrotreating reactor, contacts with the hydrotreating catalyst, and conducts the hydrotreating reaction under the conditions of the hydrotreating reaction. After the reaction effluent is separated, gas-phase materials and liquid-phase materials are obtained. The catalyst loading, reaction conditions and reaction results of the hydrogen refining unit are listed in Table 3.

As can be seen from Table 3, the obtained liquid phase material has low impurity content and low BMCI value, and is a high-quality steam cracking raw material for preparing ethylene.

Table 2

table 3

Example 6

In the present embodiment, the decontamination unit is provided with two parallel fixed-bed hydrogenation reactors 1 and 2, with raw material J as the feed, and the catalyst loading conditions, decontamination reaction conditions and reaction results are listed in Table 4.

When the reactor 1 runs to 800h, the metal content of the liquid phase material in the reaction effluent is greater than 5 μg/g, at this time it is switched to the reactor 2, and the metal content of the liquid phase material is reduced to less than 1 μg/g. The catalyst is replaced in the reactor 1, and this cycle realizes long-term operation.

Table 4

Example 7

In the present embodiment, the decontamination unit is provided with two parallel fixed-bed hydrogenation reactors 1 and 2, and the raw material K is used as the feed. The catalyst loading conditions, decontamination reaction conditions and reaction results are listed in Table 5.

When the reactor 1 runs to 1000h, the silicon content of the liquid phase material in the reaction effluent is greater than 1 μg/g, and the metal content is greater than 8 μg/g. At this time, it is switched to the reactor 2, and the silicon content and metal content of the liquid phase material are reduced. is less than 1 μg/g. The catalyst is replaced in the reactor 1, and this cycle realizes long-term operation.

table 5

Example 8

In the present embodiment, the moving bed reactor of the decontamination unit takes raw material I as the feed, and the catalyst loading situation, decontamination reaction conditions and reaction results are listed in Table 6.

As can be seen from Table 6, adopt the method of the present invention, adopt moving bed in the impurity removal unit, process the raw material I with higher impurity content, the silicon content of the gained liquid-phase reaction effluent is less than 1 μg/g, and the chlorine content is less than 0.5 μg/g, The metal content is less than 5μg/g, and the agent consumption is 10.2kg/ton oil.

Table 6

decontamination unit moving bed reactor catalyst D raw oil Raw material I Reaction pressure, MPa 1.6 Reaction temperature, °C 380 Hydrogen oil ratio, Nm³/m³ 50 Agent consumption, kg/ton of oil 10.2 Liquid-phase reaction effluent Silicon content, μg/g <1 Chlorine content, μg/g <0.5 Metal content, μg/g <5

It should be noted that the above descriptions are only arbitrary embodiments of the present invention, and are not intended to limit the present invention. For those skilled in the art, the present invention may have various modifications and changes. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims (24)

1. A method for preparing pyrolysis raw material from waste plastic oil and/or waste tire oil, comprising: (1) decontamination unit, waste plastic oil and/or waste tire oil, in the presence of hydrogen, enter the decontamination reactor and contact with the waste hydrogenation catalyst, and carry out decontamination reaction under the decontamination reaction conditions, and in the obtained reaction effluent The silicon content of the liquid phase material is less than 1μg/g, and the metal content is less than 5μg/g; (2) hydrotreating unit, the reaction effluent obtained in step (1) enters the hydrotreating reactor, contacts with the hydrotreating catalyst, and carries out the hydrotreating reaction under the hydrotreating reaction conditions, and after the reaction effluent is separated, A gas phase material and a liquid phase material are obtained, and all or part of the obtained liquid phase material is a cracking material for preparing ethylene by steam cracking. 2. method according to claim 1, is characterized in that, described waste plastic oil is the hydrocarbon that waste plastic obtains by one or more conversion methods in thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, dissolving liquefaction Material; the distillation range of waste plastic oil is 30～700℃, the silicon content is less than 10000μg/g, the chlorine content is less than 10000μg/g, and the metal content is less than 10000μg/g. 3. The method according to claim 2, wherein the waste plastics are one or more of waste plastics in fresh household garbage, waste plastics in industrial and agricultural production, and waste plastics in aged garbage, and waste plastics The type is one or more selected from PE, PP, PS, PVC. 4. method according to claim 1 is characterized in that, described waste tire oil is the hydrocarbon that waste tire obtains by one or more conversion methods in thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, dissolving liquefaction Material: The distillation range of waste tire oil is 30～700℃, the silicon content is less than 10000μg/g, the chlorine content is less than 10000μg/g, and the metal content is less than 10000μg/g. 5. The method according to claim 4, wherein the waste tires are various waste tires prepared from natural rubber and/or synthetic rubber. 6. The method according to claim 1, wherein the decontamination reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. 7. method according to claim 1, is characterized in that, described decontamination reactor is the fixed bed hydrogenation reactor of two or more parallel connection, in each reactor, is filled with waste and old hydrogenation catalyst, waste plastic oil and/ Or waste tire oil is subjected to decontamination reaction through at least one of the fixed bed hydrogenation reactors, when the waste hydrogenation catalyst in the fixed bed hydrogenation reactor is saturated with silicon or saturated with metals, waste plastic oil and/or waste tire oil. Switch the feed to other fixed bed hydrogenation reactors. 8. method according to claim 7 is characterized in that, when the silicon content of liquid phase material in the reaction effluent is greater than or equal to 1 μg/g or the metal content is greater than or equal to 5 μg/g, it is considered that waste hydrogenation in the hydrogenation reactor The catalyst is saturated with silicon or metal. 9. method according to claim 1, is characterized in that, described waste and old hydrogenation catalyst is selected from hydrocarbon oil processing field any fixed bed hydrogenation process device to be used to end-stage protective agent, end-stage catalyst, and after regeneration One or more of the protective agent and the regenerated catalyst. 10 . The method according to claim 9 , wherein the equivalent diameter of the spent hydrogenation catalyst is 0.5 to 16 mm. 11 . 11. The method according to claim 9, wherein the waste and used hydrogenation catalyst comprises, based on the total weight of the waste and used hydrogenation catalyst, the content of hydrogenation active metal oxides is 0 to 50% by weight, and the carbon content is 0-50% by weight. is 0-50 wt%, the sulfur content is 0-40 wt%, and the hydrogenation active metal is selected from one or more metals of Group VIII and Group VIB. 12. The method according to claim 11, wherein the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, the content of molybdenum oxide and/or tungsten oxide is 0 to 50% by weight, and the oxidation The content of nickel and/or cobalt oxide is 0 to 40% by weight, the content of carbon is 0 to 30% by weight, and the content of sulfur is 0 to 30% by weight. 13. The method according to claim 11, wherein the waste hydrogenation catalyst comprises, based on the total weight of the waste hydrogenation catalyst, the content of hydrogenation active metal oxides is 1-40% by weight, and the carbon content is 1-40% by weight. The hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals in an amount equal to or less than 20% by weight. 14 . The method according to claim 1 , wherein the decontamination reactor is also filled with a dechlorination agent, and the volume ratio of the dechlorination agent to the spent catalyst is 1-80:20-99. 15 . 15. The method of claim 14, wherein the dechlorination agent comprises at least one Group IA metal compound and/or at least one Group IIA metal compound, optionally selected from Cu, Fe, Zn one or more metal oxides, and carriers and/or binders; The carrier and/or binder is selected from one or more of silica, alumina, silica-alumina, zirconia, and clay. 16. The method according to claim 14, wherein the chlorine content in the liquid-phase material in the reaction effluent of step (1) is less than 0.5 μg/g. 17 . The method according to claim 1 , wherein the de-impurification reaction conditions are: hydrogen partial pressure 0.5-20.0 MPa, reaction temperature 60-500° C., volume space velocity 0.1-30 h ^-1 , volume of hydrogen oil ratio of 5～1000Nm ³ /m ³ ; the preferred de-impurification reaction conditions are: hydrogen partial pressure 1～12MPa, reaction temperature 100～450℃, volume space velocity 0.2～20h ^-1 , hydrogen oil volume ratio 5～800Nm ³ /m ³ . 18. The method according to claim 1, wherein the hydrotreating catalyst described in step (2) comprises a hydrogenation metal active component and a carrier, and is based on the total weight of the hydrotreating catalyst and is based on the oxidation The content of the hydrogenation metal active component is 5 to 50% by weight. 19. The method according to claim 18, wherein the hydrogenation metal active component is at least one metal element selected from the group VIB and at least one metal element selected from the group VIII, the VIB The metal element of the group is molybdenum and/or tungsten, and the metal element of the group VIII is cobalt and/or nickel; the content of the metal element of the group VIB is 4 based on the total weight of the hydrotreating catalyst and calculated as oxides ∼40 wt%, preferably 8∼35 wt%, and the content of the Group VIII metal element is 1∼10 wt%, preferably 2∼5 wt%. 20 . The method according to claim 1 , wherein the hydrorefining reaction conditions in step (2) are: hydrogen partial pressure of 1.0-20.0 MPa, reaction temperature of 250-430° C., and volumetric space velocity of 0.5-20 h ⁻ 20 . ^1. The volume ratio of hydrogen to oil is 50～1000Nm ³ /m ³ ; the preferred hydrotreating reaction conditions are: hydrogen partial pressure 1.0～12MPa, reaction temperature 280～400℃, volume space velocity 0.5～15h ^-1 , hydrogen oil volume ratio 100 ~800Nm ³ /m ³ . 21. The method according to claim 1, wherein the olefin content in the obtained liquid phase material in step (2) is ≤2 mass%, the sulfur content is <50 μg/g, the nitrogen content is <50 μg/g, and the silicon content is <50 μg/g. <1μg/g, chlorine content <0.5μg/g, metal content <1μg/g. 22. The system for any one of claims 1-21, comprising a decontamination unit, a hydrofinishing unit, the decontamination unit is provided with a decontamination reactor filled with spent and used hydrogenation catalysts, and the decontamination reactor is provided with at least one waste hydrogenation catalyst. Plastic oil and/or waste tire oil inlet, at least one reaction effluent outlet, the waste hydrogenation catalyst is selected from the protective agent used to the end of any fixed bed hydrogenation process device in the field of hydrocarbon oil processing, the catalyst at the end, and after One or more of the regenerated protective agent and the regenerated catalyst; The reaction effluent outlet of the decontamination unit is communicated with the feed inlet of the hydrotreating unit. The hydrotreating unit is provided with a hydrotreating reactor filled with a hydrotreating catalyst, and the reaction effluent outlet of the hydrotreating reactor is connected with the inlet of the separation unit. In communication, the separation unit is provided with at least one gas-phase material outlet and at least one liquid-phase material outlet. 23. The system according to claim 22, wherein the decontamination reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. 24. The system according to claim 22, wherein the decontamination reactor is two or more fixed-bed hydrogenation reactors connected in parallel, each fixed-bed hydrogenation reactor is filled with spent and old hydrogenation catalysts, and each fixed-bed hydrogenation reactor is The bed hydrogenation reactor is provided with at least one waste plastic oil and/or waste tire oil inlet and at least one reaction effluent outlet.

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