CN114437775B - A method and system for producing aromatic hydrocarbon extraction raw materials from waste plastic oil and/or waste tire oil - Google Patents

Abstract

The invention relates to a method and system for producing aromatic hydrocarbon extraction raw materials from waste plastic oil and/or waste tire oil. Waste plastic oil and/or waste tire oil undergoes a decontamination reaction in the decontamination unit. The resulting reaction effluent is separated to obtain the first fraction, the second fraction and the third fraction. The second fraction enters the hydrotreating unit for reaction. The three fractions enter the catalytic cracking unit for reaction, and the resulting catalytic cracking gasoline also enters the hydrorefining unit for reaction. The second liquid phase material obtained after the reaction product of the hydrorefining unit is separated is the raw material for aromatic hydrocarbon extraction. The invention can effectively remove impurities in waste plastic oil and/or waste tire oil, and is combined with a catalytic cracking unit to provide qualified raw materials for aromatic hydrocarbon extraction devices. The invention has low cost and long operating cycle.

Description

A method and system for producing aromatics extraction raw materials from waste plastic oil and/or waste tire oil

Technical Field

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

Background Art

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.

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.

Waste plastic oil and waste tire oil converted from various processes are quite different from traditional petroleum-based oils. They contain high impurities, especially high silicon content, which brings great troubles to subsequent processing. At present, there are few studies on the deep processing of waste plastic oil and waste tire oil. Many studies focus on the impact of chlorine impurities in waste plastic oil on the post-processing of waste plastic oil, but they do not realize that waste plastic oil also contains other impurities, such as silicon impurities and metal impurities, and the serious impact of these impurities on subsequent processing technology.

CN104611060A discloses a method for producing clean fuel oil using waste plastics and high aromatic components. After the high aromatic components are mixed with the waste plastic oil, they first pass through a thermal cracking reaction zone, which uses a combination of gradual temperature increase and constant temperature operation; the cracked gas obtained then enters a catalytic reaction zone, contacts with a catalyst therein to undergo a catalytic reaction, and the resulting reaction effluent is subjected to gas-liquid separation to obtain a gas product and a liquid oil product.

CN104726134A discloses a method for producing high-quality gasoline and diesel from chlorine-containing plastic oil. It is characterized in that the chlorine-containing plastic oil is injected into a high-temperature dechlorination tower equipped with active aluminum oxide for high-temperature dechlorination, a small amount of NaOH aqueous solution is sprayed 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 distillation; after catalytic distillation, the plastic oil is pressurized and enters a hydrofining tower, and the distillate oil after hydrofining 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.

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

CN102226103A discloses a method for producing gasoline and diesel using plastic oil. It is characterized in that the plastic oil is used as raw material for distillation and then hydrogenation and refining to produce high-quality gasoline and diesel. The process is characterized in that the plastic oil is first distilled to obtain a fraction less than 300°C and a fraction greater than 300°C, and then the fraction less than 300°C is subjected to hydrogenation and refining reaction on a sulfide catalyst, and the monoolefin compounds are removed by monoolefin hydrogenation and saturation reaction, and desulfurization, nitrogen removal, and colloid removal are performed to produce a gasoline and diesel mixed oil without odor and high quality, and then gasoline and diesel distillate oil are obtained by distillation. The fraction greater than 300°C after distillation must be subjected to reactive distillation and then hydrogenated 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 existing technology mainly focuses on the dechlorination and refining process of waste plastic oil, but has not yet realized that the silicon-containing compounds in the waste plastic oil will have a serious poisoning effect on the hydrogenation catalysts of the above-mentioned prior art and the catalysts of other subsequent process steps, resulting in a short operation cycle of the subsequent processing process, or in fact, it is impossible to achieve industrial operation.

Summary of the invention

The present invention aims 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 producing aromatic extraction raw materials from waste plastic oil and/or waste tire oil.

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

(1) a de-impurity unit, wherein the waste plastic oil and/or waste tire oil raw material enters a de-impurity reactor and contacts with a waste hydrogenation catalyst in the presence of hydrogen, and a de-impurity reaction is performed under de-impurity reaction conditions. The obtained reaction effluent is subjected to gas-liquid separation to obtain a first gas phase material and a first liquid phase material, wherein the silicon content of the obtained first liquid phase material is less than 1 μg/g, and the metal content is less than 5 μg/g;

The first liquid phase material is fractionated to obtain a first fraction, a second fraction and a third fraction, wherein the first fraction is a _C5 and below hydrocarbon fraction, the second fraction is a _C6 - _C8 hydrocarbon fraction, and the third fraction is a _C9 and above hydrocarbon fraction;

(2) a hydrotreating unit, wherein the second fraction obtained in step (1) enters a hydrotreating reactor, contacts a hydrotreating catalyst in the presence of hydrogen, and undergoes a hydrotreating reaction under hydrotreating reaction conditions; and the obtained reaction effluent is subjected to gas-liquid separation to obtain a second gas phase material and a second liquid phase material, wherein the obtained second liquid phase material is a raw material for aromatic extraction.

In one embodiment of the present invention, the method further comprises step (3):

(3) a catalytic cracking unit, wherein the third fraction obtained in step (1) enters the catalytic cracking unit, contacts with a catalytic cracking catalyst, and reacts under catalytic cracking reaction conditions. After separation of the reaction effluent, at least a light olefin fraction and a catalytic cracking gasoline fraction are obtained;

The obtained catalytic cracking gasoline fraction is sent to the hydrotreating unit in step (2) and enters the hydrotreating reactor.

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, the silicon content is less than 10,000 μg/g, the chlorine content is less than 10,000 μg/g, and the metal content is less than 10,000 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%.

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.

In one embodiment of the present invention, the waste tire oil is a hydrocarbon material obtained by one or more conversion methods of waste tires, including thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution liquefaction; the distillation range of the waste tire oil is 30-700°C, 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 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%.

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

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 air-tight conditions under high temperature conditions. 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.

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.

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.

In one embodiment of the present invention, in the impurity removal unit, the impurity removal reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. Waste hydrogenation catalyst is loaded in the fixed bed hydrogenation reactor and/or the moving bed reactor, and waste plastic oil and/or waste tire oil feed passes through at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor to perform impurity removal reactions such as desiliconization, dechlorination, and demetallization.

In one embodiment of the present invention, the de-doping reactor is two or more fixed-bed hydrogenation reactors connected in parallel, each reactor is loaded with spent hydrogenation catalyst, and the feed passes through at least one of the fixed-bed hydrogenation reactors for de-doping reaction. When the spent hydrogenation catalyst in the fixed-bed hydrogenation reactor is saturated with silicon or metal, the feed is switched to other fixed-bed hydrogenation reactors.

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 spent hydrogenation catalyst in the de-doping reactor is saturated with silicon or metal.

In one embodiment of the present invention, the waste hydrogenation catalyst is one or more selected from protective agents and catalysts at the end of use in any fixed bed hydrogenation process unit in the hydrocarbon oil processing field, as well as regenerated protective agents and regenerated catalysts.

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

In one embodiment of the present invention, 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.

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

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

In one embodiment of the present invention, a plurality of spent hydrogenation catalysts are loaded in layers, and along the direction of material flow, the equivalent diameter of the spent hydrogenation catalysts gradually decreases, the pore size gradually decreases, and the active metal content gradually increases.

In one embodiment of the present invention, the dechlorination agent is also loaded in the de-impurity reactor, and the loading volume ratio of the dechlorination agent to the waste catalyst is 1 to 80: 20 to 99. The waste hydrogenation catalyst and the dechlorination agent are uniformly mixed and loaded or loaded in layers.

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

In one embodiment of the present invention, the dechlorinating agent is one or more types. When there are multiple types of dechlorinating agents, they can be loaded in graded combination or mixed.

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

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;

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.

In the present invention, 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 dechlorination agent.

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.

In one embodiment of the present invention, the de-doping reaction conditions are: hydrogen partial pressure 0.5-20.0 MPa, reaction temperature 60-450° C., volume space velocity 0.1-30 h ⁻¹ , hydrogen to oil volume ratio 5-1000 Nm ³ /m ³ .

Preferred de-doping reaction conditions are: hydrogen partial pressure of 1-12 MPa, reaction temperature of 100-400° C., volume space velocity of 0.2-20 h ⁻¹ , hydrogen-to-oil volume ratio of 10-800 Nm ³ /m ³ .

In the present invention, the reaction effluent obtained from the de-doping reactor is subjected to gas-liquid separation to obtain a first gas phase material and a first liquid phase material, and the silicon content of the obtained first liquid phase material is less than 1 μg/g, the metal content is less than 5 μg/g, and the chlorine content is less than 0.5 μg/g.

The first liquid phase material is fractionated to obtain a first fraction, a second fraction and a third fraction, wherein the first fraction is a _C5 and below hydrocarbon fraction, the second fraction is a _C6 - _C8 hydrocarbon fraction, and the third fraction is a _C9 and above hydrocarbon fraction.

In the hydrotreating unit of step (2) of the present invention, the second fraction obtained in the impurity removal unit of step (1), i.e., the C ₆ -C ₈ hydrocarbon fraction, enters the hydrotreating reactor and contacts with the hydrotreating catalyst under hydrotreating reaction conditions to carry out reactions such as hydrodesulfurization, hydrodenitrogenation and olefin hydrogenation saturation.

In one embodiment of the present invention, the hydrofining reaction conditions are: hydrogen partial pressure 0.5-20.0 MPa, reaction temperature 60-450°C, volume space velocity 0.1-30 h ^-1 , hydrogen-to-oil volume ratio 5-1000 Nm ³ /m ³ ;

Preferred hydrofining reaction conditions are: hydrogen partial pressure of 1.0-12.0 MPa, reaction temperature of 100-420°C, volume space velocity of 0.2-20 h ^-1 , hydrogen-to-oil volume ratio of 10-800 Nm ³ /m ³ .

In one embodiment of the present invention, the hydrorefining catalyst comprises a hydrogenation metal active component and a carrier. The content of the hydrogenation metal active component is 5 to 50% by weight in terms of oxide, based on the total weight of the hydrorefining catalyst.

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

The reaction effluent obtained from the hydrofining reactor is separated to obtain a second gas phase material and a second liquid phase material. In one embodiment of the present invention, the obtained second liquid phase material has an aromatic content of 20 to 90% by mass, a sulfur content of <1 μg/g, a nitrogen content of <1 μg/g, a silicon content of <1 μg/g, a chlorine content of <0.5 μg/g, a total metal content of <1 μg/g, and a bromine value of <0.5 gBr/100g, which is a high-quality aromatic extraction raw material.

In one embodiment of the present invention, the third fraction obtained in step (1) enters a catalytic cracking unit, contacts with a catalytic cracking catalyst, and reacts under catalytic cracking reaction conditions.

In a preferred case, the catalytic cracking unit aims to produce more light olefins and aromatic products.

In one embodiment of the present invention, the catalytic cracking unit is selected from one or more of the catalytic cracking process technologies of DCC, CPP and HCC.

In one embodiment of the present invention, the reaction temperature of the catalytic cracking unit is 500-850°C, the catalyst-oil weight ratio is (1-50):1, the water-oil mass ratio is (0.01-1):1, and the reaction pressure is 0.1-2MPa.

In one embodiment of the present invention, the catalytic cracking catalyst is one or more of a metal oxide type catalytic cracking catalyst and a zeolite type catalytic cracking catalyst.

In one embodiment of the present invention, the composition of the zeolite-type catalytic cracking catalyst is as follows: based on the dry weight of the zeolite-type catalytic cracking catalyst, the zeolite-type catalytic cracking catalyst includes 1-50 weight% of zeolite, 5-99 weight% of inorganic oxide and 0-70 weight% of clay.

In a preferred embodiment, based on the dry weight of the zeolite, the zeolite comprises 50-100 wt% of a large-pore zeolite and 0-50 wt% of a medium-pore zeolite, the large-pore zeolite comprises at least one selected from REY, REHY, USY and high-silicon Y, the medium-pore zeolite comprises ZSM series zeolite and/or ZRP zeolite; the inorganic oxide comprises silicon oxide and/or aluminum oxide; and the clay comprises kaolin and/or halloysite.

In one embodiment of the present invention, the feed of the catalytic cracking unit includes optional catalytic cracking feedstock, which is petroleum hydrocarbon oil and/or mineral oil, the petroleum hydrocarbon oil is selected from at least one of vacuum wax oil, coker wax oil, deasphalted oil, residual oil, gasoline and diesel, and the mineral oil is selected from at least one of coal liquefaction oil, oil sands and shale oil.

In one embodiment of the present invention, the metal oxide type catalytic cracking catalyst contains alumina and/or aluminosilicate, and one or more metal oxides selected from alkali metal oxides, alkaline earth metal oxides, and Group VIII metal oxides.

In a preferred embodiment, the aluminosilicate is selected from silica-alumina, amorphous aluminum silicate, and molecular sieves.

In a preferred embodiment, the metal oxide is selected from one or more of K, Na, Ca, Fe, Co, Ni, and Mo oxides.

In one embodiment of the present invention, the reaction effluent of the catalytic cracking unit is separated to obtain a catalytic cracking catalyst and a catalytic cracking product, and the catalytic cracking product is further separated to obtain low-carbon olefins including ethylene, propylene and butene, a catalytic cracking gasoline fraction, a catalytic cracking diesel fraction and oil slurry; wherein the distillation range of the catalytic cracking gasoline fraction is 30 to 180°C.

In one embodiment of the present invention, the catalytic cracking gasoline fraction obtained by the catalytic cracking unit is circulated to the inlet of the hydrotreating unit; the hydrotreating reaction product is subjected to gas-liquid separation, and the obtained liquid phase material is fractionated to obtain a second liquid phase material that meets the aromatic feed demand, wherein the aromatic content in the second liquid phase material is 20 to 90% by mass, the sulfur content is <1 μg/g, the nitrogen content is <1 μg/g, the silicon content is <1 μg/g, the chlorine content is <0.5 μg/g, the total metal content is <1 μg/g, and the bromine value is <0.5gBr/100g, which is a high-quality aromatic extraction raw material.

Another aspect of the present invention provides a system for any of the above methods, comprising a removal unit, a hydrofining unit;

The impurity removal unit is provided with an impurity removal reactor filled with waste hydrogenation catalyst, the impurity removal reactor is provided with at least one inlet for waste plastic oil and/or waste tire oil, at least one first fraction outlet, at least one second fraction outlet, and at least one third fraction outlet, the waste hydrogenation catalyst is one or more selected from any fixed bed hydrogenation process unit in the field of hydrocarbon oil processing, including a protective agent used to the end, a catalyst at the end, and a regenerated protective agent and a regenerated catalyst;

The hydrotreating unit is provided with a hydrotreating reactor filled with a hydrotreating catalyst, a feed inlet, at least one second gas phase material outlet and at least one second liquid phase material outlet, and the second fraction outlet of the de-doping unit is connected to the feed inlet of the hydrotreating unit.

In one embodiment of the present invention, the system further comprises a catalytic cracking unit, the feed inlet of the catalytic cracking unit is connected to the third fraction outlet of the de-impurity unit, the catalytic cracking unit is provided with at least one low-carbon olefin outlet and at least one catalytic cracking gasoline fraction outlet; the catalytic cracking gasoline fraction outlet is connected to the feed inlet of the hydrotreating unit.

In one embodiment of the present invention, the de-doping 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 de-doping reactor is two or more fixed-bed hydrogenation reactors connected in parallel, each fixed-bed hydrogenation reactor is loaded with spent hydrogenation catalyst, and each fixed-bed hydrogenation reactor is provided with at least one feed inlet and at least one reaction effluent outlet.

Features of the present invention:

1. The present invention can process waste plastic oil and waste tire oil converted from various processes, and after being processed by a removal unit and a hydrorefining unit and organically combined with a catalytic cracking unit, provide high-quality aromatic extraction raw materials for the aromatic extraction process.

2. The present invention effectively removes impurities, especially silicon impurities, chlorine impurities and metal impurities, from waste plastic oil and waste tire oil in the impurity removal unit, thereby avoiding the influence of these impurities on the hydrorefining catalyst in the hydrorefining unit, thereby extending the overall operation cycle.

3. The present invention uses waste hydrogenation catalysts, which are low in cost and have good impurity removal effects. In a preferred embodiment of the present invention, a moving bed or two parallel fixed bed reactors switched in turn are used for pretreatment, achieving the purpose of long-term deep desiliconization, demetallization and dechlorination.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is a schematic diagram of one embodiment of the method for producing aromatics extraction raw materials from waste plastic oil and/or waste tire oil provided by the present invention.

DETAILED DESCRIPTION

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

FIG1 is a schematic diagram of one embodiment of the method for producing aromatics extraction raw materials from waste plastic oil and/or waste tire oil provided by the present invention. As shown in FIG1, after the waste plastic oil and/or waste tire oil from pipeline 1 is pressurized by feed pump 2, it enters heating furnace 4 from pipeline 3 together with new hydrogen from pipeline 17 and circulating hydrogen from pipeline 16 for heating. The heated mixed hydrogen material enters impurity removal unit through pipeline 5. The impurity removal unit is provided with two parallel fixed bed hydrogenation reactors 8 and 9. The fixed bed hydrogenation reactor 8 is provided with catalyst bed A, which is graded and loaded with waste hydrogenation catalyst. The fixed bed hydrogenation reactor 9 is provided with catalyst bed B, which is graded and loaded with waste hydrogenation catalyst. In one embodiment, the mixed hydrogen material enters fixed bed hydrogenation reactor 8 through pipeline 6, contacts with graded and loaded waste hydrogenation catalyst, and performs impurity removal reaction under impurity removal reaction conditions. At this time, the fixed bed hydrogenation reactor 9 is used as a standby. When the silicon or metal on the waste hydrogenation catalyst in the fixed bed hydrogenation reactor 8 is saturated, the mixed hydrogen material enters the fixed bed hydrogenation reactor 9 through pipeline 7 for reaction, and the fixed bed hydrogenation reactor 8 is cut out of the reaction system, and then the waste hydrogenation catalyst in the catalyst bed A is replaced. The reaction effluent obtained from the impurity removal unit enters the high-pressure separator 12 through pipelines 10 and 11 for gas-liquid separation, and the obtained first liquid phase material enters the fractionation tower 18 through pipeline 14, and after cutting, the first fraction, the second fraction and the third fraction are obtained, which are respectively extracted through pipelines 19, 20 and 21; the obtained first gas phase material enters the circulating hydrogen compressor 15 through pipeline 13 for pressurization, and then circulates to the inlet of the heating furnace 4 through pipeline 16.

The second fraction from pipeline 20 and the catalytic cracking gasoline fraction from pipeline 24 are mixed with the new hydrogen from pipeline 25 and the circulating hydrogen from pipeline 33, and then heated together in a heating furnace 26 and enter into a hydrotreating reactor 27, where they are contacted with a hydrotreating catalyst for reaction. The reaction effluent enters a high-pressure separator 29 via a pipeline 28 for gas-liquid separation, and the obtained second liquid phase material is extracted via a pipeline 30. The obtained second gas phase material is pressurized by a circulating hydrogen compressor 32 and then returned to the inlet of the heating furnace 26 via a pipeline 33.

The third fraction from pipeline 21 enters catalytic cracking unit 22 for catalytic cracking reaction, contacts with catalytic cracking catalyst, and reacts under catalytic cracking reaction conditions. After separation of the reaction effluent, a catalytic cracking gasoline fraction is obtained, which is sent to the inlet of the hydrotreating unit via pipeline 24; the catalytic cracking heavy fraction is extracted via pipeline 23.

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

In the embodiments, the silicon content in the hydrocarbon material is determined by the method of "Single Wavelength Dispersive X-ray Fluorescence for Determination of Silicon Content in Gasoline and Related Products" (SH/T0993-2019).

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.

The dechlorinating agent used in the embodiment is industrial dechlorinating agent RDY-100, produced by Jinan Ruidong Industrial Co., Ltd.

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

The gasoline hydrogenation final stage catalyst E used in the embodiment has a carrier of aluminum oxide, a butterfly shape, an equivalent diameter of 1.6 mm, and an active composition including: molybdenum oxide 10 wt%, cobalt oxide 3.5 wt%, carbon content 8.0 wt%, and sulfur content 7.0 wt%;

The diesel hydrofining final stage catalyst F used in the embodiment has a carrier of alumina, a butterfly shape, an equivalent diameter of 1.6 mm, and an active composition including: molybdenum oxide 26% by weight, nickel oxide 4.0% by weight, carbon content 20% by weight, and sulfur content 15% by weight;

The final hydrogenation catalyst G used in the embodiment is a residual oil hydrogenation protective agent final catalyst, the carrier is alumina, Raschig ring, equivalent diameter 6.0mm, active composition includes: molybdenum oxide ~2% by weight, nickel oxide 0.5% by weight, carbon content 40% by weight, sulfur content 5% by weight.

The hydrotreating catalyst H used in the example has a carrier of alumina, clover, an equivalent diameter of 1.6 mm, and an active metal composition of tungsten oxide 19 wt%, nickel oxide 2.0 wt%, and cobalt oxide 0.4 wt%.

The properties of the raw materials used are shown in Table 1, where raw material I is a mixed raw material of waste plastic oil and waste tire oil, the mixing ratio is 40:60 by weight, and J is waste tire oil.

Examples 1-3

The waste plastic oil and/or waste tire oil raw material enters the de-doping reactor and contacts with the waste hydrogenation catalyst in the presence of hydrogen, and performs de-doping reaction under de-doping reaction conditions. The obtained reaction effluent is separated to obtain a first gas phase material and a first liquid phase material. The obtained first liquid phase material is further separated to obtain a first fraction (C1-C5), a second fraction (C6-C8) and a third fraction (C9+).

The second fraction enters the hydrotreating reactor, contacts the hydrotreating catalyst, and undergoes a hydrotreating reaction under the hydrotreating reaction conditions. After the reaction effluent is separated, a second gas phase material and a second liquid phase material are obtained. The specific reaction conditions and product properties are shown in Table 2.

As shown in Table 2, the obtained second liquid phase material has low sulfur, low nitrogen and low bromine value, and is a high-quality aromatics extraction raw material.

Embodiment 4-5

The waste plastic oil and/or waste tire oil raw material enters the de-doping reactor and contacts with the waste hydrogenation catalyst in the presence of hydrogen, and performs de-doping reaction under de-doping reaction conditions. The obtained reaction effluent is separated to obtain a first gas phase material and a first liquid phase material. The obtained first liquid phase material is further separated to obtain a first fraction (C1-C5), a second fraction (C6-C8) and a third fraction (C9+).

The obtained second fraction enters the hydrofining reactor, contacts the hydrofining catalyst, and performs a hydrofining reaction under the hydrofining reaction conditions. After the reaction effluent is separated, a second gas phase material and a second liquid phase material are obtained. The specific reaction conditions and product properties are shown in Table 3.

The third fraction obtained enters the catalytic cracking unit, contacts with the catalytic cracking catalyst for reaction, and the reaction effluent is separated to obtain products including light olefins and catalytic cracking gasoline fractions. The catalytic cracking gasoline fraction obtained is circulated to the inlet of the hydrofining reactor to react with the second fraction. The catalytic cracking catalyst is CRP, produced by Sinopec Catalyst Branch. The catalytic cracking reaction temperature is 550°C, the reaction pressure is 0.11MPa, the catalyst-oil mass ratio is 9.0, the water-oil mass ratio is 0.2, the space velocity is 4h ^-1 , and the catalyst regeneration temperature is 715°C.

As shown in Table 3, the obtained second liquid phase material has low sulfur, low nitrogen and low bromine value, and is a high-quality aromatics extraction raw material.

Table 1

Table 2

Table 3

Example 6

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

When reactor 1 was running for 2500 hours, the silicon content of the liquid phase material in the reaction effluent was greater than 1 μg/g. At this time, the reactor was switched to reactor 2 for de-impurity reaction, and the silicon content of the liquid phase material was reduced to less than 1 μg/g. The catalyst was replaced in reactor 1, and the cycle achieved long-term operation.

Table 4

Example 7

In this embodiment, the impurity removal unit adopts a moving bed reactor, with raw material J as the feed. The catalyst loading conditions, impurity removal reaction conditions and reaction results are listed in Table 5.

As can be seen from Table 5, by adopting the method of the present invention, a moving bed is used in the de-impurity unit to treat raw material J with a high impurity content. The silicon content of the obtained first liquid phase material is less than 1 μg/g, the chlorine content is less than 0.5 μg/g, the metal content is less than 5 μg/g, and the agent consumption is 3.2 kg/ton of oil.

Table 5

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

Claims (23)

1. A method for producing aromatic hydrocarbon extraction raw materials from waste plastic oil and/or waste tire oil, including: (1) Removal unit, the raw materials of waste plastic oil and/or waste tire oil enter the removal reactor and contact the waste hydrogenation catalyst in the presence of hydrogen, and the removal reaction is carried out under the removal reaction conditions, and the resulting reaction effluent is processed After gas-liquid separation, a first gas phase material and a first liquid phase material are obtained. The silicon content of the obtained first liquid phase material is less than 1 μg/g and the metal content is less than 5 μg/g; the waste hydrogenation catalyst is selected from hydrocarbon oil processing. Any fixed-bed hydrogenation process device in the field uses protective agents and catalysts to the final stage. The waste hydrogenation catalyst includes, based on the total weight of the waste hydrogenation catalyst, the content of hydrogenation active metal oxide is 0 to 50 times. %, the carbon content is 5-50% by weight, the sulfur content is 6-40% by weight, the hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals; the decontamination reaction conditions It is: hydrogen partial pressure 0.5~20.0MPa, reaction temperature 60~450℃, volume space velocity 0.1~30h ^-1 , hydrogen to oil volume ratio 5~1000Nm ³ /m ³ ; The obtained first liquid phase material is fractionated to obtain a first fraction, a second fraction and a third fraction. The first fraction is a C ₅ and below hydrocarbon fraction, and the second fraction is a C ₆ to C ₈ hydrocarbon fraction, so The third fraction is the C ₉ and above hydrocarbon fraction; (2) Hydrotreating unit, the second fraction obtained in step (1) enters the hydrotreating reactor, contacts the hydrotreating catalyst in the presence of hydrogen, and performs a hydrotreating reaction under the hydrotreating reaction conditions; the resulting reaction flows out After gas-liquid separation of the material, a second gas phase material and a second liquid phase material are obtained, and the obtained second liquid phase material is the aromatic hydrocarbon extraction raw material. 2. The method according to claim 1, characterized in that it includes step (3): (3) Catalytic cracking unit. The third fraction obtained in step (1) enters the catalytic cracking unit, contacts the catalytic cracking catalyst, and reacts under catalytic cracking reaction conditions. After the reaction effluent is separated, at least low carbon olefins, catalytic cracking and catalytic cracking are obtained. gasoline fractions; The obtained catalytically cracked gasoline fraction is sent to the hydrotreating unit of step (2) and enters the hydrotreating reactor. 3. The method according to claim 1 or 2, characterized in that the waste plastic oil is obtained by one or more conversion methods of waste plastics including thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution and liquefaction. Hydrocarbon materials; the distillation range of waste plastic oil is 30 to 700°C, the silicon content is less than 10,000 μg/g, the chlorine content is less than 10,000 μg/g, and the metal content is less than 10,000 μg/g. 4. The method according to claim 3, characterized in that the waste plastics are one or more of waste plastics in fresh domestic garbage, waste plastics in industrial and agricultural production, and waste plastics in aged garbage. Waste plastics The type is one or more selected from PE, PP, PS, and PVC. 5. The method according to claim 1 or 2, characterized in that the waste tire oil is obtained from waste tires through one or more conversion methods including thermal cracking, thermal cracking, catalytic cracking, catalytic cracking, and dissolution and liquefaction. Hydrocarbon materials; the distillation range of waste tire oil is 30 to 700°C, the silicon content is less than 10,000 μg/g, the chlorine content is less than 10,000 μg/g, and the metal content is less than 10,000 μg/g. 6. The method according to claim 5, characterized in that the waste tires are various waste tires made of natural rubber and/or synthetic rubber. 7. The method according to claim 1, characterized in that the decontamination reactor is at least one fixed bed hydrogenation reactor and/or at least one moving bed hydrogenation reactor. 8. The method according to claim 1, characterized in that the deimpurity reactor is two or more fixed-bed hydrogenation reactors connected in parallel, each reactor is filled with a spent hydrogenation catalyst, and the feed passes through at least A fixed-bed hydrogenation reactor performs a decontamination reaction. When the spent hydrogenation catalyst in the fixed-bed hydrogenation reactor is saturated with silicon or metal, the feed is switched to other fixed-bed hydrogenation reactors. 9. The method according to claim 8, characterized in that when the silicon content of the first liquid phase material 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 spent hydrogenation catalyst in the decontamination reactor is Silicon saturation or metal saturation. 10. The method according to claim 1, characterized in that the equivalent diameter of the spent hydrogenation catalyst is 0.5-16 mm. 11. The method according to claim 1, characterized in that the spent hydrogenation catalyst includes, based on the total weight of the spent hydrogenation catalyst, a content of molybdenum oxide and/or tungsten oxide of 0 to 50% by weight. The content of nickel and/or cobalt oxide is 0 to 40% by weight, the carbon content is 5 to 30% by weight, and the sulfur content is 6 to 30% by weight. 12. The method according to claim 1, characterized in that the spent hydrogenation catalyst includes, based on the total weight of the spent hydrogenation catalyst, a content of hydrogenation active metal oxides of 1 to 40% by weight, and a carbon content of 1 to 40% by weight. The hydrogenation active metal is 5 to 20% by weight, and the hydrogenation active metal is selected from one or more of Group VIII metals and Group VIB metals. 13. The method according to claim 1, characterized in that a dechlorination agent is also filled in the decontamination reactor, and the filling volume ratio of the dechlorination agent to the spent catalyst is 1 to 80: 20 to 99. 14. The method of claim 13, wherein the dechlorination agent includes at least one Group IA metal compound and/or at least one Group IIA metal compound, optionally selected from Cu, Fe, and Zn. One or more metal oxides, as well as carriers and/or binders; The carrier and/or binder is selected from one or more of silica, alumina, silica-alumina, zirconia, and clay. 15. The method according to claim 1 or 13, characterized in that the chlorine content in the first liquid phase material of step (1) is less than 0.5 μg/g. 16. The method according to claim 1, characterized in that, the decontamination reaction conditions are: hydrogen partial pressure 1-12MPa, reaction temperature 100-400°C, volume space velocity 0.2-20h ^-1 , hydrogen-to-oil volume ratio 10-16. 800Nm ³ /m ³ . 17. The method according to claim 1, characterized in that the hydrorefining catalyst described in step (2) includes a hydrogenation metal active component and a carrier, based on the total weight of the hydrorefining catalyst, based on the oxidation rate On a physical basis, the content of the hydrogenation metal active component is 5 to 50% by weight. 18. The method according to claim 17, wherein 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 VIB The group metal element is molybdenum and/or tungsten, and the group VIII metal element is cobalt and/or nickel; based on the total weight of the hydrorefining catalyst, the content of the group VIB metal element is 4 ~40% by weight, and the content of the Group VIII metal element is 1-10% by weight. 19. The method according to claim 18, characterized in that, based on the total weight of the hydrorefining catalyst, the content of the Group VIB metal element is 8 to 35% by weight in terms of oxide, and the content of the Group VIII metal element is 8 to 35% by weight. The content of group metal elements is 2 to 5% by weight. 20. The method according to claim 1, characterized in that the hydrorefining reaction conditions in step (2) are: hydrogen partial pressure 0.5~20.0MPa, reaction temperature 60~450°C, volume space velocity 0.1~30h ^{- 1.} The volume ratio of hydrogen to oil is 5~1000Nm ³ /m ³ . 21. The method according to claim 20, characterized in that the hydrorefining reaction conditions are: hydrogen partial pressure 1.0~12.0MPa, reaction temperature 100~420°C, volume space velocity 0.2~20h ^-1 , hydrogen to oil volume ratio 10～800Nm ³ /m ³ . 22. The method according to claim 1, characterized in that, in the second liquid phase material obtained in step (2), the aromatic hydrocarbon content is 20-90 mass%, the sulfur content is <1 μg/g, the nitrogen content is <1 μg/g, and the silicon content is <1 μg/g. The content is <1μg/g, the chlorine content is <0.5μg/g, the total metal content is <1μg/g, the bromine value is <0.5gBr/100g, and it is the raw material for aromatic hydrocarbon extraction. 23. The method according to claim 2, characterized in that the reaction conditions of the catalytic cracking unit are: the reaction temperature is 500-850°C, the agent-oil weight ratio is (1-50):1, and the water-oil mass ratio is ( 0.01～1):1, the reaction pressure is 0.1～2MPa; the catalytic cracking catalyst is one or more of a metal oxide type catalytic cracking catalyst and a zeolite type catalytic cracking catalyst.