Method for hydrogenation of waste tires

Abstract

The invention provides a waste tire hydrogenation method, which comprises: S1, mixing waste tire particles, liquid oil and a catalyst in an oil slurry stirring tank to obtain oil slurry; s2, mixing the pressurized oil slurry and the heated hydrogen, feeding the mixture into a fluidized bed reactor, and reacting to obtain a reaction product; s3, separating out hot high-pressure separated gas and hot high-pressure separated oil from a reaction product in the step S2; s4, the hot high-pressure separation oil in the step S3 enters a hot low-pressure separation tank under reduced pressure to obtain hot low-pressure separation tank low oil, the hot low-pressure separation tank low oil enters a supercritical extraction device, liquid oil and carbon black are separated out, and part of the liquid oil enters the step S6; s5, treating the hot high-pressure gas in the step S3; and S6, enabling the other part of liquid oil in the step S4 to enter a fixed bed hydrofining cracking device for reaction, and enabling a reaction product to enter a product fractionating tower to separate out diesel oil and naphtha. The method provided by the invention can improve the yields of carbon black, naphtha and diesel oil produced by hydrogenation.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of oil refining and chemical industry, in particular to a method for hydrogenation of waste and old tires. BACKGROUND

[0002] With the continuous development of the automobile transportation industry, the amount of waste tires also increases sharply. Due to the characteristics of corrosion resistance and difficulty in decomposition under natural conditions, waste tires have become a "black pollution" problem that China and the world are concerned about. How to realize "reduction, harmlessness, greenness, resource utilization, reuse and recycling" of waste tires is a major issue in the rubber field that needs to be solved. The main processing technologies for waste tires at present are thermal cracking, catalytic cracking, microwave pyrolysis, and retreading utilization technologies. The effective product yield of the cracking technology is low, the properties are poor, and the subsequent processing is difficult. At the same time, the gas yield is high, which is not conducive to economic accounting.

[0003] The prior art with publication number CN202310796016 discloses a hydrogenation method of waste and old tire pyrolysis oil, which includes the following steps: (1) in the presence of hydrogen, the waste and old tire pyrolysis oil raw material is subjected to a gas phase desulfurization reaction in a first hydrogenation reactor to obtain a gas phase desulfurization reaction product; (2) the gas phase desulfurization reaction product is subjected to gas-liquid separation to obtain a gas phase component and a liquid phase component; (3) the liquid phase component is subjected to pressurization and hydrogen mixing, and then subjected to a liquid phase de-aromatics reaction in a second hydrogenation reactor to obtain a liquid phase de-aromatics reaction product; the N content in the waste and old tire pyrolysis oil raw material is 3000-10000 μg / g. The prior art mainly relates to the raw material of waste and old tire pyrolysis oil, and the processing raw material is limited. Moreover, the method cannot produce carbon black, naphtha, and diesel oil.

[0004] The prior art with publication number CN202310849576 discloses a preparation method of lubricating oil, which includes the following steps: a raw material containing waste and old rubber is contacted with a catalyst in a closed container under a hydrogen atmosphere to occur a catalytic cracking reaction to obtain a product containing lubricating oil; the catalyst includes a carrier, an acidic component, and an active component supported on the surface of the carrier; the active component is selected from at least one of ruthenium, rhodium, platinum, palladium, iridium, and nickel; the acidic component is selected from at least one of silicotungstic acid, ammonium metatungstate, phosphotungstic acid, and tungstic acid. The reaction mechanism of the prior art is catalytic cracking, and the gas yield is relatively large, but the liquid yield is relatively small.

[0005] In view of the above problems, the inventors have conducted a large number of experimental researches on the hydrogenation technology of waste and old tires, and particularly propose a hydrogenation method of waste and old tires. The method is used for hydrogenation of waste and old tires to produce carbon black, naphtha, and diesel oil, and can improve the yield of hydrogenation of carbon black, naphtha, and diesel oil. SUMMARY

[0006] Therefore, the present application aims to provide a method for hydrogenation of waste tires.

[0007] To achieve the above object, the technical scheme of the present application is as follows:

[0008] A method for hydrogenation of waste tires, comprising the following steps:

[0009] S1, the waste tires are sequentially subjected to wire drawing, cutting and grinding into waste tire particles of a certain size, the waste tire particles, liquid oil and catalyst are mixed in an oil slurry stirring tank (1) to obtain an oil slurry;

[0010] S2, the catalyst is loaded in a boiling bed reactor (5), then the oil slurry of step S1 is pressurized in a booster pump (2), the hydrogen gas is heated through a hydrogen gas heating furnace (4), and then the pressurized oil slurry and the heated hydrogen gas are mixed and introduced into the boiling bed reactor (5) to react to obtain a reaction product;

[0011] S3, the reaction product of step S2 is separated into hot high-pressure gas and hot high-pressure oil through a hot high-pressure separation tank (6);

[0012] S4, the hot high-pressure oil of step S3 is depressurized into a hot low-pressure tank (9) to obtain hot low-pressure oil, and the hot low-pressure oil is introduced into a supercritical extraction device (3) to separate liquid oil and carbon black, wherein part of the separated liquid oil is returned to step S1 for reaction, and the other part of the liquid oil is introduced into step S6;

[0013] S5, the hot high-pressure gas of step S3 is cooled through an air cooler (7) and then introduced into a cold high-pressure separation tank (10) to separate cold high-pressure gas, cold high-pressure oil and sulfur-containing sewage, the cold high-pressure gas is buffered in a circulating hydrogen buffer tank (14) and then pressurized in a circulating hydrogen compressor (12), the pressurized circulating hydrogen gas is mixed with high-purity hydrogen gas and introduced into the hydrogen gas heating furnace (4); the cold high-pressure oil and the sulfur-containing sewage are introduced into a cold low-pressure tank (11) to separate sulfur-containing dry gas, sulfur-containing sewage and cold low-pressure oil;

[0014] S6, the other part of the liquid oil in step S4 is introduced into a fixed bed hydrogenation refining and cracking device (17) to react, and the reaction product is introduced into a product fractionating column to separate diesel oil and naphtha.

[0015] The method of the present application can produce carbon black, naphtha and diesel oil, and can improve the yield of hydrogenation production of carbon black, naphtha and diesel oil, avoiding the problems of low effective product yield, poor quality, difficult subsequent processing and high gas yield of traditional cracking technology, which is not conducive to economic accounting.

[0016] Further, in step S4, the supercritical extraction device adopts a supercritical extraction solvent which is a mixture of one or more of propane, n-butane, isobutane, pentane.

[0017] Further, in step S4, the supercritical extraction device adopts a supercritical extraction solvent which is a mixture of n-butane and isobutane, wherein the weight ratio of n-butane to isobutane is 1-3:1.

[0018] By limiting the composition of the supercritical extraction solvent in the supercritical extraction device, the separation effect of liquid oil and carbon black can be improved, and the yield of carbon black can be improved.

[0019] Further, in step S4, the weight ratio of the supercritical extraction solvent to the hot low-temperature separation tank low oil is 3-5:1.

[0020] By limiting the ratio of the supercritical extraction solvent to the hot low-temperature separation tank low oil, the separation effect of liquid oil and carbon black can be improved, and the yield of carbon black can be improved.

[0021] Further, in step S1, the weight ratio of the waste tire particles to the liquid oil is 1:0.8-2.

[0022] Further, in step S1, the size of the waste tire particles is <2000 μm.

[0023] Further, in step S2, the weight ratio of the catalyst to the waste tire particles is 1-2:1.

[0024] Further, in steps S1 and S2, the catalyst is one of a microspherical catalyst and a homogeneous catalyst.

[0025] Further, in step S2, the reaction conditions are specifically: a reaction temperature of 250-450°C, a reaction pressure of 3-20 MPa, and a hydrogen oil volume ratio of 350-1500.

[0026] Further, the yield of carbon black produced in step S4 accounts for 25-50 wt% of the weight of the waste tire particles in step S1.

[0027] Compared with the prior art, the method for hydrogenation of waste tires has the following advantages:

[0028] 1) The method can produce carbon black, naphtha and diesel oil, and can improve the yield of hydrogenation to produce carbon black, naphtha and diesel oil, avoiding the problems of low yield of effective products, poor properties and difficult subsequent processing in traditional cracking technology, and high gas yield, which is not conducive to economic accounting.

[0029] 2) The present application adopts a boiling bed reactor, adopts a supported microsphere type catalyst, the catalyst can be regenerated and used, greatly reduces the use cost of the catalyst, by setting the catalyst loading and unloading tank, the online loading and unloading of the catalyst can be realized, the activity of the catalyst in the boiling bed reactor is always stable, so that the long-period stable operation of the device is ensured;

[0030] 3) The present application directly converts waste tires into oil products through a boiling bed hydrogenation, can provide high-quality raw materials for subsequent fixed bed hydrogenation cracking, avoids the high content of chlorine and unsaturated hydrocarbons in the waste tire oil generated by conventional pyrolysis, which is not conducive to the long-term stable operation of the fixed bed, and ensures the long-period stable operation of the subsequent fixed bed hydrogenation unit. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 A flow chart of the method for hydrogenation of waste tires according to the present application.

[0032] BRIEF DESCRIPTION OF DRAWINGS

[0033] 1-oil slurry stirring tank; 2-oil slurry booster pump; 3-supercritical extraction device; 4-hydrogen heating furnace; 5-boiling bed reactor; 6-hot high-pressure separation tank; 7-air cooler; 8-catalyst loading and unloading tank; 9-hot low-pressure separation tank; 10-cold high-pressure separation tank; 11-cold low-pressure separation tank; 12-circulating hydrogen compressor; 13-new hydrogen compressor; 14-circulating hydrogen buffer tank; 15-fractionating column; 16-heat exchanger; 17-fixed bed hydrogenation and cracking device. DETAILED DESCRIPTION

[0034] In order to make the above-mentioned purposes, features and advantages of the present application more obvious and easy to understand, the specific embodiments of the present application will be described in detail below with reference to the drawings.

[0035] As shown in Figure 1 The present application provides a method for hydrogenation of waste tires, comprising the following steps:

[0036] S1, the waste tires are sequentially subjected to wire drawing, cutting and grinding into waste tire particles of a certain size, the waste tire particles, liquid oil and catalyst are mixed in the oil slurry stirring tank 1 to obtain oil slurry;

[0037] S2, the catalyst is loaded in the boiling bed reactor 5, then the oil slurry of step S1 is pressurized in the booster pump 2, the hydrogen gas is heated through the hydrogen heating furnace 4, then the pressurized oil slurry and the heated hydrogen gas are mixed and introduced into the boiling bed reactor for reaction to obtain a reaction product;

[0038] S3, the reaction product of step S2 is separated by the hot high-pressure separation tank 6 to obtain hot high-pressure gas and hot high-pressure oil;

[0039] S4, the hot high oil of step S3 is reduced pressure into the hot low tank 9 to obtain the hot low tank low oil, and the hot low tank low oil is introduced into the supercritical extraction device 3 to separate liquid oil and carbon black, wherein part of the separated liquid oil is returned to step S1 to participate in the reaction, and the other part of the liquid oil is introduced into step S6;

[0040] S5, the hot high gas of step S3 is cooled by the air cooler 7 and then introduced into the cold high pressure separation tank 10 to separate cold high oil, cold high gas and sulfur-containing sewage, the cold high gas is buffered in the circulating hydrogen buffer tank 14 and then introduced into the circulating hydrogen compressor 12 to increase the pressure, and the high-pressure circulating hydrogen gas is mixed with high-purity hydrogen gas and introduced into the hydrogen heating furnace; the cold high oil and the sulfur-containing sewage are introduced into the cold low tank 11 to separate sulfur-containing dry gas, sulfur-containing sewage and cold low oil.

[0041] S6, the other part of the liquid oil in step S4 is introduced into the fixed bed hydrofining cracking device 17 to react, and the reaction product is introduced into the product fractionation tower to separate diesel and naphtha.

[0042] Specifically, in step S1, the liquid oil is one or more of the circulating solvent oil, the pyrolysis tire oil supplemented from outside the system, and the catalytic slurry oil.

[0043] Specifically, in step S1, the weight ratio of the waste tire particles to the liquid oil is 1:0.8-2.

[0044] Specifically, in step S1, the size of the waste tire particles is <2000 μm.

[0045] Specifically, in steps S1 and S2, the catalyst is one of a microspherical catalyst and a homogeneous catalyst.

[0046] Specifically, when the catalyst is a microspherical catalyst, the microspherical catalyst is a supported type, the active metal is one or more of Ni, Co, Mo and W, and the particle size of the microspherical catalyst is 0.2-1.2 mm, more preferably, the particle size of the microspherical catalyst is 0.6-1.0 mm.

[0047] Specifically, when the catalyst is a homogeneous catalyst, the catalyst is a water-soluble catalyst or an oil-soluble catalyst mixed with one or more of Ni, Co, Mo and W.

[0048] Specifically, in step S1, the addition amount of the catalyst is 50-1000 ppmw, preferably 200-500 ppmw, of the mass of the waste tire particles.

[0049] Specifically, in step S2, the weight ratio of the catalyst to the waste tire particles is 1-2:1.

[0050] Specifically, in step S2, the reaction conditions are as follows: reaction temperature 250-450℃, reaction pressure 3-20MPa, hydrogen / oil volume ratio 350-1500. Preferably, the reaction temperature is 360-410℃, the reaction pressure is 8-16MPa, and the hydrogen / oil volume ratio is 600-1200.

[0051] Specifically, in step S2, the ebullated bed reactor is one or more ebullated bed reactors connected in series.

[0052] Specifically, in step S2, the bottom of the ebullated bed reactor 5 is provided with a batch-operated catalyst loading and unloading tank 8, and a solid-liquid separator is arranged inside the catalyst loading and unloading tank 8 for separating the failed catalyst and the liquid oil. This arrangement effectively ensures the stability of the activity of the catalyst in the ebullated bed reactor.

[0053] Specifically, the pressure of the pressurized oil slurry is 10-14MPag, and the heating temperature is 200-300℃.

[0054] Specifically, in step S4, the supercritical extraction device uses a mixture of one or more of propane, n-butane, isobutane, and pentane as the solvent.

[0055] Specifically, in step S4, the supercritical extraction device uses a mixture of n-butane and isobutane as the solvent, wherein the weight ratio of n-butane to isobutane is 1-3:1.

[0056] Specifically, in step S4, the weight ratio of the supercritical extraction solvent to the hot low-oil tank is 3-5:1.

[0057] Specificly, the carbon black yield generated in step S4 accounts for 25-50wt% of the proportion of the waste tires in step S1, preferably 30-40wt%.

[0058] The technical solutions in the embodiments of the present application will be described clearly and completely below in combination with the embodiments of the present application.

[0059] Embodiment 1

[0060] The present embodiment provides a method for hydrogenation of waste tires, comprising the following steps:

[0061] (1) The waste tires are sequentially subjected to wire drawing, cutting, and grinding into 1000 micron waste tire particles. The waste tire particles, recycled solvent oil, and homogeneous catalyst are mixed in an oil slurry stirring tank 1 to obtain an oil slurry; wherein the weight ratio of the waste tire particles to the recycled solvent oil is 1:1, and the homogeneous catalyst is added in an amount of 0.5% of the mass of the waste tire particles;

[0062] (2) In the boiling bed reactor 5, fill the microspherical nickel-molybdenum catalyst, the spherical diameter is 0.4-1.5mm, the nickel+molybdenum metal content is 5%-30%, then the oil slurry of step S1 is pressurized in the pressure pump 2, the pressure is 12.0MPag, the hydrogen gas is heated through the hydrogen gas heating furnace 4, the temperature is 410℃, then the pressurized oil slurry and the heated hydrogen gas are mixed, the temperature after mixing is 300-340℃, the mixture is put into the boiling bed reactor 5 to react to obtain the reaction product; the reaction temperature is 400℃, the reaction pressure is 12.0MPag, the hydrogen oil volume ratio is 600, the weight ratio of the catalyst to the waste tire particles is 1:1;

[0063] (3) The reaction product of step (2) is separated into hot high gas and hot high oil through the hot high pressure separation tank, the operating temperature and pressure of the hot high pressure separation tank are consistent with the boiling bed reactor;

[0064] (4) The hot high oil of step (3) is depressurized into the hot low tank to obtain the hot low tank low oil, wherein the process parameters are: pressure 5.0MPaG, temperature 400℃, the gas phase at the top of the hot low pressure separation tank 9 is discharged, and the gas-liquid separation is specifically carried out through the heat exchanger 16, the liquid enters the cold low tank and then enters the fixed bed hydrogenation and cracking device, the gas enters the cold low tank and then discharges the sulfur-containing dry gas, the liquid phase at the bottom is discharged, the hot low tank low oil enters the supercritical extraction device 3, the supercritical extraction solvent used in the supercritical extraction device is a mixture of n-butane and isobutane, wherein the weight ratio of n-butane to isobutane is 2:1, the weight ratio of the supercritical extraction solvent to the hot low tank low oil is 4:1, the circulating solvent oil and carbon black are separated, wherein the liquid temperature is 140-160℃, the liquid pressure is 0.3-1.0MPaG, part of the separated circulating solvent oil continues to return to step (1) to participate in the reaction, and the other part of the circulating solvent oil enters step (6);

[0065] (5) The hot high gas of step (3) is cooled to 50℃ through the air cooler and then enters the cold high pressure separation tank to separate the cold high gas, the cold high oil and the sulfur-containing sewage, wherein the process parameters are: pressure 11.0MpaG, temperature 50℃, the cold high gas enters the circulating hydrogen buffer tank for buffering and then enters the circulating hydrogen compressor for pressurization to 15.0MPag, the pressurized circulating hydrogen is mixed with the high-purity hydrogen gas with a pressure of 15.0MPag to enter the hydrogen gas heating furnace; the cold high oil and the sulfur-containing sewage enter the cold low tank to separate the sulfur-containing dry gas, the sulfur-containing sewage and the cold low oil;

[0066] S6, the other part of the circulating solvent oil in step (4) enters the fixed bed hydrogenation and cracking device to react, and the reaction product enters the product fractionating column to separate diesel and naphtha.

[0067] Example 2

[0068] The embodiment provides a method for hydrogenation of waste tires, comprising the following steps:

[0069] (1) The waste tires are sequentially subjected to wire drawing, cutting and grinding into 1000 micron waste tire particles, the waste tire particles, waste tire oil, recycled solvent oil and homogeneous catalyst are mixed in an oil slurry stirring tank 1 to obtain an oil slurry; wherein the weight ratio of the waste tire particles, the waste tire oil and the recycled solvent oil is 1.5:1, the weight ratio of the waste tire oil and the recycled solvent oil is 3:2, and the homogeneous catalyst is added in an amount of 0.5% of the mass of the waste tire particles;

[0070] (2) A microspherical nickel-molybdenum catalyst is filled in a boiling bed reactor 5, the spherical diameter is 0.2-1.2 mm, the cobalt+molybdenum metal content is 5%-30%, then the oil slurry of step S1 is pressurized in a pressure increasing pump 2, the pressure is increased to 16.0 MPag, hydrogen gas is heated through a hydrogen gas heating furnace 4, the temperature is increased to 400℃, then the pressurized oil slurry and the heated hydrogen gas are mixed, the temperature after mixing is 280-320℃, and the mixture is introduced into the boiling bed reactor 5 to react to obtain a reaction product; the reaction temperature is 400℃, the reaction pressure is 16.0 MPag, the hydrogen oil volume ratio is 600, and the weight ratio of the microspherical nickel-molybdenum catalyst and the waste tire particles is 1:1;

[0071] (3) The reaction product of step (2) is separated into hot high separation gas and hot high separation oil through a hot high pressure separation tank 6; the operating temperature and pressure of the hot high pressure separation tank are consistent with those of the boiling bed reactor;

[0072] (4) The hot high separation oil of step (3) is depressurized into a hot low separation tank 9 to obtain hot low separation tank low oil, wherein the process parameters are as follows: the pressure is 5.0 MPaG, the temperature is 400℃, the gas phase is discharged from the top of the hot low pressure separation tank, and the liquid phase is discharged from the bottom, and the hot low separation tank low oil is introduced into a supercritical extraction device 3, wherein the supercritical extraction solvent is a mixture of n-butane and isobutane, the weight ratio of n-butane to isobutane is 2:1, the weight ratio of the supercritical extraction solvent to the hot low separation tank low oil is 4:1, and recycled solvent oil and carbon black are separated, wherein the liquid temperature is 140-160℃, the liquid pressure is 0.3-1.0 MPaG, a part of the separated recycled solvent oil is returned to step (1) to participate in the reaction, and another part of the recycled solvent oil is introduced into step (6);

[0073] (5) The hot high-pressure separation tank separates the hot high-pressure gas and the hot high-pressure oil from the reaction product of step (2). The operating temperature and pressure of the hot high-pressure separation tank are consistent with those of the ebullated-bed reactor.

[0074] S6, the other part of the circulating solvent oil in step (4) is introduced into the fixed-bed hydrofining cracking device for reaction, and the reaction product is introduced into the product fractionating column to separate diesel oil and naphtha.

[0075] Example 3

[0076] The embodiment provides a method for hydrogenation of waste tires, comprising the following steps:

[0077] (1) The waste tires are sequentially subjected to wire drawing, cutting, and grinding into 1000-micron waste tire particles. The waste tire particles, circulating solvent oil, and homogeneous catalyst are mixed in an oil slurry stirring tank 1 to obtain an oil slurry. The weight ratio of the waste tire particles to the circulating solvent oil is 1:1, and the homogeneous catalyst is added in an amount of 0.5% of the mass of the waste tire particles.

[0078] (2) The ebullated-bed reactor 5 is filled with microspherical nickel-molybdenum catalyst with a spherical diameter of 0.3-1.1 mm and a cobalt+nickel+molybdenum metal content of 5%-30%. The oil slurry of step S1 is pressurized to 15.0 MPag in the pressure increasing pump 2, the hydrogen gas passing through the hydrogen gas heating furnace 4 is heated to 430°C, and then the pressurized oil slurry and the heated hydrogen gas are mixed, and the temperature of the mixture is 270-320°C. The mixture is introduced into the ebullated-bed reactor 5 for reaction to obtain a reaction product. The reaction temperature is 400°C, the reaction pressure is 15.0 MPag, the hydrogen / oil volume ratio is 600, and the weight ratio of the catalyst to the waste tire particles is 1:1.

[0079] (3) The reaction product of step (2) is separated by a hot high-pressure separation tank to obtain hot high-pressure gas and hot high-pressure oil. The operating temperature and pressure of the hot high-pressure separation tank are consistent with those of the ebullated-bed reactor.

[0080] (4) The hot high separation oil of step (3) is reduced pressure into a hot low separation tank to obtain hot low separation tank low oil, wherein the process parameters are: pressure 5.0 MPaG, temperature 400℃, the gas phase is removed from the top of the hot low separation tank, and the liquid phase is removed from the bottom, and the hot low separation tank low oil is introduced into a supercritical extraction device, wherein the supercritical extraction solvent is a mixture of n-butane and isobutane, wherein n-butane:isobutane=2:1 (weight ratio), and the supercritical extraction solvent:hot low separation tank low oil=4:1 (weight ratio), and the circulating solvent oil and carbon black are separated, wherein the liquid temperature is 140-160℃, and the liquid pressure is 0.3-1.0 MPaG, and part of the separated circulating solvent oil continues to return to step (1) to participate in the reaction, and the other part of the circulating solvent oil enters step (6);

[0081] (5) The hot high separation gas of step (3) is cooled to 50℃ after passing through an air cooler and is introduced into a cold high separation tank to separate cold high separation gas, cold high separation oil and sulfur-containing sewage, wherein the process parameters are: pressure 11.0 MPaG, temperature 50℃, the cold high separation gas enters a circulating hydrogen buffer tank for buffering and then enters a circulating hydrogen compressor for pressure increase to 17.0 MPag, the circulating hydrogen after pressure increase is mixed with high-purity hydrogen gas at a pressure of 17.0 MPag and enters a hydrogen heating furnace; the cold high separation oil and sulfur-containing sewage enter a cold low separation tank to separate sulfur-containing dry gas, sulfur-containing sewage and cold low separation oil;

[0082] S6, the other part of the circulating solvent oil in step (4) is introduced into a fixed bed hydrofining cracking device for reaction, and the reaction product is introduced into a product fractionation tower to separate diesel and naphtha.

[0083] Comparative Example 1

[0084] The difference between this comparative example and Example 1 is that step (4) only uses n-butane as a supercritical extraction solvent, wherein the weight ratio of the supercritical extraction solvent:hot low separation tank low oil is 6:1.

[0085] In order to prove the effect of the waste tire hydrogenation upgrading in the present application, the above-mentioned Example 1, Example 2, Example 3 and Comparative Example 1 are determined by experiment.

[0086] Carbon black yield=carbon black mass / waste tire particle mass×100%;

[0087] Effective oil yield=(naphtha+diesel mass) / waste tire particle mass×100%.

[0088] The experimental determination results of the examples are shown in Table 1.

[0089] Table 1 hydrogenation results of waste tires in examples

[0090]

[0091] As can be seen from Examples 1 to 3 and Comparative Example 1, the yield of carbon black and the effective yield of carbon black obtained by the method of the present application are both effectively improved.

[0092] Although the present application has been disclosed with reference to the above embodiments, the present application is not limited to the above. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present application, and the scope of protection of the present application should be defined by the scope of claims.

Claims

1. A method for hydrogenating waste tires, characterized in that, Includes the following steps: S1. Waste tires are sequentially processed by drawing steel wire, cutting, and grinding into waste tire particles of a certain size. The waste tire particles, liquid oil, and catalyst are mixed in an oil slurry mixing tank (1) to obtain an oil slurry. S2. The catalyst is loaded into the fluidized bed reactor (5), and the oil slurry from step S1 is pressurized in the booster pump (2) and the hydrogen gas passed through the hydrogen heater (4) is heated. The pressurized oil slurry and the heated hydrogen gas are then mixed and fed into the fluidized bed reactor (5) to react and obtain the reaction product. S3. The reaction products of step S2 are separated into hot high-pressure gas and hot high-pressure oil in a hot high-pressure separator (6). S4. The hot high-grade oil from step S3 is depressurized and transferred to the hot low-grade oil tank (9) to obtain the low-grade oil in the hot low-grade oil tank. The low-grade oil in the hot low-grade oil tank is then transferred to the supercritical extraction device (3) to separate liquid oil and carbon black. Part of the separated liquid oil is returned to step S1 to participate in the reaction, and the other part of the liquid oil is transferred to step S6. S5. After the hot high-pressure gas from step S3 is cooled by the air cooler (7), it enters the cold high-pressure separator (10) to separate the cold high-pressure gas, cold high-pressure oil and sulfur-containing wastewater. The cold high-pressure gas enters the circulating hydrogen buffer tank (14) for buffering and then enters the circulating hydrogen compressor (12) for pressurization. The pressurized circulating hydrogen is mixed with high-purity hydrogen and enters the hydrogen heater (4). The cold high-pressure oil and sulfur-containing wastewater enter the cold low-pressure separator (11) to separate the sulfur-containing dry gas, sulfur-containing wastewater and cold low-pressure oil. S6. Another portion of the liquid oil from step S4 is fed into a fixed-bed hydrorefining cracking unit (17) for reaction, and the reaction products are fed into a product fractionation tower to separate diesel and naphtha.

2. The method according to claim 1, characterized in that, In step S4, the supercritical extraction solvent used in the supercritical extraction device is one or a mixture of propane, n-butane, isobutane, and pentane.

3. The method according to claim 1, characterized in that, In step S4, the supercritical extraction solvent used in the supercritical extraction device is a mixture of n-butane and isobutane, wherein the weight ratio of n-butane to isobutane is 1~3:

1.

4. The method according to claim 3, characterized in that, In step S4, the weight ratio of the supercritical extraction solvent to the hot low-temperature oil is 3~5:

1.

5. The method according to claim 1, characterized in that, In step S1, the weight ratio of the waste tire particles to the liquid oil is 1:0.8 to 2.

6. The method according to claim 1, characterized in that, In step S1, the size of the waste tire particles is <2000μm.

7. The method according to claim 1, characterized in that, In step S2, the weight ratio of the catalyst to the waste tire particles is 1~2:

1.

8. The method according to claim 1, characterized in that, In steps S1 and S2, the catalyst is either a microspherical catalyst or a homogeneous catalyst.

9. The method according to claim 1, characterized in that, In step S2, the specific reaction conditions are: reaction temperature 250-450℃, reaction pressure 3-20MPa, and hydrogen-to-oil volume ratio 350-1500.

10. The method according to claim 1, characterized in that, The carbon black produced in step S4 accounts for 25-50 wt% of the weight of the waste tire particles in step S1.

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