Plastic oil desiliconizing agent, preparation method thereof and plastic oil desiliconizing method

Abstract

The invention relates to a plastic oil desiliconization agent and a preparation method thereof, and a plastic oil desiliconization method, the plastic oil desiliconization agent comprises, by weight, 5-70% of a beta molecular sieve, 5-90% of alumina, and 5-20% of a metal component, the metal component contains lanthanide rare earth metal oxide and / or transition metal oxide. The plastic oil desiliconizing agent disclosed by the invention has good desiliconizing effect and catalytic cracking effect.

Description

A desilication agent for plastic oil, its preparation method, and a method for desilication plastic oil. Technical Field

[0001] This application relates to a desilication agent for plastic oil, its preparation method, and a method for desilication of plastic oil. Background Technology

[0003] Silicon is a common impurity element in waste plastics, primarily originating from silicon-containing substances such as silicone oil and polydimethylsiloxane (PDMS) added during the production process. Furthermore, the addition of silicone rubber and silicone resin during the pyrolysis of waste plastics is also a significant reason for the high silicon content in plastic pyrolysis oil. The silicon species in waste plastic oil mainly originate from the pyrolysis products of silicon-containing substances in the plastics, typically existing in the form of alkylcyclosiloxanes, primarily octamethylcyclotetrasiloxane and decamethylcyclopentasiloxane, with a Si content ranging from 10 to 103 μg / g. During subsequent processing of waste plastic oil, these silicon species mainly deposit on the catalyst surface, affecting catalyst activity.

[0004] Therefore, in the technical route of catalytic conversion of waste plastic oil into low-carbon olefins or oil products, the influence of silicon impurities in the waste plastic oil cannot be ignored. Measures for treating silicon impurities in waste plastic oil include desilication and silicon dissolution. CN113862018A discloses a new technology for removing organosilicon by dissolving waste plastic in a special oil. This technology can reduce the viscosity of waste plastic and improve heat transfer efficiency while removing silicon. However, this technology suffers from problems such as low removal rate and secondary pollution. Summary of the Invention

[0005] The purpose of this disclosure is to provide a desiliconizing agent for plastic oil, its preparation method, and a method for desiliconizing plastic oil. The desiliconizing agent for plastic oil disclosed herein has both good desiliconization performance and catalytic cracking performance.

[0006] To achieve the above objectives, the first aspect of this disclosure provides a desilication agent for plastic oil, wherein, based on the dry weight of the desilication agent, the desilication agent contains 5-70 wt% β-molecular sieve, 5-90 wt% alumina, and 5-20 wt% a metal component, wherein the metal component contains lanthanide rare earth metal oxides and / or transition metal oxides; the pore volume of the desilication agent is 0.38 cm³. 3 / g or more, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(30-800):(2-80).

[0007] Optionally, based on the dry weight of the plastic oil desilicifying agent, the plastic oil desilicifying agent contains 5-60% by weight of β molecular sieve, 5-85% by weight of alumina and 5-18% by weight of metal components.

[0008] The pore volume of the plastic oil desilicifying agent is 0.38-0.45 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(40-300):(5-30).

[0009] Optionally, based on the dry weight of the plastic oil desilicifying agent, the plastic oil desilicifying agent contains 5-55% by weight of β molecular sieve, 10-80% by weight of alumina and 8-15% by weight of metal components.

[0010] The pore volume of the plastic oil desilicifying agent is 0.38-0.43 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(65-200):(5-20).

[0011] Optionally, the lanthanide rare earth metal oxide is selected from one or more of lanthanum oxide, lanthanum nitrate and lanthanum carbonate, and the transition metal oxide is selected from one or more of titanium oxide, manganese oxide and nickel oxide.

[0012] A second aspect of this disclosure provides a method for preparing the plastic oil desilicifying agent provided in the first aspect of this disclosure, the method comprising:

[0013] S1. The aluminum source, water and acid are mixed for the first time to obtain the first slurry;

[0014] S2. The first slurry and the metal source are mixed for the second time to obtain a second slurry; wherein the metal source contains lanthanide rare earth metal oxides and / or transition metal oxides;

[0015] S3. The second slurry and the β molecular sieve are mixed in a third step, and the resulting slurry is spray-dried and calcined.

[0016] Optionally, the solid content of the first slurry is 20-40% by weight, and the pH value is 2-5; the conditions for the first mixing include: a temperature of 20-50°C and a time of 20-80 min.

[0017] The second slurry has a solid content of 25-40% by weight and a pH value of 3-6; the second mixing conditions include a temperature of 20-30°C and a time of 20-60 min.

[0018] The conditions for the third mixing include: a temperature of 20-50°C and a time of 10-60 minutes.

[0019] Optionally, the aluminum source is selected from one or more of aluminum hydroxide, aluminum oxide, gibbsite, boehmite, boehmite, diatomite, and pseudoboehmite.

[0020] The acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid;

[0021] The metal source is selected from one or more of lanthanum carbonate, lanthanum hydroxide, lanthanum chloride, manganese chloride, and titanium dioxide.

[0022] The third aspect of this disclosure provides a method for desilicifying plastic oil, the method comprising: contacting the plastic oil with a plastic oil desilicifying agent to perform desilicification treatment, wherein the plastic oil desilicifying agent is the plastic oil desilicifying agent provided in the first aspect of this disclosure.

[0023] Optionally, the desilication treatment method includes: a temperature of 150-250℃ and an agent-to-oil ratio of 5-20.

[0024] Optionally, the desilication pretreatment is carried out in a fluidized bed reactor or a conveyor bed reactor, and the plastic oil is introduced from the bottom of the fluidized bed reactor or the bottom of the conveyor bed reactor.

[0025] Through the above technical solution, the desiliconizing agent disclosed herein has superior desiliconizing ability. When used in catalytic cracking, it can effectively remove silicon from plastic oil while improving the selectivity of coke and dry gas, and increasing the total liquid product yield.

[0026] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Detailed Implementation

[0027] The following provides a detailed description of specific embodiments of this disclosure. It should be understood that the specific embodiments described herein are for illustrative and explanatory purposes only and are not intended to limit this disclosure.

[0028] The first aspect of this disclosure provides a desilication agent for plastic oil, which, based on its dry weight, contains 5-70 wt% β-molecular sieve, 5-90 wt% alumina, and 5-20 wt% a metal component, wherein the metal component contains lanthanide rare earth metal oxides and / or transition metal oxides; the pore volume of the desilication agent is 0.38 cm³. 3 / g or more, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(30-800):(2-80).

[0029] The desiliconizing agent disclosed herein contains a specific ratio of β-molecular sieve, alumina, and metal components. The β-molecular sieve has the effect of converting organosilicon to capture and fix organosilicon in plastic oil and promoting the catalytic cracking of macromolecular hydrocarbons in plastic oil. Alumina also plays the role of capturing organosilicon. The metal components can form stable metal silicate compounds with the captured and fixed silicon. Through the synergistic effect of β-molecular sieve, alumina, and metal components, the desiliconizing agent disclosed herein has superior desiliconizing ability. When used in catalytic cracking, it can effectively remove silicon from plastic oil while also improving the selectivity of coke and dry gas and increasing the total liquid product yield.

[0030] In a preferred embodiment of this disclosure, based on the dry weight of the plastic oil desilication agent, the plastic oil desilication agent contains 5-60 wt% β-molecular sieve, 5-85 wt% alumina, and 5-18 wt% metal components; the pore volume of the plastic oil desilication agent is 0.38-0.45 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(40-300):(5-30).

[0031] In a preferred embodiment of this disclosure, based on the dry weight of the plastic oil desilication agent, the plastic oil desilication agent contains 5-55% by weight of β-molecular sieve, 10-80% by weight of alumina, and 8-15% by weight of metal components; the pore volume of the plastic oil desilication agent is 0.38-0.43 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(65-200):(5-20).

[0032] According to this disclosure, lanthanide rare earth metals and transition metals are well known to those skilled in the art. For example, lanthanide rare earth metals are selected from lanthanum, cerium, etc., and transition metals are selected from titanium, chromium, vanadium, nickel, zinc, manganese, and cobalt. In one embodiment, the lanthanide rare earth metal oxide is selected from one or more of lanthanum oxide, lanthanum nitrate, and lanthanum carbonate, and the transition metal oxide is selected from one or more of titanium oxide, manganese oxide, and nickel oxide.

[0033] The second aspect of this disclosure provides a method for preparing the desilicifying agent for plastic oil provided in the first aspect of this disclosure. The method includes: S1, mixing an aluminum source, water, and an acid to obtain a first slurry; S2, mixing the first slurry with a metal source to obtain a second slurry; wherein the metal source contains lanthanide rare earth metal oxides and / or transition metal oxides; S3, mixing the second slurry with a β molecular sieve to obtain a third slurry, and spray-drying and calcining the obtained slurry.

[0034] The method disclosed herein can prepare a plastic oil desiliconizing agent that has both good desiliconization and catalytic cracking properties. When used in the catalytic cracking process, it can effectively remove silicon from the plastic oil while improving the selectivity of coke and dry gas and increasing the total liquid product yield.

[0035] According to this disclosure, the solid content and pH value of the first slurry can vary within a wide range. In one specific embodiment of this disclosure, the solid content of the first slurry is 20-40% by weight, and the pH value is 2-5. The conditions for the first mixing include a temperature of 20-50°C and a time of 20-80 min.

[0036] According to this disclosure, the solid content and pH value of the second slurry can vary within a wide range. In one specific embodiment of this disclosure, the solid content of the second slurry is 25-40% by weight, and the pH value is 3-6. The conditions for the second mixing include a temperature of 20-30°C and a time of 20-60 min.

[0037] In one specific embodiment of this disclosure, the conditions for the third mixing include: a temperature of 20-50°C and a time of 10-60 minutes. In this disclosure, mixing can be performed using a stirring method, such as magnetic stirring or mechanical stirring, and the mixing time can be the same as the stirring time.

[0038] According to this disclosure, the aluminum source can be any aluminum source known to those skilled in the art, and can be any aluminum source that can be dissolved by acid. In one specific embodiment of this disclosure, the aluminum source is selected from one or more of aluminum hydroxide, aluminum oxide, gibbsite, boehmite, boehmite, boehmite, and boehmite; wherein, aluminum oxide can include, but is not limited to, p-alumina, χ-alumina, η-alumina, γ-alumina, κ-alumina, δ-alumina, θ-alumina, etc.

[0039] According to this disclosure, the acid may be selected from one or more of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid; the metal source may be a metal source containing lanthanide rare earth metals and / or transition metals, for example, it may be selected from one or more of lanthanum carbonate, lanthanum hydroxide, lanthanum chloride, manganese chloride and titanium dioxide.

[0040] According to this disclosure, calcination can be carried out in apparatus well known in the art, such as a tube furnace or a muffle furnace, and this disclosure does not impose any specific limitations. The calcination atmosphere can be an air atmosphere, and the calcination conditions can include a temperature of 500-700°C and a time of 30-90 minutes.

[0041] The third aspect of this disclosure provides a method for desilicifying plastic oil, the method comprising: contacting the plastic oil with a plastic oil desilicifying agent to perform desilicification treatment, wherein the plastic oil desilicifying agent is the plastic oil desilicifying agent provided in the first aspect of this disclosure.

[0042] The method for desiliconizing plastic oil disclosed herein uses a desiliconizing agent that has both good desiliconization performance and catalytic cracking performance. The method disclosed herein can effectively remove silicon from plastic oil while more effectively improving the selectivity of coke and dry gas, and increasing the total liquid product yield.

[0043] In one specific embodiment of this disclosure, the desilication treatment method includes: a temperature of 150-250°C and an agent-to-oil ratio of 5-20; preferably, the temperature is 150-200°C and the agent-to-oil ratio is 5-10.

[0044] In one specific embodiment of this disclosure, the desilication pretreatment is carried out in a fluidized bed reactor or a conveyor bed reactor, and the plastic oil is introduced from the bottom of the fluidized bed reactor or the bottom of the conveyor bed reactor.

[0045] The present disclosure will be further illustrated by the following examples, but the present disclosure is not limited thereto.

[0046] In this disclosure, the weight on a dry basis refers to the weight after calcination at about 800°C for 1 hour.

[0047] In this disclosure, the solid content of a substance refers to the ratio of the weight of the substance after high-temperature roasting to its weight before roasting, that is, the solid content of the substance = 100% - the water content of the substance.

[0048] In this disclosure, the desilicifying agent-to-oil ratio refers to the mass ratio of the desilicifying agent to the plastic oil.

[0049] In this disclosure, the pore volume of the desiliconizing agent is determined using the water droplet pore volume method, according to NB / SH / T0955-2017, pore volume method for catalytic cracking catalysts.

[0050] In the examples and comparative examples:

[0051] Boehmite was supplied by Shandong Aluminum Plant (solid content 60.8% by weight). Unless otherwise specified, all chemical reagents used in the comparative examples and embodiments were commercially available and of chemical purity.

[0052] Example 1

[0053] S1. Add 280g of pseudoboehmite (calculated as Al2O3) to deionized water at 25℃, disperse evenly, add hydrochloric acid, and contact for 30 minutes to obtain the first slurry with a solid content of 15% by weight.

[0054] S2. The first slurry is mixed with lanthanum carbonate (containing 50g of La2O3) at 30℃ and stirred for 30 minutes to obtain the second slurry;

[0055] S3. Mix the second slurry with 100g of β molecular sieve at 28℃ for 25 minutes. Spray dry the resulting third slurry to obtain a solid. Calcine the solid at 600℃ for 2 hours to obtain plastic oil desilicifying agent A1.

[0056] The composition, preparation parameters and wear index of plastic oil desilicifying agent A1 are listed in Table 1.

[0057] Examples 2-6

[0058] Plastic oil desilicone agents A2-A6 were prepared according to the method in Example 1, with the only difference being the different formulations used in the preparation. The formulation parameters, bulk density, and wear index are listed in Table 1.

[0059] Comparative Example 1

[0060] (1) Add SB powder (containing 560g of Al2O3) to deionized water, disperse evenly, then add formic acid to dissolve, and after 30 minutes, the first slurry is obtained. The pH value of the first slurry is measured to be 3.3.

[0061] (2) 1046g of deionized water-dispersed MgO slurry (containing 440g of MgO) was added to the first slurry and kept at 74℃ for 60 minutes to obtain the second slurry. The pH value of the second slurry was measured to be 9.1 and the solid content was 26% by weight. The second slurry was spray-dried and shaped, and then directly calcined at 730℃ for 3h. The calcined sample was then sieved, and particles with a particle size of 20-40μm were selected to obtain desilication agent B1.

[0062] The formulation, preparation parameters, bulk density and wear index of desilication agent B1 are listed in Table 2.

[0063] Comparative Example 2

[0064] (1) Add 560g of SB powder (calculated as Al2O3) to deionized water, disperse it evenly, add formic acid, and after contacting for 30 minutes, the first slurry is obtained. The pH value of the first slurry is 2.8 and the solid content is 20% by mass.

[0065] (2) 1046g of MgO slurry dispersed in deionized water (containing 440g of MgO) was added to the first slurry. After contacting at 56℃ for 60 minutes, the second slurry was obtained. The pH value of the second slurry was measured to be 9.1 and the solid content was 26% by mass. The second slurry was spray-dried and shaped, and then directly calcined at 730℃ for 2h to obtain desilication agent B2.

[0066] The formulation, preparation parameters, bulk density, and wear index of desilication agent B2 are listed in Table 2.

[0067] Comparative Example 3

[0068] Desilication agent B3 was prepared using the same method as in Example 1, except that the formulation used for the preparation of the desilication agent was different. The formulation parameters, bulk density and wear index are listed in Table 1.

[0069] The formulation, preparation parameters, bulk density, and wear index of desilication agent B3 are listed in Table 1.

[0070] Examples 7-12 illustrate the performance of plastic oil desilication agents in desilication plastic oils.

[0071] Examples 7-12

[0072] The desilication performance and catalytic cracking performance of the desilication agent on plastic oil were investigated on an ACE unit. The plastic oil entered from the bottom of the reactor and contacted the desilication agent. Desilication pretreatment was performed at a reaction temperature of 150°C and an agent-to-oil ratio of 6. The properties of the plastic oil used are shown in Table 3, and the evaluation conditions and results are shown in Table 4.

[0073] Comparative Examples 4-6 are used to illustrate the desilication performance of the comparative desilication agents.

[0074] Comparative Examples 4-6

[0075] The desilication performance of the desilication agent on plastic oil was investigated using the same method as in Example 7, except that the desilication agent used was the same as that prepared in Comparative Examples 1-3. The evaluation conditions and results are shown in Table 4.

[0076] Table 1

[0077]

[0078]

[0079]

[0080] Table 2

[0081] Comparative Example 1 Comparative Example 2 SB powder (as Al2O3) / g 560 560 Acid Type: Formic acid Formic acid pH of First Slurry: 3.3 2.8 Solid Content of First Slurry / wt%: 20 20 Magnesium Oxide (as MgO) / g: 440 440 pH of Second Slurry: 9.1 9.1 Solid Content of Second Slurry / wt%: 26 26 Calcination Conditions: 730℃ / 3h 730℃ / 2h Bulk Density / g·cm³ -3 0.77-0.81 Wear Index / h-1 2.4 Alumina content, 56.56% by weight; Magnesium oxide content, 44.44% by weight. surface

[0082] Table 3

[0083] Plastic oil properties density (g / cm³) 3 (20℃))0.9048 viscosity (80℃) / (mm 2 / s)18.54 viscosity (100℃) / (mm 2 / s) 10.89 Pour point / ℃ 38 Aniline point / ℃ 92.5 Residual carbon / % 2.8 Refractive index (70℃) 1.4912 Element content / mass% C 86.09 H 12.51 S 0.65 N 0.28 Si 0.15 Boiling range (D1160) / ℃ Initial boiling point 2335% 29510% 33330% 39550% 42970% 47090% 539 surface

[0084] Table 4

[0085]

[0086]

[0087] As can be seen from the above, the plastic oil desiliconizing agent disclosed herein has superior desiliconizing ability. When used in catalytic cracking processes, it can more effectively improve the selectivity of coke and dry gas and increase the total liquid product yield.

[0088] The preferred embodiments of this disclosure have been described in detail above. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0089] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0090] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A desilication agent for plastic oil, comprising, based on the dry weight of the desilication agent, 5-70 wt% β-molecular sieve, 5-90 wt% alumina, and 5-20 wt% a metal component, wherein the metal component comprises lanthanide rare earth metal oxides and / or transition metal oxides; and wherein the pore volume of the desilication agent is 0.38 cm³. 3 / g or more, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(30-800):(2-80).

2. The desilicifying agent for plastic oil according to claim 1, wherein, Based on the dry weight of the plastic oil desilication agent, the plastic oil desilication agent contains 5-60 wt% β-molecular sieve, 5-85 wt% alumina, and 5-18 wt% metal components; the pore volume of the plastic oil desilication agent is 0.38-0.45 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(40-300):(5-30).

3. The plastic oil desilicifying agent according to claim 1, wherein, Based on the dry weight of the plastic oil desilication agent, the plastic oil desilication agent contains 5-55% by weight of β molecular sieve, 10-80% by weight of alumina, and 8-15% by weight of metal components; the pore volume of the plastic oil desilication agent is 0.38-0.43 cm³. 3 / g, the weight ratio of the β molecular sieve, the alumina and the metal component is 100:(65-200):(5-20).

4. The desilicifying agent for plastic oil according to claim 1, wherein, The lanthanide rare earth metal oxides are selected from one or more of lanthanum oxide, lanthanum nitrate and lanthanum carbonate, and the transition metal oxides are selected from one or more of titanium oxide, manganese oxide and nickel oxide.

5. A method for preparing the desilicone agent for plastic oil according to any one of claims 1-4, the method comprising: S1. The aluminum source, water and acid are mixed for the first time to obtain the first slurry; S2. The first slurry and the metal source are mixed for the second time to obtain a second slurry; wherein the metal source contains lanthanide rare earth metal oxides and / or transition metal oxides; S3. The second slurry and the β molecular sieve are mixed for the third time, and the resulting slurry is spray-dried and calcined.

6. The method according to claim 5, wherein, The first slurry has a solid content of 20-40% by weight and a pH value of 2-5; the first mixing conditions include a temperature of 20-50°C and a time of 20-80 min; the second slurry has a solid content of 25-40% by weight and a pH value of 3-6; the second mixing conditions include a temperature of 20-30°C and a time of 20-60 min; the third mixing conditions include a temperature of 20-50°C and a time of 10-60 min.

7. The method according to claim 5, wherein, The aluminum source is selected from one or more of aluminum hydroxide, aluminum oxide, gibbsite, boehmite, boehmite, diaspore, and pseudoboehmite; the acid is selected from one or more of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid; and the metal source is selected from one or more of lanthanum carbonate, lanthanum hydroxide, lanthanum chloride, manganese chloride, and titanium dioxide.

8. A method for desilicifying plastic oil, the method comprising: The plastic oil is contacted with a plastic oil desilication agent to perform desilication treatment, wherein the plastic oil desilication agent is the plastic oil desilication agent according to any one of claims 1-4.

9. The method according to claim 8, wherein, The desilication treatment method includes: a temperature of 150-250℃ and an agent-to-oil ratio of 5-20.

10. The method according to claim 8, wherein, The desilication pretreatment is carried out in a fluidized bed reactor or a conveyor bed reactor, and the plastic oil is introduced from the bottom of the fluidized bed reactor or the bottom of the conveyor bed reactor.

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