Aromatic hydrocarbon production method by coupling conversion of CO and polyolefins
A binary functional catalyst with metal and molecular sieve structures selectively produces high-value aromatic hydrocarbons from polyolefins and CO at low temperatures, addressing the inefficiencies of existing methods and reducing emissions.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Applications
- Current Assignee / Owner
- DALIAN INSTITUTE OF CHEMICAL PHYSICS CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2023-10-31
- Publication Date
- 2026-05-28
AI Technical Summary
Existing methods for recycling polyolefins produce low-value products due to random and disordered C-C bond breaking, and there is a lack of economically viable techniques for producing high-value aromatic hydrocarbons from polyolefins and carbon monoxide at low temperatures.
A binary functional catalyst comprising a metal and a molecular sieve with MFI, MEL, or MWW topological structures is used to couple CO and polyolefins at low temperatures, activating both reactants to selectively produce aromatic hydrocarbons.
The catalyst achieves high selectivity and yield of benzene, toluene, and xylene under mild conditions, with yields twice that of conventional thermal decomposition, and reduces CO2 emissions by utilizing CO without hydrogen.
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Abstract
Description
[Technical Field]
[0001] This invention belongs to the technical field of producing high-value chemical products such as aromatic hydrocarbons by coupling conversion of CO and polyolefins, and specifically relates to a catalyst and a method for producing aromatic hydrocarbons by coupling conversion of CO and polyolefins. [Background technology]
[0002] Plastics are important organic synthetic polymer materials and are widely used in various fields such as packaging, agriculture, construction, and automobiles. By 2019, the annual global production of plastics had already reached 460 million tons, making it one of the most produced synthetic materials. Of this, polyolefin plastics, represented by polyethylene and polypropylene, account for approximately 55% of the total plastic production. However, because polyolefins are chemically inert, large quantities of them are used in single-use products, and recycling remains difficult. The serious environmental pollution problems caused by this have already attracted the attention of researchers.
[0003] In polyolefins, the C(sp) on their skeleton 3 )-C(sp 3 The C-C bond is very stable and difficult to break. Therefore, when recovering polyolefins, it is necessary to introduce additional energy to break the C-C bond. However, in conventional polyolefin recovery technologies, such as pyrolysis and hydrolysis, the breaking of the C-C bond is random and disordered, and the resulting product is a pyrolysis oil mainly composed of long-chain alkanes or alkenes. This product has a wide boiling point range, relatively low added value, and cannot selectively produce high-value-added products. For this reason, there is a lack of economically viable driving force for the pyrolysis of plastics.
[0004] Carbon monoxide molecules are unsaturated metastable molecules that are chemically stable in terms of decomposition. At room temperature, carbon monoxide does not react with acids or alkalis, but when mixed with air, it forms an explosive mixture that can burn or explode under open flame or high temperatures, making it a flammable and explosive gas. The oxidation state of the carbon element in carbon monoxide molecules is +2, and it can be oxidized to +4, giving it reducing properties, and can also be reduced to a low oxidation state, giving it oxidizing properties. As a main component of synthesis gas and various other gases, carbon monoxide is an important raw material for synthesizing a range of basic organic chemical industrial products and intermediates. Using carbon monoxide as a starting material, almost all basic chemical products can be produced, such as ammonia, phosgene, algol, acids, anhydrides, esters, aldehydes, ethers, amines, alkanes, and alkenes. Furthermore, by utilizing the property of carbon monoxide to react with transition metals to produce carbonyl metal complexes and their derivatives, various homogeneous phase reaction catalysts necessary for organic chemical industrial production can be manufactured. In addition, carbon monoxide can be used as a chain termination agent in polyethylene polymerization reactions. Some studies have shown that high-value chemicals and liquid fuels (e.g., low-carbon olefins, aromatic hydrocarbons, or higher alcohols) can be produced using CO and H2 under high temperature and pressure conditions. However, at present, the acquisition of H2 resources is heavily dependent on the consumption of fossil energy (coal, oil, and natural gas). In the absence of superior "green hydrogen" acquisition technologies, the use of large quantities of H2 resources means increased CO2 emissions. Therefore, realizing the resource utilization of CO under conditions that do not use hydrogen is both more attractive and a greater challenge.
[0005] Aromatic hydrocarbons, particularly benzene, toluene, and xylene (BTX), are essential raw materials for the organic chemical industry with high demand, and are generally obtained by catalytic reforming and rectification of naphtha. Obtaining aromatic hydrocarbons under mild conditions by catalytic pyrolysis using discarded polyolefins is an economically viable technique. Zhang et al. at the University of California, Santa Barbara, converted polyolefins to long-chain alkyl aromatic hydrocarbons at 280°C using a Pt / γ-Al2O3 catalyst, achieving a yield of over 70% of aromatic hydrocarbons. While this method enables conversion at mild temperatures such as 280°C, the product contains very little of the higher-value-added benzene, toluene, and xylene (Non-Patent Literature 1). No techniques have yet been reported for producing high-value-added aromatic hydrocarbons by coupling conversion of CO with polyolefins at relatively low temperatures, e.g., below 300°C. [Prior art documents] [Non-patent literature]
[0006] [Non-Patent Document 1] Fan Zhang et al. Science 370(2020)437-441 [Overview of the Initiative] [Problems that the invention aims to solve]
[0007] This invention has been made in view of the above-mentioned problems, and provides a catalyst and a method for producing aromatic hydrocarbons by coupling conversion of CO and polyolefin. [Means for solving the problem]
[0008] The technical means of the present invention are as follows: The present invention provides a catalyst for producing aromatic hydrocarbons by coupling conversion of carbon monoxide and polyolefin, wherein the catalyst is a binary functional catalyst consisting of a metal and a molecular sieve, and the conversion reaction is carried out in a kettle reactor under the action of the catalyst using carbon monoxide and polyolefin as reaction raw materials. The catalyst is a binary functional catalyst in which one functional component consists of a metal, a metal oxide, or both, and the other functional component consists of a molecular sieve, wherein the metal and metal oxide components exert an effect of activating CO, and the molecular sieve exerts an effect of activating polyolefin, and the molecular sieve is a molecular sieve having MFI, MEL, and MWW topological structures.
[0009] In the above technical means, preferably, the metal or metal oxide comprises one or more elements from Fe, Co, Ni, Mn, Ce, Cu, Ru, Zn, Ga, Rh, Pd, Ir, and Pt, and the mass fraction of the metal or metal oxide with respect to the binary functional catalyst is 0.1 wt% to 60 wt%, preferably 0.5 wt% to 50 wt%.
[0010] In the above technical means, preferably, the metal or metal oxide is directly supported on a molecular sieve, or the metal or metal oxide is dispersed on a metal oxide support and then physically mixed with the molecular sieve to constitute a dual-function catalyst, wherein the metal oxide support is Al2O3, TiO2, CeO2, ZnO, MoO x , MnO x Includes one or more of the following.
[0011] In the above technical means, preferably, the skeletal elements of the molecular sieve having the MFI, MEL, and MWW topological structures include at least one of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B, and Si-O-Al-Ge, and preferably the molecular sieve having the MFI, MEL, and MWW topological structures is at least one of MCM-22, ZSM-11, or ZSM-5.
[0012] In the above technical means, preferably, the molecular sieve having the MFI, MEL, and MWW topological structures contains a moderate acid, and the amount of moderate acid sites is ≥0.1 mol / kg, preferably ≥0.2 mol / kg, and more preferably ≥0.25 mol / kg.
[0013] The acid strength is defined by the NH3-TPD peak, and there are three levels of acidity: weak, medium-strong, and strong. The NH3-TPD corresponds to the position of the NH3 desorption peak. The position of the desorption peak is determined by recording the thermal conduction signal of NH3 desorption with a TCD under standard test conditions, i.e., the ratio of sample mass w to carrier gas flow rate f (w / f) = 100 g·h / L and the heating rate 10 °C / min, drawing a desorption curve, and classifying the inorganic solid into three levels of acid strength according to the peak position of the curve. A weak acid refers to an acidic site where the NH3 desorption temperature is less than 245 °C, a medium-strong acid refers to an acidic site where the NH3 desorption temperature is between 275 and 500 °C, and a strong acid refers to an acidic site where the NH3 desorption temperature is greater than 500 °C. The molecular sieve may be synthesized in the laboratory or commercially purchased, as long as it satisfies the requirements of the present invention.
[0014] In the above technical means, preferably, the metal or metal oxide is compounded with the molecular sieve by physical mixing or support, and preferably, the metal or metal oxide is compounded with the molecular sieve by immersion, deposition and sedimentation, gas phase deposition, or physical mixing.
[0015] In the above technical means, preferably, the binary functional catalyst is pre-reduced, and the pre-reducing conditions are that the reducing atmosphere is H2 or CO, the reduction temperature is 300°C to 500°C, and the reduction time is 0.5h to 10h.
[0016] In the above technical means, the present invention further provides a method for producing aromatic hydrocarbons by coupling conversion of carbon monoxide and polyolefin. Carbon monoxide and polyolefin are used as reaction raw materials, a conversion reaction is carried out in a kettle reactor, and the catalyst provided by the above technical means is used.
[0017] In the above technical means, preferably, the polyolefin includes one or more of polyethylene, polypropylene, and polybutylene, and plastic products or used waste plastics processed from the above polyolefin as raw materials.
[0018] In the above technical means, preferably, the pressure of the carbon monoxide is 0.2 to 6 MPa, preferably 0.5 to 3 MPa, the reaction temperature is 180 to 400 °C, preferably 230 to 300 °C, and the mass ratio of the catalyst to the polyolefin is ≥ 1:500, preferably ≥ 1:100.
[0019] In the above technical means, preferably, when the reaction is carried out in a batch reactor, the residence time of the reactants is 0.5 to 20 h, preferably 1 to 10 h, more preferably 2 to 10 h.
[0020] In the above technical means, preferably, when the reaction is carried out in a moving bed reactor, the gas hourly space velocity (GHSV) of the reaction is 20 to 2000 mL·g -1 ·h -1 and preferably 20 to 1000 mL·g -1 ·h -1 and more preferably 80 to 1000 mL·g -1 ·h -1 is.
Advantages of the Invention
[0021] According to the present invention, it has the following advantages. 1. Different from the conventional plastic pyrolysis technology, the technical means of the present invention uses a composite catalyst to couple CO and polyolefin in one step (one-step) to realize highly selective conversion to high-value-added aromatic hydrocarbons such as benzene, toluene, and xylene. By adding CO, not only can it be used as a raw material for aromatic hydrocarbons, but it can also react with the H species generated by hydrogen transfer in the aromatization process, thereby suppressing the generation of alkanes and improving the selectivity of the aromatic hydrocarbon component.
[0022] 2. Unlike the high-temperature thermal decomposition mechanism of polyolefins, at low temperatures (reaction temperature below 300°C), polyolefins cannot produce aromatic hydrocarbons through the dehydrogenation aromatization process (Equation 1), but can produce aromatic hydrocarbons solely through the hydrogen transfer aromatization process (Equation 2). Therefore, the yield of aromatic hydrocarbons at low temperatures is limited by its reaction mechanism and does not exceed 50%. [ka] [ka]
[0023] This invention utilizes hydrogen spillover between catalyst components to consume hydrogen leaked from the hydrogen transfer aromatization reaction of the molecular sieve using CO, thereby preventing the formation of alkanes and disrupting the conventional reaction equilibrium. This allows for the highly selective production of high-value aromatic hydrocarbon products under relatively mild reaction conditions (reaction temperature below 300°C), making it highly applicable.
[0024] 3. The present invention uses polyolefin as a raw material. The polyolefin may be not only polyolefin itself, but also plastic products made by processing polyolefin as a raw material, such as plastic bags, plastic containers, wraps, various films, and waste food packaging. Because the raw material has a wide supply source and high potential for use, this is an efficient and scalable method of utilizing polyolefin.
[0025] 4. The present invention can be applied not only to the resource utilization of CO exhaust gas generated in production processes such as petroleum refining, coke production in the metallurgical industry, and steelmaking, but also to the resource utilization of high-concentration CO exhaust gas generated in production processes for synthesizing ammonia and methanol in the chemical industry. Furthermore, it can be applied to the resource utilization of exhaust gas containing both CO and CO2. Therefore, it has a wide range of raw material sources, high applicability, significantly promotes the utilization of CO, and can reduce CO2 emissions.
[0026] 5. The catalyst of the present invention can be recycled after undergoing a regeneration process of air roasting and hydrogen reduction, without significant catalyst loss, and can greatly reduce cost problems caused by catalyst deactivation.
[0027] 6. The present invention not only provides a simple manufacturing process for the composite catalyst, operates under mild conditions, and simultaneously achieves high value-added utilization of polyolefins and CO during the reaction process, but also results in a product with high space-time yield and selectivity, with a yield of 50-80% for mixed aromatic hydrocarbons, and the proportion of benzene, toluene, and xylene in the aromatic hydrocarbons being 60% or more. The yield of aromatic hydrocarbons is approximately twice that of the conventional thermal decomposition process of polyolefins under inert gas conditions. [Modes for carrying out the invention]
[0028] The present invention will be described in more detail below with reference to examples, but the scope of the claims of the present invention is not limited by these examples. Furthermore, the examples only illustrate some of the conditions for achieving this objective, and do not mean that this objective cannot be achieved unless these conditions are met.
[0029] 1. Manufacturing of molecular sieves In this invention, the medium-strength acid is the H spectrum of the solid-state NMR ( 1 Acidity is measured by methods such as 1H NMR, NH3-TPD, infrared spectroscopy, and chemical titration. However, the method of measuring acidity is not limited to the methods described above.
[0030] The molecular sieves having the MFI, MEL, and MWW topological structures described in this invention can be produced by various methods and conditions, and in this invention, production by hydrothermal synthesis is described as an example.
[0031] 1) Molecular sieves having an MFI topology structure are manufactured by the following process. The oxide SiO2:Al2O3:Na2O:R:H2O = 5:0.02:2:1.5:200 (mass ratio) is used to weigh out 30% silica sol (mass concentration), aluminum sulfate, sodium hydroxide, tetrapropylammonium hydroxide (R), and deionized water as raw materials. The mixture is stirred at 30°C and aged for 2 hours. After 2 hours, it is transferred to a hydrothermal reaction vessel and crystallized at 180°C for 48 hours. The mixture is rapidly cooled to room temperature in a water bath, and repeated centrifugation washing is performed until the pH of the supernatant reaches 7. The precipitate is dried at 110°C for 17 hours, and then roasted in an air atmosphere at 600°C for 3 hours to obtain a ZSM-5 molecular sieve with an MFI topology structure, which is designated as component 1.
[0032] 2) Molecular sieves having a MEL topological structure are manufactured by the following process. Silica sol, aluminum isopropoxide, sodium hydroxide, TBAOH(R), and deionized water are weighed as raw materials in the oxide SiO2:Al2O3:Na2O:R:H2O = 10:0.3:1:2:200 (mass ratio). After stirring overnight at room temperature, the gel is placed in a 65°C oven to dry, then pulverized and placed in a crystallization vessel. A certain amount of deionized water is added, and crystallization is carried out at 170°C for 3 days. The resulting product is subjected to suction filtration, washing, drying, and ammonium exchange, and then roasted in a muffle oven at 600°C for 6 hours to obtain a ZSM-11 molecular sieve having a MEL topology structure, which is designated as component 2.
[0033] The skeletal element composition of the molecular sieve having the MFI, MEL, and MWW topological structures may be at least one of Si-O, Si-Al-O, Si-Al-PO, Si-Al-BO, and Si-Al-Ge-O. [Table 1]
[0034] 2. Manufacturing of a dual-function catalyst A binary functional catalyst is formed by compounding a metal and a molecular sieve using methods such as immersion, deposition, gas-phase deposition, or physical mixing. Here, as an example, a binary functional catalyst is produced by the immersion method. The immersion process can be carried out by either isovolume immersion or overvolume immersion, as described below. The metal source is dissolved in deionized water and placed in the precursor solution. A molecular sieve is placed in the precursor solution and stirred thoroughly to uniformly disperse the precursor solution and its solutes onto the molecular sieve. Subsequently, the molecular sieve with the required metal oxide modification is obtained by drying and roasting. When employing an isovolume immersion method, the pore volume V of the molecular sieve p It is necessary to measure this beforehand. The volume of the precursor solution used is V0 = V p Therefore, when employing the over-immersion method, the volume of the precursor solution used is V0 <V p That is the case. The manufacturing process and parameter characteristics of the catalyst are specifically shown in Tables 2 and 3. [Table 2]
[0035] 3. Examples of catalytic reactions This catalyst can be used in a kettle-type reactor. In the reaction apparatus, a gas flow meter is installed to control the gas flow rate, and the product is quantitatively analyzed using gas chromatography. Let's explain using a kettle reactor as an example. Mix 2g of the catalyst of the present invention with 40g of polyolefin and place in a kettle reactor. Replace the air in the reactor with CO, inject CO gas (containing 5% Ar as an internal standard for chromatographic analysis) at 0.2 to 6 MPa, and raise the temperature to 180°C to 300°C to carry out the reaction. Quantitative analysis of the product is performed by chromatography. The gas phase product is analyzed using Ar as an internal standard, and the yield is calculated. After collecting the liquid product, it is analyzed using n-undecane as an internal standard, and the yield is calculated. The reaction performance can be altered by changing the reaction temperature, reaction pressure, and the mass ratio of CO to polyolefin supply. The performance is as follows: The total selectivity for aromatic hydrocarbons reaches 60-80%, with benzene, toluene, and xylene (BTX) accounting for more than 60% of the aromatic hydrocarbons. The addition of CO not only serves as a raw material for aromatic hydrocarbons, but also reacts with hydrogen species generated by hydrogen transfer in the aromatization process, thereby suppressing the formation of alkanes and improving the selectivity of aromatic hydrocarbon components. The applications of the catalyst and the data on its effects are specifically shown in Table 3. [Table 3]
[0036] The metal component contained in catalyst L used in Comparative Example 1 and its manufacturing method are the same as those of catalyst A. The molecular sieve component used is replaced with a molecular sieve of component 5, which is commercially available at the Nankai University Catalyst Factory and has a three-dimensional 8-membered ring pore.
[0037] The metal components contained in catalyst M used in Comparative Example 2 and the method of its production are the same as those of catalyst A. The molecular sieve component used is replaced with a molecular sieve of component 6, which is commercially available at the Nankai University Catalyst Factory and has a three-dimensional 12-membered ring pore.
[0038] The metal component contained in catalyst N used in Comparative Example 3 and its manufacturing method are the same as those of catalyst A. The molecular sieve component used is replaced with a molecular sieve of component 7, which is commercially available at the Nankai University Catalyst Factory and has pores with coexistence of one-dimensional 8-membered rings and 12-membered rings.
[0039] The metal component contained in catalyst O used in Comparative Example 4 and its manufacturing method are the same as those of catalyst A. The molecular sieve component used is replaced with a molecular sieve of component 8, which is commercially available at the Nankai University Catalyst Factory and has a one-dimensional 10-membered ring pore.
[0040] The reaction results of Comparative Examples 1-4 demonstrate that molecular sieves with different topological structures significantly affect product selectivity. SAPO-34, with its three-dimensional 8-membered ring pore structure, is unfavorable for the conversion of polyolefins and the generation of aromatic hydrocarbon products, while being suitable for the generation of hydrocarbons with short carbon chains, resulting in an aromatic hydrocarbon yield of only 4%. The USY molecular sieve with its three-dimensional 12-membered ring pore has relatively large pore openings, which allows for the very easy generation of heavy aromatic hydrocarbons (e.g., naphthalene), which are then deactivated by coal accumulation. As a result, the yield of heavy aromatic hydrocarbons and coal accumulation is high, with heavy aromatic hydrocarbons accounting for 68% of all aromatic hydrocarbon products. The commercially available MOR molecular sieve with a coexistence of one-dimensional 8-membered and 12-membered rings, and the SAPO-11 molecular sieve with its one-dimensional 10-membered ring pore, are unfavorable for the aromatization process, producing mainly decomposed gasoline as the product, with a low aromatic hydrocarbon content and an aromatic hydrocarbon yield of only 21%.
[0041] The metal component contained in catalyst P used in Comparative Example 5 and its manufacturing method are the same as those of catalyst A, but the molecular sieve component used is replaced with the molecular sieve of component 9, and the acid density of its medium-strong acid is only 0.07 mmol / g. The reaction performance of Comparative Example 5 was extremely poor, which is probably because the acid density was extremely low, resulting in a very weak aromatization ability of the reaction. Therefore, a certain medium-strong acid density is very important.
[0042] The catalyst Q used in Comparative Example 6 was obtained by directly immersing Pt in γ-Al2O3. As a result, almost no CO was converted, the conversion rate of polyolefins was very low, and both the yield of aromatic hydrocarbons and the yield of BTX were very low.
[0043] The molecular sieve component used in R in Comparative Example 7 is the same as that used in catalyst A (component 1), the only difference being that it does not contain the metal Pt component. Since the molecular sieve has almost no ability to catalytically activate CO, only olefins react in the catalytic reaction process. That is, olefins are catalyzed by the molecular sieve and directly undergo the aromatization reaction, but the yield of aromatic hydrocarbons is not high (38%), and mainly long-chain alkanes are produced, and the conversion rate of CO is only 0.02 g·g. (ポリオレフィン) ·h -1 Therefore, it is not possible to produce aromatic hydrocarbons with very low and high selectivity and to utilize CO.
[0044] Comparative Examples 6 and 7 show that when only one functional component, either a metal oxide or a molecular sieve, is present, the reaction effect is poor and the excellent reaction performance described in the present invention is completely absent.
[0045] Both the catalyst used in Comparative Example 8 and the catalyst used in Example 1 are catalyst A, but no olefin was added in Comparative Example 8. The experimental results show that when polyolefin is not added, CO is not effectively converted.
[0046] Both the catalyst used in Comparative Example 9 and the catalyst used in Example 1 are catalyst A, but in Comparative Example 9, CO was not added, and N2 was used as the pressurized atmosphere gas. The experimental results showed that when CO is not introduced, polyolefins can be converted to aromatic hydrocarbons by a dual-function catalyst consisting of a metal and a molecular sieve, and the reaction results were similar to those of Comparative Example 7, with a relatively low yield of aromatic hydrocarbons, only 36%, indicating that it does not possess the excellent reaction performance described in the present invention.
[0047] The reaction results in Comparative Examples 8 and 9 demonstrate that the conversion of CO and the conversion of polyolefins are mutually coupled and supportive. In the absence of polyolefins, CO is not effectively converted. Furthermore, in the absence of CO, polyolefins are not highly selectively converted to aromatic hydrocarbons, and the amount of alkane byproducts increases.
[0048] The catalyst used in Comparative Example 10 was the same as catalyst A used in Example 1. However, in Comparative Example 10, the partial pressure of CO was low, resulting in insufficient CO. Therefore, the effect of CO in promoting the selective production of aromatic hydrocarbons was small. Consequently, it is extremely important to ensure sufficient CO to promote the catalytic reaction.
[0049] The table above shows that the topological structure of the molecular sieve, its acidity, the supply ratio of CO to polyolefin waste plastics, and the compatibility between the metal or metal oxide and the molecular sieve all play extremely important roles and directly influence the selectivity of mixed aromatic hydrocarbons, the conversion rate of CO, and the content of benzene, toluene, and xylene in the aromatic hydrocarbons.
[0050] (Note) (Note 1) Carbon monoxide and polyolefin are used as reaction raw materials, and a binary functional catalyst is used as the catalyst, wherein one functional component consists of a metal, a metal oxide, or both, and the other functional component consists of a molecular sieve. The molecular sieve is a molecular sieve having MFI, MEL, and MWW topological structures. A method for producing aromatic hydrocarbons by coupling conversion of carbon monoxide and polyolefin, characterized in that the metal element in the metal or metal oxide includes one or more of Fe, Co, Ni, Mn, Ce, Cu, Ru, Zn, Ga, Rh, Pd, Ir, and Pt.
[0051] (Note 2) The manufacturing method according to Appendix 1, characterized in that the pressure of the carbon monoxide is 0.2 to 6 MPa, the reaction temperature is 180 to 400°C, and the mass ratio of the catalyst to the polyolefin is ≥ 1:500.
[0052] (Note 3) The mass fraction of the metal or metal oxide in the binary functional catalyst is 0.1 wt% to 60 wt%, and the binary functional catalyst is constructed by directly supporting the metal or metal oxide on the molecular sieve or by dispersing it on a metal oxide support and then physically mixing it with the molecular sieve, and the metal oxide support is Al2O3, TiO2, ZrO2, CeO2, ZnO, MoO x , MnO x The manufacturing method according to Appendix 1, characterized by including one or more of the above.
[0053] (Note 4) The manufacturing method according to Appendix 1, characterized in that the skeletal elements of the molecular sieve having the aforementioned MFI, MEL, and MWW topological structures include at least one of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B, and Si-O-Al-Ge, and the molecular sieve having the aforementioned MFI, MEL, and MWW topological structures is preferably at least one of MCM-22, ZSM-11, or ZSM-5.
[0054] (Note 5) The production method according to Appendix 1, characterized in that the molecular sieve having the aforementioned MFI, MEL, and MWW topological structures contains a moderate acid, and the amount of moderate acid sites is ≥0.1 mol / kg.
[0055] (Note 6) The manufacturing method according to Appendix 1, characterized in that the metal or metal oxide is compounded with a molecular sieve by physical mixing or support, and the support is provided by immersion, deposition, or gas phase deposition to support the metal or metal oxide on the molecular sieve.
[0056] (Note 7) The manufacturing method according to Appendix 1, characterized in that the metal and metal oxide component in the dual-function catalyst exhibit an activating effect on CO, and the molecular sieve exhibits an activating effect on polyolefins.
[0057] (Note 8) The manufacturing method according to Appendix 1, characterized in that the binary functional catalyst is pre-reduced, the reducing atmosphere is H2 or CO, the reduction temperature is 300°C to 500°C, and the reduction time is 0.5h to 10h.
[0058] (Note 9) When the reaction is carried out in a kettle reactor, the residence time of the reactants is 0.5 to 20 hours, and when the reaction is carried out in a moving bed reactor, the gas space velocity of the reaction is 20 to 2000 mL·g. -1 ·h -1 The manufacturing method described in Appendix 2, characterized in that it is the same as described above.
[0059] (Note 10) The manufacturing method according to Appendix 1, characterized in that the polyolefin includes one or more of polyethylene, polypropylene, and polybutylene, and plastic products or used waste plastics processed using the polyolefin as a raw material.
Claims
1. Carbon monoxide and polyolefin are used as reaction raw materials, and a binary functional catalyst is used as the catalyst, wherein one functional component consists of a metal, a metal oxide, or both, and the other functional component consists of a molecular sieve. The molecular sieve is a molecular sieve having MFI, MEL, and MWW topological structures. A method for producing aromatic hydrocarbons by coupling conversion of carbon monoxide and polyolefin, characterized in that the metal element in the metal or metal oxide includes one or more of Fe, Co, Ni, Mn, Ce, Cu, Ru, Zn, Ga, Rh, Pd, Ir, and Pt.
2. The manufacturing method according to claim 1, characterized in that the pressure of the carbon monoxide is 0.2 to 6 MPa, the reaction temperature is 180 to 400°C, and the mass ratio of the catalyst to the polyolefin is ≥ 1:
500.
3. The mass fraction of the metal or metal oxide relative to the binary functional catalyst is 0.1 wt% to 60 wt%, and the binary functional catalyst is constructed by directly supporting the metal or metal oxide on the molecular sieve or by dispersing it on a metal oxide support and then physically mixing it with the molecular sieve, wherein the metal oxide support is Al ２ O ３ , TiO ２ , ZrO ２ , CEO ２ ZnO, MoO ｘ MnO ｘ The manufacturing method according to claim 1, characterized by comprising one or more of the above.
4. The manufacturing method according to claim 1, characterized in that the skeletal elements of the molecular sieve having the MFI, MEL, and MWW topological structures include at least one of Si-O, Si-O-Al, Si-O-Al-P, Si-O-Al-B, and Si-O-Al-Ge, and the molecular sieve having the MFI, MEL, and MWW topological structures is preferably at least one of MCM-22, ZSM-11, or ZSM-5.
5. The production method according to claim 1, characterized in that the molecular sieve having the aforementioned MFI, MEL, and MWW topological structures contains a moderate acid, and the amount of moderate acid sites is ≥ 0.1 mol / kg.
6. The manufacturing method according to claim 1, characterized in that the metal or metal oxide is compounded with a molecular sieve by physical mixing or support, and the support is made by supporting the metal or metal oxide on the molecular sieve by immersion, deposition, or gas phase deposition.
7. The manufacturing method according to claim 1, characterized in that the metal and metal oxide component in the dual-function catalyst exhibit an activating effect on CO, and the molecular sieve exhibits an activating effect on polyolefins.
8. The aforementioned dual-function catalyst is pre-reduced, and the reducing atmosphere is H ２ The manufacturing method according to claim 1, characterized in that CO is used, the reduction temperature is 300°C to 500°C, and the reduction time is 0.5h to 10h.
9. When the reaction is carried out in a batch reactor, the residence time of the reactants is 0.5 to 20 h, and when the reaction is carried out in a moving bed reactor, the gas hourly space velocity of the reaction is 20 to 2000 mL·g －１ ·h －１ The production method according to claim 2, characterized in that it is as described above.
10. The manufacturing method according to claim 1, characterized in that the polyolefin includes one or more of polyethylene, polypropylene, and polybutylene, and plastic products or used waste plastics processed using the polyolefin as a raw material.