Biomass pyrolytic oil and heavy oil co-catalytic cracking method based on bi-metal synergy

Abstract

The invention discloses a biomass pyrolytic oil and heavy oil co-catalytic cracking method based on bimetallic synergy, which comprises the following steps: firstly, adding a rare earth metal compound to convert acidic organic matters in biomass pyrolytic oil into rare earth metal carboxylate (acidic); then, phenolic organic matters in the biomass pyrolysis oil are converted into alkaline earth metal phenolate (alkaline) by adopting an alkaline earth metal compound, so that acidic organic matters are removed, and rare earth metal carboxylate can neutralize the alkaline earth metal phenolate to a certain extent, so that the alkalinity of a co-catalytic cracking system is reduced, and the conversion capacity of the biomass pyrolysis oil and heavy oil is improved; the method increases the yield of liquefied gas and gasoline, reduces the yield of coke and dry gas, prolongs the service life of the catalyst, has the characteristics of simple operation, easily available raw materials and environmental friendliness, and has wide industrial application prospects.

Description

Technical Field

[0001] The present invention belongs to the technical field of energy and chemical industry, and in particular relates to a co-catalytic cracking method of biomass pyrolysis oil and heavy oil based on bimetallic synergy. Technical Background

[0002] The mixing and co-cracking of biomass pyrolysis oil and heavy oil is a common and effective method to achieve the upgrading and high-quality utilization of biomass pyrolysis oil. Biomass pyrolysis oil contains a large amount of oxygen-containing organic compounds (such as acids, phenols, aldehydes, esters, alcohols, ketones, ethers, etc.), accounting for up to about 35%. Among them, the relative content of phenolic organic matter exceeds 30% of the oxygen-containing components, and the relative content of acidic organic matter accounts for 13%-26% of the oxygen-containing components. In the co-catalytic cracking process, the oxygen-containing organic compounds in biomass pyrolysis oil will generate unsaturated polycyclic compounds under the catalytic action of molecular sieves. These compounds are easily deposited on the catalyst surface, resulting in a significant increase in coke yield. Among them, acidic organic matter has a corrosive effect on the catalyst, causing catalyst poisoning and deactivation, etc., affecting the catalytic efficiency. Phenolic organic compounds are adsorbed on the catalyst surface, occupying the acidic active sites of the catalyst, reducing the active sites on the catalyst surface, and thus reducing the reaction rate and conversion efficiency. Phenolic organic compounds can react with the metal centers (such as molybdenum, tungsten, nickel, etc.) in the catalyst, preventing the metal active sites from participating in the hydrogenation reaction, resulting in catalyst deactivation. In addition, heavy metals (such as nickel, vanadium, etc.) contained in the deoxygenated products and heavy oils can also form macromolecular polycyclic compounds rich in heavy metals during the reaction. These compounds are further deposited on the catalyst pores and surface, combined with oxygen-containing unsaturated polycyclic compounds, aggravating coke formation, reducing catalyst activity, and causing rapid catalyst deactivation. Therefore, how to effectively remove oxygenated organic compounds in biomass pyrolysis oil and combat heavy metal pollution are the keys to achieving co-cracking of biomass pyrolysis oil and heavy oil.

[0003] The inventor previously applied for a patent for a method for co-catalytic cracking of biomass oil and heavy oil. The method first prepares an alkaline earth metal complex, reacts the alkaline earth metal complex with phenolic organic matter in biomass pyrolysis oil to form a metal-phenol complex, then adds an extractant to dissolve the metal-phenol complex in the extractant, and finally mixes the extracted layer solution with the heavy oil to perform catalytic cracking. During the catalytic cracking process, the alkaline earth metal in the metal-phenol complex reacts with the heavy metal ions (Ni2+, V 3+) competitive coordination occurs, such as forming alkali metal vanadate (MVO4) with vanadic acid, achieving the effect of passivating heavy metals. This method has good dephenolization effect and heavy metal ion capture ability, but there are still the following problems: (1) The metal-phenol complex produced in the process has strong alkalinity. Excessive metal-phenol complex will destroy the acid center of the catalyst, inhibit the cracking free radical chain reaction, lead to enhanced condensation reaction, increase coke yield, and accumulate coke precursors, reduce the C / H ratio of the product, increase the proportion of diesel and heavy oil, and reduce the output of liquefied gas and gasoline, affecting the quality of oil products; (2) During the process, the alkaline earth metal complex can only remove a very small amount of acidic organic matter, and cannot avoid the corrosion of the acidic organic matter on the catalyst, resulting in catalyst poisoning, deactivation, etc., and the catalyst stability needs to be improved; (3) Although the alkaline earth metal complex is easier to form with phenolic organic matter, achieving better dephenolization effect, it also complicates the dephenolization process and is not easy to be applied in industry. In view of this, the present invention provides another co-catalytic cracking method of biomass pyrolysis oil and heavy oil. Summary of the Invention

[0004] In order to solve the above problems, the purpose of the present invention is to provide a method for co-catalytic cracking of biomass pyrolysis oil and heavy oil. First, rare earth metal compounds are added to convert acidic organic matter in the biomass pyrolysis oil into rare earth metal carboxylates (acidic), and then alkaline earth metal compounds are used to convert phenolic organic matter in the biomass pyrolysis oil into alkaline earth metal phenolates (alkaline). Not only are the acidic organic matter removed, but the rare earth metal carboxylates can also neutralize the alkaline earth metal phenolates to a certain extent, reducing the alkalinity of the co-catalytic cracking system, improving the conversion capacity of biomass pyrolysis oil and heavy oil, increasing the yield of liquefied gas and gasoline, reducing the yield of coke and dry gas, and at the same time improving the stability of the catalyst.

[0005] A method for co-catalytic cracking of biomass pyrolysis oil and heavy oil, specifically comprising:

[0006] (1) adding a rare earth metal compound to biomass pyrolysis oil and heating it to 40-100° C., wherein the rare earth metal compound reacts with the acidic organic matter in the biomass pyrolysis oil to form a rare earth metal carboxylate;

[0007] (2) adding an alkaline earth metal compound to the biomass pyrolysis oil containing rare earth metal carboxylates in step (1), stirring and mixing, and reacting at 60-100° C., wherein the alkaline earth metal compound reacts with phenolic organic matter in the biomass pyrolysis oil to form alkaline earth metal phenolates, and then adding an extractant after the reaction, mixing uniformly at 30-50° C., and separating the solution into layers, wherein the upper layer is the biomass pyrolysis oil phase, and the lower layer is the extraction phase containing rare earth carboxylates and metal phenolates;

[0008] (3) The layered solution treated in step (2) is mixed evenly with heavy oil, and then catalytic cracking is carried out at 500-550° C. under the action of a catalyst.

[0009] During the catalytic cracking reaction of biomass pyrolysis oil and heavy oil, rare earth metal carboxylates and alkaline earth metal phenolates will not undergo thermal cracking and enter the liquid product, but will be preferentially adsorbed and enriched on the catalyst surface. Under high temperature water vapor conditions, the metals in rare earth metal carboxylates and alkaline earth metal phenolates react with heavy metal ions (Ni 2+ 、V 3+ ) undergo competitive coordination, such as with vanadic acid to form rare earth-heavy metal complex salts, achieving the passivation of heavy metals. This invention creatively converts the deoxidation product into a passivation active ingredient in situ, achieving a highly efficient coupling of deoxidation and heavy metal resistance.

[0010] In step (1) of the present invention, the molar ratio of the rare earth metal compound to the acidic organic matter in the biomass pyrolysis oil is 1:2-4, preferably 1:2-3.

[0011] In step (1) of the present invention, the rare earth metal compound includes one or more of lanthanum oxide, lanthanum chloride, cerium chloride, europium chloride, yttrium chloride, lanthanum nitrate, cerium nitrate, yttrium aluminum chloride, and strontium chloride. Correspondingly, the central metal of the rare earth metal carboxylate is one or more of cerium, lanthanum, yttrium, europium, and strontium, preferably one of lanthanum and cerium.

[0012] In step (1) of the present invention, a rare earth metal compound is added to the biomass pyrolysis oil, stirred and mixed, and the temperature is raised to 40-100°C, preferably 80°C, and the reaction is carried out at a constant temperature for 2-3 hours. The rare earth metal compound mainly acts as a deacidifying agent and reacts with the acidic organic matter in the biomass pyrolysis oil to form a rare earth metal carboxylate.

[0013] In step (2) of the present invention, the molar ratio of the alkaline earth metal compound to the phenolic organic matter in the biomass pyrolysis oil is 1-4:2-5, preferably 1:2-3.

[0014] In step (2) of the present invention, the alkaline earth metal compound is one or more of calcium chloride, magnesium chloride, barium chloride, magnesium ethoxide, barium hydroxide, calcium amide, calcium carbonate, magnesium tert-butoxide, and strontium chloride. Correspondingly, the central metal ion of the alkali metal phenoxide is one or more of magnesium ion, calcium ion, barium ion, and strontium ion, preferably one of magnesium ion and calcium ion.

[0015] In step (2) of the present invention, an alkaline earth metal compound is added to the biomass pyrolysis oil containing rare earth metal carboxylates, stirred and mixed, and the temperature is raised to 60-100°C, preferably 80°C, and the reaction is carried out at a constant temperature for 2-6 hours. The alkaline earth metal compound mainly acts as a dephenolizing agent and reacts with phenolic organic matter in the biomass pyrolysis oil to form alkaline earth metal phenolate.

[0016] After the reaction in step (2) of the present invention is completed, the molar ratio of the rare earth metal carboxylate to the alkaline earth metal phenolate is 1-3:1-2.

[0017] In step (2) of the present invention, the molar ratio of the total amount of rare earth metal carboxylate and alkaline earth metal phenate to the extractant is 1:1-3, most preferably 1:2.

[0018] In step (2) of the present invention, the extractant is a polar solvent, a substance with strong hydrophilicity, such as an acid ester extractant, an amide solvent, a pyridine extractant, an ionic liquid, etc.

[0019] The extractant is a polar solvent capable of simultaneously extracting rare earth metal carboxylates and alkaline earth metal phenates and is substantially immiscible with non-polar biomass substances such as alkanes and aromatic hydrocarbons. Specifically, it includes one or more of 2-ethoxyethyl acetate, 2-ethylhexylphosphonate, dimethylsulfamide, dimethylamide, pyridine, and tetraalkylammonium salts, preferably one or more of 2-ethoxyethyl acetate and 2-ethylhexylphosphonate. The rare earth metal carboxylates and alkaline earth metal phenates are cerium acetate and magnesium-guaiacol salt, cerium acetate and calcium phenate, lanthanum acetate and calcium phenate, cerium acetate and magnesium-guaiacol salt, cerium glycerate and barium phenate, lanthanum p-hydroxybenzoate and magnesium-guaiacol salt, etc., preferably lanthanum acetate and calcium phenate or cerium acetate and magnesium-guaiacol salt. The ligand compound contains rare earth metal ions and alkali metal ions that can undergo coordination reactions and proton transfer reactions with oxygen-containing acid compounds and phenols in biomass pyrolysis oil to generate metal salts with high adsorption properties. The metal salts can react with metal ions in heavy oil.

[0020] In step (2) of the present invention, the extractant is slowly added to the biomass pyrolysis oil containing rare earth metal carboxylates and alkaline earth metal phenolates, and stirred at 30° C.-50° C. until the solution is clearly separated, and the extraction is completed.

[0021] Patent No. 202510667896.7, a method for co-catalytic cracking of biomass oil and heavy oil. The present invention has no restrictions on the type and raw materials of the biomass pyrolysis oil. Conventional biomass pyrolysis oil can meet the requirements, including but not limited to one or more of lignocellulosic oil (oxygen content of 35%, such as sawdust, bark, straw, etc.), agricultural waste oil (oxygen content of 40%, such as sugarcane bagasse, corn stalks), industrial waste oil (oxygen content of 15%, such as food processing waste), and wet biomass pyrolysis oil (oxygen content of 20%, such as algae). To better exert the beneficial effects of the invention, preferably, the content of oxygenated organic compounds in the biomass pyrolysis oil is no more than 30%, and the water content is no more than 15%.

[0022] The mass ratio of the biomass pyrolysis oil added in step (2) of the present invention to the heavy oil added in step (3) is 0.2-0.4:1, preferably 0.3:1. After the treated biomass pyrolysis oil and heavy oil are mixed, they are preheated to 180-260°C, preferably 240°C, and then enter the catalytic cracking unit to react at 500-550°C.

[0023] The present invention has no special requirements for the heavy oil. The feedstock oil of conventional catalytic cracking units, such as residual oil and shale oil, can meet the requirements of the present invention. It should be noted that in order to better exert the effect of the present invention, preferably, the total amount of nickel and vanadium in the heavy oil is not more than 20 mg / g.

[0024] In step (3) of the present invention, the biomass pyrolysis oil and heavy oil are fully stirred and then uniformly injected into the fluidized bed reactor through a nozzle. Under the action of the catalyst, a catalytic cracking reaction occurs at a reaction temperature of 500-550°C, generating gas, liquid and coke. The cracking products are separated from the catalyst, gas and liquid by a cyclone separator.

[0025] The present invention has no special requirements on the type of catalytic cracking catalyst. Conventional catalytic cracking catalysts including Y-type molecular sieve, ZSM-5 molecular sieve, beta molecular sieve, SAPO-41 molecular sieve, etc. can meet the requirements of the present invention. However, in order to achieve better experimental results, the catalyst is ensured to be fluidized particles, usually with a particle size between 20-150 μm.

[0026] The present invention has no special requirements on the reactor form and reaction conditions of the catalytic cracking unit. Reactors corresponding to conventional catalytic cracking processes, catalytic cracking processes, double riser processes, and MIP processes can all meet the requirements of the present invention.

[0027] There are no specific requirements for the reaction temperature or catalyst-to-oil ratio in the catalytic cracking process described herein. The catalyst-to-oil ratio is the ratio of the mass of feedstock entering the reactor to the mass of catalyst circulating per unit time in the catalytic cracking reaction. However, to achieve optimal reaction performance, a catalyst-to-oil ratio of 6:1 is recommended at 500°C.

[0028] Compared with existing technologies, this method significantly improves the light oil yield, reduces the ratio of coke to dry gas, reduces the formation of coke, and greatly optimizes the economy and environmental friendliness of the catalytic cracking process.

[0029] Compared with the traditional catalytic cracking method of directly blending biomass pyrolysis oil and heavy oil, the method of co-catalytic cracking of biomass pyrolysis oil and heavy oil provided by the present invention has the advantages of high biomass pyrolysis oil blending ratio, simultaneous deoxidation and heavy metal pollution resistance of biomass pyrolysis oil, good deoxidation effect, high heavy metal passivation efficiency, simple process flow, and less pollution.

[0030] Compared with the prior art, the present invention has the following significant effects:

[0031] 1) Efficient dual-component removal of oxygenated compounds: Rare earth metal compounds have a strong affinity for carboxylates, reacting with the carboxyl groups in carboxylates to form stable metal carboxylates. This complex exhibits pronounced chelating properties, effectively securing metal ions in the solvent and preventing their recirculation into the system. Through coordination, the reaction between rare earth metal compounds and carboxylates enables targeted removal of metallic impurities from the solution. Rare earth metals can efficiently form complexes with both single carboxylic acids and complex molecules with multiple carboxyl groups, demonstrating broad applicability and high stability. Alkaline earth metal compounds have a high affinity for phenoloxy groups and react with phenolic organic compounds to form stable metal phenolates with chelating coordination vacancies, preventing phenols from recirculating into the system. Alkaline earth metal compounds can specifically remove phenolic compounds through acid-base reactions. They can efficiently complex both monophenols and diphenols, offering a wide range of applications.

[0032] 2) Process Optimization: Simplify the traditional deoxidation and passivation processes, carry out deoxidation and heavy metal pollution prevention simultaneously, reduce process steps and costs, significantly increase the yield of liquefied gas and gasoline, reduce the yield of coke and dry gas, and achieve outstanding economic benefits and environmental performance.

[0033] 3) Dual-component deoxidation and passivation: First, rare earth metal compounds are added to convert acidic organic matter in biomass pyrolysis oil into rare earth metal carboxylates (acidic), and then alkaline earth metal compounds are used to convert phenolic organic matter in biomass pyrolysis oil into alkaline earth metal phenate (alkaline). Not only the acidic organic matter is removed, but also the rare earth metal carboxylates can neutralize the metal phenate to a certain extent, reducing the alkalinity of the co-catalytic cracking system. The metal and heavy metal ions (Ni in the composite system formed by rare earth metal carboxylates and alkaline earth metal phenate) 2+ 、V 3+ ) undergo competitive coordination, such as forming rare earth-heavy metal complex salts with vanadic acid, which can passivate heavy metals and realize the dual functions of biomass pyrolysis oil, removal of oxygen-containing organic compounds and anti-vanadium pollution. The generated metal vanadates are highly stable, effectively reducing the toxic effects of heavy metals on the catalyst and increasing the service life of the catalyst. Specific embodiments

[0034] The present invention is described in detail below by way of examples. It is necessary to point out that the following examples are only used to further illustrate the present invention and are not to be construed as limiting the scope of protection of the present invention. Those skilled in the art may make some non-essential improvements and adjustments to the present invention based on the above disclosure.

[0035] If no specific experimental steps or conditions are specified in the Examples and Comparative Examples, the conventional experimental steps or conditions described in the literature in the field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0036] The raw materials and equipment involved in the present invention are all commercially available and can meet the implementation of the technical solution of the present invention. However, for the convenience of comparison, the raw materials from the following sources are used in the following examples:

[0037] The catalyst was obtained from the catalyst plant of Lanzhou Petrochemical Company. The heavy oil feedstock was the feedstock oil from the 3 million t / a heavy oil catalytic cracking unit of PetroChina Lanzhou Petrochemical Company, and its properties are shown in Table 1. The biomass pyrolysis oil was obtained from LynasRare Earths Limited in Australia, and its properties are shown in Table 2. Calcium hydroxide, magnesium hydroxide, magnesium oxide, calcium oxide, anhydrous ethanol, diamine diol, ethylenediamine, tris(hydroxymethyl)aminomethane, terpyridine, methanol, diethylenetriamine, dimethylformamide (DMF), and dimethylacetamide were all of analytical grade and produced by Sinopharm Group.

[0038] Table 1 Properties of heavy oil feedstock

[0039]

[0040]

[0041] Table 2 Biomass pyrolysis oil raw material properties

[0042] Relative molecular mass 278g / mol Density (70℃) <![CDATA[1.2g / cm 3 ]]> Saturated hydrocarbon content 10％ Aromatic content 22.5％ Gum content 15％ Oxygen content 30wt% Hydrogen content 7wt% Carbon content 47.5wt% Nitrogen content 0.3wt% Sulfur content <0.1wt% Acid value 75mg KOH / g Viscosity (40℃) 60cP Ash content 0.3wt%

[0043] Example 1

[0044] 1) Removal of oxygenated organic compounds (especially acidic organic matter) in biomass pyrolysis oil:

[0045] According to the molar ratio of rare earth metal compound to acidic organic matter in biomass pyrolysis oil of 1:2, cerium chloride was added to the biomass pyrolysis oil, stirred and mixed evenly, heated to 50℃, and kept at constant temperature for 1.5h. 3+ The rare earth metal ions react with carboxylic acids (such as fatty acids and aromatic acids) in biomass pyrolysis oil to form rare earth metal carboxylates through coordination with carboxyl groups.

[0046] 2) Removal of oxygenated organic compounds (especially phenolic organic compounds) in biomass pyrolysis oil:

[0047] The alkaline earth metal compound magnesium tert-butoxide was added to biomass pyrolysis oil containing rare earth metal carboxylates at a molar ratio of 1:2. The mixture was stirred and then heated to 80°C for 2 hours. The phenolic organic matter (ArOH) in the biomass pyrolysis oil reacted with the magnesium tert-butoxide to form the alkaline earth metal phenate Mg(OAr)2, where (OAr) represents the phenate group. The molar ratio of rare earth metal carboxylates to alkaline earth metal phenates in the biomass pyrolysis oil was 1:1. The extractant dimethylsulfamide was added to the biomass pyrolysis oil and stirred continuously at 40°C. The molar ratio of the total rare earth metal carboxylates and alkaline earth metal phenates to the extractant was 1:1. The solution separated into two layers: the upper layer was the biomass pyrolysis oil phase, and the lower layer was the extraction phase containing rare earth metal carboxylates and alkaline earth metal phenates.

[0048] 3) Mixing of biomass pyrolysis oil and heavy oil

[0049] The layered solution treated in step 2) was added to the heavy oil and stirred to mix evenly. The mass ratio of biomass pyrolysis oil to heavy oil was 0.3:1. The mixture was then preheated to 220°C, and ZSM-5 molecular sieve was added. Catalytic cracking was carried out in a fixed bed reactor at 500°C for 15 minutes.

[0050] Example 2

[0051] Except step 1), the rest of this embodiment is the same as that of embodiment 1.

[0052] 1) Removal of oxygenated organic compounds (especially acidic organic matter) in biomass pyrolysis oil:

[0053] According to the molar ratio of rare earth metal compound lanthanum chloride: acidic organic matter in biomass pyrolysis oil of 1:2, lanthanum chloride was added to biomass pyrolysis oil, stirred and mixed evenly, heated to 40 ° C, and kept at constant temperature for 3 hours. Rare earth metal ion La 3+ The rare earth metal ions react with carboxylic acids (such as fatty acids and aromatic acids) in biomass pyrolysis oil to form rare earth metal carboxylates through coordination with carboxyl groups.

[0054] Example 3

[0055] Except step 1), the rest of this embodiment is the same as that of embodiment 1.

[0056] 1) Removal of oxygenated organic compounds (especially acidic organic matter) in biomass pyrolysis oil:

[0057] According to the molar ratio of rare earth metal compound yttrium aluminum chloride: acidic organic matter in biomass pyrolysis oil of 1:3, yttrium aluminum chloride was added to the biomass pyrolysis oil and stirred to mix evenly, the temperature was raised to 60℃, and the reaction was kept at constant temperature for 5h. The rare earth metal ion Y 3+The rare earth metal ions react with carboxylic acids (such as fatty acids and aromatic acids) in biomass pyrolysis oil to form rare earth metal-carboxylates through coordination with carboxyl groups.

[0058] Example 4

[0059] Except step 2), the rest of this embodiment is the same as that of embodiment 1.

[0060] 2) Removal of oxygenated organic compounds (especially phenolic organic compounds) in biomass pyrolysis oil:

[0061] The alkaline earth metal compound was added to the biomass pyrolysis oil containing rare earth metal carboxylates at a molar ratio of 1:2 (alkaline earth metal salt calcium chloride CaCl2) to phenolic organic matter in the biomass pyrolysis oil, and the mixture was stirred and uniformly mixed. The mixture was then heated to 60°C and kept at this temperature for 2.5 hours. The alkaline earth metal ions reacted with the oxygen-containing organic compounds in the biomass pyrolysis oil, particularly the phenolic organic matter, to form alkaline earth metal phenolates (such as Ca(O-Ar)2). The molar ratio of rare earth metal carboxylates to alkaline earth metal phenolates in the biomass pyrolysis oil was 1:1. The extractant dimethylsulfamide was added to the biomass pyrolysis oil and stirred continuously at 40°C. The molar ratio of the total amount of rare earth metal carboxylates and alkaline earth metal phenolates to the extractant was 1:1. The solution was separated into two layers, the upper layer being the biomass pyrolysis oil phase and the lower layer being the extraction phase containing rare earth metal carboxylates and alkaline earth metal phenolates.

[0062] Example 5

[0063] Except step 2), the rest of this embodiment is the same as that of embodiment 2.

[0064] 2) Removal of oxygenated organic compounds (especially phenolic organic compounds) in biomass pyrolysis oil:

[0065] Calcium chloride was added to the biomass pyrolysis oil containing rare earth metal carboxylates at a molar ratio of 1:2 (alkaline earth metal salt calcium chloride CaCl2) to phenolic organic compounds in the biomass pyrolysis oil, and the mixture was stirred and uniformly mixed. The mixture was then heated to 60°C and kept at this temperature for 2.5 hours. The alkali metal ions reacted with the oxygen-containing organic compounds in the biomass pyrolysis oil, particularly the phenolic organic compounds, to form alkaline earth metal phenolates (such as Ca(O-Ar)2). The molar ratio of rare earth metal carboxylates to alkaline earth metal phenolates in the biomass pyrolysis oil was 1:1. The extractant dimethylsulfamide was added to the biomass pyrolysis oil and stirred continuously at 40°C. The molar ratio of the total amount of rare earth metal carboxylates and alkaline earth metal phenolates to the extractant was 1:1. The solution was separated into two layers: the upper layer was the biomass pyrolysis oil phase, and the lower layer was the extraction phase containing rare earth metal carboxylates and alkaline earth metal phenolates.

[0066] Example 6

[0067] In this embodiment, the molar ratio of the rare earth metal compound to the acidic organic matter in the biomass pyrolysis oil in step 1) is 1:3, and the molar ratio of the alkaline earth metal compound to the phenolic organic matter in the biomass pyrolysis oil in step 2) is adjusted to 3:2. After the reaction with the acid and phenol, the molar ratio of the rare earth metal carboxylate:alkaline earth metal phenolate in the biomass pyrolysis oil remains 1:1. Other aspects are the same as in Example 1.

[0068] Example 7

[0069] In this embodiment, except that the molar ratio of the rare earth metal compound to the acidic organic matter in the biomass pyrolysis oil in step 1) is 1:2.5, and the molar ratio of the alkaline earth metal salt to the phenolic organic matter in the biomass pyrolysis oil in step 2) is adjusted to 4:5, after the reaction with the acid and phenol, the molar ratio of the rare earth metal carboxylate:alkaline earth metal phenolate in the biomass pyrolysis oil remains 1:1, all other aspects are the same as in Example 1.

[0070] Example 8

[0071] In this embodiment, except that the molar ratio of the alkaline earth metal compound to the phenolic organic matter in the biomass pyrolysis oil in step 2) is 1:1, and the molar ratio of the rare earth metal salt to the acidic organic matter in the biomass pyrolysis oil in step 1) is adjusted to 1:2, after the reaction with the acid and phenol, the molar ratio of the rare earth metal carboxylate: the alkaline earth metal phenolate in the biomass pyrolysis oil is still 1:1, all other aspects are the same as those in Example 5.

[0072] Example 9

[0073] In this embodiment, except that the molar ratio of rare earth metal carboxylate to alkaline earth metal phenate is controlled to be 3:2 in step 2), the feed ratio of rare earth metal compound to alkaline earth metal compound needs to be adjusted to 3:2 in step 1). All other aspects are the same as those of Example 5.

[0074] Example 10

[0075] In this embodiment, except that the molar ratio of rare earth metal carboxylate to alkaline earth metal phenate in step 2) is 2:1, the feed ratio of rare earth metal compound to alkaline earth metal compound needs to be adjusted to 2:1 in step 1. All other steps are the same as those in Example 5.

[0076] Example 11

[0077] This embodiment is the same as Example 9 except that in step 2), the molar ratio of the total amount of rare earth metal carboxylate and alkaline earth metal phenate to the extractant is 1:2.

[0078] Example 12

[0079] This embodiment is the same as Example 9 except that in step 2), the molar ratio of the total amount of rare earth metal carboxylate and alkaline earth metal phenate to the extractant is 1:3.

[0080] The optimal amount of extractant was determined by Examples 9, 11 and 12 to avoid incomplete removal of rare earth metal carboxylates and alkaline earth metal phenates due to too little extractant and the introduction of new impurities due to too much extractant.

[0081] Example 13

[0082] This example is the same as Example 11 except that the extractant in step 2) is adjusted to 2-ethoxyethyl acetate.

[0083] Example 14

[0084] This example is the same as Example 11 except that the extractant in step 2) is adjusted to 2-ethylhexylphosphonate.

[0085] Example 15

[0086] This embodiment is the same as Example 11 except that the mass ratio of biomass pyrolysis oil to heavy oil in step 3) is changed to 0.2:1.

[0087] Example 16

[0088] This embodiment is the same as Example 11 except that the mass ratio of biomass pyrolysis oil to heavy oil in step 3) is changed to 0.4:1.

[0089] Comparative Example 1

[0090] Compared with the embodiment, this comparative example 1 does not add rare earth metal compounds to the biomass pyrolysis oil, and all other aspects are the same, specifically:

[0091] The alkaline earth metal compound magnesium tert-butoxide was added to the biomass pyrolysis oil at a molar ratio of 1:2. The mixture was stirred and evenly mixed. The temperature was raised to 80°C and the reaction was maintained at this temperature for 2 hours. The phenolic organic matter (ArOH) in the biomass pyrolysis oil reacted with the magnesium tert-butoxide to form the alkaline earth metal phenate Mg(OAr)2. The extractant dimethylsulfamide was added to the biomass pyrolysis oil and stirred continuously at 40°C. The molar ratio of alkaline earth metal phenoxide to extractant was 1:1. The solution was separated into layers, with the upper layer being the biomass pyrolysis oil phase and the lower layer being the extraction phase containing the alkaline earth metal phenoxide.

[0092] The extracted layer solution was added to the heavy oil and stirred to mix evenly. The mass ratio of biomass pyrolysis oil to heavy oil was 0.3:1. It was then preheated to 220°C, ZSM-5 molecular sieve was added, and catalytic cracking was carried out in a fixed bed reactor at 500°C for 15 minutes.

[0093] Comparative Example 2

[0094] Compared with the embodiment, this comparative example 1 does not add alkaline earth metal compounds to the biomass pyrolysis oil, and all other conditions are the same, specifically:

[0095] According to the molar ratio of rare earth metal compound to acidic organic matter in biomass pyrolysis oil of 1:2, cerium chloride was added to the biomass pyrolysis oil, stirred and mixed evenly, heated to 50℃, and kept at constant temperature for 1.5h. 3+ The rare earth metal ions react with carboxylic acids (such as fatty acids and aromatic acids) in biomass pyrolysis oil to form rare earth metal carboxylates through coordination with carboxyl groups.

[0096] The extractant dimethylsulfamide was added to the biomass pyrolysis oil and stirred at 40°C. The molar ratio of rare earth metal carboxylate to extractant was 1:1. The solution was separated into layers, with the upper layer being the biomass pyrolysis oil phase and the lower layer being the extraction phase containing alkaline earth metal phenolate.

[0097] The extracted layer solution was added to the heavy oil and stirred to mix evenly. The mass ratio of biomass pyrolysis oil to heavy oil was 0.3:1. It was then preheated to 220°C, ZSM-5 molecular sieve was added, and catalytic cracking was carried out in a fixed bed reactor at 500°C for 15 minutes.

[0098] Comparative Example 3

[0099] According to the technical solutions disclosed in patents CN101643666A and CN102585890A, biomass pyrolysis oil was deacidified and dephenolized, and then blended with heavy oil at a ratio of 0.3:1. The nickel passivation agent antimony pentoxide hydrosol used in patent CN102513163A (a water-soluble catalytic cracking metal passivator and its preparation method) and the vanadium passivation agent were lanthanum tartrate solution. Catalytic cracking experiments were carried out under the conditions of step 3 of Example 1.

[0100] Table 3 shows the experimental results for catalytic cracking of biomass pyrolysis oil and heavy oil from Examples 1-15 and Comparative Examples 1-3. Conventional detection devices can be used for subsequent product detection in the present invention. To better verify the effectiveness of the present invention, it is recommended to use a gas chromatograph (GC) for detection of dry gas and liquefied gas, a distillation apparatus or simulated distillation apparatus for detection of gasoline, diesel, and heavy oil, and a thermogravimetric analyzer for detection of coke.

[0101] Table 3 ACE evaluation results

[0102]

[0103] It can be seen from the data in the above table that, compared with the comparative example, the co-refined heavy oil treated by this method has a higher conversion rate, lower coke and dry gas yields, stronger heavy oil cracking ability, higher gasoline and liquefied gas yields, and exhibits excellent resistance to heavy metal pollution.

[0104] Of course, the present invention may have many other embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art may make various corresponding changes and modifications based on the present invention, but these corresponding changes and modifications should all fall within the scope of protection of the claims of the present invention.

Claims

1. A method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy, characterized in that: Specifically: (1) adding a rare earth metal compound to biomass pyrolysis oil and heating it to 40-100° C., wherein the rare earth metal compound reacts with the acidic organic matter in the biomass pyrolysis oil to form a rare earth metal carboxylate; (2) adding an alkaline earth metal compound to the biomass pyrolysis oil containing rare earth metal carboxylates in step (1), stirring and mixing, and reacting at 60-100° C., wherein the alkaline earth metal compound reacts with phenolic organic matter in the biomass pyrolysis oil to form alkaline earth metal phenolates, and then adding an extractant after the reaction, mixing uniformly at 30-50° C., and separating the solution into layers, wherein the upper layer is the biomass pyrolysis oil phase, and the lower layer is the extraction phase containing rare earth carboxylates and metal phenolates; (3) The layered solution treated in step (2) is mixed evenly with heavy oil, and then catalytic cracking is carried out at 500-550° C. under the action of a catalyst.

2. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: The molar ratio of the rare earth metal compound to the acidic organic matter in the biomass pyrolysis oil is 1:2-4.

3. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: In step (1), the rare earth metal compound includes one or more of lanthanum oxide, lanthanum chloride, cerium chloride, europium chloride, yttrium chloride, lanthanum nitrate, cerium nitrate, yttrium aluminum chloride, and strontium chloride.

4. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: The molar ratio of the alkaline earth metal compound to the phenolic organic matter in the biomass pyrolysis oil is 1-4:2-5.

5. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: In step (2), the alkaline earth metal compound is one or more of calcium chloride, magnesium chloride, barium chloride, magnesium ethoxide, barium hydroxide, calcium amide, calcium carbonate, magnesium tert-butoxide, and strontium chloride.

6. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: After the reaction in step (2) is completed, the molar ratio of the rare earth metal carboxylate to the alkaline earth metal phenolate is 1-3:1-2.

7. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: In step (2), the molar ratio of the total amount of rare earth metal carboxylate and alkaline earth metal phenate to the extractant is 1:1-3.

8. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: The extractant includes one or more of 2-ethoxyethyl acetate, 2-ethylhexylphosphonate, dimethylsulfamide, dimethylamide, pyridine, and tetraalkylammonium salts.

9. The method for co-catalytic cracking of biomass pyrolysis oil and heavy oil based on bimetallic synergy according to claim 1, characterized in that: The mass ratio of the biomass pyrolysis oil added in step (2) to the heavy oil added in step (3) is 0.2-0.4:

1. The treated biomass pyrolysis oil and heavy oil are mixed, preheated to 180-260°C, and then enter the catalytic cracking unit to react at 500-550°C.

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