CN115703076B - Catalyst for processing fossil energy substances, material, method for catalytically pyrolyzing fossil energy substances, and method for processing oil shale - Google Patents

Abstract

The invention relates to the technical fields of mining and fossil energy, and specifically relates to a catalyst used in processing fossil energy substances, a material used for processing fossil energy substances, and a method for catalytically pyrolyzing fossil energy substances. , a method of processing oil shale. The catalyst contains active components, and the active components are selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives, which can significantly reduce the activation of the pyrolysis processing of fossil energy materials. able.

Description

Catalysts and materials for processing fossil energy materials, methods for catalytic pyrolysis of fossil energy materials, and methods for processing oil shale

Technical Field

The present invention relates to the field of mining and fossil energy technology, and in particular to a catalyst used in processing fossil energy materials, a material used for processing fossil energy materials, a method for catalytically pyrolyzing fossil energy materials, and a method for processing oil shale.

Background Art

The limited reserves of conventional fossil energy represented by crude oil and the increasing demand for energy have made the energy crisis one of the main bottlenecks that restrict and hinder the sustainable and healthy development of human society. In addition to vigorously developing renewable non-fossil energy such as biomass energy, geothermal energy, wind energy, solar energy, hydropower, and ocean energy, the effective development and utilization of unconventional fossil energy represented by oil shale, shale oil, and heavy oil has also attracted widespread attention from the fields of science and technology and all sectors of society. It is considered to be one of the important ways and opportunities to supplement or replace conventional fossil energy. As an important unconventional fossil energy, oil shale is a type of high-ash dense sedimentary rock with lamellar structure characteristics. At present, the world's proven oil shale resource reserves are as high as about 10 trillion tons, which is about 689 billion tons after conversion to shale oil, while the world's recoverable crude oil reserves are about 170 billion tons. From the perspective of reserves, the former is basically nearly 4 times the latter. At present, my country's proven oil shale reserves are as high as about 719.9 billion tons, which can be converted into about 47.6 billion tons of shale oil, ranking second in the world. This shows its huge development potential and important strategic significance.

Treating oil shale by heating in a non-oxidizing or weakly oxidizing anaerobic or oxygen-poor environment is one of the important ways to study oil shale at the laboratory level and exploit it at the industrial scale. To a certain extent, heating treatment runs through almost every link of the oil shale mining process. Although people have developed various heating methods to provide effective thermal energy drive for its mining, the use of a large amount of thermal energy has greatly increased its energy consumption, time, environment and equipment costs.

Therefore, there is an urgent need for a solution that can reduce the activation energy during the pyrolysis process of fossil energy materials, such as oil shale.

Summary of the invention

The purpose of the present invention is to overcome the problem of high activation energy in the existing pyrolysis processing of fossil energy materials, and to provide a catalyst for use in processing fossil energy materials, a material for processing fossil energy materials, a method for catalytic pyrolysis of fossil energy materials, and a method for processing oil shale, which can significantly reduce the activation energy of pyrolysis processing of fossil energy materials.

In order to achieve the above objectives, the first aspect of the present invention provides a catalyst for use in processing fossil energy materials, the catalyst comprising an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

Preferably, the structural formula of the phthalocyanine and/or its derivative is as shown in formula (I), and the structural formula of the porphyrin and/or its derivative is as shown in formula (II):

Wherein, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently a substituent group bonded to the structural formula of formula (I) or formula (II) by chemical synthesis; and/or, any two adjacent side groups among R ₁ -R ₁₆ and R' ₁ -R' ₁₂ may or may not form a ring;

Wherein, M and M' are each independently selected from metal elements and/or non-metal elements.

The second aspect of the present invention provides a material for processing fossil energy materials, the material comprising a catalyst and a fossil energy material, wherein the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives;

Wherein, the weight ratio of the catalyst to the fossil energy material is 1:5000 to 10:1, preferably 1:1 to 1:1000.

A third aspect of the present invention provides a method for catalytic pyrolysis of fossil energy materials, the method comprising: contacting a catalyst with the fossil energy material in an atmosphere lacking oxygen or inert gas or non-oxidizing gas and performing a pyrolysis reaction to reduce the activation energy of the pyrolysis reaction and obtain a pyrolysis product;

Wherein, the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

A fourth aspect of the present invention provides a method for processing oil shale, the method comprising: mixing a catalyst with oil shale and performing a pyrolysis reaction in an atmosphere lacking oxygen or inert gas or non-oxidizing gas to obtain a pyrolysis product, so as to reduce the activation energy of the pyrolysis reaction of the oil shale;

Wherein, the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

Compared with the prior art, the present invention has the following advantages:

(1) From the perspective of diversity, the classical inorganic catalytic system represented by minerals, metal oxides, metal salts, etc. has certain limitations, which greatly limits the range of catalytic materials available for selection in practice. In the technical solution provided by the present invention, among the selected catalysts, phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives are selected as active components, especially the compounds represented by formula (I)/formula (II) are directly used as catalysts, which can reduce the activation energy of the pyrolysis reaction process of fossil energy materials. The macrocyclic central cavity of such compounds can be filled with more than 70 kinds of metal elements or non-metal elements including transition metals, rare earth metals, alkali metals, alkaline earth metals, etc. More importantly, through molecular science engineering, various chemical functional groups or substituents (for example, _R1 - _R16 and _R'1 - _R'12 , including but not limited to the functional groups or substituents listed in the specification of the present invention (for example only), as long as they can be bonded to the macrocyclic molecular system through chemical synthesis) can be grafted onto the macrocyclic molecular system, and various ligands (including but not limited to the ligands listed in the specification of the present invention (for example only), as long as they can form a coordination relationship with the central metal of the macrocyclic molecular system) can also be grafted onto the central metal. These factors give this type of compound rich diversity and flexibility, and thus provide a rich and diverse material basis for its application as an oil shale pyrolysis catalyst.

(2) The composite catalytic material loaded on the carrier can exert the catalytic performance of the carrier and the catalyst at the same time, so the composite catalytic material is one of the important catalytic systems that has received much attention. The extremely low solubility of classical catalytic materials based on metal oxides and inorganic minerals in solvents has brought certain difficulties to the realization of the composite of such traditional catalysts with other carriers from a practical level. In contrast, the phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives, especially the compounds shown in formula (I)/formula (II) used in the present invention have good solubility in many solvents, which facilitates the composite with other carriers by simple solvent impregnation, and is conducive to the construction of a wide variety of new composite catalytic materials based on the compounds shown in (I)/formula (II) for oil shale pyrolysis.

(3) In the present invention, the catalyst based on the compound shown in (I) can reduce the activation energy of the pyrolysis process by about 25%; the catalyst based on the compound shown in (II) can reduce the activation energy of the pyrolysis process by about 10%.

(4) Although the reduction in the activation energy of pyrolysis of oil shale by the compound represented by (I)/formula (II) loaded on the carrier is only about 12%, its loading amount is only about 0.07%. On the one hand, this indicates the excellent catalytic activity of this type of catalytic material. On the other hand, this shows that by adopting a composite catalytic system, the reduction in the activation energy of pyrolysis of oil shale can be achieved with an extremely low dosage of the compound represented by (I)/formula (II). Improve the oil and gas yield of processing fossil energy materials (such as oil shale).

BRIEF DESCRIPTION OF THE DRAWINGS

Figure 1A is the TG curve of the original Moroccan oil shale system without phthalocyanine derivatives at different heating rates; Figure 1B is the DTG curve of the original Moroccan oil shale system without phthalocyanine derivatives at different heating rates; Figure 1C is the TG curve of the Moroccan oil shale system containing phthalocyanine derivatives at different heating rates; Figure 1D is the DTG curve of the Moroccan oil shale system containing phthalocyanine derivatives at different heating rates.

FIG2A is a curve showing the relationship between ln(β/T ^1.92 ) and 1/T of the original Moroccan oil shale system without phthalocyanine derivatives based on the Starink approximate equation; FIG2B is a curve showing the relationship between ln(β/T ^1.92 ) and 1/T of the Moroccan oil shale system containing phthalocyanine derivatives based on the Starink approximate equation;

FIG2C is an activation energy curve of two pyrolysis systems at different conversion rates obtained based on the Starink method for the original Moroccan oil shale system without phthalocyanine derivatives (OS for short) and the Moroccan oil shale system with phthalocyanine derivatives (OS+Catalyst for short);

FIG2D is a curve showing the relationship between ln(β) and 1/T of the original Moroccan oil shale system without phthalocyanine derivatives based on the FWO method fitting; FIG2E is a curve showing the relationship between ln(β) and 1/T of the Moroccan oil shale system containing phthalocyanine derivatives based on the FWO method fitting;

FIG2F is an activation energy curve of two pyrolysis systems at different conversion rates obtained based on the FWO method for the original Moroccan oil shale system without phthalocyanine derivatives (OS for short) and the Moroccan oil shale system with phthalocyanine derivatives (OS+Catalyst for short);

FIG2G is a relationship curve between ln(β/T ² ) and 1/T based on the KAS method fitting of the original Moroccan oil shale system without phthalocyanine derivatives; FIG2H is a relationship curve between ln(β/T ² ) and 1/T based on the KAS method fitting of the Moroccan oil shale system containing phthalocyanine derivatives;

FIG2I is an activation energy curve of two pyrolysis systems at different conversion rates obtained based on the KAS method, namely, the original Moroccan oil shale system without phthalocyanine derivatives (OS for short) and the Moroccan oil shale system with phthalocyanine derivatives (OS+Catalyst for short).

FIG. 3 is an EGA-MS graph of a pristine Moroccan oil shale system without phthalocyanine derivatives (solid line) and a Moroccan oil shale system with phthalocyanine derivatives (dashed line).

Figure 4A is the TG curve of the original Moroccan oil shale system without porphyrin derivatives at different heating rates; Figure 4B is the DTG curve of the original Moroccan oil shale system without porphyrin derivatives at different heating rates; Figure 4C is the TG curve of the Moroccan oil shale system containing porphyrin derivatives at different heating rates; Figure 4D is the DTG curve of the Moroccan oil shale system containing porphyrin derivatives at different heating rates.

FIG5A is a curve showing the relationship between ln(β/T ^1.92 ) and 1/T based on the Starink approximate equation for the original Moroccan oil shale system without porphyrin derivatives; FIG5B is a curve showing the relationship between ln(β/T ^1.92 ) and 1/T based on the Starink approximate equation for the Moroccan oil shale system with porphyrin derivatives;

FIG5C is an activation energy curve at different conversion rates of two pyrolysis systems obtained based on the Starink method for the original Moroccan oil shale system without porphyrin derivatives (OS for short) and the Moroccan oil shale system with porphyrin derivatives (OS+Catalyst for short);

FIG5D is a curve showing the relationship between ln(β) and 1/T of the original Moroccan oil shale system without porphyrin derivatives based on the FWO method fitting; FIG5E is a curve showing the relationship between ln(β) and 1/T of the Moroccan oil shale system containing porphyrin derivatives based on the FWO method fitting;

FIG5F is an activation energy curve at different conversion rates of two pyrolysis systems obtained based on the FWO method, namely, the original Moroccan oil shale system without porphyrin derivatives (OS for short) and the Moroccan oil shale system with porphyrin derivatives (OS+Catalyst for short);

FIG5G is a relationship curve between ln(β/T ² ) and 1/T based on the KAS method fitting of the original Moroccan oil shale system without porphyrin derivatives; FIG5H is a relationship curve between ln(β/T ² ) and 1/T based on the KAS method fitting of the Moroccan oil shale system containing porphyrin derivatives;

Figure 5I is the activation energy curves of two pyrolysis systems at different conversion rates obtained based on the KAS method, namely, the original Moroccan oil shale system without porphyrin derivatives (OS for short) and the Moroccan oil shale system with porphyrin derivatives (OS+Catalyst for short).

FIG. 6 is an EGA-MS graph of an original Moroccan oil shale system without porphyrin derivatives (solid line) and a Moroccan oil shale system with porphyrin derivatives (dashed line).

DETAILED DESCRIPTION

The endpoints and any values of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values should be understood to include values close to these ranges or values. For numerical ranges, the endpoint values of each range, the endpoint values of each range and the individual point values, and the individual point values can be combined with each other to obtain one or more new numerical ranges, which should be regarded as specifically disclosed in this article.

The first aspect of the present invention provides a catalyst for use in processing fossil energy materials, wherein the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

In the present invention, unless otherwise specified, the catalyst may contain other components, such as a carrier, in addition to the active component.

In some embodiments of the present invention, preferably, the structural formula of the phthalocyanine and/or its derivative is as shown in formula (I), and the structural formula of the porphyrin and/or its derivative is as shown in formula (II):

Wherein, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently a substituent group bonded to the structural formula of formula (I) or formula (II) by chemical synthesis; and/or, any two adjacent side groups among R ₁ -R ₁₆ and R' ₁ -R' ₁₂ may or may not form a ring;

Wherein, M and M' are each independently selected from metal elements and/or non-metal elements.

In the present invention, unless otherwise specified, the chemical synthesis method has a wide range of options, as long as the substituent groups of R ₁ -R ₁₆ and R' ₁ -R' ₁₂ can be bonded to the molecular skeleton of formula (I) or formula (II).

In the present invention, unless otherwise specified, non-metallic elements refer to non-metallic elements other than C.

In some embodiments of the present invention, preferably, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, unsubstituted or substituted C ₁ -C ₂₀ alkyl, unsubstituted or substituted C ₁ -C ₂₀ alkoxy, unsubstituted or substituted C ₆ -C ₃₀ aryl, unsubstituted or substituted C ₄ -C ₃₀ heterocyclic aromatic group, unsubstituted or substituted C ₂ -C ₂₀ ester group, unsubstituted or substituted C ₂ -C ₂₀ carbonyl group, unsubstituted or substituted C ₂ -C ₂₀ ether group, alkenyl group, alkynyl group, amine group, amide group, nitro group, carboxyl group, sulfonyl group, hydroxyl group or thiol group.

In the present invention, unless otherwise specified, an unsubstituted C ₁ -C ₂₀ alkyl group refers to a C ₁ -C ₂₀ alkyl group that contains no other elements except C and H; a substituted C ₁ -C ₂₀ alkyl group refers to a C ₁ -C ₂₀ alkyl group that contains other elements, such as halogen, O, N, and S, except C and H.

In the present invention, unless otherwise specified, an unsubstituted C ₁ -C ₂₀ alkoxy group refers to a C ₁ -C ₂₀ alkoxy group that contains no other elements except C, H and O; a substituted C ₁ -C ₂₀ alkoxy group refers to a C ₁ -C ₂₀ alkoxy group that contains other elements, such as halogen, N and S, except C, H and O.

In the present invention, unless otherwise specified, an unsubstituted C ₆ -C ₃₀ aryl group refers to a C ₆ -C ₃₀ aryl group that contains no other elements except C and H; a substituted C ₆ -C ₃₀ aryl group refers to a C ₆ -C ₃₀ aryl group that contains other elements, for example, halogen, O, N, and S, except C and H.

In some embodiments of the present invention, further preferably, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, unsubstituted or substituted C ₁ -C ₁₆ alkyl, unsubstituted or substituted C ₁ -C ₁₆ alkoxy, unsubstituted or substituted C ₆ -C ₁₈ aryl, unsubstituted or substituted C ₅ -C ₁₈ heterocyclic aromatic group, unsubstituted or substituted C ₂ -C ₁₂ ester group, unsubstituted or substituted C ₂ -C ₁₂ carbonyl, amine group, amide group, nitro group, carboxyl group, sulfonyl group, hydroxyl group or thiol group.

In some embodiments of the present invention, more preferably, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ alkoxy, C ₆ -C ₁₀ aryl.

According to a preferred embodiment of the present invention, preferably, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, F, methyl, methoxy, ethyl, n-propyl, isopropyl, tert-butyl, phenyl, benzyl.

In some embodiments of the present invention, preferably, the substituents present in R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from halogen, amine, nitro, sulfonate, hydroxyl, thiol, O, N, S, preferably selected from halogen, amine, hydroxyl, thiol, O, N, S, and more preferably selected from F, O, N, S.

In some embodiments of the present invention, preferably, any two adjacent side groups in R ₁ -R ₁₆ and R' ₁ -R' ₁₂ form a ring or not, and the formed ring may or may not have a substituent.

In some embodiments of the present invention, preferably, the ring formation forms a saturated or unsaturated cyclic structure, and the cyclic structure may or may not contain heteroatoms.

In some embodiments of the present invention, preferably, the ring structure is selected from polycyclic rings containing or not containing heteroatoms, saturated or unsaturated and/or their derivatives, preferably selected from aromatic rings and/or their derivatives, benzene and/or their derivatives, naphthalene and/or their derivatives, anthracene and/or their derivatives, phenanthrene and/or their derivatives, pyridine and/or their derivatives, pyridazine and/or their derivatives, pyrazine and/or their derivatives, pyrimidine and/or their derivatives; further preferably selected from benzene and/or its derivatives, naphthalene and/or its derivatives, anthracene and/or its derivatives, pyridine and/or its derivatives, pyrazine and/or its derivatives, pyrimidine and/or its derivatives; more preferably selected from benzene and/or its derivatives, naphthalene and/or its derivatives, anthracene and/or its derivatives, pyridine and/or its derivatives, pyrazine and/or its derivatives, pyrimidine and/or its derivatives.

In some embodiments of the present invention, preferably, M and M' are each independently selected from transition metal elements, rare earth metal elements, alkali metal elements, alkaline earth metal elements, and non-metal elements.

In some embodiments of the present invention, preferably, the transition metal element is selected from metal elements of Group IB, Group IIB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIII.

According to a preferred embodiment of the present invention, preferably, M and M' are each independently selected from Co, Mn, Cu, Fe, Ni, Zn, V, La, Sm, and Si.

In some embodiments of the present invention, preferably, the M and M' are each independently bound to a ligand, and the ligand is preferably selected from halogen, oxygen, and oxygen-containing groups, and more preferably selected from -Cl, -O, -OH, and -OCH ₃ .

In the present invention, unless otherwise specified, the catalyst is an active component, i.e., phthalocyanine and/or its derivatives, and/or, porphyrin and/or its derivatives; in addition to the active components, the catalyst may also contain other substances, for example, a carrier.

In the present invention, when the catalyst is a compound represented by formula (I)/formula (II), the source of the catalyst has a wide range of choices, as long as the catalyst has a compound represented by formula (I)/formula (II). Preferably, the catalyst can be prepared or purchased, and the present invention will not be elaborated here.

In some embodiments of the present invention, preferably, based on the total amount of the catalyst, the content of the active component in the catalyst is 0.0003-62 wt%, preferably 0.006-30 wt%.

In some embodiments of the present invention, preferably, the catalyst further comprises a carrier. More preferably, the catalyst may further comprise various functional reagents added to the catalyst, such as including but not limited to a binder, an auxiliary agent, and the like.

In the present invention, when the catalyst contains the compound represented by formula (I)/formula (II) and a carrier, the source of the catalyst has a wide range of choices, as long as the catalyst contains the compound represented by formula (I)/formula (II) and a carrier. The catalyst can be prepared or purchased, and the present invention will not be elaborated here.

In the present invention, the type of the carrier has a wide selection range and is a conventional carrier in the art. Preferably, the carrier is selected from at least one of porous materials, molecular sieves, inorganic oxides, resins, metal organic framework materials, carbon black, graphite, graphene and/or its derivatives, and minerals.

In some embodiments of the present invention, preferably, the molecular sieve is selected from natural molecular sieves and/or artificial molecular sieves, preferably at least one selected from SBA molecular sieves, MCM molecular sieves, ZSM molecular sieves, HZSM molecular sieves, CMS molecular sieves, ITQ molecular sieves, MSU molecular sieves, CHA molecular sieves, TS molecular sieves, X-type molecular sieves, Y-type molecular sieves and A-type molecular sieves.

In some embodiments of the present invention, preferably, the inorganic oxide is selected from at least one of zirconium oxide, magnesium oxide, aluminum oxide, silicon oxide, zinc oxide, iron oxide, nickel oxide, copper oxide and cobalt oxide.

In some embodiments of the present invention, preferably, the mineral is selected from at least one of pyrite, illite, montmorillonite, kaolinite, bentonite, attapulgite and oil shale ash.

In some embodiments of the present invention, preferably, the fossil energy material is selected from at least one of oil shale, heavy oil and shale oil.

In the present invention, the catalyst containing the compound represented by formula (I)/formula (II) is used to process fossil energy materials, especially oil shale, so as to effectively reduce the pyrolysis activation energy of the fossil energy materials.

In the present invention, there is a wide range of choices for the processing method. Preferably, the processing method is catalytic pyrolysis.

In the present invention, unless otherwise specified, the pyrolysis activation energy parameter is obtained through the relationship curve between the weight loss rate and temperature of the fossil energy material.

In the present invention, unless otherwise specified, the activation energy change rate parameter is obtained by performing data analysis on the relationship curves between the weight loss rate and temperature of the pyrolysis systems containing catalysts and those without catalysts to obtain their respective pyrolysis activation energies, and by comparing the activation energies of the pyrolysis systems containing catalysts and those without catalysts.

The present invention also provides an application of the catalyst of the present invention in the processing of fossil energy materials.

The second aspect of the present invention provides a material for processing fossil energy materials, the material comprising a catalyst and a fossil energy material, wherein the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives;

Wherein, the weight ratio of the catalyst to the fossil energy material is 1:5000 to 10:1, preferably 1:1 to 1:1000.

In the present invention, unless otherwise specified, the structural formula of phthalocyanine and/or its derivatives, the structural formula of porphyrin and/or its derivatives, the type of catalyst, and the type of fossil energy material are all in accordance with the above-mentioned definitions, and the present invention will not be elaborated herein.

In the present invention, unless otherwise specified, the weight ratio of the catalyst to the fossil energy material refers to the weight ratio of the active component in the catalyst to the fossil energy material.

The third aspect of the present invention provides a method for catalytic pyrolysis of fossil energy materials, the method comprising: contacting a catalyst with the fossil energy material in an atmosphere lacking oxygen or inert gas or non-oxidizing gas and performing a pyrolysis reaction to reduce the activation energy of the pyrolysis reaction and obtain a pyrolysis product;

Wherein, the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

In the present invention, unless otherwise specified, the structural formula of phthalocyanine and/or its derivatives, the structural formula of porphyrin and/or its derivatives, the type of catalyst, and the type of fossil energy material are all in accordance with the above-mentioned definitions, and the present invention will not be elaborated herein.

In some embodiments of the present invention, preferably, the method comprises the following steps:

(1) mixing the catalyst with a fossil energy material in an atmosphere lacking oxygen or containing an inert gas or a non-oxidizing gas to obtain a mixture;

(2) subjecting the mixture to a pyrolysis reaction in an atmosphere lacking oxygen or containing an inert gas or a non-oxidizing gas to reduce the activation energy of the pyrolysis reaction and obtain a pyrolysis product.

In the present invention, in step (1), the mixing method has a wide range of options, as long as the catalyst and the fossil energy material are mixed evenly. Preferably, the mixing method is selected from grinding or soaking.

In some embodiments of the present invention, preferably, when the catalyst is an active component, i.e., the compound represented by formula (I)/formula (II), the catalyst is mixed with the fossil energy material in the form of solid powder, and then ground to obtain a mixture with an average particle size of 1×10 ⁸ -0.001 μm. The average particle size of the catalyst is 5×10 ⁴ -0.001 μm, preferably 500-0.002 μm.

In the present invention, unless otherwise specified, when the pyrolysis reaction is carried out above ground, there is a requirement for the average particle size of the catalyst, that is, the average particle size of the catalyst is 5×10 ⁴ -0.001 μm, preferably 500-0.002 μm; when the pyrolysis reaction is carried out underground, there is no requirement for the average particle size of the catalyst. The main reason is that when the pyrolysis reaction is carried out underground, the underground ore is mainly broken by fracturing or underground explosion. The particle size range of the ore can be hundreds of meters or even larger, which is equivalent to rocks of various sizes formed by underground explosions. The catalyst can only be attached to the rock surface of the underground oilstone channel.

In some embodiments of the present invention, preferably, when the catalyst comprises a compound represented by formula (I)/formula (II) and a carrier, the compound represented by formula (I)/formula (II) is first dissolved in a solvent to obtain a compound solution with a concentration of 1× ^10-10-10 mol/L, and then the carrier is immersed in the solution to perform solid-liquid separation, and the solid-liquid separation product is mixed with a fossil energy material to obtain a mixture.

In some embodiments of the present invention, preferably, the weight ratio of the catalyst to the fossil energy material is 1:5000 to 10:1, preferably 1:1 to 1:1000. The weight of the catalyst is based on the weight of the active component, that is, the weight of phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

In the present invention, the conditions for the pyrolysis reaction have a wide range of selection. Preferably, the conditions for the pyrolysis reaction include: a temperature of 0-1000°C, preferably 100-800°C; a time of 0.001s-5 years, preferably 0.2-24h; a heating rate of 8000°C/s-0°C/min, preferably 5000°C/s-0°C/min.

In the present invention, unless otherwise specified, the heating rate parameter of the pyrolysis reaction depends on the heating method; when the Curie point heating method is used, the heating rate can be as high as 10,000°C/min, while when other heating methods are used, the heating rate can be as low as 0.001°C/min. At the same time, when the pyrolysis reaction is carried out at a constant temperature, the heating rate parameter is 0°C/min.

In the present invention, unless otherwise specified, the time parameter of the pyrolysis reaction depends on the specific process conditions. When the pyrolysis reaction is carried out underground, the time parameter of the pyrolysis reaction can be 2-6 years, or can be several months or several days.

In some embodiments of the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, argon and neon, preferably nitrogen.

In some embodiments of the present invention, preferably, the non-oxidizing gas is selected from at least one of carbon dioxide, carbon monoxide, hydrogen and gaseous water.

In a specific embodiment of the present invention, the oxygen-deficient or non-oxidizing gas atmosphere refers specifically to an oxygen-deficient condition underground.

In some embodiments of the present invention, preferably, the pyrolysis reaction is carried out above ground or underground.

In a specific embodiment of the present invention, preferably, when the pyrolysis reaction is carried out underground, the catalyst is directly transported to the underground reaction site, or the catalyst is transported to the underground reaction site via a fluid load.

In the present invention, the fluid has a wide range of choices and can be a gas or a liquid, for example, water, an organic solvent, air, _CO2 gas, nitrogen, helium, etc.

The method provided by the present invention uses an active component containing a compound represented by formula (I)/formula (II) as a catalyst to carry out a pyrolysis reaction with a fossil energy material (especially oil shale) in an atmosphere lacking oxygen or in an inert gas or a non-oxidizing gas to reduce the activation energy of the pyrolysis reaction and obtain a pyrolysis product.

A fourth aspect of the present invention provides a method for processing oil shale, the method comprising: mixing a catalyst with oil shale and performing a pyrolysis reaction in an atmosphere lacking oxygen or inert gas or non-oxidizing gas to obtain a pyrolysis product, so as to reduce the activation energy of the pyrolysis reaction of the oil shale;

Wherein, the catalyst comprises an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

In the present invention, unless otherwise specified, the structural formula of phthalocyanine and/or its derivatives, the structural formula of porphyrin and/or its derivatives, and the definition of the catalyst are in accordance with the above-mentioned definitions, and the present invention will not be elaborated herein.

In some embodiments of the present invention, preferably, the method comprises the following steps:

(1) mixing the catalyst with oil shale in an atmosphere lacking oxygen or containing an inert gas or a non-oxidizing gas to obtain a mixture;

(2) In an atmosphere of inert gas or oxygen-deficient, non-oxidizing gas, the mixture is subjected to a pyrolysis reaction to obtain a pyrolysis product, thereby reducing the activation energy of the pyrolysis reaction of the oil shale.

In the present invention, in step (1), the mixing method has a wide range of options, as long as the catalyst and the oil shale are mixed uniformly. Preferably, the mixing method is selected from grinding or soaking.

In some embodiments of the present invention, preferably, when the catalyst is a compound represented by formula (I)/formula (II), the catalyst is mixed with a fossil energy material in the form of solid powder, and then ground to obtain a mixture with an average particle size of 1×10 ⁸ -0.001 μm. The average particle size of the catalyst is 5×10 ⁴ -0.001 μm, preferably 500-0.002 μm.

In the present invention, unless otherwise specified, when the pyrolysis reaction is carried out above ground, there is a requirement for the average particle size of the catalyst, that is, the average particle size of the catalyst is 5×10 ⁴ -0.001 μm, preferably 500-0.002 μm; when the pyrolysis reaction is carried out underground, there is no requirement for the average particle size of the catalyst. The main reason is that when the pyrolysis reaction is carried out underground, the underground ore is mainly broken by fracturing or underground explosion. The particle size range of the ore can be hundreds of meters or even larger, which is equivalent to rocks of various sizes formed by underground explosions. The catalyst can only be attached to the rock surface of the underground oilstone channel.

In some embodiments of the present invention, preferably, when the catalyst comprises a compound represented by formula (I)/formula (II) and a carrier, the compound represented by formula (I)/formula (II) is first dissolved in a solvent to obtain a compound solution with a concentration of 1× ^10-10-10 mol/L, and then the carrier is immersed in the solution to perform solid-liquid separation, and the solid-liquid separation product is mixed with oil shale to obtain a mixture.

In some embodiments of the present invention, preferably, the weight ratio of the catalyst to the oil shale is 1:5000 to 10:1, preferably 1:1 to 1:1000. The weight of the catalyst is based on the weight of the active component, that is, the weight of phthalocyanine and/or its derivatives, and/or porphyrin and/or its derivatives.

In the present invention, the conditions for the pyrolysis reaction have a wide range of selection. Preferably, the conditions for the pyrolysis reaction include: a temperature of 0-1000°C, preferably 100-800°C; a time of 0.001s-5 years, preferably 0.2-24h; a heating rate of 8000°C/s-0°C/min, preferably 5000°C/s-0°C/min.

In the present invention, unless otherwise specified, the heating rate parameter of the pyrolysis reaction depends on the heating method; when the Curie point heating method is used, the heating rate can be as high as 10,000°C/min, while when other heating methods are used, the heating rate can be as low as 0.001°C/min. At the same time, when the pyrolysis reaction is carried out at a constant temperature, the heating rate parameter is 0°C/min.

In the present invention, unless otherwise specified, the time parameter of the pyrolysis reaction depends on the specific process conditions. When the pyrolysis reaction is carried out underground, the time parameter of the pyrolysis reaction can be 2-6 years, or can be several months or several days.

In some embodiments of the present invention, preferably, the inert gas is selected from at least one of nitrogen, helium, argon and neon, preferably nitrogen.

In some embodiments of the present invention, preferably, the non-oxidizing gas is selected from at least one of carbon dioxide, carbon monoxide, hydrogen and gaseous water.

In a specific embodiment of the present invention, the oxygen-deficient, non-oxidizing gas atmosphere refers specifically to an oxygen-deficient condition underground.

In some embodiments of the present invention, preferably, the pyrolysis reaction is carried out above ground or underground.

In a specific embodiment of the present invention, preferably, when the pyrolysis reaction is carried out underground, the catalyst is directly transported to the underground reaction site, or the catalyst is transported to the underground reaction site via a fluid load.

In the present invention, the fluid has a wide range of choices and can be a gas or a liquid, for example, water, an organic solvent, air, _CO2 gas, nitrogen, helium, etc.

The method provided by the present invention uses an active component containing a compound represented by formula (I)/formula (II) as a catalyst to carry out a pyrolysis reaction with oil shale in an atmosphere lacking oxygen or in an inert gas or a non-oxidizing gas to obtain a pyrolysis product, thereby reducing the activation energy of the pyrolysis reaction of the oil shale.

The present invention will be described in detail below through examples.

Example 1

The catalytic performance of a phthalocyanine derivative having a structure of formula (I) as a catalyst for the pyrolysis reaction of Moroccan oil shale is studied, wherein in formula (I), R ₁ -R ₁₆ are all F, and any two adjacent side groups in R ₁ -R ₁₆ do not form a ring; M is Co; based on the total amount of the above catalyst, the content of active components in the above catalyst is 6.86wt%.

The method includes:

Thermogravimetric (TG) analysis experiments were carried out with or without the participation of this catalyst: when the catalyst was involved, 10 mg of Moroccan oil shale below 74 μm and 1 mg of catalyst powder sample were spread in a crucible, and the heating rates were 10℃/min, 15℃/min, 20℃/min, 25℃/min and 30℃/min, respectively, and the temperature was raised from 35℃ to 980℃. The carrier gas was dry high-purity nitrogen, and the flow rate was maintained at 50mL/min during the experiment (the flow rates of the purge gas and the protective gas were both 25mL/min). When there was no catalyst involved, except for the experiment with 10 mg of Moroccan oil shale powder sample below 74 μm, other conditions were the same as the TG analysis experiment with the participation of the catalyst.

Based on TG analysis, the catalytic performance of this catalyst for the pyrolysis reaction of Moroccan oil shale was investigated using three multiple scanning rate methods: Starink method, Flynn-Wall-Ozawa method (FWO method) and Kissinger-Akahira-Sunose method (KAS method). The series of TG (Figure 1A and Figure 1C) and DTG (Figure 1B and Figure 1D) data obtained at different heating rates were analyzed and processed, and the changes in the apparent activation energy of the pyrolysis reaction of Moroccan oil shale caused by the catalyst were evaluated using three multiple scanning rate methods; among them, the approximate equations of the Starink method, FWO method and KAS method are shown in equations (1)-(3) respectively:

As shown in Figure 2, the results based on these three fitting methods indicate that after the introduction of this catalytic material into the system, the apparent activation energy corresponding to each conversion rate from 0.1 to 0.9 showed a decreasing trend (decreased by 14.21%-22.23%), and the activation energy of the Moroccan oil shale pyrolysis reaction decreased by an average of 17.37%, which confirms the reliability of the data obtained by these three methods.

At the same time, EGA-MS analysis experiments were carried out with or without the participation of this catalyst: when the catalyst was involved, 1 mg of Moroccan oil shale with an average particle size of less than 74 μm and 0.1 mg of catalyst powder sample were spread in the pyrolysis cup, the heating rate was 10℃/min, the temperature was raised from 55℃ to 1000℃, the carrier gas was dry high-purity helium, and the total flow rate was maintained at 12.1 mL/min during the experiment, of which the purge flow rate and column flow rate were 3 mL/min and 0.82 mL/min, respectively. In addition, the column head pressure was 80 kPa, the range of m/z was 10-800, the GC column (without stationary phase), the column box temperature, and the GC and MS injection port temperatures were all 300℃. When there was no phthalocyanine catalyst involved, except for the experiment of 1 mg of Moroccan oil shale powder sample with an average particle size of less than 74 μm, other conditions were the same as the TG analysis experiment with the participation of the catalyst.

As shown in Figure 3, with (dashed line) or without (solid line) the participation of this catalyst, the pyrolysis process of Moroccan oil shale can be divided into two stages. Among them, the introduction of the above catalyst significantly enhances the TIC signal of the first peak, that is, the Moroccan oil shale system containing phthalocyanine derivatives can significantly improve the oil and gas yield of Moroccan oil shale.

Example 2

The catalytic performance of the porphyrin derivative having the structure of formula (II) as a catalyst for the pyrolysis reaction of Moroccan oil shale, wherein _R'2 , _R'3 , R'5, _R'6 , _R'8 , _R'9 , _R'11 and _R'12 of the compound of formula (II) are all H, and _{R'1 , R'4} , _R'7 and _R'10 are all Any two adjacent side groups in _R'1 - _R'12 do not form a ring; M' is Mn, and M' is bound to the ligand -Cl; based on the total amount of the above catalyst, the content of the active component in the above catalyst is 6.86wt%.

The method includes:

Thermogravimetric (TG) analysis experiments were carried out with or without the catalyst: When the catalyst was present, 10 mg of Moroccan oil shale with an average particle size of less than 74 μm and 1 mg of catalyst powder were spread in a crucible, and the heating rates were 10°C/min, 15°C/min, 20°C/min, 25°C/min and 30°C/min, respectively, and the temperature was raised from 35°C to 980°C. The carrier gas was dry high-purity nitrogen, and the flow rate was maintained at 50 mL/min during the experiment (the flow rates of the purge gas and the protective gas were both 25 mL/min). When the catalyst was not present, except for the 10 mg Moroccan oil shale powder with an average particle size of less than 74 μm, the other conditions were the same as the TG analysis experiment with the catalyst.

In order to evaluate the effect of the catalyst on the pyrolysis of Moroccan oil shale, we also used three multiple rate methods, namely the Starink method, the FWO method and the KAS method, to analyze and process the series of TG (Figure 4A and Figure 4C) and DTG (Figure 4B and Figure 4D) data obtained at different heating rates, and used three multiple scanning rate methods to evaluate the changes in the apparent activation energy of the Moroccan oil shale pyrolysis reaction caused by the catalyst.

As shown in Figure 5, the results based on these three fitting methods show that after the introduction of catalytic materials into the system, the apparent activation energies corresponding to the conversion rates from 0.1 to 0.9 all showed a decreasing trend (decreased by approximately 2.77%-6.65%), and the activation energy of the oil shale pyrolysis reaction decreased by an average of 4.41%, reaching similar conclusions, which confirms the reliability of the data obtained by these three methods.

At the same time, we also conducted EGA-MS analysis experiments with or without the participation of this catalyst: when this catalyst was involved, 1 mg of Moroccan oil shale with an average particle size of less than 74 μm and 0.1 mg of catalyst powder sample were spread in the pyrolysis cup, the heating rate was 10℃/min, the temperature was raised from 55℃ to 1000℃, the carrier gas was dry high-purity helium, and the total flow rate was maintained at 12.1 mL/min during the experiment, of which the purge flow rate and column flow rate were 3 mL/min and 0.82 mL/min, respectively. In addition, the column head pressure was 80 kPa, the m/z range was 10-800, the GC column (without stationary phase), the column box temperature, and the GC and MS injection port temperatures were all 300℃. When there was no porphyrin catalyst involved, except for the experiment of 1 mg of Moroccan oil shale powder sample with an average particle size of less than 74 μm, other conditions were the same as the TG analysis experiment with the participation of this catalyst.

As shown in Figure 6, the pyrolysis process of Moroccan oil shale can be divided into two stages with (dashed line) or without (solid line) the participation of this catalyst. Among them, the introduction of the above catalyst significantly enhances the TIC signal of the first peak, that is, the Moroccan oil shale system containing porphyrin derivatives can significantly improve the oil and gas yield of Moroccan oil shale.

The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims (26)

1. A method for processing oil shale, characterized in that the method includes: mixing a catalyst with oil shale and performing a pyrolysis reaction under an oxygen-deficient or inert atmosphere or a non-oxidizing gas atmosphere to obtain a pyrolysis reaction. The product is used to reduce the activation energy of oil shale pyrolysis reaction, wherein the catalyst includes an active component, and the active component is selected from phthalocyanine and/or its derivatives, and/or porphyrin and/or or its derivatives; Wherein, the weight ratio of the catalyst and fossil energy materials is 1:5000~10:1. 2. The method according to claim 1, wherein the structural formula of the phthalocyanine and/or its derivatives is as shown in formula (I), and the structural formula of the porphyrin and/or its derivatives is as shown in formula (II) Shown: Formula (I) Formula (II) Wherein, R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently a substituent group bonded to the structural formula of formula (I) or formula (II) through chemical synthesis; and/or, R ₁ -R ₁₆ And any two adjacent side groups in R' ₁ to R' ₁₂ form a ring or not; Wherein, M and M' are each independently selected from metallic elements and/or non-metallic elements. 3. The method according to claim 2, wherein R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, unsubstituted or substituted C ₁ -C ₂₀ alkyl, unsubstituted Substituted or substituted C ₁ -C ₂₀ alkoxy group, unsubstituted or substituted C ₆ -C ₃₀ aryl group, unsubstituted or substituted C ₄ -C ₃₀ heterocyclic aryl group, unsubstituted or substituted C ₂ -C ₂₀ ester group, unsubstituted or substituted C ₂ -C ₂₀ carbonyl group, unsubstituted or substituted C ₂ -C ₂₀ ether group, alkenyl group, alkynyl group, amine group, amide group, nitro group, Carboxyl, sulfo, hydroxyl or sulfhydryl group. 4. The method according to claim 3, wherein R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, unsubstituted or substituted C ₁ -C ₁₆ alkyl, unsubstituted Substituted or substituted C ₁ -C ₁₆ alkoxy group, unsubstituted or substituted C ₆ -C ₁₈ aryl group, unsubstituted or substituted C ₅ -C ₁₈ heterocyclic aryl group, unsubstituted or substituted C ₂ -C ₁₂ ester group, unsubstituted or substituted C ₂ -C ₁₂ carbonyl group, amine group, amido group, nitro group, carboxyl group, sulfo group, hydroxyl group or mercapto group. 5. The method according to claim 3, wherein R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, halogen, C ₁ -C ₄ alkyl, C ₁ -C ₄ Alkoxy group, C ₆ -C ₁₀ aryl group. 6. The method according to claim 3, wherein R ₁ -R ₁₆ and R' ₁ -R' ₁₂ are each independently selected from H, F, methyl, methoxy, ethyl, n-propyl, iso Propyl, tert-butyl, phenyl, benzyl. 7. The method according to claim 3, wherein the substituents present in _R1 - _R16 and _R'1 - _R'12 are each independently selected from the group consisting of halogen, amino, nitro, sulfo, hydroxyl, and mercapto. ,O,N,S. 8. The method according to claim 7, wherein the substituents present in _R1 - _R16 and _R'1 - _R'12 are each independently selected from the group consisting of halogen, amino, hydroxyl, mercapto, O, N, S . 9. The method of claim 7, wherein the substituents present in _R1 - _R16 and _R'1 - _R'12 are each independently selected from F, O, N, S. 10. The method according to any one of claims 2-9, wherein any two adjacent side groups in R ₁ -R ₁₆ and R' ₁ -R' ₁₂ form a ring or not, and The ring formed may or may not have substituents on it. 11. The method according to claim 10, wherein the ring formation forms a saturated or unsaturated cyclic structure, and the cyclic structure contains or does not contain heteroatoms. 12. The method according to claim 11, wherein the cyclic structure is selected from polycyclic rings with or without heteroatoms, saturated or unsaturated, and/or derivatives thereof. 13. The method according to claim 12, wherein the cyclic structure is selected from the group consisting of aromatic rings and/or derivatives thereof, benzene and/or derivatives thereof, naphthalene and/or derivatives thereof, anthracene and/or derivatives thereof. Derivatives, phenanthrene and/or its derivatives, pyridine and/or its derivatives, pyridazine and/or its derivatives, pyrazine and/or its derivatives, pyrimidine and/or its derivatives. 14. The method according to claim 13, wherein the cyclic structure is selected from the group consisting of benzene and/or its derivatives, naphthalene and/or its derivatives, anthracene and/or its derivatives, pyridine and/or its derivatives compounds, pyrazine and/or its derivatives, pyrimidine and/or its derivatives. 15. The method according to claim 14, wherein the cyclic structure is selected from benzene and/or its derivatives, naphthalene and/or its derivatives, anthracene and/or its derivatives, pyridine and/or its derivatives things. 16. The method according to any one of claims 2-9, wherein M and M' are each independently selected from transition metal elements, rare earth metal elements, alkali metal elements, alkaline earth metal elements, and non-metal elements; The transition metal element is selected from metal elements of Group IB, Group IIB, Group IVB, Group VB, Group VIB, Group VIIB or Group VIII. 17. The method of claim 16, wherein M and M' are each independently selected from Co, Mn, Cu, Fe, Ni, Zn, V, La, Sm, Si. 18. The method according to claim 16, wherein M and M' are each independently combined with a ligand, and the ligand is selected from halogen, oxygen, and oxygen-containing groups. 19. The method of claim 18, wherein the ligand is selected from -Cl, -O, -OH, _-OCH3 . 20. The method of claim 1, wherein the content of the active component in the catalyst is 0.0003-62 wt% based on the total amount of the catalyst. 21. The method of claim 20, wherein the content of the active component in the catalyst is 0.006-30 wt% based on the total amount of the catalyst. 22. The method according to claim 20, wherein the catalyst further comprises a carrier; the carrier is selected from the group consisting of molecular sieves, inorganic oxides, carbon black, graphite, graphene and/or derivatives thereof, and at least one of minerals. A sort of. 23. The method according to claim 22, wherein the molecular sieve is selected from the group consisting of SBA type molecular sieve, MCM type molecular sieve, ZSM type molecular sieve, HZSM type molecular sieve, CMS type molecular sieve, ITQ type molecular sieve, MSU type molecular sieve, CHA type molecular sieve, At least one of TS type molecular sieve, X type molecular sieve, Y type molecular sieve and A type molecular sieve; The inorganic oxide is selected from at least one of zirconium oxide, magnesium oxide, aluminum oxide, silicon oxide, zinc oxide, iron oxide, nickel oxide, copper oxide and cobalt oxide; The mineral is selected from at least one selected from the group consisting of pyrite, illite, montmorillonite, kaolinite, bentonite, activated clay and oil shale ash. 24. The method according to claim 1, wherein the weight ratio of the catalyst and fossil energy material is 1:1~1:1000. 25. The method of claim 1, wherein the inert atmosphere is selected from at least one of nitrogen, helium, argon and neon; The non-oxidizing gas is selected from at least one of carbon dioxide, carbon monoxide, hydrogen and gaseous water; The conditions of the pyrolysis reaction include: temperature is 100-1000°C; time is 0.2-24h; temperature rise rate is 10-30°C/min. 26. The method of claim 25, wherein the inert atmosphere is selected from nitrogen; The conditions for the pyrolysis reaction include: the temperature is 100-800°C.