A laminated catalyst, its preparation method and application

Abstract

The present invention discloses a superimposed catalyst and its preparation method and application. The superimposed catalyst comprises an active component and a carrier for carrying the active component, wherein the carrier is a composite carrier formed by molybdenum-doped gallium magnesium oxide alumina and a molecular sieve, and the pore expander used to prepare the composite carrier is anthracene, and the elements contained in the active component include any one or a combination of two or more of chromium, cobalt and zirconium. The present invention obtains gas, liquid and solid three-phase products by subjecting inferior heavy oil to thermal cracking and catalytic reaction, wherein the liquid phase product is subjected to hydrogenation treatment to obtain two fractions of naphtha fraction and diesel, wherein the naphtha fraction can be used as a cracking raw material for an ethylene device, and the diesel fraction is a qualified diesel product; the gas obtained after the inferior heavy oil is pyrolyzed and catalyzed can be used as a fuel; and the method completely converts the inferior heavy oil, thereby improving the ton value-added rate of the inferior heavy oil raw material.

Description

Technical Field

[0001] The present invention belongs to the technical field of clean production of inferior heavy oil, and relates to a polymerization catalyst, a preparation method thereof and an application thereof, in particular to a polymerization catalyst and a preparation method thereof, and an application of the polymerization catalyst in the production of clean fuels from inferior heavy oil. Background Art

[0002] At present, the world's oil resources are becoming increasingly scarce and the prices are rising. However, inferior heavy oil petrochemical by-products such as ethylene tar and catalytically discarded slurry have not been effectively utilized. On the other hand, with the improvement of people's living standards, the demand for clean fuels such as liquefied gas, gasoline and diesel is increasing day by day. Therefore, it is of great practical significance to process these inferior heavy oils and convert them into clean fuels.

[0003] Ethylene tar is a by-product of the ethylene cracking unit in the petrochemical industry. Its distillation range is generally 600-700°C, belonging to the heavy fraction range. At present, ethylene tar is mainly sold as heavy fuel oil or carbon black raw material. Patents CN1970688A, CN106883871A and some enterprises have developed comprehensive utilization methods for ethylene tar, such as extracting naphthalene and its series products from it, using light components to synthesize petroleum resins, preparing carbon fiber asphalt and carbon fibers from heavy tar, and preparing activated carbon from heavy fractions above 540°C. However, its comprehensive utilization rate is only about 50%, and there is room for further improvement; CN109609182A uses the delayed coking method to treat ethylene tar, and the yield of high-value-added products is about 80%, including more than 10% of heavier wax oil, and the yield of high-value-added light fuels is relatively low.

[0004] In Patent CN101608132A, the whole fraction of ethylene tar is co-refined with vacuum residue as the feedstock for delayed coking, resulting in low liquid yield and low yield of light fuel oil products. Moreover, the quality of the obtained products, namely coker gasoline, diesel, and wax oil, is still poor and further processing is required. The methods disclosed in Patents CN103805248A, CN103773497A, CN103102974A, CN103102979A, and CN103102975A, etc. adopt processing means different from those of the present invention. The processing methods disclosed in Patents CN102703101A and CN104611060A are to send ethylene tar and its mixtures to a distillation catalytic furnace for distillation catalysis to produce gasoline, diesel, and combustible gas products. For the former, the catalyst used in the distillation catalytic furnace is a petroleum heavy oil catalyst, and the non-hydrogenation catalyst GG-12 catalyst for processing shale oil and medium-temperature coal tar. This catalyst is used for liquid raw materials and does not belong to the polymerization catalyst. The highest total yield of light fuel is only about 92%. Although the latter uses one or several of molecular sieves and silica-alumina catalysts, the process route is different from that of the present invention, and the sulfur and nitrogen contents in the pyrolysis catalytic liquid phase products are relatively high, with the lowest being 135 μg / g and 85 μg / g, and the product properties need to be further improved.

[0005] Catalytically withdrawn slurry oil, as a by-product of catalytic cracking units in the petrochemical industry, is mainly sold as cheap fuel oil or slightly co-refined into coking units, resulting in a waste of petroleum resources. Currently, the annual output of catalytic slurry oil in China is approximately 7.5 million tons. With the increasing heavy quality of petroleum resources, the feedstock of catalytic units is becoming increasingly inferior, and the output of catalytic slurry oil will also show an increasing trend. In the current situation where refining profits are decreasing day by day, developing a more economically viable technical route for catalytic slurry oil is an urgent problem to be solved by refineries. Summary of the Invention

[0006] The main object of the present invention is to provide a polymerization catalyst, its preparation method, and its application to overcome the deficiencies of the prior art.

[0007] To achieve the foregoing invention object, the technical solutions adopted by the present invention include:

[0008] An embodiment of the present invention provides a polymerization catalyst, which includes an active component and a carrier for supporting the active component. The carrier is a composite carrier formed by alumina doped with molybdenum and magnesium gallate and a molecular sieve, and the pore-expanding agent used for preparing the composite carrier is anthracene. The elements contained in the active component include any one or a combination of two or more of chromium, cobalt, and zirconium. The pore diameter of the polymerization catalyst is 15 - 25 nm, and the specific surface area is 450 - 650 m 2 / g.

[0009] An embodiment of the present invention also provides a preparation method of the foregoing polymerization catalyst, which includes:

[0010] (1) A mixed system containing pseudoboehmite, molybdenum-doped gallium manganite, pore expander, extrusion aid and peptizing acid is subjected to kneading, drying and calcination treatments to obtain alumina containing molybdenum-doped gallium manganite, wherein the pore expander includes anthracene;

[0011] (2) Molecular sieve, the alumina containing molybdenum-doped gallium manganite, water and binder are mixed and subjected to extrusion, drying and calcination treatments to obtain the composite support;

[0012] (3) The composite support is impregnated in a mixed solution containing a metal active component precursor and a nonionic surfactant, and then subjected to drying and calcination treatments to obtain the oligomerization catalyst.

[0013] The embodiment of the present invention also provides the use of the foregoing oligomerization catalyst in the field of producing clean fuels from inferior heavy oil.

[0014] The embodiment of the present invention also provides a method for producing clean fuels from inferior heavy oil, which includes:

[0015] Subjecting inferior heavy oil to thermal cracking reaction to obtain cracking gas with an end boiling point less than 150 °C and cracking gas with an initial boiling point greater than 150 °C;

[0016] Subjecting the cracking gas with an end boiling point less than 150 °C to catalytic reaction under the condition of an oligomerization catalyst to obtain a catalytic product, wherein the oligomerization catalyst uses the foregoing oligomerization catalyst;

[0017] And mixing the cracking gas with an initial boiling point greater than 150 °C with the catalytic product for hydrotreating to obtain gasoline and diesel.

[0018] The embodiment of the present invention also provides a system for producing clean fuels from inferior heavy oil, which is applied to the foregoing method and includes:

[0019] A thermal cracking reaction unit, which can at least subject inferior heavy oil to thermal cracking reaction to obtain cracking gas with an end boiling point less than 150 °C and cracking gas with an initial boiling point greater than 150 °C;

[0020] A catalytic reaction unit, which can at least make the cracking gas with an end boiling point less than 150 °C contact with the superposition catalyst to carry out catalytic reaction to obtain a catalytic product;

[0021] And a hydrotreating reaction unit, which is at least used for hydrotreating the liquid phase product in the catalytic product and the cracking gas with an initial boiling point greater than 150 °C to obtain gasoline and diesel.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] (1) In the present invention, inferior heavy oil is subjected to thermal cracking and catalytic reaction to obtain gas, liquid, and solid phase products. Among them, the liquid phase product is subjected to hydrotreating to obtain naphtha fraction (also gasoline fraction) and diesel fraction. The naphtha fraction can be used as the cracking feedstock for the ethylene plant, and the diesel fraction is a qualified diesel product; the gas obtained after the pyrolysis catalysis of inferior heavy oil can be used as fuel; the solid product obtained can be used as the feed for the POX gasification unit. This method enables the complete conversion of inferior heavy oil and improves the value-added rate per ton of the inferior heavy oil raw material;

[0024] (2) The catalyst used in the catalytic reaction in the present invention is a polymerization catalyst, which can convert C3 and C4 olefin components in the cracked gas with a final boiling point of less than 150 °C after pyrolysis catalysis into unsaturated hydrocarbons such as C8, C9, and C12 through polymerization reaction. In this way, the gas yield is significantly reduced and more liquid phase products are obtained. The subsequent liquid phase product is subjected to hydrotreating to be converted into more gasoline and diesel products. More clean oil products mean that the added value of the inferior heavy oil raw material is further increased, thereby further improving the comprehensive economy of inferior heavy oil;

[0025] (3) The polymerization catalyst in the present invention uses an organic compound - anthracene as a pore-expanding agent. Utilizing its characteristics, during the carrier calcination process, it experiences a process of first becoming a gas and finally burning out to carbon, which is different from the pore-forming processes of other conventional physical pore-expanding agents such as carbon black, cellulose, and starch. When anthracene reaches its boiling point, it first becomes a gas and slowly escapes from the alumina carrier, and at this time, numerous primary pores are formed; as the temperature rises, it finally burns out to become carbon, and more secondary pores are formed. The effect of pore formation twice enables it to have a better pore-expanding effect on the premise that the addition amount is significantly less than that of conventional physical pore-expanding agents, avoiding the problem that the mechanical strength of the carrier decreases due to the large addition amount of conventional physical pore-expanding agents and the large particles formed during burnout;

[0026] (4) The present invention provides a method and catalyst with high raw material utilization rate, good product properties, and good comprehensive economy for inferior heavy oil with low added value, which is very beneficial for the emission reduction and efficiency increase of refineries. Description of the Drawings

[0027] In order to more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the drawings required for use in the description of the embodiments or the prior art. Obviously, the drawings in the following description are only some embodiments recorded in the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can also be obtained based on these drawings.

[0028] Figure 1 It is the process schematic diagram for producing clean fuel using inferior heavy oil in a typical embodiment of the present invention.

[0029] Reference numerals: 1 - inferior heavy oil, 2 - thermal cracking reaction unit, 3 - cracked gas with an end boiling point of less than 150 °C, 4 - catalytic reaction unit, 5 - gas-liquid separator, 6 - gas-phase product, 7 - liquid-phase product; 8 - cracked gas with an initial boiling point of greater than 150 °C, 9 - solid-phase product, 10 - mixture, 11 - hydrotreating reaction unit, 12 - liquefied gas, 13 - gasoline, 14 - diesel, 15 - a small amount of unconverted oil. Detailed implementation manners

[0030] In view of the deficiencies of the prior art, through long-term research and a large number of practices, the inventors of this case have proposed the technical solution of the present invention. The technical solution of the present invention will be described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts belong to the scope of protection of the present invention.

[0031] Specifically, as an aspect of the technical solution of the present invention, a superposed catalyst involved therein includes an active component and a carrier carrying the active component. The carrier is a composite carrier formed by alumina doped with molybdenum-doped magnesium gallate and molecular sieve, and the pore-expanding agent used for preparing the composite carrier is anthracene. The elements included in the active component include any one or a combination of two or more of chromium, cobalt, and zirconium. The pore diameter of the superposed catalyst is 15 - 25 nm, and the specific surface area is 450 - 650 m 2 / g.

[0032] In some preferred embodiments, the active component includes a metal oxide formed by any one or two or more elements of chromium, cobalt, and zirconium.

[0033] In some preferred embodiments, the content of the active component in the superposed catalyst is 1.0 - 15.0 wt%, the content of alumina doped with molybdenum-doped magnesium gallate is 40.0 - 80.0 wt%, and the content of molecular sieve is 1.0 - 10.0 wt%.

[0034] In some preferred embodiments, the mass ratio of molybdenum-doped magnesium gallate to alumina in the alumina doped with molybdenum-doped magnesium gallate is 1.0 - 15.0:100.

[0035] In some preferred embodiments, the molecular sieve includes, but is not limited to, Y-type molecular sieve.

[0036] Furthermore, the specific surface area of the molecular sieve is 600 - 630 m 2 / g, and the pore volume is 0.40 - 0.45 ml / g.

[0037] In some preferred embodiments, the molar ratio of alumina containing molybdenum-doped gallium magnesium oxide to molecular sieve in the composite support is 1:6 to 8.

[0038] Another aspect of the embodiments of the present invention also provides a method for preparing the foregoing oligomerization catalyst, which includes:

[0039] (1) Subjecting a mixed system containing pseudoboehmite, molybdenum-doped gallium magnesium oxide, pore-expanding agent, extrusion aid and peptizing acid to kneading, drying and calcination treatments to obtain alumina containing molybdenum-doped gallium magnesium oxide, wherein the pore-expanding agent includes anthracene;

[0040] (2) Mixing molecular sieve, the alumina containing molybdenum-doped gallium magnesium oxide with water and binder, and subjecting to extrusion, drying and calcination treatments to obtain the composite support;

[0041] (3) Immersing the composite support in a mixed solution containing a precursor of a metal active component and a nonionic surfactant, and then subjecting to drying and calcination treatments to obtain the oligomerization catalyst.

[0042] In some preferred embodiments, step (1) specifically includes: mixing pseudoboehmite, molybdenum-doped gallium magnesium oxide, pore-expanding agent and extrusion aid, and then adding peptizing acid to the obtained mixture at a rate of 3-10 g / min at 40-80 °C.

[0043] Further, the pore-expanding agent is anthracene, and the mass ratio of the pore-expanding agent to pseudoboehmite is 1.0-3.0:100.

[0044] In some preferred embodiments, the peptizing acid includes any one or a combination of two or more of nitric acid, phosphoric acid, citric acid, hydrochloric acid, acetic acid, etc., and is not limited thereto, and the addition amount is based on satisfying the shaping of the support.

[0045] In some preferred embodiments, the extrusion aid includes any one or a combination of two or more of starch, sawdust powder, polyvinyl alcohol, methyl cellulose, polyethylene glycol, etc., and is not limited thereto.

[0046] In some preferred embodiments, the binder includes small-pore alumina; the pore volume of the small-pore alumina is 0.3-0.5 ml / g, the average pore diameter is 2-4 nm, and the addition amount is based on satisfying the shaping of the support.

[0047] Further, the content of the extrusion aid in the mixed system is 4-10 wt%.

[0048] In some preferred embodiments, in step (1), the temperature of the drying treatment is 100-140 °C, the time is 3-7 h; the temperature of the calcination treatment is 350-500 °C, and the calcination time is 5-10 h.

[0049] In some preferred embodiments, the temperature of the drying treatment in step (2) is 100 - 140 °C, and the time is 3 - 7 h; the temperature of the calcination treatment is 350 - 500 °C, and the calcination time is 5 - 10 h.

[0050] In some preferred embodiments, step (3) specifically includes: mixing a metal active component precursor, a non-ionic surfactant, and water to form a metal active component precursor solution, and then placing the composite support in the metal active component precursor solution and performing an impregnation treatment at 20 - 30 °C for 5 - 10 h.

[0051] Furthermore, the concentration of metal oxide in the metal active component precursor solution is 5 - 50 g / 100 mL.

[0052] In some preferred embodiments, the metal active component precursor includes any one or more water-soluble compounds of chromium, cobalt, and zirconium metal elements, and is not limited thereto.

[0053] Furthermore, the metal active component precursor includes any one or a combination of two or more of chromium nitrate, cobalt nitrate, cobalt acetate, and zirconium nitrate, and is not limited thereto.

[0054] In some preferred embodiments, the non-ionic surfactant includes fatty alcohol polyether, and is not limited thereto.

[0055] Furthermore, the mass ratio of the non-ionic surfactant to the composite support is 2 - 10:100.

[0056] In some preferred embodiments, the method for preparing molybdenum-doped gallium manganate includes: reacting a mixed reaction system containing gallium nitrate, magnesium nitrate, sodium polyacrylate, ammonium molybdate, and oxalic acid solution, and then performing drying, calcination, and grinding treatments to obtain molybdenum-doped gallium manganate.

[0057] Furthermore, the mass ratio of gallium nitrate, magnesium nitrate, sodium polyacrylate, and ammonium molybdate is 100 - 110:100 - 120:20 - 30:1.

[0058] Another aspect of the embodiments of the present invention also provides the use of the foregoing stacking catalyst in the field of producing clean fuels from inferior heavy oil.

[0059] Another aspect of the embodiments of the present invention also provides a method for producing clean fuels from inferior heavy oil, which includes:

[0060] Subjecting the inferior heavy oil to a thermal cracking reaction to obtain a cracked gas with an end boiling point less than 150 °C and a cracked gas with an initial boiling point greater than 150 °C;

[0061] Subject the pyrolysis gas with an end boiling point less than 150°C to a catalytic reaction under the conditions of a polymerization catalyst to obtain a catalytic product, wherein the polymerization catalyst used is the aforementioned polymerization catalyst;

[0062] In addition, mix the pyrolysis gas with an initial boiling point greater than 150°C with the catalytic product and conduct hydrotreating to obtain gasoline and diesel.

[0063] Specifically, the method for producing clean fuels from inferior heavy oil includes: first subject the inferior heavy oil to a thermal pyrolysis reaction. As the pyrolysis temperature rises, the rising pyrolysis gas flows through the catalytic reaction zone (catalytic reaction unit), and this catalytic reaction unit is filled with the polymerization catalyst described in the present invention. When the temperature reaches 150°C, close the rising pyrolysis gas cut-off valve, and let the pyrolysis gas with a temperature greater than 150°C flow out from the bypass and mix with the polymerization reaction product. This mixture then enters the subsequent hydrotreating reaction unit together, and through processes such as hydrotreating reaction and separation, gasoline, diesel, and a small amount of unreacted oil are obtained. The unreacted oil is recycled back to the fresh feed for further reaction. The gas obtained from the thermal pyrolysis catalysis of inferior heavy oil can be used as fuel; the solid product obtained can be used as the feed for a coal gasification device.

[0064] In some more specific typical implementation cases, a method for the thermal pyrolysis catalysis of inferior heavy oil may include:

[0065] (1) The inferior heavy oil enters the thermal pyrolysis reaction unit for reaction. As the pyrolysis temperature rises, the rising pyrolysis gas flows through the catalytic reaction unit, and this reaction unit is filled with the polymerization catalyst described in the present invention. When the temperature reaches 150°C, close the rising pyrolysis gas cut-off valve;

[0066] (2) Let the rising pyrolysis gas with an initial boiling point greater than 150°C flow out from the bypass and mix with the polymerization reaction product;

[0067] (3) The mixture obtained in the above (2) enters the subsequent hydrotreating reaction unit together, passes through the pre-hydrotreating refining reaction zone and the hydrocracking reaction zone in sequence, and the hydrocracking product obtained is separated to obtain liquefied gas, gasoline, diesel, and a small amount of unreacted oil.

[0068] In some preferred implementation schemes, the method specifically includes: subject the inferior heavy oil to a thermal pyrolysis reaction under the conditions of a temperature of 100 - 580°C and a reaction pressure of 0 - 5 MPa to obtain the pyrolysis gas with an end boiling point less than 150°C and the pyrolysis gas with an initial boiling point greater than 150°C, and it is not limited to this.

[0069] Furthermore, the starting temperature of the thermal pyrolysis reaction is 100 - 200°C, the reaction termination temperature is 460 - 580°C, and the heating rate is 5 - 50°C / h.

[0070] In some preferred embodiments, the method specifically includes: continuously inputting the pyrolysis gas with an end boiling point less than 150°C into a reaction device provided with a polymerization catalyst, and carrying out a catalytic reaction at a temperature of 90 - 150°C, a pressure of 2.0 - 4.0 MPa, and a liquid hourly space velocity of 20 - 30 h -1 to obtain the catalytic product.

[0071] In some preferred embodiments, the method specifically includes: mixing the pyrolysis gas with an initial boiling point greater than 150°C with the liquid-phase component in the catalytic product for hydrotreating and separation to obtain gasoline, diesel, and unreacted inferior heavy oil.

[0072] In some preferred embodiments, the method specifically includes: mixing the liquid-phase reaction product separated from the catalytic product with the pyrolysis gas with an initial boiling point greater than 150°C in a hydrotreating process, that is, successively carrying out a pre-hydrofining reaction and a hydrocracking reaction, and then separating to obtain naphtha (also referred to as gasoline) and diesel fractions.

[0073] In some embodiments, separation of naphtha and diesel can be achieved by fractionation and other means. For example, in some more specific embodiments, the cut point between the naphtha and diesel fractions is 145 - 155°C. The naphtha fraction can be used as a pyrolysis feedstock in an ethylene pyrolysis unit, and the diesel fraction is dispatched as a qualified diesel product. The gaseous products and the gaseous products obtained from pyrolysis catalysis can be collected together and used as fuel gas.

[0074] Furthermore, both the pre-hydrofining reaction and the hydrocracking reaction can adopt a fixed-bed hydrogenation process, and a one-stage series process can also be adopted for the pre-hydrofining reaction and the hydrocracking reaction.

[0075] In some preferred embodiments, the hydrotreating includes a pre-hydrofining reaction and a hydrocracking reaction.

[0076] Furthermore, the conditions for the pre-hydrofining reaction include: a reaction temperature of 260 - 300°C, a hydrogen partial pressure of 10.0 - 16.0 MPa, a hydrogen-oil volume ratio of 900∶1 - 1500∶1, and a liquid hourly space velocity of 0.8 - 1.5 h -1 .

[0077] Furthermore, the conditions for the hydrocracking reaction include: a reaction temperature of 340 - 390°C, a hydrogen partial pressure of 10.0 - 16.0 MPa, a hydrogen-oil volume ratio of 900∶1 - 1500∶1, and a liquid hourly space velocity of 0.5 - 1.5 h -1 .

[0078] In some preferred embodiments, the inferior heavy oil includes any one or a combination of two or more of ethylene C9 fraction, ethylene tar, catalytic cracking light cycle oil, catalytic cracking slurry oil, MIP diesel oil in the petrochemical industry, heavy benzene, naphthalene oil, wash oil, anthracene oil fraction in the coal coking industry, shale oil, and 150-600 °C fraction of oil sand asphalt, and is not limited thereto.

[0079] In some preferred embodiments, the mass ratio of the oligomerization catalyst to the inferior heavy oil is 1.0-10.0:100.

[0080] In some preferred embodiments, the catalyst used in the hydrotreating includes a hydrotreating catalyst.

[0081] Further, the hydrotreating catalyst includes a hydroprotection catalyst, a pre-hydrofining catalyst, a hydrofining catalyst, and a hydrocracking catalyst.

[0082] The process of the present invention is simple and the raw materials are cheap and easily available. It can not only realize the complete utilization of petrochemical by-products resources of inferior heavy oil, is green and environmentally friendly, but also the yield of clean gasoline and diesel fuel oil can reach more than 93%, and the value-added rate per ton of inferior heavy oil is increased.

[0083] Another aspect of the embodiments of the present invention also provides a system for producing clean fuel from inferior heavy oil, which is applied to the foregoing method, and includes:

[0084] A thermal cracking reaction unit, which can at least cause the inferior heavy oil to undergo a thermal cracking reaction to obtain cracked gas with an end boiling point less than 150 °C and cracked gas with an initial boiling point greater than 150 °C;

[0085] A catalytic reaction unit, which at least causes the cracked gas with an end boiling point less than 150 °C to contact with the oligomerization catalyst to undergo a catalytic reaction to obtain a catalytic product;

[0086] And a hydrotreating reaction unit, which is at least used to perform hydrotreating on the liquid phase product in the catalytic product and the cracked gas with an initial boiling point greater than 150 °C to obtain gasoline and diesel;

[0087] Further, the hydrotreating reaction unit includes a pre-hydrofining reaction unit and a hydrocracking reaction unit.

[0088] Further, the thermal cracking reaction unit and the catalytic reaction unit are respectively arranged in two or more independent reactors.

[0089] In some embodiments, the pre-hydrofining reaction unit and the hydrocracking reaction unit of the hydrotreating unit are respectively arranged in two or more independent different reactors.

[0090] Furthermore, the catalyst used in the pre-hydrofining reaction unit includes a pre-hydrofining catalyst and / or a hydrogenation protection catalyst. The pre-hydrofining catalyst can be selected from pre-hydrofining catalysts in the petrochemical industry.

[0091] Furthermore, the hydrogenation protection catalyst used in the pre-hydrofining reaction unit can be a conventional residue oil hydrogenation protection agent or a residue oil hydrodemetallization catalyst.

[0092] In some embodiments, the hydrocracking reaction unit adopts a grading loading method of a hydrofining catalyst and a hydrocracking catalyst, where both the hydrofining catalyst and the hydrocracking catalyst can be one or more hydrofining or cracking catalysts in the petrochemical industry.

[0093] In some embodiments, in the pre-hydrofining reaction unit, a hydrogenation protection catalyst and a pre-hydrofining catalyst are sequentially loaded along the flow direction of the mixed stream of the liquid-phase reaction product of the oligomerization reaction and the cracked gas at a temperature higher than 150°C (for example, from top to bottom), while the hydrocracking reaction unit is loaded with a hydrofining catalyst and a hydrocracking catalyst.

[0094] The hydrogenation protection catalyst, the pre-hydrofining catalyst, and the hydrocracking catalyst can also be respectively selected from the types listed above, and will not be described repeatedly here.

[0095] In some more preferred embodiments, the hydrogenation protection catalyst accounts for 5% to 40% of the loading volume of the pre-hydrofining catalyst.

[0096] In some more preferred embodiments, the loading volume ratio of the hydrofining catalyst to the hydrocracking catalyst is 1:1 to 3:1.

[0097] In some embodiments, the system may further include a separation unit, which is at least used for condensing and gas-liquid separating the catalytic product to form a gas product and a liquid product; furthermore, it is at least used for separating the product formed by hydrogenation treatment of the mixture of the liquid-phase reaction product of the oligomerization reaction and the cracked gas at a temperature higher than 150°C to obtain liquefied gas, naphtha, and diesel.

[0098] In some more typical embodiments, the process flow diagram of the process for producing clean fuels from inferior heavy oil in the present invention is as Figure 1As shown in the figure, it may include: First, the inferior heavy oil 1 is passed through the thermal cracking reaction unit 2. As the pyrolysis temperature rises, the cracked gas 3 with an end boiling point less than 150°C flows through the catalytic reaction unit 4. When it reaches 150°C, the rising path valve is closed, and the catalytic reaction product passes through the gas-liquid separator 5 to obtain the gas-phase product 6 and the liquid-phase product 7. The cracked gas 8 with an initial boiling point greater than 150°C is mixed with the liquid-phase product 7 from the bypass to form a mixture 10. The mixture 10 enters the hydrotreating reaction unit 11. After the hydrotreating reaction process, gasoline 13, diesel 14, and a small amount of unconverted oil 15 are obtained. The unconverted oil 15 is recycled back to the inferior heavy oil 1 for further reaction. The obtained liquefied gas 12 and the gas-phase product 6 are used as fuels together. The solid-phase product 9 obtained by pyrolysis can be used as the feed for the coal gasification device.

[0099] The technical solutions of the present invention will be further described in detail below in conjunction with several preferred embodiments and the accompanying drawings. This embodiment is implemented on the premise of the technical solution of the invention, and the detailed implementation methods and specific operation processes are given. However, the protection scope of the present invention is not limited to the following embodiments.

[0100] In the following embodiments, the experimental materials used, unless otherwise specified, can be obtained from conventional biochemical reagent companies.

[0101] Preparation of molybdenum-doped gallium magnesate: Dissolve 150 g of oxalic acid in 1 L of deionized water to obtain an oxalic acid solution; then add 2.0 mol of gallium nitrate and 4.0 mol of magnesium nitrate to the above 100 ml of oxalic acid solution, mix well; add 130 g of sodium polyacrylate; then add an aqueous solution containing 5.0 g of ammonium molybdate, continuously stir for about 30 min, and after sufficient reaction, obtain the molybdenum-doped gallium magnesate finished product through drying, calcination, and grinding.

[0102] Example 1: Preparation of the polymerization catalyst C1

[0103] (1) Take 50 g of pseudo-boehmite, add 2.5 g of molybdenum-doped gallium magnesate, 0.6 g of anthracene, and 2.5 g of talc powder (extrusion aid), mix well; at 80°C, dropwise add an aqueous solution containing nitric acid at a dropping rate of 6.5 g / min, and knead evenly; dry at 140°C for 3 h, and then calcine at 350°C for 7.5 h to prepare alumina containing molybdenum-doped gallium magnesate.

[0104] (2) Mix 7 g of molecular sieve (the molar ratio of the molecular sieve to the alumina containing molybdenum-doped gallium magnesate is 7, specific surface area 615 m 2 / g, pore volume 0.42 ml / g), the alumina containing molybdenum-doped gallium magnesate prepared in step (1), deionized water, and a binder evenly. The binder is small-pore alumina with a pore volume of 0.4 ml / g and an average pore diameter of 3 nm. The addition amount is based on meeting the forming requirement. Extrude into a cylindrical bar with a diameter of 2.0 mm, dry at 140°C for 7 h, and then calcine at 350°C for 7.5 h to prepare a composite support.

[0105] (3) At 25 °C, the above composite support was impregnated with an impregnation solution prepared from cobalt acetate and zirconium nitrate for 7.5 h with equal volume, and then dried at 150 °C and calcined at 500 °C for 5.5 h to obtain a polymerization catalyst, the composition of which is: cobalt oxide 8.0 wt%, zirconium oxide 5.0 wt%, molecular sieve 5.6%, and the balance is alumina.

[0106] The specific surface area of this catalyst was measured by the BET characterization method to be 480 m 2 / g, and the average pore diameter was 20 nm. This polymerization catalyst was named C1.

[0107] Example 2: Preparation of polymerization catalyst C2

[0108] (1) Take 60 g of pseudo-boehmite, add 3.0 g of molybdenum-doped gallium manganate, 0.7 g of anthracene, and 3.2 g of talc powder (extrusion aid), and mix evenly; at 60 °C, dropwise add an aqueous solution containing nitric acid at a dropping rate of 3 g / min, and knead evenly; after drying at 100 °C for 5 h, calcine at 500 °C for 5 h to make alumina containing molybdenum-doped gallium manganate;

[0109] (2) 10 g of molecular sieve (the molar ratio of the molecular sieve to the alumina containing molybdenum-doped gallium manganate is 6, specific surface area 600 m 2 / g, pore volume 0.45 ml / g) and the alumina containing molybdenum-doped gallium manganate in step (1) were mixed evenly with deionized water and a binder. The binder was small-pore alumina with a pore volume of 0.5 ml / g and an average pore diameter of 4 nm. The addition amount was based on meeting the forming requirement, and it was extruded into a cylindrical bar with a diameter of 1.5 mm, dried at 100 °C for 5 h, and then calcined at 500 °C for 5 h to make a composite support.

[0110] (3) Then at 20 °C, the above composite support was impregnated with an impregnation solution prepared from chromium nitrate and zirconium nitrate for 5.0 h with equal volume, and then dried at 100 °C and calcined at 650 °C for 1.0 h to obtain a polymerization catalyst, and the final composition of the catalyst is: chromium oxide 4.0 wt%, zirconium oxide 9.0 wt%, molecular sieve 6.2%, and the balance is alumina.

[0111] The specific surface area of this catalyst was measured by the BET characterization method to be 500 m 2 / g, and the average pore diameter was 18 nm. This polymerization catalyst was named C2.

[0112] Example 3: Preparation of polymerization catalyst C3

[0113] (1) Take 55 g of pseudo-boehmite, add 3.5 g of molybdenum-doped gallium magnesate, 1.0 g of anthracene, and 3.5 g of sesbania powder (extrusion aid), and mix them evenly. Dropwise add an aqueous solution containing nitric acid at 40 °C at a dropping rate of 10 g / min, and knead evenly. After drying at 120 °C for 7 h, calcine at 425 °C for 10 h to prepare alumina containing molybdenum-doped gallium magnesate.

[0114] (2) 12 g of molecular sieve (the molar ratio of molecular sieve to alumina containing molybdenum-doped gallium magnesate is 8, specific surface area 630 m 2 / g, pore volume 0.40 ml / g) and the alumina containing molybdenum-doped gallium magnesate in step (1) are mixed evenly with deionized water and a binder. The binder is small-pore alumina with a pore volume of 0.3 ml / g and an average pore diameter of 2 nm. The addition amount is based on meeting the forming requirements. Extrude into 2.5-mm cylindrical bars, dry at 120 °C for 3 h, and then calcine at 425 °C for 10 h to prepare a composite support.

[0115] (3) Then, at 30 °C, impregnate the above composite support with an impregnation solution prepared from cobalt acetate and chromium nitrate for 10.0 h by equal volume, and then dry at 125 °C and calcine at 525 °C for 10.0 h to obtain a polymerization catalyst. The final composition of the catalyst is: cobalt oxide 8.0 wt%, chromium oxide 7.0 wt%, molecular sieve 8.1%, and the balance is alumina.

[0116] Using the BET characterization method, the specific surface area of this catalyst is measured to be 600 m 2 / g, and the average pore diameter is 16 nm. This polymerization catalyst is named C3.

[0117] In the following examples, the inferior heavy oil used in Example 4 and Example 6 is ethylene tar, and the catalytic slurry oil used in Example 5. Their properties are listed in Table 1.

[0118] The thermal cracking reaction zone and the catalytic reaction zone are respectively in two reaction kettles. The mixture of the liquid-phase reaction product of the catalytic reaction and the pyrolysis gas with an initial boiling point greater than 150 °C enters the hydrotreating unit. The pre-hydrofining reaction zone and the hydrocracking reaction zone adopt a one-stage series process and consist of two reactors. The first reactor, the pre-hydrofining reactor, is filled with the commercially available hydroprotection agent FZC-103 and the pre-hydrofining catalyst FHRS-1 from top to bottom. The second reactor, the hydrocracking reactor, is filled with the commercially available hydrofining catalyst 3936 and the hydrocracking catalyst FC-36 in the petrochemical industry. The hydrotreating liquid-phase product is separated and distilled to obtain naphtha and diesel fractions, and the cut-off point is about 145 °C.

[0119] It should be further noted that all kinds of reaction participants and process conditions adopted in the following embodiments are relatively typical examples. However, after a large number of tests verified by the inventors of this case, other types of reaction participants and other process conditions listed above are also applicable and can achieve the technical effects claimed in the present invention.

[0120] Example 4

[0121] The process conditions of the thermal cracking / oligomerization catalytic reaction of ethylene tar, the resulting gas products, the mixture of the catalytic liquid product and the cracked gas with an initial boiling point greater than 150 °C, and the yields and properties of the three products of the residue are shown in Table 2. The catalyst used in the oligomerization catalytic reaction zone is C1 catalyst, and the catalyst dosage is 5.5 wt% of ethylene tar. The process conditions of the pre-hydrofining / hydrocracking of the mixture of the catalytic reaction liquid product and the cracked gas with an initial boiling point greater than 150 °C are shown in Table 3, where the volume ratios of the hydrogenation protective agent to the pre-hydrofining catalyst and the pre-hydrofining catalyst to the hydrocracking catalyst are 1:20 and 2:1 respectively. The properties of the gasoline fraction and diesel fraction finally obtained from the reaction are shown in Table 4.

[0122] Example 5

[0123] Compared with Example 4, the catalyst used in the catalytic reaction zone is C2 catalyst, and the catalyst dosage is 10.0 wt% of ethylene tar. The process conditions of the pre-hydrofining / hydrocracking of the mixture of the catalytic reaction liquid product and the cracked gas with an initial boiling point greater than 150 °C are shown in Table 3, where the volume ratios of the hydrogenation protective agent to the pre-hydrofining catalyst and the pre-hydrofining catalyst to the hydrocracking catalyst are 2:5 and 2:1 respectively, and the reaction results are shown in Table 4.

[0124] Example 6

[0125] Compared with Example 4, the catalyst used in the catalytic reaction zone is C3 catalyst, and the catalyst dosage is 1.0 wt% of catalytic slurry. The process conditions of the pre-hydrofining / hydrocracking of the mixture of the catalytic reaction liquid product and the cracked gas with an initial boiling point greater than 150 °C are shown in Table 3, where the volume ratios of the hydrogenation protective agent to the pre-hydrofining catalyst and the pre-hydrofining catalyst to the hydrocracking catalyst are 2:9 and 3:1 respectively, and the reaction results are shown in Table 4.

[0126] Table 1 Properties of inferior heavy oil

[0127] Name Ethylene tar Catalytic slurry oil Density (20 °C), kg·m-3 1007.8 998.2 S, μg·g-1 361 10890 N, μg·g-1 204 1954 Four components, wt% Saturates 5.0 30.5 Aromatics 38.9 42.8 Resin 32.5 21.0 Asphaltenes 23.6 5.7 Distillation range, °C IBP / 10% / 30% / 50% 139 / 198 / 238 / 321 149 / 199 / 268 / 302 70% / 90% / 95% / EBP 380 / 400 / - / - 370 / 401 / - / -

[0128] Table 2 Thermal cracking / catalytic process conditions and product properties

[0129]

[0130]

[0131] After sampling and analysis, the content of C1 - C6 alkanes in the gas - phase products of Example 5 in Table 2 is about 78.2%, and the rest is H 2 , CO 2 , O 2 , N 2 and CO, etc., which can be used as fuel gas; the properties of the residue of Example 5 are: C content 93.2%, H content 2.6%, S content 0.24%, ash content 4.1%, which are close to the properties of petroleum coke, the raw material of the POX (Partial Oxidation) coal gasification unit, and can be used as the blending raw material for the coal gasification unit.

[0132] Table 3 Process Conditions of the Hydrotreating Unit

[0133]

[0134]

[0135] Table 4 Properties of Diesel Fraction and Naphtha Fraction

[0136] Name Example 4 Example 5 Example 6 Diesel fraction properties Yield, wt% 65.2 66.4 67.2 <![CDATA[Density (20 °C), g / cm 3 > 0.8592 0.8610 0.8588 Sulfur content, μg / g 5 9 4 Distillation range / °C 50％ 198 191 195 90％ 224 241 255 95％ 300 299 301 Cetane number 48.2 48.0 48.5 Naphtha fraction properties Yield, wt% 25.1 22.4 24.5 <![CDATA[Density (20 °C), g / cm 3 > 0.7601 0.7521 0.7359 Sulfur content, μg / g 4 6 3

[0137] In this example, the yields of naphtha fraction and diesel fraction are both calculated based on inferior heavy oil.

[0138] It can be seen from Table 2 and Table 4 that by using the combined processing method of thermal cracking, oligomerization, catalysis / hydrogenation for inferior heavy oil, the gas yield is significantly reduced, and more liquid - phase products are obtained. The total light - fuel yield is more than 95.4%, which means a better value - added rate per ton of raw materials. In this way, the inferior heavy - oil raw material is completely converted, and both the product quality and the raw - material conversion rate are better than those of the prior art.

[0139] In addition, the inventors of this case also referred to the foregoing examples and conducted experiments with other raw materials, process operations, and process conditions described in this specification, and all obtained relatively ideal results.

[0140] It should be understood that the technical solution of the present invention is not limited by the above - mentioned specific implementation cases. Any technical deformation made according to the technical solution of the present invention without departing from the purpose of the present invention and the scope protected by the claims falls within the protection scope of the present invention.

Claims

1. A superposed catalyst, characterized in that It includes an active component and a carrier for supporting the active component. The carrier is a composite carrier formed by alumina containing molybdenum-doped magnesium gallate and molecular sieve. The elements contained in the active component include chromium and zirconium. The pore diameter of the oligomerization catalyst is 15 - 25 nm, and the specific surface area is 450 - 650 m 2 / g; the content of the active component in the oligomerization catalyst is 1.0 - 15.0 wt%, the content of alumina containing molybdenum-doped magnesium gallate is 40.0 - 80.0 wt%, and the content of molecular sieve is 1.0 - 10.0 wt%; the mass ratio of molybdenum-doped magnesium gallate to alumina in the alumina containing molybdenum-doped magnesium gallate is 1.0 - 15.0:100; the preparation method of the superposed catalyst comprises: (1) subjecting a mixed system containing pseudoboehmite, molybdenum-doped magnesium gallate, pore expander, extrusion aid and peptizing acid to kneading, drying and calcination treatments to obtain alumina containing molybdenum-doped magnesium gallate, wherein the pore expander is selected from anthracene; (2) mixing molecular sieve, the alumina containing molybdenum-doped magnesium gallate with water and binder, and subjecting to extrusion, drying and calcination treatments to obtain the composite support; (3) impregnating the composite support in a mixed solution containing metal active component precursor and non-ionic surfactant, and then subjecting to drying and calcination treatments to obtain the superposed catalyst; the preparation method of the molybdenum-doped magnesium gallate comprises: reacting a mixed reaction system containing gallium nitrate, magnesium nitrate, sodium polyacrylate, ammonium molybdate and oxalic acid solution, and then subjecting to drying, calcination and grinding treatments to obtain molybdenum-doped magnesium gallate; the mass ratio of gallium nitrate, magnesium nitrate, sodium polyacrylate to ammonium molybdate is 100-110:100-120:20-30:

1.

2. The superposed catalyst according to claim 1, characterized in that: the active component is selected from metal oxides formed by two elements of chromium and zirconium; And / or, the molecular sieve is selected from Y-type molecular sieves; the specific surface area of the molecular sieve is 600~630m 2 / g, and the pore volume is 0.40~0.45 mL / g; and / or, the molar ratio of the alumina containing molybdenum-doped magnesium gallate to the molecular sieve in the composite support is 1:6-8.

3. The superposed catalyst according to claim 1, characterized in that, step (1) specifically comprises: mixing pseudoboehmite, molybdenum-doped magnesium gallate, pore expander and extrusion aid, and then adding peptizing acid to the obtained mixture at a rate of 3-10 g / min at 40-80 °C; the mass ratio of the pore expander to pseudoboehmite is 1.0-3.0:100; and / or, the peptizing acid is selected from any one or a combination of two or more of nitric acid, phosphoric acid, citric acid, hydrochloric acid, acetic acid; and / or, the extrusion aid is selected from any one or a combination of two or more of starch, sesbania powder, polyvinyl alcohol, methyl cellulose, polyethylene glycol; the content of the extrusion aid in the mixed system is 4-10 wt%; and / or, the temperature of the drying treatment in step (1) is 100-140 °C, and the time is 3-7 h; the temperature of the calcination treatment is 350-500 °C, and the calcination time is 5-10 h.

4. The superposed catalyst according to claim 1, characterized in that, the temperature of the drying treatment in step (2) is 100-140 °C, and the time is 3-7 h; the temperature of the calcination treatment is 350-500 °C, and the calcination time is 5-10 h; and / or, the binder is selected from small-pore alumina; the pore volume of the small-pore alumina is 0.3-0.5 mL / g, and the average pore diameter is 2-4 nm.

5. The superposed catalyst according to claim 1, characterized in that, Step (3) specifically includes: mixing a metal active component precursor, a non-ionic surfactant and water to form a metal active component precursor solution, and then placing the composite support in the metal active component precursor solution and impregnating it at 20-30°C for 5-10 h; the concentration of metal oxide in the metal active component precursor solution is 5-50 g / 100 mL; and / or, the metal active component precursor is selected from chromium nitrate and zirconium nitrate; and / or, the non-ionic surfactant is selected from fatty alcohol polyethers; the mass ratio of the non-ionic surfactant to the composite support is 2-10:

100.

6. Use of the oligomerization catalyst according to any one of claims 1-5 in the field of producing clean fuels from inferior heavy oil.

7. A method for producing clean fuels from inferior heavy oil, characterized in that it includes: subjecting the inferior heavy oil to a thermal cracking reaction to obtain a cracked gas with an end boiling point less than 150°C and a cracked gas with an initial boiling point greater than 150°C; subjecting the cracked gas with an end boiling point less than 150°C to a catalytic reaction under the conditions of an oligomerization catalyst to obtain a catalytic product; wherein, the oligomerization catalyst uses the oligomerization catalyst according to any one of claims 1-5; and, mixing the cracked gas with an initial boiling point greater than 150°C with the catalytic product for hydrotreating to thereby produce gasoline and diesel.

8. According to the method of claim 7, characterized in that it specifically includes: subjecting the inferior heavy oil to a thermal cracking reaction at a temperature of 100-580°C and a reaction pressure of 0-5 MPa to obtain the cracked gas with an end boiling point less than 150°C and the cracked gas with an initial boiling point greater than 150°C; wherein, the starting temperature of the thermal cracking reaction is 100-200°C, the reaction termination temperature is 460-580°C, and the heating rate is 5-50°C / h; And / or, the method specifically includes: continuously inputting the pyrolysis gas with an end boiling point less than 150°C into a reaction device provided with a polymerization catalyst, and performing a catalytic reaction under the conditions of a temperature of 90 to 150°C, a pressure of 2.0 to 4.0 MPa, and a liquid hourly space velocity of 20 to 30 h -1 to obtain the catalytic product; and / or, the method specifically includes: mixing the cracked gas with an initial boiling point greater than 150°C with the liquid phase component in the catalytic product for hydrotreating and separation to produce gasoline, diesel and unconverted inferior heavy oil; And / or, the hydrotreating includes a pre-hydrofining reaction and a hydrocracking reaction; wherein, the conditions of the pre-hydrofining reaction include: the reaction temperature is 260 to 300 °C, the hydrogen partial pressure is 10.0 to 16.0 MPa, the hydrogen-oil volume ratio is 900:1 to 1500:1, and the liquid hourly space velocity is 0.8 to 1.5 h -1 ; the conditions of the hydrocracking reaction include: the reaction temperature is 340 to 390 °C, the hydrogen partial pressure is 10.0 to 16.0 MPa, the hydrogen-oil volume ratio is 900:1 to 1500:1, and the liquid hourly space velocity is 0.5 to 1.5 h -1 .

9. According to the method of claim 7, characterized in that: the inferior heavy oil is selected from any one or a combination of two or more of ethylene C9 fraction, ethylene tar, catalytic cracking light cycle oil, catalytic cracking external slurry, MIP diesel in the petrochemical industry, heavy benzene, naphthalene oil, wash oil, anthracene oil fraction in the coal coking industry, shale oil, and 150-600°C fraction of oil sand asphalt; and / or, the mass ratio of the oligomerization catalyst to the inferior heavy oil is 1.0-10.0:100; and / or, the catalyst used during the hydrotreating is selected from hydrotreating catalysts; the hydrotreating catalysts include hydrotreating protection catalysts, pre-hydrotreating refining catalysts, hydrotreating refining catalysts and hydrocracking catalysts.

10. A system for producing clean fuels from inferior heavy oil, which is applied to the method according to any one of claims 7-9, characterized in that it includes: a thermal cracking reaction unit, which can at least subject the inferior heavy oil to a thermal cracking reaction to obtain a cracked gas with an end boiling point less than 150°C and a cracked gas with an initial boiling point greater than 150°C; A catalytic reaction unit, which at least brings the pyrolysis gas with an end boiling point less than 150°C into contact with a polymerization catalyst to carry out a catalytic reaction to obtain a catalytic product; wherein, the polymerization catalyst is the polymerization catalyst described in any one of claims 1-5; And a hydrotreating reaction unit, which is at least used to carry out hydrotreating on the liquid phase product in the catalytic product mixed with the pyrolysis gas with an initial boiling point greater than 150°C, so as to obtain gasoline and diesel; Wherein, the hydrotreating reaction unit includes a pre-hydrofining reaction unit and a hydrocracking reaction unit.

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