CN114870890B - Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof - Google Patents

Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof Download PDF

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CN114870890B
CN114870890B CN202210216141.1A CN202210216141A CN114870890B CN 114870890 B CN114870890 B CN 114870890B CN 202210216141 A CN202210216141 A CN 202210216141A CN 114870890 B CN114870890 B CN 114870890B
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catalyst
molecular sieve
mass
aromatic hydrocarbon
metal
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CN114870890A (en
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孙晓明
朱志荣
赵国庆
侯晓灿
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Ningbo Zhongjin Petrochemical Co ltd
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/80—Mixtures of different zeolites
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/48—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing arsenic, antimony, bismuth, vanadium, niobium tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
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    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/54—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
    • B01J29/084—Y-type faujasite
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1096—Aromatics or polyaromatics
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/30—Aromatics
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention relates to the technical field of chemical catalysts and discloses a catalyst for deeply removing olefin in aromatic hydrocarbon and a preparation method thereof, wherein the catalyst comprises 50-150% by mass of molecular sieve, 5-40% by mass of binder, 0-20% by mass of metal and/or metal oxide and 0-10% by mass of auxiliary agent; the metal is one or more of hydrogenation metal and alkaline earth metal. The catalyst has good reaction activity, low bromine index of the product and small aromatic hydrocarbon loss; the catalyst has long service life, and compared with the existing hydrofining catalyst and clay catalyst, the catalyst has greatly prolonged service life; the catalyst can be regenerated for multiple times and reused, so that the generation of solid waste is greatly reduced, and the catalyst is friendly to the environment.

Description

Catalyst for deeply removing olefin in aromatic hydrocarbon and preparation method thereof
Technical Field
The invention relates to the technical field of chemical catalysts, in particular to a catalyst for deeply removing olefin in aromatic hydrocarbon and a preparation method thereof.
Background
The production of aromatic hydrocarbons plays a very important role in the petrochemical industry, representing a state of the art of petrochemical industry. Aromatic hydrocarbon products are applied to various fields such as synthetic resin, fiber, rubber, additives, fuel, medicine, pesticide, organic synthetic intermediates, special chemicals and the like, and widely influence national economic development and improvement of the living standard of people. The traditional arene producing technology includes disproportionation and alkyl transfer technology, carbon octaarene isomerization technology, PX separating technology, etc. and the new technology is mainly toluene methanol alkylation, light hydrocarbon aromatization and catalytic cracking light cycle oil arene converting technology, and these technologies are updated continuously to adapt to the development of arene market. However, a certain amount of olefin impurities exist in the aromatic hydrocarbon product, so that not only the purity and specification of the aromatic hydrocarbon product are affected, but also the part of olefin is active in property, colloid is easy to form, the quality of the aromatic hydrocarbon product is affected, and the follow-up chemical process is adversely affected, so that the further processing and utilization of the aromatic hydrocarbon are affected. Therefore, in order to obtain qualified aromatic hydrocarbon raw materials and ensure the smooth proceeding of subsequent processes, the olefin impurities in the aromatic hydrocarbon are required to be deeply removed.
At present, the production process for removing trace olefin impurities in aromatic hydrocarbon by refineries at home and abroad mainly comprises hydrofining and clay refining. The catalyst used in hydrofining is typically composed of a hydrogenation metal and an auxiliary agent, and is mainly saturated with trace olefins, thereby removing them from aromatic hydrocarbons. The reaction temperature of the non-noble metal catalyst is higher, the space velocity is relatively lower, a small amount of polymer is easy to form, and the noble metal catalyst has higher aromatic hydrocarbon loss and higher catalyst cost in spite of better catalytic effect. Clay refining mainly utilizes clay catalytic superposition capability and pore canal adsorption capability to carry out alkylation, polymerization and other reactions on trace olefins contained in aromatic hydrocarbon to generate high boiling point compounds, and then the high boiling point compounds are adsorbed by clay or removed in a subsequent separation process. Clay catalysts have a short life and are not renewable, need to be replaced frequently, break the continuity of industrial production, and can generate a large amount of solid waste, thus bringing great pressure to environmental protection.
Disclosure of Invention
The invention aims to provide a catalyst for deeply removing olefin in aromatic hydrocarbon and a preparation method thereof, which can promote hydrogenation to saturate olefin, catalyze olefin to be overlapped and adsorbed, and has the characteristics of high catalytic activity, lower aromatic hydrocarbon loss, long service life of the catalyst, wide application range and low catalyst cost.
The aim of the invention is realized by the following technical scheme:
in a first aspect, the invention provides a catalyst for deeply removing olefin in aromatic hydrocarbon, which comprises 50-150% of molecular sieve, 5-40% of binder, 0-20% of metal and/or metal oxide and 0-10% of auxiliary agent; the metal is one or more of hydrogenation metal and alkaline earth metal.
The molecular sieve is an artificially synthesized aluminosilicate crystal with an open multidimensional structure. Compared with clay, the molecular sieve has higher specific surface, stronger carbon capacity and longer service life. The acidity of the molecular sieve is generated by unsaturated coordination of skeleton atoms, so that the acidity is basically unchanged after high-temperature regeneration, and the regeneration performance is good. Therefore, the molecular sieve can be used as a catalyst to have longer service life, so that the number of times of catalyst replacement is reduced, and the environment is protected. The metal or metal oxide can be used as an active component to improve the catalytic efficiency of the catalyst, and the hydrogenation metal, alkaline earth metal and molecular sieve are compounded to improve the selectivity of olefin hydrogenation catalysis, reduce the loss of aromatic hydrocarbon and achieve the purpose of deeply removing trace olefin in the aromatic hydrocarbon.
Preferably, the hydrogenation metal is platinum, palladium, rhodium, nickel, cobalt, iron, copper or molybdenum; the alkaline earth metal is beryllium, magnesium, calcium, strontium or barium.
The choice of metal is particularly important for the catalytic activity of the catalyst and for the selectivity of the reaction.
Preferably, the molecular sieve is one or more of a Y molecular sieve, an MWW series molecular sieve, an X molecular sieve, a USY molecular sieve, an SBA-15 molecular sieve, a ZSM-5 molecular sieve, a beta molecular sieve and an AIPO-5 phosphorus aluminum molecular sieve.
Preferably, the MWW series molecular sieve is MCM-36, MCM-49 or MCM-56 molecular sieve.
Preferably, the binder is one or more of silica sol, alumina, natural clay, water glass, methylcellulose, paraffin, starch, plastic resin, bentonite and dextrin.
Preferably, the auxiliary agent is one or more of sesbania powder, methylcellulose, sodium carboxymethylcellulose, glycerol, lubricating oil, graphite, stearic acid, paraffin, rosin and polyacrylamide.
Preferably, the auxiliary agent is a gel modifier, and the preparation method comprises the following steps:
mixing tetraethyl titanate, tetraethyl ammonium hydroxide, ethanol and water, adding sesbania powder, heating to 25-40 ℃, stirring and reacting for 10-30 min, and adding glutaraldehyde to obtain a mixed solution; heating polyvinyl alcohol to dissolve in N, N-dimethylformamide, dripping the polyvinyl alcohol into the mixed solution, reacting for 3-5 h at 110-130 ℃, and drying to obtain the gel modifier.
Because the binder is added into the molecular sieve catalyst, metal or metal oxide is difficult to enter the molecular sieve framework, the catalyst inside the pore channel has lower reaction activity, and for the reaction of removing olefin in aromatic hydrocarbon, the olefin is a trace doped impurity, and the catalyst is more required to have more catalytic active centers and stronger pore channel adsorption removal capacity, so that effective catalysis can be realized, and the catalysis effect can be improved. The gel modifier can form a titanium skeleton on the outer layer of the molecular sieve in the preparation process of the molecular sieve, so that the active reaction center is increased. Moreover, because the gel is mainly formed by sesbania powder and polyvinyl alcohol, and the sesbania powder is used as a pore forming agent of a common molecular sieve catalyst, the catalyst obtains a certain pore channel structure, the polyvinyl alcohol is used as a macromolecular structure frame to provide the mechanical strength of a titanium skeleton, and micropores are formed after the gel structure is sintered and dehydrated, so that the active center is increased, and the catalytic effect is optimized.
In addition, the gel modifier can form a cross-linked structure inside, has higher combination stability, and the obtained gel with certain viscosity can also increase the interaction between metal/metal oxide and molecular sieve, improve the loading efficiency and enhance the reactivity of the catalyst.
Preferably, the mass ratio of the tetraethyl titanate to the tetraethyl ammonium hydroxide to the ethanol to the water is 1:0.4 to 1: 5-10: 50-200 parts; the mass ratio of sesbania powder to glutaraldehyde to polyvinyl alcohol is 10:0.1 to 0.3:2 to 5; the molecular weight of the polyvinyl alcohol is 1.5 x 10 4 ～2.0*10 4 The method comprises the steps of carrying out a first treatment on the surface of the The mass concentration of the polyvinyl alcohol in the N, N-dimethylformamide is 5-8%.
The mass ratio among sesbania powder, glutaraldehyde and polyvinyl alcohol can influence the crosslinking effect, the too high crosslinking degree causes too high viscosity, the loading effect of metal and metal oxide is not facilitated, and a more uniform pore structure is not easy to form. The gel modifier containing the polyvinyl alcohol can form a micropore structure and increase the specific surface area due to dehydration in the preparation process of the catalyst, but the molecular weight and the concentration of the polyvinyl alcohol can influence the loading effect of metal and metal oxide and the micropore forming effect.
In a second aspect, the invention also provides a preparation method of the catalyst for deeply removing olefin in aromatic hydrocarbon, which comprises the following steps:
(1) Respectively crushing the molecular sieve, the binder and the auxiliary agent, and fully and uniformly mixing;
(2) Adding a solvent into the mixed material, and then mixing, extruding and forming to obtain a formed catalyst;
(3) The shaped catalyst is impregnated with supported metal and/or metal oxide by an isovolumetric method, and then dried and roasted to obtain the catalyst.
The invention directly mixes and extrudes the molecular sieve, binder and auxiliary agent to form, and adds solvent to process to strengthen the cohesiveness and prolong the service life of the catalyst. And the molecular sieve can be activated in an acidic way, so that the activated molecular sieve has a certain capacity of removing olefin, the catalyst has good reactivity, the bromine index of the product is low, and the aromatic hydrocarbon loss is small.
Preferably, in the step (2), the solvent is water, an acid solution, a carboxymethyl cellulose solution or a methyl cellulose solution; the mass ratio of liquid to solid after adding the solvent is 0.05-3: 1.
preferably, in the step (3), the firing is performed at a temperature of 350 to 650 ℃ for 0.5 to 5 hours.
Compared with the prior art, the invention has the following beneficial effects:
(1) The catalyst has good reaction activity, the bromine index of the product is low, and the aromatic hydrocarbon loss is small;
(2) The catalyst has long service life, and compared with the existing hydrofining catalyst and clay catalyst, the catalyst has greatly prolonged service life;
(3) The catalyst can be regenerated for multiple times and reused, so that the generation of solid waste is greatly reduced, and the catalyst is friendly to the environment.
Detailed Description
The technical scheme of the present invention is described below by using specific examples, but the scope of the present invention is not limited thereto:
general examples
1. Preparation of catalyst for deeply removing olefin in aromatic hydrocarbon
The catalyst comprises 50-150% of molecular sieve, 5-40% of binder, 0-20% of metal and/or metal oxide and 0-10% of auxiliary agent.
Wherein the metal is one or more of hydrogenation metal and alkaline earth metal, the hydrogenation metal is platinum, palladium, rhodium, nickel, cobalt, iron, copper or molybdenum, and the alkaline earth metal is beryllium, magnesium, calcium, strontium or barium.
The molecular sieve is one or more of a Y molecular sieve, an MWW series molecular sieve, an X molecular sieve, a USY molecular sieve, an SBA-15 molecular sieve, a ZSM-5 molecular sieve, a beta molecular sieve and an AIPO-5 phosphorus aluminum molecular sieve, and the MWW series molecular sieve is an MCM-36, an MCM-49 or an MCM-56 molecular sieve.
The binder is one or more of silica sol, aluminum oxide, natural clay, water glass, methylcellulose, paraffin, starch, plastic resin, bentonite and dextrin.
The auxiliary agent is one or more of extrusion aid, pore-expanding agent and strength auxiliary agent, including one or more of sesbania powder, dry starch, methyl cellulose, sodium carboxymethyl cellulose, glycerol, lubricating oil, graphite, stearic acid, paraffin, rosin and polyacrylamide.
The auxiliary agent can also be a gel modifier, and the preparation method comprises the following steps:
mixing tetraethyl titanate, tetraethyl ammonium hydroxide, ethanol and water, wherein the mass ratio of the tetraethyl titanate to the tetraethyl ammonium hydroxide to the ethanol to the water is 1:0.4 to 1: 5-10: 50-200 parts; then adding sesbania powder, heating to 25-40 ℃ and stirring for reaction for 10-30 min, wherein the mass ratio of the sesbania powder to the tetraethyl titanate is 1:0.05 to 0.1, and glutaraldehyde is added to obtain a mixed solution; heating and dissolving polyvinyl alcohol in N, N-dimethylformamide, wherein the mass ratio of sesbania powder to glutaraldehyde to polyvinyl alcohol is 10:0.1 to 0.3:2 to 5, and the molecular weight of the polyvinyl alcohol is 1.5 to 10 4 ～2.0*10 4 The mass concentration of the polyvinyl alcohol in the N, N-dimethylformamide is 5-8%, the polyvinyl alcohol is added into the mixed solution in a dropwise manner, the mixed solution reacts for 3-8 hours at the temperature of 110-130 ℃, and the gel modifier is obtained after drying.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the molecular sieve, the binder and the auxiliary agent, and fully and uniformly mixing;
(2) Adding water, acid solution, carboxymethyl cellulose solution or methyl cellulose solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.05-3: 1, the acid solution is one or more of inorganic acid or organic acid, wherein the inorganic acid is nitric acid, sulfuric acid, hydrochloric acid or phosphoric acid, and the organic acid is formic acid, acetic acid, oxalic acid or citric acid; then extruding and forming to obtain a formed catalyst, wherein the shape of the formed catalyst can be columnar, clover-shaped, saddle-shaped or annular;
(3) The shaped catalyst is impregnated with the supported metal and/or metal oxide by an isovolumetric method, then dried and calcined at the temperature of 350-650 ℃ for 0.5-5 h to obtain the catalyst.
2. Performance testing
Loading the catalyst into a fixed bed reactor, and performing one or more treatment steps of passivation treatment, hydrogen reduction and nitrogen purging for 0.5-5 h -1 The aromatic hydrocarbon raw material (bromine index of the aromatic hydrocarbon raw material is 953.4mgBr/100 g) is introduced into a reactor, the reaction temperature is 120-250 ℃, the hydrogen pressure is 0.5-4.0 MPa, and the reactants and the products are measured by a bromine valence bromine index instrument.
Wherein, the passivation treatment conditions are as follows: the passivation atmosphere is nitrogen containing a small amount of oxygen, the oxygen content is 0-10%, and the passivation time is 0.1-50 h; the conditions for hydrogen reduction were: the hydrogen reduction temperature is 50-500 ℃ and the reduction time is 0.1-50 h; the nitrogen purge conditions were: the nitrogen purging temperature is 100-500 ℃ and the purging time is 0.1-50 h.
Example 1
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of sesbania powder.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Pulverizing Y molecular sieve, MCM-36 molecular sieve, aluminum oxide and sesbania powder respectively, and mixing thoroughly;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Example 2
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 70% by mass of ZSM-5 molecular sieve, 26% by mass of alumina, 0.2% by mass of platinum, 1% by mass of molybdenum oxide, 5% by mass of barium oxide and 4% by mass of sesbania powder.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing ZSM-5 molecular sieve, alumina and sesbania powder, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst was impregnated with 0.2 mass% of platinum, 1 mass% of molybdenum oxide and 5 mass% of barium oxide by the equal volume method, and then dried, and calcined at 400 ℃ for 4 hours to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, and then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, followed byThen for 1.0h -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Example 3
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 95% by mass of MCM-56 molecular sieve, 24% by mass of silica sol, 0.8% by mass of nickel, 4% by mass of molybdenum oxide, 0.8% by mass of magnesium oxide and 5% by mass of sesbania powder.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing an MCM-56 molecular sieve, silica sol and sesbania powder, and fully and uniformly mixing;
(2) Mixing the mixed materials after adding water, wherein the mass ratio of liquid to solid after adding the solvent is 1.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst was impregnated with nickel in an amount of 0.8 mass% and molybdenum oxide in an amount of 4 mass% and magnesium oxide in an amount of 0.8 mass% by the equal volume method, and then dried, and calcined at 550 c for 2.5 hours to obtain a catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Example 4
The difference from example 1 is that: the auxiliary agent is gel modifier.
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of gel modifier.
The preparation method of the gel modifier comprises the following steps:
5g of tetraethyl titanate and 3g of tetraethylMixing ammonium hydroxide, 35g of ethanol and 500mL of water, adding 62.5g of sesbania powder, heating to 30 ℃, stirring and reacting for 20min, and adding 1.25g of glutaraldehyde to obtain a mixed solution; 18.5g of polyvinyl alcohol (molecular weight 1.6 x 10 4 ) Heating and dissolving the mixture in N, N-dimethylformamide to obtain 7% polyvinyl alcohol, dropwise adding the polyvinyl alcohol into the mixture, reacting at 120 ℃ for 6 hours, and drying to obtain the gel modifier.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the Y molecular sieve, the MCM-36 molecular sieve, the alumina and the gel modifier, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Example 5
The difference from example 1 is that: the auxiliary agent is gel modifier.
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of gel modifier.
The preparation method of the gel modifier comprises the following steps:
5g of tetraethyl titanate, 4g of tetraethyl ammonium hydroxide, 40g of ethanol and 750mL of water are mixed, and 62.5g of sesbania powder is added to riseStirring and reacting for 20min at the temperature of 40 ℃, and adding 1g of glutaraldehyde to obtain a mixed solution; 21g of polyvinyl alcohol (molecular weight 1.5 x 10 4 ) Heating and dissolving the mixture in N, N-dimethylformamide to obtain the mass concentration of polyvinyl alcohol of 5%, dropwise adding the polyvinyl alcohol into the mixture, reacting for 5 hours at 110 ℃, and drying to obtain the gel modifier.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the Y molecular sieve, the MCM-36 molecular sieve, the alumina and the gel modifier, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Comparative example 1
The difference from example 1 is that: an equal mass of clay catalyst was used.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Comparative example 2
The difference from example 1 is that: using equal mass Pd/Al 2 O 3 Industrial catalysts.
5g of the above catalyst was charged into a fixed bed reactionA reactor for hydrogen reduction at 250℃for 2 hours, then adjusting the reaction temperature to 180℃and the reaction pressure to 2.0MPa, then for 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Comparative example 3
The difference from example 4 is that: the gel modifier is not added with polyvinyl alcohol.
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of gel modifier.
The preparation method of the gel modifier comprises the following steps:
5g of tetraethyl titanate, 3g of tetraethyl ammonium hydroxide, 35g of ethanol and 500mL of water are mixed, 62.5g of sesbania powder is added, the temperature is raised to 30 ℃ and the mixture is stirred and reacted for 20min, 1.25g of glutaraldehyde is added to obtain a mixed solution, and the mixed solution is dried to obtain the gel modifier.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the Y molecular sieve, the MCM-36 molecular sieve, the alumina and the gel modifier, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Comparative example 4
The difference from example 4 is that: in the preparation process of the gel modifier, the mass ratio of sesbania powder, glutaraldehyde and polyvinyl alcohol exceeds a limit range.
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of gel modifier.
The preparation method of the gel modifier comprises the following steps:
5g of tetraethyl titanate, 3g of tetraethyl ammonium hydroxide, 35g of ethanol and 500mL of water are mixed, 62.5g of sesbania powder is added, the temperature is raised to 30 ℃ and the mixture is stirred and reacted for 20min, and 4g of glutaraldehyde is added to obtain a mixed solution; 18.5g of polyvinyl alcohol (molecular weight 1.6 x 10 4 ) Heating and dissolving the mixture in N, N-dimethylformamide to obtain 7% polyvinyl alcohol, dropwise adding the polyvinyl alcohol into the mixture, reacting at 120 ℃ for 6 hours, and drying to obtain the gel modifier.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the Y molecular sieve, the MCM-36 molecular sieve, the alumina and the gel modifier, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing the aromatic hydrocarbon raw material into the reactor, taking the product at the outlet of the reactor, and analyzing the bromine index of the product by using a bromine index tester.
Comparative example 5
The difference from example 4 is that: in the preparation process of the gel modifier, the molecular weight of the polyvinyl alcohol is 3.0 x 10 4 The mass concentration of polyvinyl alcohol in N, N-dimethylformamide was 12%.
The catalyst for deeply removing olefin in aromatic hydrocarbon comprises 55% by mass of Y molecular sieve, 15% by mass of MCM-36 molecular sieve, 26% by mass of alumina, 8% by mass of beryllium oxide, 1% by mass of molybdenum oxide and 4% by mass of gel modifier.
The preparation method of the gel modifier comprises the following steps:
5g of tetraethyl titanate, 3g of tetraethyl ammonium hydroxide, 35g of ethanol and 500mL of water are mixed, 62.5g of sesbania powder is added, the temperature is raised to 30 ℃ and the mixture is stirred and reacted for 20min, and 1.25g of glutaraldehyde is added to obtain a mixed solution; 18.5g of polyvinyl alcohol (molecular weight 3 x 10 4 ) Heating and dissolving the mixture in N, N-dimethylformamide to obtain the polyvinyl alcohol with the mass concentration of 12%, dropwise adding the polyvinyl alcohol into the mixture, reacting for 6 hours at 120 ℃, and drying to obtain the gel modifier.
The preparation method of the olefin catalyst for deeply removing the aromatic hydrocarbon comprises the following steps:
(1) Respectively crushing the Y molecular sieve, the MCM-36 molecular sieve, the alumina and the gel modifier, and fully and uniformly mixing;
(2) Adding nitric acid solution into the mixture, mixing, and adding solvent to obtain a liquid-solid mass ratio of 0.5:1, then extruding and forming to obtain a clover-shaped formed catalyst;
(3) The molded catalyst is impregnated and loaded with 8 mass percent of beryllium oxide and 1 mass percent of molybdenum oxide by an equal volume method, and then dried, and baked for 3 hours at the temperature of 500 ℃ to obtain the catalyst.
5g of the above catalyst was charged into a fixed bed reactor, reduced with hydrogen at 250℃for 2 hours, then the reaction temperature was adjusted to 180℃and the reaction pressure was adjusted to 2.0MPa, then the reaction time was 1.0 hour -1 Introducing aromatic hydrocarbon raw material into reactor, taking out outlet product of reactor and using bromine index to testThe bromine index was analyzed by an instrument.
Table 1 results of performance testing of catalysts of examples and comparative examples
Specific results are shown in table 1, and the catalyst has the advantages of good activity, low bromine index of the product and small aromatic hydrocarbon loss, and the prepared catalyst can be regenerated for multiple times and reused, so that the generation of solid waste is greatly reduced, and the catalyst is environment-friendly. Further, the catalyst life was long, and it was found from examples 1 and comparative examples 1 to 2 that the life was significantly longer than that of the conventional hydrorefining catalyst and clay catalyst. In addition, as is clear from examples 1 and 4 to 5, the gel-like modifier added in the present invention can further enhance the catalytic effect, mainly by increasing the active reaction sites and the microporous structure. Further, as is clear from examples 4 and 3, the absence of added polyvinyl alcohol results in a decrease in mechanical strength of the titanium skeleton during firing, a deterioration in stability, failure to form a microporous structure, and a decrease in reactive sites. From example 4 and comparative example 4, it is apparent that the mass ratio of sesbania powder, glutaraldehyde and polyvinyl alcohol exceeds the limit range, and especially that too much glutaraldehyde is added to cause too much crosslinking degree and thus viscosity, which is unfavorable for the loading effect of metal and metal oxide, and is difficult to form a relatively uniform pore structure, and the catalytic effect is also lowered. From examples 4 and 5, it is apparent that the molecular weight and concentration of polyvinyl alcohol are too high, and that a gel structure having too high viscosity is formed at the time of crosslinking by dropping, which affects not only the loading effect of metal and metal oxide but also the formation effect of micropores.
The foregoing description is only of the preferred embodiments of the present invention, and is not intended to limit the scope of the invention, but rather is intended to cover any equivalents of the structures disclosed herein or modifications in the equivalent processes, or any application of the structures disclosed herein, directly or indirectly, in other related arts.

Claims (4)

1. The preparation method of the catalyst for deeply removing the olefin in the aromatic hydrocarbon is characterized in that the raw materials of the catalyst comprise 50-70% by mass of molecular sieve, 5-26% by mass of binder, 9-20% by mass of metal and/or metal oxide and 4-10% by mass of auxiliary agent; the metal is one or more of hydrogenation metal and alkaline earth metal; the hydrogenation metal is platinum, palladium, rhodium, nickel, cobalt, iron, copper or molybdenum; the alkaline earth metal is beryllium, magnesium, calcium, strontium or barium; the molecular sieve is one or more of a Y molecular sieve, an MWW series molecular sieve, an X molecular sieve, an SBA-15 molecular sieve, a ZSM-5 molecular sieve, a beta molecular sieve and an AIPO-5 phosphorus aluminum molecular sieve; the binder is one or more of silica sol, alumina, water glass, methylcellulose, paraffin, starch, bentonite and dextrin;
the auxiliary agent is a gel modifier, and the preparation method comprises the following steps:
mixing tetraethyl titanate, tetraethyl ammonium hydroxide, ethanol and water, adding sesbania powder, heating to 25-40 ℃, stirring and reacting for 10-30 min, and adding glutaraldehyde to obtain a mixed solution; heating polyvinyl alcohol to dissolve in N, N-dimethylformamide, dripping the polyvinyl alcohol into the mixed solution, reacting for 3-5 hours at 110-130 ℃, and drying to obtain a gel modifier; the mass ratio of sesbania powder to glutaraldehyde to polyvinyl alcohol is 10:0.1 to 0.3: 2-5; the molecular weight of the polyvinyl alcohol is 1.5X10 4 ~2.0×10 4 The method comprises the steps of carrying out a first treatment on the surface of the The mass concentration of the polyvinyl alcohol in the N, N-dimethylformamide is 5-8%;
the preparation method of the catalyst comprises the following steps:
(1) Respectively crushing the molecular sieve, the binder and the auxiliary agent, and fully and uniformly mixing;
(2) Adding a solvent into the mixed material, and then mixing, extruding and forming to obtain a formed catalyst;
(3) The shaped catalyst is impregnated with supported metal and/or metal oxide by an isovolumetric method, and then dried and roasted to obtain the catalyst.
2. The method for preparing an olefin catalyst for deep aromatic hydrocarbon removal according to claim 1, wherein the MWW series molecular sieve is MCM-36, MCM-49 or MCM-56 molecular sieve.
3. The method for preparing the catalyst for deeply removing olefin from aromatic hydrocarbon according to claim 1, wherein the mass ratio of tetraethyl titanate, tetraethyl ammonium hydroxide, ethanol and water is 1: 0.4-1: 5-10: 50-200.
4. The method for preparing an olefin catalyst for deep aromatic hydrocarbon removal according to claim 1, wherein in the step (2), the solvent is water or an acid solution; the mass ratio of liquid to solid after adding the solvent is 0.05-3: 1, a step of; in the step (3), the roasting is carried out for 0.5-5 hours at the temperature of 350-650 ℃.
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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795550A (en) * 1987-04-03 1989-01-03 Uop Inc. Removal of trace olefins from aromatic hydrocarbons
CN1448474A (en) * 2002-04-04 2003-10-15 中国石油化工股份有限公司 Cytalyst for reformed formation oil selective hydrogen removing olefin
CN102000599A (en) * 2010-11-09 2011-04-06 中国海洋石油总公司 Preparation method of catalyst for deeply desorbing trace olefins in aromatic hydrocarbon
CN102220158A (en) * 2010-04-15 2011-10-19 中国石油化工股份有限公司 Method for reducing olefins in aromatic hydrocarbons
CN102233274A (en) * 2010-04-28 2011-11-09 中国石油化工股份有限公司 Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof
CN105080592A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Aromatic olefin-reducing catalyst and use thereof
CN110354861A (en) * 2019-07-31 2019-10-22 黄河三角洲京博化工研究院有限公司 A kind of catalyst and preparation method thereof for removing alkene
CN113398907A (en) * 2021-07-06 2021-09-17 山东京博石油化工有限公司 Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in olefin removal of reformed C5 oil

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4795550A (en) * 1987-04-03 1989-01-03 Uop Inc. Removal of trace olefins from aromatic hydrocarbons
CN1448474A (en) * 2002-04-04 2003-10-15 中国石油化工股份有限公司 Cytalyst for reformed formation oil selective hydrogen removing olefin
CN102220158A (en) * 2010-04-15 2011-10-19 中国石油化工股份有限公司 Method for reducing olefins in aromatic hydrocarbons
CN102233274A (en) * 2010-04-28 2011-11-09 中国石油化工股份有限公司 Catalyst for reducing alkene content in aromatic hydrocarbon, and a preparation method thereof
CN102000599A (en) * 2010-11-09 2011-04-06 中国海洋石油总公司 Preparation method of catalyst for deeply desorbing trace olefins in aromatic hydrocarbon
CN105080592A (en) * 2014-05-14 2015-11-25 中国石油化工股份有限公司 Aromatic olefin-reducing catalyst and use thereof
CN110354861A (en) * 2019-07-31 2019-10-22 黄河三角洲京博化工研究院有限公司 A kind of catalyst and preparation method thereof for removing alkene
CN113398907A (en) * 2021-07-06 2021-09-17 山东京博石油化工有限公司 Hydrogenation catalyst, preparation method thereof and application of hydrogenation catalyst in olefin removal of reformed C5 oil

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