CN110252325B - Industrial naphthalene selective hydrogenation catalyst and preparation method thereof - Google Patents

Industrial naphthalene selective hydrogenation catalyst and preparation method thereof Download PDF

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CN110252325B
CN110252325B CN201810201966.XA CN201810201966A CN110252325B CN 110252325 B CN110252325 B CN 110252325B CN 201810201966 A CN201810201966 A CN 201810201966A CN 110252325 B CN110252325 B CN 110252325B
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carbon nano
catalyst
roasting
nano tube
naphthalene
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CN110252325A (en
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尹宏峰
许杰
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Ningbo Institute of Material Technology and Engineering of CAS
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B01J35/615—
    • B01J35/635—
    • B01J35/647—
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0207—Pretreatment of the support
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/148—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound
    • C07C7/163—Purification; Separation; Use of additives by treatment giving rise to a chemical modification of at least one compound by hydrogenation
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Abstract

The invention discloses an industrial naphthalene selective hydrogenation catalyst and a preparation method thereof. The catalyst comprises a metal active component and a modified carrier loading the metal active component, wherein the carrier is mainly formed by kneading, molding, drying and roasting carbon nano tubes and alumina, the metal active component comprises a metal oxide, and the metal oxide contains VIB group and/or VIII group metal elements. The catalyst has the pore diameter of 8-10 nm accounting for more than 90% of the total pore volume, the pore volume of 0.6-0.8 ml/g, and the specific surface area of 240-300 m2(ii) in terms of/g. Compared with the prior art, the catalyst provided by the invention has the advantages of concentrated ideal pore size distribution, proper pore volume and large specific surface area, has good selective hydrogenation activity on sulfur-containing impurity thianaphthene in industrial naphthalene, and is suitable for producing refined naphthalene by selective hydrogenation of industrial naphthalene.

Description

Industrial naphthalene selective hydrogenation catalyst and preparation method thereof
Technical Field
The invention relates to a selective hydrogenation catalyst, in particular to a selective hydrogenation catalyst for producing refined naphthalene from industrial naphthalene, namely a selective hydrogenation catalyst for sulfur-containing compounds in industrial naphthalene, heavy benzonaphthalene or crude naphthalene.
Background
Naphthalene is an important chemical raw material, is mainly used for preparing phthalic anhydride and dye intermediates by catalytic oxidation, and is also used as a cement water reducing agent, a surfactant, a plasticizer, polyester, synthetic fibers, a medicament and the like. More than 70 percent of domestic naphthalene depends on the coking industry, the technology for producing industrial naphthalene from coal tar is mature, but the purity of the industrial naphthalene is only 95 percent and can not meet the requirement of the industrial naphthalene as a raw material of fine chemicals, and the fine chemicals produced by taking the naphthalene as the raw material all need refined naphthalene with the purity of more than 99 percent. The main impurities in the industrial naphthalene are benzothiophene, the content of the benzothiophene is about 2-3%, and a small amount of tetralin, quinoline, beta-methylnaphthalene and ash are contained, and the impurities are relatively easy to remove relative to the benzothiophene, so the key point of purifying and refining the naphthalene by the industrial naphthalene is to remove thianaphthene.
The heavy benzonaphthalene is derived from heavy benzol, and the heavy benzol is a byproduct generated in the crude benzene hydrogenation process in the coal chemical industry. The method for preparing refined naphthalene from heavy benzonaphthalene, industrial naphthalene or crude naphthalene includes physical method, chemical method and combination method. The physical method mainly comprises an emulsion membrane method, a crystallization method and a rectification method; the chemical methods mainly comprise an aldehyde condensation method, an acid oxidation method and a selective hydrogenation method, wherein the selective hydrogenation is less in domestic research and development, and compared with the selective hydrogenation of mature crude benzene, the selective hydrogenation of crude naphthalene is still in the beginning stage.
In the selective hydrogenation technology of crude naphthalene proposed by Kawasaki, the catalyst is selected from Ni-Co-Mo, aluminum/carbon, Pt-Ni-Mo, Pd-alumina, etc., and the catalyst reacts at 100-300 ℃ under 0-2 MPa, and the sulfur content in the refined naphthalene is 0.025 wt%. In the technology, part of naphthalene is hydrogenated to generate tetralin, thereby influencing the yield of refined naphthalene. In order to obtain high refined naphthalene yield, seven steps are needed after selective hydrogenation to obtain refined naphthalene with improved yield.
The process proposed by French Petroleum uses a supported catalyst whose active component comprises at least one metal of groups VIII and VI and optionally phosphorus. The specific surface area of the catalyst is 220m at most2(ii)/g, and an average pore diameter of greater than 10 nm. The selective hydrogenation reaction temperature is 150-325 ℃, the pressure is 0.1-0.9 MPa, the content of the byproduct tetralin in the liquid flow before entering the next stripping/crystallization procedure is about 3.0%, and the yield of refined naphthalene is only 97%. In order to further improve the yield of refined naphthalene, a method of recycling tetralin to the inlet of the hydrogenation reactor and combining a stripping/crystallization process is adopted.
It can be seen that the problem in the prior art is the formation of tetralin by-product, thus affecting the yield of refined naphthalene, while the use of the tetralin recycle method compensates for some of the yield to some extent, but consumes more hydrogen feed, thus increasing the processing cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst for producing refined naphthalene by selective hydrogenation of industrial naphthalene, which is a selective hydrogenation catalyst with good selective hydrogenation activity and activity stability.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following steps:
the embodiment of the invention provides an industrial naphthalene selective hydrogenation catalyst which comprises a metal active component and a modified carrier loaded with the metal active component.
Furthermore, the carrier is mainly formed by kneading, molding, drying and roasting the carbon nano tube and the alumina.
Further, the metal active component comprises a metal oxide, and the metal oxide contains a metal element in a VIB group and/or a VIII group.
Furthermore, the pores with the pore diameter of 8-10 nm in the catalyst account for more than 90% of the total pore volume, the pore volume is 0.6-0.8 ml/g, and the specific surface area is 240-300 m2/g。
Further, the catalyst comprises 40-90 wt% of modified carrier and 5-15 wt% of metal active component.
The embodiment of the invention also provides a preparation method of the industrial naphthalene selective hydrogenation catalyst, which comprises the following steps:
1) preparing a carbon nano tube dispersion liquid;
2) uniformly mixing alumina and the carbon nano tube dispersion liquid obtained in the step 1), extruding and forming, and then drying and roasting to obtain a modified carrier;
3) adding a nonionic surfactant containing an aromatic group functional group into an aqueous solution of a precursor of a metal active component to form a mixed solution, wherein the precursor of the metal active component is selected from water-soluble compounds containing VIB-group and/or VIII-group metal elements, and the metal active component is selected from metal oxides;
4) soaking the modified carrier obtained in the step 2) in the mixed liquid obtained in the step 3), and then drying and roasting to obtain the selective hydrogenation catalyst.
Further, the carbon nanotube dispersion liquid in step 1) is prepared in the presence of a surfactant.
Further, the step 1) specifically comprises:
firstly, dissolving the surfactant in water at the temperature of 40-70 ℃, wherein the surfactant is preferably a surfactant containing an aromatic group functional group such as polyethylene glycol octyl phenyl ether Triton X-100;
then adding a certain amount of carbon nano tubes into the surfactant aqueous solution (the concentration is preferably 0.5-2.0 wt%) and uniformly stirring, preferably, ultrasonic stirring can be adopted, the ultrasonic time is 5-30 min, and the stirring temperature is 0-5 ℃; after ultrasonic stirring, preferably, removing undispersed agglomerated particles by centrifugal sedimentation, wherein the centrifugal speed is 1500-2000 r/min, and the centrifugal time is 30-60 min; and after the centrifugation is finished, filtering the dispersion liquid by using filter cloth to obtain the stable carbon nano tube dispersion liquid. Preferably, the mesh number of the filter cloth is 300-500 meshes.
Further, step 2) comprises: mixing alumina and carbon nano tube dispersion liquid, adding a pore-expanding agent and an extrusion aid, extruding into strips, forming, and then drying and roasting; preferably, the temperature of the drying treatment is 80-160 ℃; preferably, the roasting treatment temperature is 400-700 ℃, and the roasting time is 1-15 h; and/or the drying temperature adopted in the step 3) is 80-160 ℃, the roasting temperature is 400-650 ℃, and the roasting time is 1-15 h.
Further, the VIB group or VIII group metal element is selected from any one or the combination of more than two of molybdenum, tungsten, cobalt and nickel; preferably, the metal oxide includes any one or a combination of two or more of molybdenum trioxide, tungsten trioxide, nickel oxide, and cobalt oxide; further preferably, the metal oxide is selected from molybdenum trioxide and/or tungsten trioxide, and the content of the metal oxide in the catalyst is 4-9 wt%; further preferably, the metal oxide is selected from nickel oxide and/or cobalt oxide, and the content of the metal oxide in the catalyst is 2-6 wt%.
Furthermore, the amount of the carbon nano tube is 0.5-1.2 wt% of the total mass of the modified carrier, and particularly preferably 0.6-1.0 wt%.
Further, the usage amount of the pore-expanding agent is 1.0-4.0 wt% of the total mass of the modified carrier.
Furthermore, the amount of the extrusion aid is 1.0-2.0 wt% of the total mass of the modified carrier.
Further, the dosage of the surfactant in the step 2) is 0.5-1.0 time of that of the carbon nano tube.
Further, the surfactant used in the step 2) and the step 3) is a nonionic surfactant containing an aromatic group functional group.
Furthermore, the carbon nano tube adopts a short multi-wall carbon nano tube, the tube diameter of the short multi-wall carbon nano tube is less than 8nm, and a specific surface is shownThe surface is larger than 500m2A length of 0.5 to 2.0 μm/g.
The embodiment of the invention also provides a specific application of the catalyst in selective hydrogenation of industrial naphthalene.
In some embodiments, the catalyst is suitable for use in the process of producing refined naphthalene by selective hydrogenation of sulfur-containing compounds in heavy benzonaphthalene, industrial naphthalene or crude naphthalene in the coal coking industry.
In some embodiments, the catalyst is characterized in that the reaction volume space velocity for the industrial naphthalene selective hydrogenation reaction process condition is 0.3-1.0 h-1The hydrogen partial pressure of the system reaction pressure is 4.0-6.0 MPa, the reaction temperature is 340-360 ℃, and the hydrogen-oil ratio is 500-1000. Preferably, the volume space velocity of the reaction is 0.5-0.7 h-1The reaction pressure of the system is 5.0MPa, the reaction temperature is 345-355 ℃, and the hydrogen-oil ratio is 600-800.
Compared with the prior art, the invention has the advantages that:
1. the catalyst is added with the short multi-walled carbon nano-tube in the preparation process of the modified carrier, so that the pore diameter of the prepared catalyst is 8-10 nm and accounts for more than 90% of the total pore volume, and the pore diameter is designed according to the molecular volume of the main impurity thianaphthene in industrial naphthalene. The calculation of quantum chemical gaussian software shows that the three-dimensional spatial structure of the thianaphthene molecules is approximately regarded as a sphere, the diameter of the sphere is about 7-10 angstroms, and the diameter of the naphthalene molecules is larger than 10 angstroms. Therefore, the short multi-walled carbon nano-tube with the determined tube diameter ratio is added into the preparation process of the modified alumina carrier (namely the modified carrier), so that the original small-hole modified carrier has more concentrated hole distribution while being changed into the modified carrier with the suitably smaller specific surface. The melting point of carbon nanotubes is the highest of the known materials and they do not deform and collapse when fired at high temperatures. The pore-expanding agent is added to further expand the space around the short multi-walled carbon nanotube with the diameter less than 8nm and further improve the proportion of the pores with the diameter of 8-10 nm to the total pore volume so as to obtain better hydrogenation activity of the thianaphthene. The pore diameter of the catalyst enables more thianaphthene molecules to enter the inner surface of the catalyst for reaction, and keeps naphthalene molecules out of the pores to prevent the naphthalene molecules from being subjected to hydrogenation reaction and being converted into other compounds. This results in a significant increase in the yield of the final refined naphthalene. 2. The catalyst of the invention adopts a method that the small-pore alumina is added into the carbon nano tube water dispersion, a pore-expanding agent and an extrusion aid are added, a modified carrier is prepared by mixing, kneading, drying and roasting, and then the VIB group or VIII group metal active component is impregnated, so that the catalyst has better hydrogenation activity and activity stability, most thianaphthene is hydrogenated and converted into ethylbenzene with a reduced boiling point, and finally the ethylbenzene is separated from naphthalene by distillation, so that the purity and the yield of the naphthalene are further improved.
3. The catalyst and the selective hydrogenation reaction process condition provided by the invention can ensure that the thianaphthene is subjected to hydrogenation reaction, and the naphthyl is not reacted, so that a better desulfurization effect can be obtained, and the yield of refined naphthalene is favorably improved.
Detailed Description
In view of the deficiencies in the prior art, the inventors of the present invention have made extensive studies and extensive practices to propose the technical solution of the present invention, and further explain the technical solution, the implementation process and the principle thereof, etc.
One aspect of an embodiment of the present invention provides a method for preparing an industrial naphthalene selective hydrogenation catalyst, including:
1) firstly, preparing a carbon nano tube dispersion liquid;
2) uniformly mixing alumina and the carbon nano tube dispersion liquid obtained in the step 1), extruding and forming, and then drying and roasting to obtain a carrier;
3) adding the nonionic surfactant used in the step 2) into an aqueous solution of a precursor of a metal active component to form a mixed solution, wherein the precursor of the metal active component is selected from water-soluble compounds containing VIB group and/or VIII group metal elements, and the metal active component is selected from metal oxides, then soaking the carrier obtained in the step 2) into the mixed solution, and then carrying out drying and roasting treatment to obtain the selective hydrogenation catalyst.
In some embodiments, the industrial naphthalene selective hydrogenation catalyst is composed of 4-9 wt% of a group VIB metal, 2-6 wt% of a group VIII metal, and a modified support. The modified carrier is added with carbon nano-tubes in the preparation processModifying, and loading the active component on the modified. In the catalyst, the pores with the pore diameter of 8-10 nm account for more than 90% of the total pore volume, the pore volume is 0.6-0.8 ml/g, and the specific surface area is 240-300 m2/g。
In some embodiments, the industrial naphthalene selective hydrogenation catalyst comprises 40 to 90wt% of a carrier and 5 to 15wt% of a metal active component.
In some embodiments, the group VIB or group VIII metal element is selected from any one or combination of two or more of molybdenum, tungsten, cobalt, and nickel, but is not limited thereto.
In some embodiments, in the catalyst of the present invention, the metal oxide includes any one or a combination of two or more of molybdenum trioxide, tungsten trioxide, nickel oxide, and cobalt oxide, but is not limited thereto. Preferably, the water-soluble compound includes any one or a combination of two or more of ammonium molybdate, ammonium metatungstate, nickel nitrate, basic nickel carbonate, cobalt nitrate and cobalt acetate, but is not limited thereto.
In some embodiments, the modified carrier is prepared by mixing alumina and carbon nanotube dispersion, adding pore-expanding agent and extrusion aid, extruding into strips, drying, and roasting; preferably, the drying treatment temperature is 80-160 ℃, and the drying is carried out for 1-6 h; preferably, the roasting treatment temperature is 400-700 ℃, and the roasting time is 1-15 h, particularly preferably 3-5 h.
In some embodiments, the drying temperature adopted in the step 3) is 80-160 ℃, and the drying time is 1-6 hours; preferably, the roasting temperature is 400-650 ℃, and the roasting time is 1-9 h, particularly preferably 3-5 h.
In some embodiments, the amount of the nonionic surfactant used in step 3) is 2 to 10 wt% based on the total mass of the carrier. Further, the nonionic surfactant used in step 2) is a nonionic surfactant such as polyethylene glycol octyl phenyl ether Triton X-100, but is not limited thereto. The effect of adding the nonionic surfactant in the step 3) of the invention is to enable the active metal to be more fully impregnated, and improve the loading amount and the dispersity of the active metal components.
In some embodiments, the alumina has a pore volume of 0.3 to 0.6ml/g and an average pore diameter of 2 to 10 nm.
In some embodiments, when the modified carrier is formed, the extrusion aid and pore-expanding agent can be selected from those well known in the art, and the pore-expanding agent is 1.0-4.0 wt%, preferably 3.0-4.0 wt% of the weight of the carrier. For example, a pore-expanding agent which is well known in the field of sesbania powder, starch, polyvinyl alcohol, methyl cellulose and the like can be selected to further improve the pore structure of the carrier. The extrusion aid accounts for 1.0-2.0 wt% of the weight of the carrier.
In some embodiments, the amount of the carbon nanotubes used in the modified support is 0.5 to 1.2wt%, and particularly preferably 0.6 to 1.0wt%, based on the total mass of the modified support.
In some embodiments, the carbon nanotube dispersion can be prepared according to methods known in the art. Preferably, the carbon nanotube dispersion is prepared from carbon nanotubes in the presence of a surfactant; particularly preferably, the surfactant is dissolved in water at the temperature of 40-70 ℃, and is preferably a surfactant containing an aromatic group functional group, such as polyethylene glycol octyl phenyl ether Triton X-100; the aromatic ring of the aromatic group can adsorb the carbon nano tube more firmly by using the surfactant containing the aromatic group functional group, so that the carbon nano tube is dissolved in water more uniformly. Then adding a certain amount of carbon nano tubes into the surfactant aqueous solution (the concentration is preferably 0.5-2.0 wt%), and uniformly stirring, preferably, ultrasonic stirring can be adopted, and the ultrasonic time is 5-30 min; the purpose of ultrasonic stirring is to obtain a more uniform and stable carbon nanotube solution, in order to prevent the foaming phenomenon caused by the existence of the surfactant, the ultrasonic stirring is carried out at 0-5 ℃, preferably for 5min, the ultrasonic stirring is continued after stopping for 3-5 min, and the total ultrasonic time is 5-30 min; preferably, the non-dispersed agglomerated particles can be removed by centrifugal sedimentation, the centrifugal rate is 1500-2000 r/min, and the centrifugal time is 30-60 min; and after the centrifugation is finished, filtering the dispersion liquid by using filter cloth to obtain the stable carbon nano tube dispersion liquid. Preferably, the mesh number of the filter cloth is 300-500 meshes. Particularly preferably, the carbon nano-meterThe tube is short multi-wall carbon nanotube with diameter less than 8nm and specific surface more than 500m2A length of 0.5 to 2 μm per gram.
The embodiment of the invention also provides a process for producing refined naphthalene by the selective hydrogenation of the catalyst in heavy benzonaphthalene, industrial naphthalene or crude naphthalene in the coal coking industry. In some embodiments of the invention, the volume space velocity of the selective hydrogenation reaction is 0.5-0.7 h-1The hydrogen partial pressure of the system reaction pressure is 5.0MPa, the reaction temperature is 345-355 ℃, and the hydrogen-oil ratio is 600-800, the heavy phenylnaphthalene, the industrial naphthalene or the crude naphthalene, the main impurity of which is thianaphthene, can convert more than 99.8 percent of thianaphthene into ethylbenzene through a section of selective hydrogenation reaction, the naphthalene hardly reacts, the boiling point of the ethylbenzene is obviously lower than that of the naphthalene, so a refined naphthalene product with higher purity and yield can be obtained by adopting a distillation method. Such desirable results are mainly due to the "tailor-made" of the catalyst channels, the use of short multi-walled carbon nanotubes and pore-expanding agents, which makes the pore size distribution of the catalyst of the present invention highly concentrated, only thianaphthene enters the inner surface of the catalyst for reaction, and naphthalene is excluded. The technical solution of the present invention is further explained below with reference to several examples.
The following examples all use the active metal impregnation solution. The method for preparing the impregnation solution is illustrated by taking the active metals tungsten and nickel as examples: taking a certain amount of deionized water, adding ammonium metatungstate (or ammonium molybdate) and nickel nitrate (or basic nickel carbonate, cobalt nitrate and cobalt acetate) crystals, standing after all the crystals are dissolved, and filtering to obtain a metal impregnation solution, wherein WO3Or MoO3The content of NiO or CoO is 10.0-25.0 g/100ml, and the content of NiO or CoO is 7.0-15.0 g/100 ml. The preparation of metal impregnation solutions is well known in the art and reference is made to the relevant literature.
The following examples all use carbon nanotube dispersions. The preferred preparation process of the carbon nanotube aqueous dispersion is as follows: 1) dissolving 15g of polyethylene glycol octyl phenyl ether Triton X-100 in 976g of water, and stirring at 40 ℃ until a transparent solution is obtained;
2) adding 20g of short multi-walled carbon nanotube CNT402 (product of Takajiki technologies Co., Ltd., Beijing Deke), stirring to completely wet the carbon nanotube with the dispersant aqueous solution;
3) under the ultrasonic condition, the dispersion liquid is dispersed more uniformly. After stirring for 5 minutes, stopping stirring for 5 minutes, and continuing ultrasonic stirring for 30 minutes; preferably, the ultrasonic operation can be carried out in an environment at 0 ℃ until no particulate matters exist in water.
4) After the completion of the ultrasonic treatment, the dispersion was subjected to centrifugal sedimentation to remove non-dispersed agglomerate. The centrifugation speed is 1800r/min, and the centrifugation time is 45 min;
5) and after the centrifugation is finished, filtering the upper-layer liquid by using 500-mesh filter cloth to obtain the stable carbon nano tube dispersion liquid. The precipitate was dried to constant weight and recorded as 4.3 g. Thermogravimetric analysis is carried out on the precipitate, and the thermal weight loss rate at 450 ℃ is recorded to be about 20 percent, namely the content of the dispersant in the precipitate;
6) thus, 993g of a carbon nanotube dispersion having a content of about 1.7% was prepared and used.
Example 1
(1) Preparation of modified support
And uniformly mixing 100g of small-pore alumina (which can be common small-pore alumina powder with the pore volume of 0.3-0.6 ml/g sold in the market), 60g of the carbon nano tube dispersion liquid and 4g of sesbania powder, adding 50ml of aqueous solution containing 2g of citric acid, kneading, extruding and molding, drying at 100 ℃ for 5 hours, and roasting at 600 ℃ for 3 hours to obtain the strip-shaped carrier.
(2) Preparation of the catalyst:
a. preparation of the Metal impregnation solution As described above, a tungsten-nickel solution was taken (WO)320.0g/100ml of NiO, 7.0g/100ml of NiO), adding Triton X-100 which is polyethylene glycol octyl phenyl ether, and adding about 6g of the mixture to prepare an aqueous solution;
b. taking 100g of the modified carrier prepared in the step (1), adding the modified carrier into a prepared aqueous solution (containing metal ions), soaking, and filtering;
c. putting the product obtained in the step 2) b into an oven, and drying for 3h at 120 ℃;
d. and finally, putting the dried product in a muffle furnace, and calcining for 5 hours at 550 ℃ to obtain the selective hydrogenation catalyst for treating the crude naphthalene, wherein the catalyst is named as A.
The catalyst A contained 8.0 wt% of tungsten in the carrier, 2.8 wt% of nickel in the carrier, and 10.8 wt% of the total amount of active metals. The BET (specific surface area tester) method is adopted, and the specific surface area of the A catalyst is 280m2The pore volume is 0.68 ml/g. The pores with the pore diameter of 8.0-10.0nm account for 96% of the total pore volume.
Example 2
(1) Preparation of the support
Uniformly mixing 100g of small-pore alumina (common small-pore alumina powder with the pore volume of 0.3-0.6 ml/g sold in the market), 36g of carbon nanotube dispersion liquid and 3g of sesbania powder, adding 50ml of aqueous solution containing 1.5g of citric acid, kneading, extruding and molding, drying at 120 ℃ for 3 hours, and roasting at 500 ℃ for 4 hours to obtain the strip-shaped carrier.
(2) Preparation of the catalyst:
a. preparation of the Metal impregnation solution As described above, a tungsten-nickel solution was taken (WO)3Content 10.0g/100ml, NiO content 10.0g/100ml)40ml, adding polyethylene glycol octyl phenyl ether Triton X-100 with the addition of about 8g to prepare an aqueous solution; b. taking 100g of the carrier prepared in the step (1), adding the carrier into a prepared aqueous solution (containing metal ions) for soaking, and filtering;
c. putting the product obtained in the step (2) b into an oven, and drying for 6h at 100 ℃;
d. and finally, putting the dried product in a muffle furnace, and calcining for 3h at 600 ℃ to obtain the selective hydrogenation catalyst for treating the crude naphthalene, wherein the catalyst is named as B.
The catalyst B contained 4.0wt% of tungsten, 4.0wt% of nickel and 8.0 wt% of active metals. The specific surface area of the B catalyst is 258m by adopting a BET method2The pore volume is 0.62 ml/g. The pores with the pore diameter of 8.0-10.0nm account for 93% of the total pore volume.
Example 3
(1) Preparation of the support
Uniformly mixing 100g of small-pore alumina (common small-pore alumina powder with the pore volume of 0.3-0.6 ml/g sold in the market), 48g of carbon nanotube dispersion liquid and 3.5g of sesbania powder, adding 50ml of aqueous solution containing 1.0g of citric acid, kneading, extruding and molding, drying at 140 ℃ for 1h, and roasting at 400 ℃ for 5h to obtain the strip-shaped carrier.
(2) Preparation of the catalyst
a. Preparation of the Metal impregnation solution As described above, a tungsten-nickel solution was taken (WO)3Content 15.0g/100ml, NiO content 12.5g/100ml)40ml, adding polyethylene glycol octyl phenyl ether Triton X-100 with the addition of about 4g to prepare an aqueous solution; b. taking 100g of the carrier prepared in the step (1), adding the carrier into a prepared aqueous solution (containing metal ions) for soaking, and filtering;
c. putting the product obtained in the step b2 in an oven, and drying for 2h at 140 ℃;
d. and finally, putting the dried product in a muffle furnace, and calcining for 4 hours at the temperature of 450 ℃ to obtain the selective hydrogenation catalyst for treating the crude naphthalene, wherein the catalyst is named as C.
The catalyst C contained 6.0 wt% of tungsten, 5.0 wt% of nickel and 11.0 wt% of active metals. Using the BET method, the specific surface area of the C catalyst is 268m2The pore volume is 0.64 ml/g. The pores with the pore diameter of 8.0-10.0nm account for 95% of the total pore volume.
Comparative example 1
(1) Preparation of the carrier: the procedure of example 3 was followed except that the carbon nanotube powder was not added.
(2) Preparation of the catalyst: the same as in example 3.
Thus, a comparative catalyst DC was prepared, which contained the same amount of tungsten and nickel in the carrier as catalyst C. Using the BET method, the specific surface area of the DC catalyst is 156m2The pore volume is 0.49 ml/g. The pores with the pore diameter of 8.0-10.0nm account for 79 percent of the total pore volume. The ideal pore size distribution of the catalyst is obviously dispersed. As can be seen from the above examples, the specific surface area, the pore volume and the proportion of the ideal pore diameter of 8-10 nm to the total pore volume of the catalyst prepared by the method of the invention are obviously greater than those of the catalyst obtained in the comparative example.
The raw oil used for evaluating the activity of the catalysts A to C obtained in examples 1 to 3 of the invention and the activity of the DC catalyst obtained in the comparative example is industrial naphthalene, the range of the fraction is 172-246 ℃, and the density is 1150kg/m3The sulfur content is 5360 mug/g, wherein the naphthalene content is 97.0 percent, the thianaphthene content is 2.3 percent, and the others are compounds such as indene, beta-methylnaphthalene and the like. The evaluation condition is that the volume space velocity of the selective hydrogenation reaction is 0.5h-1The system reaction hydrogen partial pressure is 5.0MPa, the reaction temperature is 350 ℃, and the hydrogen-oil ratio is 650. The small-sized device filled with the catalyst adopts a fixed bed hydrogenation catalyst sulfurization step well known by a person skilled in the art, a product sample with initial activity is taken when the device is operated for 50 hours after sulfurization is finished, the product sample is taken after the device is continuously operated for 3000 hours, the sulfur content in the product sampled twice is analyzed and detected, and the content of naphthalene and thianaphthene in the selective hydrogenation product is analyzed by a GC-MS (gas chromatography-mass spectrometry) analysis method, so that the obtained data are listed in Table 1.
TABLE 1 Activity and stability data of catalysts A to C obtained in examples 1 to 3 and of catalyst DC obtained in the comparative example
Figure BDA0001594751130000091
As can be seen from Table 1, the catalysts A to C obtained in examples 1 to 3 of the present invention have high desulfurization rates, no side reaction of hydrogenation of naphthalene to tetralin, and desulfurization rates of more than 99.8%, which are significantly superior to those of the existing catalysts. Namely, the desulfurization activity selectivity is high, and more remarkably, the activity stability is good. Compared with the catalyst of the comparative example, the catalyst obtained by the invention has high activity and good activity stability for producing refined naphthalene by selectively hydrogenating industrial naphthalene, heavy benzonaphthalene or crude naphthalene. Therefore, the catalyst of the invention has good selective hydrogenation activity, so that the yield of refined naphthalene is higher than that of the prior similar catalyst for the same raw material.
It should be understood that the above-mentioned embodiments are merely illustrative of the technical concepts and features of the present invention, which are intended to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and therefore, the protection scope of the present invention is not limited thereby. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.

Claims (10)

1. Selective addition of industrial naphthaleneThe method for producing refined naphthalene by using hydrogen is characterized in that the method adopts the process condition that the volume space velocity of the reaction is 0.3-1.0 h-1The hydrogen partial pressure of the system reaction pressure is 4.0-6.0 MPa, the reaction temperature is 340-360 ℃, and the hydrogen-oil ratio is 500-1000;
the industrial naphthalene selective hydrogenation catalyst adopted by the method comprises 40-90 wt% of modified carrier and 5-15 wt% of metal active component, and the pores with the pore diameter of 8-10 nm in the catalyst account for more than 90% of the total pore volume, the pore volume is 0.6-0.8 ml/g, and the specific surface area is 240-300 m2/g；
The modified carrier is mainly formed by mixing, kneading, molding, drying and roasting a carbon nano tube and alumina, the metal active component comprises a metal oxide, the metal oxide comprises VIB group and/or VIII group metal elements, the VIB group metal elements are selected from any one or combination of more than two of molybdenum and tungsten, the VIII group metal elements are selected from any one or combination of more than two of cobalt and nickel, the pore volume of the alumina is 0.3-0.6 ml/g, the average value of the pore diameter is 2-10 nm, and the using amount of the carbon nano tube is 0.5-1.2 wt% of the total mass of the modified carrier; the carbon nano tube is a short multi-walled carbon nano tube, the tube diameter of the short multi-walled carbon nano tube is less than 8nm, and the specific surface area is more than 500m2The material is used for drying, wherein the material is used for drying, the material is used for roasting, and the material is used for roasting, wherein the material is used for roasting, and the material is used for roasting, wherein the material is used for roasting, and the material is used for roasting, the length is 0.5-2.0 mu m, the temperature of the drying is 80-160 ℃, the temperature of the roasting is 400-700 ℃, and the roasting time is 1-15 h.
2. The method of claim 1, wherein: the metal oxide is selected from any one or combination of more than two of molybdenum trioxide, tungsten trioxide, nickel oxide and cobalt oxide.
3. The method of claim 2, wherein: the metal oxide is selected from molybdenum trioxide and/or tungsten trioxide.
4. The method of claim 2, wherein: the metal oxide is selected from nickel oxide and/or cobalt oxide.
5. The method of claim 1, wherein: the amount of the carbon nano tube is 0.6-1.0 wt% of the total mass of the modified carrier.
6. The method of claim 1, wherein the catalyst is prepared by a method comprising:
1) dissolving a surfactant containing an aromatic group functional group in water at the dissolving temperature of 40-70 ℃, adding the carbon nano tube into the obtained surfactant aqueous solution, and uniformly dispersing to form a carbon nano tube dispersion liquid;
2) uniformly mixing alumina and the carbon nano tube dispersion liquid obtained in the step 1), adding a pore-expanding agent and an extrusion aid, extruding into strips, forming, drying and roasting to obtain a modified carrier, wherein the usage amount of the pore-expanding agent is 1.0-4.0 wt% of the total mass of the modified carrier, and the usage amount of the extrusion aid is 1.0-2.0 wt% of the total mass of the modified carrier;
3) adding a surfactant containing aromatic group functional groups into an aqueous solution of a precursor of a metal active component to form a mixed solution, wherein the precursor of the metal active component is selected from water-soluble compounds containing VIB-group and/or VIII-group metal elements;
4) soaking the modified carrier obtained in the step 2) in the mixed liquid obtained in the step 3), and then drying and roasting to obtain the selective hydrogenation catalyst.
7. The method of claim 6, wherein: the surfactant containing the aromatic group functional group is polyethylene glycol octyl phenyl ether Triton X-100.
8. The method of claim 6, wherein step 1) further comprises: adding the carbon nano tube into a surfactant aqueous solution, carrying out ultrasonic stirring for 5-30 min at the stirring temperature of 0-5 ℃, then removing undispersed agglomerate particles by adopting a centrifugal sedimentation mode, wherein the centrifugal speed is 1500-2000 r/min, the centrifugal time is 30-60 min, and filtering the dispersion liquid by using a filter cloth with 300-500 meshes after the centrifugation is finished to obtain the stable carbon nano tube dispersion liquid.
9. The method of claim 6, wherein: the amount of the pore-expanding agent is 3.0-4.0 wt% of the total mass of the modified carrier.
10. The method of claim 6, wherein: the dosage of the surfactant containing the aromatic functional groups in the step 3) is 0.5-1.0 time of the mass of the carbon nano tube.
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