CN107626344B - Catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, preparation and application - Google Patents
Catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, preparation and application Download PDFInfo
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Abstract
The invention provides a catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, belonging to the technical field of aromatic hydrocarbon hydrogenation catalysts. The catalyst comprises an active component, a binder, an organic auxiliary agent and an inorganic auxiliary agent: the active components are two or three of Ni, Mo and W, and account for 35-95% of the total mass of the catalyst according to metal oxides; the organic auxiliary agent is a water-soluble oxygen-containing compound, and the content of the organic auxiliary agent is 0.1-1% of the total amount of the metal oxide; the inorganic auxiliary agent is P, B, F water-soluble salts or one or more mixtures of oxyacids, and the content of the inorganic auxiliary agent accounts for 0.1-2% of the total mass of the catalyst; the remainder being adhesive. The invention also provides a preparation method and application of the catalyst, and the catalyst is applied to the preparation of tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation. The catalyst has good activity and stability, the conversion rate of industrial naphthalene reaches 98%, and the selectivity sum of tetrahydronaphthalene and decahydronaphthalene is more than 98%; meanwhile, the proportion of the tetrahydronaphthalene and the decahydronaphthalene in the product can be adjusted according to the reaction conditions.
Description
Technical Field
The invention belongs to the technical field of aromatic hydrocarbon hydrogenation catalysts, and particularly relates to a catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, and preparation and application thereof.
Background
Tetrahydronaphthalene and decahydronaphthalene are important organic chemical products and have wide application. As an important fine chemical product, tetralin can be widely applied to the industrial fields of paint, coating, printing ink, hard alloy, medicine, paper making and the like, and is also used for producing tetralone. Decahydronaphthalene is used as an excellent high-boiling-point organic solvent, is the best solvent in the dry spinning process for producing polyethylene fibers, and is an essential additive for improving the thermal stability of aviation kerosene. Because tetrahydronaphthalene and decahydronaphthalene have wide application and large demand, the supply is not in demand at the present stage, and a large amount of import is needed, so the price is high.
Tetrahydronaphthalene and decahydronaphthalene are mainly prepared by catalytic hydrogenation of naphthalene. The coal tar yield of China is very high, and the naphthalene is rich in resources. Therefore, the catalytic hydrogenation of naphthalene to prepare tetrahydronaphthalene and decahydronaphthalene with higher added values has important industrial significance. At present, the technology for producing decahydronaphthalene by naphthalene hydrogenation is monopolized mainly abroad. A few companies, Degussa AG in Germany, Chemos GmbH in Europe, DuPont in USA, Dow chemical Ltd, Sigma-Aldrich, etc., can produce decahydronaphthalene products, and there is no commercial naphthalene hydrogenation technology in China.
The existing industrial naphthalene hydrogenation for preparing tetrahydronaphthalene or decahydronaphthalene mainly has the defects of single product, strict raw material requirement, complex catalyst manufacturing process, higher production cost, strict operation conditions, shorter life cycle and the like, and is not beneficial to the industrial production of the tetrahydronaphthalene and the decahydronaphthalene from naphthalene.
Disclosure of Invention
The catalyst is simple in production process, mild in operation condition, low in cost and good in stability, is applied to the preparation of the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation, and can be simultaneously realized by adjusting the proportion of the tetrahydronaphthalene and the decahydronaphthalene in the product by changing the operation condition.
The purpose of the invention is realized by the following technical scheme:
one of the purposes of the invention is to provide a catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, which is characterized by comprising an active component, a binder, an organic auxiliary agent and an inorganic auxiliary agent:
the active components are two or three of Ni, Mo and W, and account for 35-95% of the total mass of the catalyst according to the metal oxide;
the organic auxiliary agent is a water-soluble oxygen-containing compound, and the content of the organic auxiliary agent is 0.1-1% of the total amount of the metal oxide;
the inorganic auxiliary agent is P, B, F water-soluble salts or one or more mixtures of oxyacids, and the content of the inorganic auxiliary agent accounts for 0.1-2% of the total mass of the catalyst;
the remainder being adhesive.
In the catalyst, the active component metal composite oxide mainly plays a role in hydrogenation; the organic auxiliary agent mainly plays a role in hole expansion; the inorganic auxiliary agent can improve the distribution of the acid centers of the catalyst and can reduce the reduction difficulty of metal; the binder mainly plays a role in binding and forming. The content of each component is obtained by optimizing through a plurality of tests, and the content outside the range has low conversion rate of naphthalene.
The inorganic assistant and the organic assistant are added into the catalyst, so that the conversion rate of naphthalene can be obviously improved, side reactions are reduced, the total yield of tetrahydronaphthalene and decahydronaphthalene is improved, and the ratio of decahydronaphthalene to tetrahydronaphthalene can be adjusted in a large range according to process conditions.
As a specific example of the catalyst for preparing the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation, the active components are Ni-Mo/Ni-W/Ni-Mo-W three systems; in a Ni-Mo/Ni-W system, nickel oxide accounts for 10-20% of the total mass of the metal oxide, and the balance is molybdenum oxide or tungsten oxide; in the Ni-Mo-W system, nickel oxide accounts for 8-26% of the total mass of the metal oxide, molybdenum oxide accounts for 20-40% of the total mass of the metal oxide, and the balance is tungsten oxide. When the active component is within the above range, the catalyst activity is best.
As a specific example of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to the present invention, the water-soluble oxygen-containing compound is an organic acid, an alcohol, an aldehyde, a ketone, an ester, or an ether. More preferred are EDTA, PEG, PEO, PAM, ethanol, polyethylene glycol, carboxylic acid, and the like. The organic assistant mainly plays a role of a pore-expanding agent to form a channel for a catalyst chemical reaction, and the preferable organic assistant has the advantages of sufficient combustion at 450 ℃, proper pore diameter and the like, and is beneficial to hydrogenation of naphthalene to prepare tetrahydronaphthalene and decahydronaphthalene.
As a specific example of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, the binder is any one or more of pseudo-boehmite, alumina, silica, ZSM-5 molecular sieve, mordenite, X molecular sieve, Y molecular sieve and MCM-41 molecular sieve. The adhesive has the main function of adhesion and formation, and can provide a certain acidic central position, thereby improving the yield of decahydronaphthalene and tetrahydronaphthalene prepared by naphthalene hydrogenation.
As a specific example of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to the present invention, the inorganic auxiliary agent is preferably one or more of phosphoric acid, potassium phosphate, ammonium tetraborate, and potassium fluoride. The inorganic auxiliary agent can improve the distribution of the acid centers of the catalyst and reduce the reduction difficulty of metal, thereby improving the activity of the catalyst.
The second purpose of the invention is to provide a preparation method of a catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, which comprises the following steps:
1) preparation of metal composite oxide: placing a precursor of the active metal, an auxiliary agent and deionized water in a high-pressure reaction kettle, washing and drying a product after reaction to obtain a metal composite oxide;
2) adding a bonding agent and an auxiliary agent for forming: grinding the metal composite oxide into powder, adding the adhesive, the organic auxiliary agent, the inorganic auxiliary agent and deionized water, uniformly mixing, kneading, aging, extruding and molding;
3) roasting: drying the extruded catalyst precursor, and roasting to prepare the catalyst finished product.
Compared with the existing preparation technology of hydrogenation catalyst for preparing naphthalene by hydrothermal synthesis, the preparation method has the following advantages: determining the optimal range of each component; the inorganic assistant and the organic assistant are added, so that the conversion rate of naphthalene is obviously improved, the tetrahydronaphthalene and the decahydronaphthalene are co-produced, the side reaction is reduced, the total yield of the tetrahydronaphthalene and the decahydronaphthalene is improved, and the ratio of the decahydronaphthalene to the tetrahydronaphthalene can be adjusted in a large range according to the process conditions.
As a specific example of the preparation method of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to the present invention, the active metal precursor is nickel nitrate, nickel sulfate, nickel acetate, ammonium tungstate, alkali tungstate, ammonium molybdate, and alkali molybdate.
As a specific embodiment of the preparation method of the catalyst for preparing the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation, in the preparation process of the metal composite oxide, the auxiliary agent is urea or citric acid, the high-pressure reaction temperature is 120-220 ℃, and the time is 4-24 hours; the drying temperature is 100-120 ℃; in the forming process of adding the adhesive and the auxiliary agent, the powder is 150-200 meshes, and the aging time is 1-6 h; in the roasting process, the drying temperature is 100-120 ℃, the roasting temperature is 350-500 ℃, and the roasting time is 3-6 hours.
The invention also aims to provide application of the catalyst for preparing the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation, and the application of the catalyst in preparing the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation.
As a specific example of the application of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, the catalyst needs to be pretreated by sulfide before being applied in the preparation of tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, and the sulfurization operation is as follows: treating the catalyst for 8-36 h at 240-360 ℃ by using sulfide, wherein the sulfide is one or more of dimethyl disulfide, carbon disulfide, ethanethiol, isopropylmercaptan and methyl sulfide.
Specifically, the vulcanization conditions were: the hydrogen partial pressure is 1.5-6 Mpa, the reaction temperature is 240-360 ℃, and the volume airspeed is 0.5-4 h-1The hydrogen-oil ratio is 200-1000: 1, and the vulcanization time is 8-36 h.
As a specific example of the application of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to the present invention, the operating conditions of the catalyst applied in preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation are as follows: the reaction temperature is 200-400 ℃, the hydrogen partial pressure is 2-9 Mpa, and the liquid air speed is 1-10 h-1The hydrogen-oil ratio is 300-1500: 1. This operating condition is the optimum range for the catalyst disclosed in the present invention: under the conditions of low temperature, low pressure, low hydrogen-oil ratio and high airspeed, the product mainly contains tetrahydronaphthalene; under the conditions of high temperature, high pressure, high hydrogen-oil ratio and low space velocity, the product is mainly decahydronaphthalene. The ratio of tetrahydronaphthalene to decahydronaphthalene can be adjusted by varying the above operating conditions.
As a specific example of the application of the catalyst for preparing the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation, the molar ratio of the tetrahydronaphthalene to the decahydronaphthalene in a product obtained by applying the catalyst to the preparation of the tetrahydronaphthalene and the decahydronaphthalene by the industrial naphthalene hydrogenation is 0.05-8.
Compared with the prior art, the invention has the following beneficial effects:
1. the catalyst has good activity and stability, the service life cycle is more than 1 year, and the catalyst is suitable for various raw material naphthaline, including industrial naphthaline and refined naphthaline, the conversion rate of the naphthaline is 98 percent, and the sum of the selectivity of tetrahydronaphthaline and decahydronaphthaline is more than 98 percent; meanwhile, the ratio of the tetrahydronaphthalene to the decahydronaphthalene in the product can be adjusted according to reaction operation conditions, so that the molar ratio of the tetrahydronaphthalene to the decahydronaphthalene is 0.05-8.
2. The catalyst solves the problems of low conversion rate, short service life cycle and complex catalyst manufacturing process in the prior art for preparing tetrahydronaphthalene and decahydronaphthalene by naphthalene hydrogenation, overcomes the defects of single naphthalene hydrogenation product and strict requirement on raw materials, ensures that the proportion of the naphthalene hydrogenation product is adjustable, and is beneficial to industrial production.
3. The preparation process of the catalyst is simple and scientific, the operation is convenient, the equipment is simple, and the investment cost is low.
Drawings
FIG. 1 is a schematic view of a catalyst activity measuring apparatus according to an embodiment of the present invention.
Reference numerals: 1-raw material bottle, 2-plunger pump, 3-valve, 4-mass flowmeter, 5-three-way valve, 6-pressure gauge, 7-reactor, 8-condenser, 9-gas-liquid separator, 10-back pressure valve, 11-product, 12-gas washing bottle.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The catalyst activity evaluation apparatus of this example was evaluated by using a micro fixed bed reactor as shown in FIG. 1. The main products after the reaction comprise tetrahydronaphthalene, decalin and trace cumene, ethylcyclohexane, ethylbenzene and other by-products. The evaluation of the reaction product was carried out by an Agilent 7820 chromatograph using OV101 type chromatography column. In the present invention, wt.% is a mass fraction. The conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated according to the following formulas:
the conversion of naphthalene (mass fraction of naphthalene in the feed-mass fraction of naphthalene in the product)/mass fraction of naphthalene in the feed 100%
Tetrahydronaphthalene selectivity-the mole fraction of tetrahydronaphthalene in the product/mole fraction of naphthalene converted-100%
Decalin selectivity-the mole fraction of decalin in product/mole fraction of naphthalene converted-100%
The starting materials in this example are all commercially available.
Example 1
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 5.01g (3g nickel oxide) of basic nickel carbonate, 30.24g (26g tungsten oxide) of ammonium metatungstate, 100g deionized water and 0.2g of citric acid, and reacting for 8 hours at 140 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into powder of 150-200 meshes, adding 0.22g of ammonium phosphate, 0.3g of PEO (polyoxyethylene), 2g of ZSM-5 molecular sieve and a certain amount of deionized water, kneading the mud (the amount of the deionized water is determined according to the requirement of strip extrusion), aging the kneaded mud mass for 2h, and extruding the mixture into strips, wherein the specification of the extruded strips is phi 1.3X 2-8mm clover type. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace for 4 hours at 500 ℃ to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 30.9 g.
In the catalyst prepared above, the active component metal oxide accounts for 93.9% of the total mass of the catalyst, the simple substance phosphorus accounts for 0.11% of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounted for 10.3% of the total metal oxide, the remainder was tungsten oxide, and PEO was added to account for 1% of the metal oxide component.
2. And (3) vulcanization of the catalyst: 10ml of the catalyst is filled in a fixed bed reactor, and a layer of quartz sand with the thickness of 2cm is paved on the upper part and the lower part of the catalyst respectively. After the catalyst is filled, the catalyst is vulcanized by using a dimethyl disulfide/cyclohexane solution with the mass fraction of 5 percent, the vulcanization is carried out for 36 hours at the temperature of 240 ℃, and the space velocity of the vulcanizing liquid is 1 hour-1The hydrogen/oil ratio was 700:1 and the hydrogen partial pressure was 4 MPa.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare a naphthalene/cyclohexane solution with the mass fraction of 10%, and pumping the solution into the fixed bed reactor by using a plunger pump. The naphthalene is industrial naphthalene, and the content of the naphthalene is C10H8Calculated by 95 percent, the content of the thianaphthene compounds is 3 percent, and the content of the inorganic salt is 2 percent. The reaction conditions were as follows: the reaction temperature is 300 ℃, the hydrogen partial pressure is 5Mpa, the liquid air speed is 1h-1, and the hydrogen-oil ratio is 800: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
Example 2
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 8.35g (5g of nickel oxide) of basic nickel carbonate, 26.97g (22g of molybdenum oxide) of ammonium molybdate, 100g of deionized water and 0.4g of urea, and reacting for 12h at 180 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into powder of 150-200 meshes, adding 5.5g of phosphoric acid (concentration 85%), 0.03g of PEG (polyvinyl alcohol), 65g of pseudo-boehmite (ignition loss rate of about 20% at 400 ℃) and a certain amount of deionized water, kneading, aging the kneaded mud mass for 2h, and extruding into strips with the specification of phi 1.3X 2-8mm clover shape. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace at 350 ℃ for 4 hours to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 76.8 g.
In the prepared catalyst, the active component metal oxide accounts for 35.1 percent of the total mass of the catalyst, the simple substance phosphorus accounts for 1.9 percent of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounts for 18.5 percent of the total amount of the metal oxide, the rest is molybdenum oxide, and the added organic auxiliary agent PEG accounts for 0.11 percent of the metal oxide component.
2. And (3) vulcanization of the catalyst: 10ml of the catalyst is filled in a fixed bed reactor, and a layer of quartz sand with the thickness of 2cm is paved on the upper part and the lower part of the catalyst respectively. After the catalyst is filled, the catalyst is vulcanized by using carbon disulfide/cyclohexane solution with the mass fraction of 5 percent, the vulcanization is carried out for 8 hours at the temperature of 360 ℃, and the space velocity of the vulcanization liquid is 1 hour-1The hydrogen/oil ratio was 700:1 and the hydrogen partial pressure was 3 MPa.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare a naphthalene/cyclohexane solution with the mass fraction of 10%, and pumping the solution into the fixed bed reactor by using a plunger pump. The naphthalene is industrial naphthalene, and the content of the naphthalene is C10H8Calculated by 95 percent, the content of the thianaphthene compounds is 3 percent, and the content of the inorganic salt is 2 percent. The reaction conditions were as follows: the reaction temperature is 300 ℃, the hydrogen partial pressure is 5Mpa, the liquid air speed is 1h-1, and the hydrogen-oil ratio is 600: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
Example 3
This example is a comparative example of example 2, on the basis of example 2, the inorganic assistant phosphoric acid and the organic assistant PEG are not added, other operations are completely consistent with example 2, and the influence of the organic and inorganic assistants on the performance of the catalyst is examined.
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 8.35g (5g of nickel oxide) of basic nickel carbonate, 26.97g (22g of molybdenum oxide) of ammonium molybdate, 100g of deionized water and 0.4g of urea, and reacting for 12h at 180 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into powder of 150-200 meshes, adding 65g of pseudo-boehmite (the loss rate of burning is about 20% at 400 ℃) and a certain amount of deionized water, kneading, aging the kneaded mud dough for 2h, and extruding into strips, wherein the specification of the extruded strips is phi 1.3X 2-8mm clover type. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace at 350 ℃ for 4 hours to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 74.9 g.
The active component metal oxide in the catalyst prepared above accounts for 36% of the total catalyst, and the balance is the binder. In the metal oxide, nickel oxide was 18.5% of the total amount of the metal oxide, and the remainder was molybdenum oxide.
2. And (3) vulcanization of the catalyst: the same as in example 2.
3. Evaluation of catalyst Activity: the same as in example 2. The results of activity evaluation are shown in Table 1.
Example 4
This example is a comparative example of example 2, and the operation of example 2 is completely the same as that of example 2 except that no inorganic auxiliary agent phosphoric acid is added, and the influence of the inorganic auxiliary agent on the catalyst performance is examined.
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 8.35g (5g of nickel oxide) of basic nickel carbonate, 26.97g (22g of molybdenum oxide) of ammonium molybdate, 100g of deionized water and 0.4g of urea, and reacting for 12h at 180 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into powder of 150-200 meshes, adding 0.03g of PEG (polyvinyl alcohol), 65g of pseudo-boehmite (the loss rate of burning is about 20% at 400 ℃) and a certain amount of deionized water, kneading the mud, aging the kneaded mud dough for 2h, and extruding into strips, wherein the specification of the extruded strips is phi 1.3 x 2-8mm clover. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace at 350 ℃ for 4 hours to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 75 g.
The active component metal oxide in the catalyst prepared above accounts for 36% of the total catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounts for 18.5 percent of the total amount of the metal oxide, the rest is molybdenum oxide, and the added organic auxiliary agent PEG accounts for 0.11 percent of the metal oxide component.
2. And (3) vulcanization of the catalyst: same example 2
3. Evaluation of catalyst Activity: the same as in example 2. The results of activity evaluation are shown in Table 1.
Example 5
This example is a comparative example of example 2, on the basis of example 2, no organic auxiliary agent PEG is added, other operations are completely consistent with example 2, and the influence of the organic auxiliary agent on the performance of the catalyst is examined
The metal oxide accounts for 35.2 percent of the total mass of the catalyst, the simple substance phosphorus accounts for 1.9 percent of the total mass of the catalyst, and the balance is the caking agent. In the metal oxide, nickel oxide was 18.5% of the total amount of the metal oxide, and the remainder was molybdenum oxide.
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 8.35g (5g of nickel oxide) of basic nickel carbonate, 26.97g (22g of molybdenum oxide) of ammonium molybdate, 100g of deionized water and 0.4g of urea, and reacting for 12h at 180 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into powder of 150-200 meshes, adding 5.5g of phosphoric acid (concentration 85%), 65g of pseudo-boehmite (ignition loss rate of about 20% at 400 ℃) and a certain amount of deionized water, kneading the mud, aging the kneaded mud dough for 2h, and extruding into strips, wherein the specification of the extruded strips is phi 1.3 x 2-8mm clover. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace at 350 ℃ for 4 hours to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 76.6 g.
In the prepared catalyst, the active component metal oxide accounts for 35.2 percent of the total mass of the catalyst, the simple substance phosphorus accounts for 1.9 percent of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide was 18.5% of the total amount of the metal oxide, and the remainder was molybdenum oxide.
2. And (3) vulcanization of the catalyst: the same as in example 2.
3. Evaluation of catalyst Activity: the same as in example 2. The results of activity evaluation are shown in Table 1.
Example 6
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: 19.39g of nickel nitrate (5g of nickel oxide), 9.81g of ammonium molybdate (8g of molybdenum oxide), 19.77g of ammonium metatungstate (17g of tungsten oxide), 100g of deionized water and 0.5g of urea are weighed and put into a high-pressure reaction kettle to react for 8 hours at the temperature of 150 ℃. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into 150-200 mesh powder, adding 2.2g phosphoric acid (concentration 85%), 0.3g PAM (polyacrylamide), 30g SB powder (loss on ignition at 400 ℃ is about 20%), and a certain amount of deionized water, kneading, aging the kneaded mud mass for 2h, and extruding into strips with the specification of phi 1.3X 2-8mm clover type. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace for 4 hours at 400 ℃ to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 51.6 g.
In the catalyst prepared by the method, the active component metal oxide accounts for 58.1 percent of the total mass of the catalyst, the simple substance phosphorus accounts for 1.1 percent of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounts for 16.7% of the total amount of the metal oxide, molybdenum oxide accounts for 26.7% of the total amount of the metal oxide, the balance is molybdenum oxide, and the added organic auxiliary agent PAM accounts for 1% of the metal oxide component.
2. And (3) vulcanization of the catalyst: 10ml of the catalyst is filled in a fixed bed reactor, and a layer of quartz sand with the thickness of 2cm is paved on the upper part and the lower part of the catalyst respectively. After being filled with the catalyst, the catalyst is vulcanized by carbon disulfide/cyclohexane solution with the mass fraction of 5 percent, 32Vulcanizing at 0 ℃ for 24 hours and vulcanizing liquid airspeed of 1 hour-1The hydrogen/oil ratio was 700:1 and the hydrogen partial pressure was 4 MPa.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare a naphthalene/cyclohexane solution with the mass fraction of 10%, and pumping the solution into the fixed bed reactor by using a plunger pump. The content of the naphthalene is C10H8The content was found to be 99%. The reaction conditions were as follows: the reaction temperature is 300 ℃, the hydrogen partial pressure is 5Mpa, the liquid air speed is 1h-1, and the hydrogen-oil ratio is 600: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
Example 7
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 15.51g (4g of nickel oxide) of basic nickel carbonate, 12.26g (10g of molybdenum oxide) of ammonium molybdate, 23.26g (20g of tungsten oxide) of ammonium metatungstate, 100g of deionized water and 0.4g of urea, and reacting for 8 hours at 150 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into 150-200 mesh powder, adding 2.7g phosphoric acid (concentration 85%), 0.3g PAM (polyacrylamide), 20g SB powder (loss on ignition at 400 deg.C is about 20%), and a certain amount of deionized water, kneading, aging for 2h, extruding into strips with specification of 1.3X 2-8mm clover type. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace for 4 hours at 400 ℃ to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 48.2 g.
In the catalyst prepared above, the metal oxide accounts for 70.5% of the total mass of the catalyst, the simple substance phosphorus accounts for 1.5% of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounted for 11.8% of the total metal oxide, molybdenum oxide accounted for 29.4% of the total metal oxide, and the remaining metal oxide was molybdenum oxide. The organic auxiliary agent PAM accounts for 0.88 percent of the metal oxide component.
2. Sulfidation of catalysts: 10ml of the catalyst is filled in a fixed bed reactor, and a layer of quartz sand with the thickness of 2cm is paved on the upper part and the lower part of the catalyst respectively. After the catalyst is filled, the catalyst is vulcanized by using carbon disulfide/cyclohexane solution with the mass fraction of 5 percent, the vulcanization is carried out for 24 hours at the temperature of 320 ℃, and the space velocity of the vulcanization liquid is 1 hour-1The hydrogen/oil ratio was 700:1 and the hydrogen partial pressure was 4 MPa.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare a naphthalene/cyclohexane solution with the mass fraction of 10%, and pumping the solution into the fixed bed reactor by using a plunger pump. The naphthalene is industrial naphthalene, and the content of the naphthalene is C10H8Calculated by 95 percent, the content of the thianaphthene compounds is 3 percent, and the content of the inorganic salt is 2 percent. The reaction conditions were as follows: the reaction temperature is 300 ℃, the hydrogen partial pressure is 5Mpa, and the liquid air speed is 1h-1Hydrogen-oil ratio 600: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
Example 8
This example is a comparative example, and on the basis of example 7, the amount of the active metal component added was adjusted so that the metal oxide content in the prepared catalyst was 25.1% of the total amount of the catalyst, and the effect of the active metal oxide on the catalyst performance was examined.
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: weighing 15.51g (4g of nickel oxide) of basic nickel carbonate, 12.26g (10g of molybdenum oxide) of ammonium molybdate, 23.26g (20g of tungsten oxide) of ammonium metatungstate, 100g of deionized water and 0.4g of urea, and reacting for 8 hours at 150 ℃ in a high-pressure reaction kettle. And (3) filtering and taking out a reaction product, washing the reaction product for 3 to 4 times by using deionized water, and drying the reaction product at the temperature of 120 ℃. Grinding the dried metal oxide into 150-200 meshes of powder, adding 7.6g of phosphoric acid (concentration 85%), 0.3g of PAM (polyacrylamide), 130g of SB powder (loss on ignition at 400 ℃ is about 20%), and a certain amount of deionized water, kneading the mud (the amount of the deionized water is determined according to the requirement of strip extrusion), aging the kneaded mud mass for 2h, and extruding the mixture into strips, wherein the specification of the strips is phi 1.3X 2-8mm clover type. Drying the extruded strips at 120 ℃, and finally roasting the extruded strips in a muffle furnace for 4 hours at 400 ℃ to obtain the finished product of the cloverleaf type catalyst, wherein the total mass of the catalyst is 135.4 g.
In the catalyst prepared above, the metal oxide accounts for 25.1% of the total mass of the catalyst, the simple substance phosphorus accounts for 1.5% of the total mass of the catalyst, and the balance is the binder. In the metal oxide, nickel oxide accounted for 11.8% of the total metal oxide, molybdenum oxide accounted for 29.4% of the total metal oxide, and the remaining metal oxide was molybdenum oxide. The organic auxiliary agent PAM accounts for 0.88 percent of the metal oxide component.
2. And (3) vulcanization of the catalyst: the same as in example 7.
3. Evaluation of catalyst Activity: the same as in example 7. The results of the experiment are shown in table 1.
Example 9
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: the same as in example 7.
2. And (3) vulcanization of the catalyst: the same as in example 7.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare a naphthalene/cyclohexane solution with the mass fraction of 10%, and pumping the solution into the fixed bed reactor by using a plunger pump. The content of the naphthalene is C10H8Calculated by 95 percent, the content of the thianaphthene compounds is 3 percent, and the content of the inorganic salt is 2 percent. The reaction conditions were as follows: the reaction temperature is 280 ℃, the hydrogen partial pressure is 3.5Mpa, and the liquid air speed is 4h-1Hydrogen to oil ratio 500: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
Example 10
The preparation and application of the catalyst of this example are as follows:
1. preparation of the catalyst: the same as in example 7.
2. And (3) vulcanization of the catalyst: the same as in example 7.
3. Evaluation of catalyst Activity: after the vulcanization is finished, nitrogen is used for purging for 1h, and then hydrogen is introduced to the set reaction pressure. Dissolving naphthalene in cyclohexane to prepare the productA 10% fraction naphthalene/cyclohexane solution was then pumped into the fixed bed reactor using a plunger pump. The content of the naphthalene is C10H8Calculated by 95 percent, the content of the thianaphthene compounds is 3 percent, and the content of the inorganic salt is 2 percent. The reaction conditions were as follows: the reaction temperature is 260 ℃, the hydrogen partial pressure is 3Mpa, and the liquid air speed is 6h-1Hydrogen to oil ratio 300: 1. After 24h of reaction, the product is analyzed, and the conversion rate of naphthalene, the selectivity of tetrahydronaphthalene and the selectivity of decahydronaphthalene are calculated. The results of the experiment are shown in table 1.
In order to further illustrate the beneficial effect of the catalyst in the preparation of tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, the catalyst is mixed with Ni-Mo/Al in Hangzhou oil refinery2O3The catalyst and the RN10 catalyst were compared, and the performance of industrial naphthalene hydrogenation by the different catalysts was investigated under the same conditions for evaluation of sulfidation and activity as in example 4. The results of activity evaluation of the various catalysts after sulfiding are shown in table 1 below.
TABLE 1 results of activity evaluation of different catalysts
As can be seen from Table 1 above, the catalysts prepared by the method of the present invention (examples 1, 2, 6, 7, 9 and 10) can achieve a commercial naphthalene conversion of 99.3% or more, even 100%. When no inorganic or organic auxiliary agent is added (example 3, example 4 and example 5), the activity of the catalyst is obviously reduced, and meanwhile, the addition of the inorganic auxiliary agent and the organic auxiliary agent also has great influence on the selectivity of the tetrahydronaphthalene and the decahydronaphthalene in the product, mainly because the addition of the inorganic or organic auxiliary agent can change the microstructure of the catalyst, thereby influencing the selectivity of the tetrahydronaphthalene and the decahydronaphthalene. The reduction in the content of metal active oxides (example 8) also leads to a reduction in the naphthalene conversion and, at the same time, to an impairment of the product selectivity. From the example 9 and the example 10, it can be seen that, when the same catalyst is used and the reaction conditions are different, the molar ratio of tetrahydronaphthalene to decahydronaphthalene is also greatly changed, and the molar ratio of tetrahydronaphthalene to decahydronaphthalene in the product of the present invention can be adjusted from 0.05 to 8, and can be selected according to the requirements of specific products.
According to the formula with Ni-Mo/Al2O3The catalyst is compared with the RN10 catalyst, so that the performance of the catalyst is obviously superior to that of the existing catalyst, the conversion rate of the catalyst to naphthalene is obviously improved, the prepared product has a larger molar ratio adjusting range, the molar ratio of the RN10 catalyst to tetrahydronaphthalene and decahydronaphthalene in industrial naphthalene hydrogenation is 4-7.5, and the adjustability is not high.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (6)
1. The catalyst for preparing the tetrahydronaphthalene and the decahydronaphthalene by the hydrogenation of the industrial naphthalene is characterized by being prepared from the following raw materials comprising an active component, a binder, an organic auxiliary agent and an inorganic auxiliary agent:
the active components are three systems of Ni-Mo/Ni-W/Ni-Mo-W; in a Ni-Mo/Ni-W system, nickel oxide accounts for 10-20% of the total mass of the metal oxide, and the balance is molybdenum oxide or tungsten oxide; in a Ni-Mo-W system, nickel oxide accounts for 8-26% of the total mass of the metal oxide, molybdenum oxide accounts for 20-40% of the total mass of the metal oxide, and the balance is tungsten oxide, wherein the active component accounts for 35-95% of the total mass of the catalyst according to the metal oxide;
the organic auxiliary agent is organic acid, aldehyde, ketone, ester and ether, and the content of the organic auxiliary agent is 0.1-1% of the total amount of the metal oxide;
the inorganic auxiliary agent is P, B, F water-soluble salts or one or more mixtures of oxyacids, and the content of the inorganic auxiliary agent accounts for 0.1-2% of the total mass of the catalyst in terms of elements;
the rest is adhesive, and the adhesive is any one or more of pseudo-boehmite, alumina, silica, ZSM-5 molecular sieve, mordenite, X molecular sieve, Y molecular sieve and MCM-41 molecular sieve;
the preparation method of the catalyst comprises the following steps:
1) preparation of metal composite oxide: putting a precursor of active metal, urea or citric acid and deionized water into a high-pressure reaction kettle, washing and drying a product after reaction to obtain a metal composite oxide;
2) adding a bonding agent and an auxiliary agent for forming: grinding the metal composite oxide into powder, adding the adhesive, the organic auxiliary agent, the inorganic auxiliary agent and deionized water, uniformly mixing, kneading, aging, extruding and molding;
3) roasting: drying the extruded catalyst precursor, and roasting to prepare the catalyst finished product.
2. The catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to claim 1, wherein in the preparation process of the metal composite oxide, the temperature of the high-pressure reaction is 120-220 ℃ and the time is 4-24 h; the drying temperature is 100-120 ℃; in the forming process of adding the adhesive and the auxiliary agent, the powder is 150-200 meshes, and the aging time is 1-6 h; in the roasting process, the drying temperature is 100-120 ℃, the roasting temperature is 350-500 ℃, and the roasting time is 3-6 hours.
3. The use of the catalyst according to claim 1 for the hydrogenation of industrial naphthalene to produce tetrahydronaphthalene and decahydronaphthalene, wherein the catalyst is used for the hydrogenation of industrial naphthalene to produce tetrahydronaphthalene and decahydronaphthalene.
4. The application of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to claim 3, wherein the catalyst needs to be pretreated by sulfide before being applied to the preparation of the tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation, and the sulfurization operation is as follows: treating the catalyst for 8-36 h at 240-360 ℃ by using sulfide, wherein the sulfide is one or more of dimethyl disulfide, carbon disulfide, ethanethiol, isopropylmercaptan and methyl sulfide.
5. The application of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to claim 3, wherein the operating conditions of the catalyst applied in preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation are as follows: the reaction temperature is 200-400 ℃, the hydrogen partial pressure is 2-9 Mpa, and the liquid air speed is 1-10 h-1The hydrogen-oil ratio is 300-1500: 1.
6. The application of the catalyst for preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation according to claim 1, wherein the molar ratio of tetrahydronaphthalene to decahydronaphthalene in the product obtained by applying the catalyst in preparing tetrahydronaphthalene and decahydronaphthalene by industrial naphthalene hydrogenation is 0.05-8.
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