CN112657536A - Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof - Google Patents
Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides an arene olefin removal catalyst, and a preparation method and application thereof, wherein the main components of the catalyst comprise a molecular sieve, a binder and a metal oxide, and the acid content of the medium strong acid of the catalyst is more than 80% based on 100% of the acid content of the medium strong acid of a roasted product after the molecular sieve and the binder are combined. The preparation of the catalyst was carried out as follows: mixing the molecular sieve with a binder and then roasting; placing the roasted product in a metal compound solution, and carrying out microwave treatment; dripping precipitator solution into the solution under the action of microwave; and continuously performing drying treatment by using the microwave effect, and then roasting to obtain the catalyst. The catalyst has high acid content, and the acid content of the catalyst is not changed greatly after the metal element is loaded, specifically, compared with the acid content before the metal element is loaded, the acid content of the strong acid is more than 80% of that before the metal element is loaded, and therefore, most of acid sites are reserved after the metal element is loaded.
Description
Technical Field
The invention relates to the field of removing olefin from aromatic hydrocarbon, in particular to a catalyst for removing olefin from aromatic hydrocarbon, and specifically relates to a catalyst for removing olefin from aromatic hydrocarbon, and a preparation method and application thereof.
Background
The triphenyl products in the aromatic hydrocarbon are mainly from an aromatic hydrocarbon combination unit, an ethylene unit and an oil refining unit, and a certain amount of olefin impurities are inevitably generated in the aromatic hydrocarbon mixture in the production process. These olefin impurities are unstable under conditions of high temperature, light and the like, are easy to generate new components, have great influence on the color, texture and the like of a final product, and have irreversible damage to the normal operation of downstream equipment. Such as the irreversible adsorption of olefins into the adsorbent during xylene adsorption separation in an aromatics complex, has a very adverse effect on the process. In order to obtain qualified p-xylene products and ensure the smooth proceeding of subsequent processes, trace olefin impurities are removed after the working procedures of reforming, aromatic hydrocarbon extraction, isomerization and toluene disproportionation.
In the early aromatic purification process, clay was used as the olefin removal catalyst. The clay has low activity, short service life, large dosage and no regeneration, and the waste clay can only be buried. Along with the application of a low-pressure reforming process, the colloid content in the reformate aromatic material is increased, the service life of the clay is obviously reduced, and the influence of frequent replacement of the clay on the environment and the production safety of enterprises is realized, so that a molecular sieve olefin removal refining technology and a hydrogenation technology are developed. The molecular sieve catalyst is used to replace industrial clay, and its relatively large surface area and acid amount are used to realize long one-way service life and total service life. The hydrogenation process has the advantage of long period, but the process is complex, the aromatic hydrocarbon is lost, and the one-time investment cost of the catalyst is high.
The molecular sieve non-hydrogenation catalyst needs to be ex-situ regenerated after each inactivation, and needs to be moved out of the reactor for regeneration, and the activity of the molecular sieve catalyst is easily reduced due to high-temperature carbon burning in the regeneration process of the molecular sieve.
CN104907090A introduces a catalyst for refining and removing olefin from catalytic reformate and a preparation method thereof, which comprises 30-70% of Al2O3And 30-70% of molecular sieve, and soaking Al in the catalyst by a method2O3The catalyst is loaded on a molecular sieve catalyst carrier for preparation, and the activity after regeneration is uncontrollable. For this purpose, further modifying elements and methods for the catalyst are required.
Chinese patents CN102008976A, CN102041035A, CN101992117A, CN102039160A, CN101993714A, etc. adopt molecular sieves as main active ingredients, and are modified by various methods to adapt to the reaction, thereby preventing the catalyst from being deactivated too quickly, but in the modification method of metal elements, the metal elements are easy to combine with acid centers in the modification process, so the acid loss of the molecular sieves is large, and the catalyst performance is limited.
The invention relates to a preparation method of a catalyst for removing olefin, which is invented by Chinese patent CN102008976A, wherein the catalyst is composed of a main active component of a ReUSY molecular sieve with high silica-alumina ratio, a second active component of a mordenite molecular sieve and a binder of alumina. The rare earth ions combine with the acid, and the amount of active acid centers decreases.
The invention of Chinese patent CN101993714A relates to a method for removing olefin from reformate without hydrogen, which adopts a catalyst containing 10-90 parts of molecular sieve, at least one element selected from Cl, Br and S or oxide thereof, F, P element or oxide thereof, and 10-90 parts of alumina or silica binder.
Chinese patent CN101992117A discloses a reformed oil non-hydroolefin removal catalyst, which adopts a novel catalyst containing 10-90 parts of molecular sieve, at least one element selected from Cl, Br and S or an oxide thereof, at least one element selected from F, P or an oxide thereof, and 10-90 parts of alumina or a silica binder. The halide cannot be retained during regeneration, and cannot be used for industrial catalysts.
Chinese patent CN102039160A describes a catalyst for removing olefin from reformate, which comprises at least one metal or oxide of Ni, Mo, Zr and Nb, at least one element or oxide of Cl, Br and S, at least one element or oxide of F, P, 20-90 parts of molecular sieve and 10-80 parts of at least one element or oxide of SiO2、Al2O3Or mixtures thereof, effective to extend catalyst life for the first cycle of the catalyst.
Chinese patent CN102220158A, etc. describes a method for non-hydroolefin removal from reformate by using a catalyst containing at least one metal or oxide thereof selected from Ni, Nb, Cu and rare earth, 20-90 parts of molecular sieve and 10-80 parts of at least one metal or oxide thereof selected from SiO2、Al2O3Or mixtures thereof. The method adopts modification methods such as halide, S and the like, but cannot be applied industrially because of no problems of reproducibility and environmental protection. In order to make up for the loss of acidity by adopting the method of modifying the metal elements, elements such as Zr and the like are added, but the regeneration performance of the catalyst is reduced.
The catalyst adopts the molecular sieve as a main catalytic activity source, and the acid center of the molecular sieve is irreversibly changed, so that the overall performance of the regenerated catalyst cannot be controlled.
Disclosure of Invention
Aiming at the problems in the prior art, in the invention, metal removal is combined with acid centers in the molecular sieve modification process, so that the medium-strength acid amount in the molecular sieve catalyst is reserved, the service life of the catalyst is prolonged, and the problem of short service life of the conventional molecular sieve catalyst is solved.
The invention aims to provide an arene olefin removal catalyst, which comprises the components of a molecular sieve, a binder and a metal oxide, wherein the medium-strong acid content of the catalyst is more than 80%, preferably more than 90%, based on 100% of the medium-strong acid content of a roasted product after the molecular sieve and the binder are combined.
In the prior art, metal elements of the modified catalyst are easily combined with acid centers of a molecular sieve, so that the acid centers of the catalyst are passivated, and the performance of the catalyst is influenced. In the application, the metal element can avoid the acid center of the molecular sieve, and is easier to combine with the binder compared with the molecular sieve, and meanwhile, the metal oxide is combined with the binder after roasting, so that the regeneration performance of the catalyst is better improved, and the adverse effect of the binder on a reaction product is also avoided.
Wherein the amount of the medium-strong acid is NH3TPD/Desorption peak area result meter above 350 ℃.
In a preferred embodiment, in the catalyst, the weight parts of each component are as follows:
50-100 parts of molecular sieve, preferably 65-90 parts;
4.99-50 parts of binder, preferably 10-34 parts;
0.01 to 16 parts of metal oxide, preferably 0.01 to 10 parts, and more preferably 1 to 6 parts.
The above-mentioned parts by weight of the components are to be understood as the weight ratio of the components (it is to be noted that: it is not limited based on 100 parts by weight of the catalyst); it is also understood that the molecular sieve based on (50 to 100 parts, preferably 65 to 90 parts): the binder is 4.99-50 parts by weight, preferably 10-34 parts by weight; the weight part of the metal oxide is 0.01-16 parts, preferably 0.01-10 parts, and more preferably 1-6 parts.
In a preferred embodiment, the molecular sieve is selected from at least one of Y-type molecular sieve, ZSM-5 type molecular sieve, ZSM-12 type molecular sieve, beta type molecular sieve, MCM-22 type molecular sieve and MCM-56 type molecular sieve, preferably from Y-type molecular sieve, beta type molecular sieve and MCM-22 type molecular sieve.
In a preferred embodiment, the binder is selected from at least one of alumina, kaolin, attapulgite, bentonite, diatomaceous earth and silica, preferably from alumina and/or silica.
In a preferred embodiment, the metal oxide is selected from at least one oxide of Cr, Mg, Cu, Zn, Ga, rare earth metal, Sr, Ba, Bi, preferably from at least one oxide of rare earth metal, Mg, Ga.
The second purpose of the invention is to provide a preparation method of the aromatic hydrocarbon olefin-removing catalyst, which comprises the following steps:
step 1, mixing the components including the molecular sieve and the binder and then roasting;
step 2, placing the roasted product in the step 1 into a metal compound solution, and performing microwave treatment;
step 3, dripping a precipitator solution into the solution under the action of microwaves;
and 4, continuously performing drying treatment by using the microwave effect, and then roasting to obtain the catalyst.
In a preferred embodiment, the process comprises the following raw material components in amounts:
50-100 parts of molecular sieve, preferably 65-90 parts;
4.99-50 parts of binder, preferably 10-34 parts;
0.01 to 16 parts of a metal compound, preferably 0.01 to 10 parts, and more preferably 1 to 6 parts.
Wherein the parts by weight of the metal compound are based on the weight of the corresponding metal oxide.
The above-mentioned amount parts of each component can be understood as the weight ratio of each component (it is to be noted that: it is not limited based on 100 parts of the total amount of raw materials); it is also understood that the molecular sieve based on (50 to 100 parts, preferably 65 to 90 parts): the amount of the binder is 4.99-50 parts, preferably 10-34 parts; the amount of the metal compound is 0.01-16 parts, preferably 0.01-10 parts, and more preferably 1-6 parts.
In a preferred embodiment, in step 1 and step 4, the temperature of the roasting is 400 to 800 ℃, preferably 450 to 650 ℃.
In a preferred embodiment, in step 2, the metal compound is at least one selected from the group consisting of a metal chloride, a metal nitrate compound, and a metal acetate compound, for example, a metal nitrate compound.
In a further preferred embodiment, the metal is selected from at least one of Cr, Mg, Cu, Zn, Ga, rare earth metals, Sr, Ba, Bi, preferably from at least one of rare earth metals, Mg, Ga.
In a preferred embodiment, in the step 2, the liquid-solid ratio of the roasted product to the metal compound solution is 0.1 to 15, preferably 1 to 7.
In a preferred embodiment, in step 2 and step 3, the microwave conditions are as follows: the temperature is 40-180 ℃, the power is more than 2 w/g of roasted product, and the treatment time is 0.2-20 h.
In a further preferred embodiment, in step 2 and step 3, the microwave conditions are as follows: the temperature is 60-120 ℃, the power is 5-20 w/g of the roasted product, and the treatment time is 0.5-8 h.
Wherein, the microwave function is that polar ions (metal ions) are not easy to combine with the molecular sieve under the microwave function, but if the microwave is not available, the molecular sieve can be directly combined with the polar ions; polar ions are separated from the molecular sieve under the action of microwaves, and are loaded on the binder of the catalyst under the action of a precipitator, and the calcined metal oxide is combined with the binder, so that the regeneration performance of the catalyst is better improved, and the adverse effect of the binder on reaction products is also avoided.
In a preferred embodiment, in step 3, the precipitating agent is selected from at least one of ammonium carbonate, ammonia, urea, 8-hydroxyquinoline, dimethylglyoxime.
In a further preferred embodiment, the precipitant solution is present in a concentration of 0.2 to 30% by weight, preferably 0.5 to 15% by weight.
Wherein, the concentration of the precipitant solution needs to be controlled, and too high or too low concentration can cause uneven precipitation.
In a preferred embodiment, in step 3, the dropping speed of the precipitant solution is 0.1 to 100g/min, preferably 1 to 20 g/min.
Wherein, too fast or too slow dropping speed can affect the precipitation effect, resulting in uneven precipitation.
The microwave action is carried out under the condition that the power is more than 2 w/g of the roasted product when the precipitating agent is introduced, and the solid (namely the catalyst) can be recovered after the vapor phase is cooled under the condition of continuous addition.
In the invention, the microwave is not used for promoting the loading, the molecular sieve adopted by the invention is mainly in a hydrogen type, the loaded metal ions are directly loaded on the molecular sieve under the action of no microwave, but under the microwave condition, the polar metal ions are directly dissociated under the action of the microwave except for the molecular sieve framework to form ions, and the ions are combined into a solid through a precipitator so as to prevent the acidic combination with the molecular sieve. If not precipitated under microwave conditions, the metal ions can be uniformly bound to the molecular sieve. Therefore, the effect of the microwave in the present invention is not to uniformly load the metal element on the molecular sieve, but to combine the metal element with the precipitant to avoid the acidic center of the molecular sieve.
In a preferred embodiment, in step 4, the microwave conditions are as follows: the temperature is 40-180 ℃, the power is more than 1 w/g of roasted product, and the processing time is 0.2-20 h.
In a further preferred embodiment, in step 4, the conditions of the microwaves are as follows: the temperature is 60-120 ℃, the power is 5-20 w/g molecular sieve, and the processing time is 0.5-8 h.
Wherein, when the step 4 is drying, the water quantity is small, the microwave power is also reduced, and the temperature is reduced due to the evaporation of water.
In a preferred embodiment, in the step 4, the roasting temperature is 400-800 ℃ and the roasting time is 0.5-20 h.
In a further preferred embodiment, in the step 4, the temperature of the roasting is 450 to 650 ℃ and the time is 0.5 to 12 hours.
Wherein, after the microwave heating dehydration process, the catalyst is obtained after the subsequent roasting without liquid water.
In a preferred embodiment, the amount of the strong acid in the catalyst obtained is 80% or more, preferably 90% or more, based on 100% of the amount of the strong acid in the calcined product of step 1.
In the invention, the microwave is not used for promoting the loading, the method is mainly characterized in that the molecular sieve is in a hydrogen form, if the loaded metal ions are not provided with microwaves, the loaded metal ions are directly loaded on the molecular sieve, but under the microwave condition, the polar metal ions are directly dissociated under the action of the microwaves except for the molecular sieve framework to form ions, and the ions are combined into a solid through a precipitator so as to prevent the acidic combination with the molecular sieve, so that the acid content of the catalyst is maintained. If not precipitated under microwave conditions, the metal ions can be uniformly bound to the molecular sieve.
The method reduces the loss of acid centers in the catalyst, prolongs the one-way service life of the catalyst by reserving more acid centers of the catalyst, and improves the one-way service life of the catalyst by more than 20 percent through modification. The catalyst is regenerated for many times, thereby prolonging the total service life of the catalyst by more than 30 percent.
The third object of the present invention is to provide a catalyst obtained by the preparation method of the second object of the present invention.
The fourth object of the present invention is to provide the use of the catalyst of one or three objects of the present invention in the deolefination of aromatic hydrocarbons.
Compared with the prior art, the invention has the following beneficial effects:
(1) the catalyst has high acid content, and the calculated amount of the catalyst does not change greatly after the metal element is loaded, specifically, compared with the catalyst before the metal element is loaded, the acid content of strong acid is more than 80% before the metal element is loaded, which indicates that most of acid sites are reserved after the metal element is loaded;
(2) the catalyst has longer total service life, can be repeatedly regenerated and utilized, for example, the catalyst can be repeatedly regenerated for 4-8 times, and the recovery rate of the service life of the catalyst after each regeneration is still more than 95%.
Detailed Description
While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.
The starting materials used in the examples and comparative examples are, if not particularly limited, those disclosed in the prior art, and may be, for example, obtained commercially directly or prepared according to the production methods disclosed in the prior art. In the examples and comparative examples, reagent grade chemicals were used in addition to the molecular sieves, binders, sesbania powder, which were commercially available industrial samples.
The composition of each component of the catalyst can be calculated by the feeding amount.
Example 1
100g of USY molecular sieve and 40g of pseudoboehmite (the content of alumina is 65 percent) are taken, 8g of sesbania powder is added, kneaded and dried, and roasted for 3 hours at the temperature of 600 ℃ to obtain a roasted product. It is passed through NH3TPD characterization gave a medium strong acid content of 0.4 mmol/g.
Taking 10g of the roasted product, adding a mixed aqueous solution of lanthanum nitrate, gallium nitrate and magnesium nitrate (the molar ratio is 1:1:1 and the total weight of oxides is 0.5g) into a liquid-solid ratio of 0.2, treating the mixture for 2 hours in a microwave oven at a set power of 300w and a temperature of 120 ℃, then dropwise adding 10g of 10% ammonium carbonate solution at a power of 300w and a temperature of 120 ℃ (the dropwise adding speed is 2 g/min), and continuing to dry the mixture for 2 hours at a temperature of 100 ℃ by using a microwave with a power of 200 w. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 100 parts of molecular sieve, 26 parts of alumina and 7.4 parts of total metal oxide.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.38 mmol/g.
In reformate with bromine index of 1500mgBr/100g, at 18h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.9MPa, until the life of the catalyst was evaluated to be 85 hours at an outlet of 100mgBr/100g bromine index.
Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 82 hours under the same conditions and requirements as described above. The same was repeated four more times, and the catalyst lives were 72 hours each.
Example 2
Taking 100g of beta molecular sieve and 30g of kaolin, adding 8g of sesbania powder, kneading, drying, roasting for 3 hours at 600 ℃ to obtain a roasted product, and performing NH treatment on the roasted product3TPD characterization gave a medium strong acid content of 0.36 mmol/g.
Taking 10g of a roasted product, adding a mixed aqueous solution of copper sulfate and bismuth nitrate (the molar ratio is 3:1, and the total weight is 1.18g in terms of oxide) into the mixed aqueous solution at a liquid-solid ratio of 10, treating the mixed aqueous solution in a microwave oven at a set power of 400w and a temperature of 90 ℃ for 6 hours, then dropwise adding 30g of 5% urea solution at a power of 100w and a temperature of 120 ℃ (the dropwise adding speed is 10 g/min), and continuing to dry the mixed aqueous solution at the temperature of 120 ℃ by using microwaves at a power of 200w for 4 hours. Then, the catalyst is obtained by roasting for 2 hours at 600 ℃ under the air atmosphere. The main components of the catalyst are as follows: 100 parts of molecular sieve, 30 parts of kaolin and 16.2 parts of metal oxide in total.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.35 mmol/g.
The aromatic hydrocarbon isomerization unit carbon octaaromatic hydrocarbon material with the bromine index of 220mgBr/100g is used for 30h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.0MPa, until the life of the catalyst was evaluated at 120 hours at an exit of 20mgBr/100g bromine index.
Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 116 hours under the same conditions and requirements as above. The same was repeated four more times, with catalyst lifetimes of 108 hours each.
Example 3
Taking 95g of ZSM-5 molecular sieve and 12.5g of silica sol (containing 40 percent of silicon dioxide), adding 8g of sesbania powder, kneading, drying, roasting for 3 hours at 600 ℃ to obtain a roasted product, and performing NH reaction on the roasted product3TPD characterization gave a medium strong acid content of 0.32 mmol/g.
10g of the roasted product is taken, mixed aqueous solution of nitric acid and chromium acetate (0.002 g of nitric acid and 1.0g of nitric acid calculated by the total weight of oxides) is added into the mixed aqueous solution under the liquid-solid ratio of 15, the mixed aqueous solution is treated for 20 hours under the set power of 20w and the temperature of 90 ℃ in a microwave oven, 0.2g of 5 percent ammonia water solution is dripped under the set power of 20w and the temperature of 90 ℃ (the dripping speed is 0.1 g/min), and the drying treatment is carried out for 2 hours under the condition of 120 ℃ by continuing the power of 500w microwave. Then, the catalyst was calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 95 parts of molecular sieve, 5 parts of silicon dioxide and 0.02 part of total metal oxide.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.32 mmol/g.
Extracting material in an aromatic hydrocarbon combined device with bromine index of 2220mgBr/100g for 3h-1The catalyst life evaluation reaction was carried out at a temperature of 170 ℃ under 1.0MPa, until the life of the catalyst was evaluated to be 80 hours at an outlet of 60mgBr/100g bromine index.
Then, the catalyst was calcined at 650 ℃ for 2 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 76 hours under the same conditions and requirements as described above. The same was repeated four more times, and the catalyst lives were 75 hours each.
Example 4
Taking 95g of ZSM-5 molecular sieve and 12.5g of silica sol (containing 40 percent of silicon dioxide), adding 8g of sesbania powder, kneading, drying, roasting for 3 hours at 600 ℃ to obtain a roasted product, and performing NH reaction on the roasted product3TPD characterization gave a medium strong acid content of 0.32 mmol/g.
10g of the roasted product is taken, mixed aqueous solution of nitric acid and chromium acetate (0.002 g of nitric acid and 1.0g of nitric acid calculated by the total weight of oxides) is added into the mixed aqueous solution under the liquid-solid ratio of 15, the mixed aqueous solution is treated for 20 hours under the set power of 20w and the temperature of 90 ℃ in a microwave oven, 0.2g of 5 percent ammonia water solution is dripped under the set power of 20w and the temperature of 90 ℃ (the dripping speed is 0.1 g/min), and the drying treatment is carried out for 2 hours under the condition of 120 ℃ by continuing the power of 500w microwave. Then, the catalyst was calcined at 400 ℃ for 4 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 95 parts of molecular sieve, 5 parts of silicon dioxide and 0.02 part of total metal oxide.
The catalyst is passed over NH3TPD characterization gave a medium strength acid content of 0.32mmol/g。
Extracting material in an aromatic hydrocarbon combined device with bromine index of 2220mgBr/100g for 3h-1The catalyst life evaluation reaction was carried out at a temperature of 170 ℃ under 1.0MPa, until the life of the catalyst was evaluated to be 80 hours at an outlet of 60mgBr/100g bromine index.
Then, the catalyst was calcined at 650 ℃ for 2 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 76 hours under the same conditions and requirements as described above. The same was repeated four more times, and the catalyst lives were 75 hours each.
Example 5
Adding 8g of sesbania powder into 40g and 20g of diatomite of an MCM-22 molecular sieve and a beta molecular sieve respectively, kneading and drying, roasting for 2 hours at 800 ℃ to obtain a roasted product, and performing NH (NH) treatment on the roasted product3TPD characterization gave a medium strong acid content of 0.36 mmol/g.
Taking 10g of a roasted product, adding a mixed aqueous solution of nitric acid, barium acetate and zinc nitrate (the molar ratio of barium to zinc is 1:3, the total weight is 1.1g of the oxide, and the nitric acid is 1.0g) into a liquid-solid ratio of 10, treating the mixture for 20 hours at a temperature of 90 ℃ in a microwave oven with a set power of 20w, then dropwise adding 20g of 5% dimethylglyoxime solution at a power of 800w and 180 ℃ (the dropwise adding speed is 20 g/min), and continuously drying the mixture for 2 hours at a temperature of 120 ℃ by using 500w power microwaves. Then, the catalyst was calcined at 600 ℃ for 3 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 80 parts of molecular sieve, 20 parts of diatomite and 11.8 parts of total metal oxide.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.31 mmol/g.
Reforming in an aromatic hydrocarbon combined device with bromine index of 800mgBr/100g within 10h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.2MPa, until the life of the catalyst was evaluated to be 92 hours at an outlet of 100mgBr/100g bromine index.
Then, the catalyst was calcined at 500 ℃ for 8 hours in an air atmosphere to regenerate the catalyst, and the lifetime of the regenerated catalyst was 89 hours under the same conditions and requirements as described above. The same was repeated four more times, and the catalyst lives were 85 hours each.
Example 6
Taking 30g of MCM-56 molecular sieve and beta molecular sieve respectively, 1220 g of ZSM-10 g of bentonite and 14g of pseudo-boehmite (the weight content contains 65 percent of alumina), adding 8g of sesbania powder, kneading, drying, roasting at 550 ℃ for 3 hours to obtain a roasted product, and performing NH reaction on the roasted product3TPD characterization gave a medium strong acid content of 0.30 mmol/g.
Taking 30g of a roasted product, adding a mixed aqueous solution of nitric acid, strontium acetate, calcium nitrate, cerium nitrate and lanthanum nitrate (the molar ratio of strontium, calcium, cerium and lanthanum is 1:1:3:3, the total weight of the oxide is 2.0g, and the nitric acid is 1.0g) into a liquid-solid ratio of 6, treating the mixture for 20 hours in a microwave oven at a set power of 200w and a temperature of 40 ℃, dropwise adding 100g of 30% 8-hydroxyquinoline solution at a dropwise adding speed of 200 g/min at a power of 1000w and a temperature of 180 ℃, and continuously drying the mixture for 8 hours at a temperature of 80 ℃ by using 1000w power of microwaves. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 80 parts of molecular sieve, 10 parts of bentonite, 9 parts of alumina and 7.4 parts of total metal oxide.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.28 mmol/g.
Reforming in an aromatic hydrocarbon combined device with a bromine index of 1500mgBr/100g in 7h-1The catalyst life evaluation reaction was carried out at a temperature of 190 ℃ under 2.8MPa, until the life of the catalyst was evaluated to be 98 hours at an outlet of 100mgBr/100g bromine index.
Then, the catalyst was calcined at 580 ℃ for 3 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 95 hours under the same conditions and requirements as described above. The same was repeated four more times, the catalyst life being 90 hours each.
Example 7
Taking 30g of beta molecular sieve, 20g of USY molecular sieve and 50g of kaolin, adding 8g of sesbania powder, kneading, drying, roasting at 550 ℃ for 3 hours to obtain a roasted product, and carrying out NH treatment on the roasted product3TPD characterization gave a medium strong acid content of 0.24 mmol/g.
Taking 50g of a roasted product, adding a mixed aqueous solution of nitric acid, copper nitrate, cerium nitrate and lanthanum nitrate (the molar ratio of strontium, calcium, cerium and lanthanum is 1:2:2, calculated by the total weight of oxides is 2.0g, and the amount of nitric acid is 1.0g) into a liquid-solid ratio of 3, treating the mixture for 0.2 hour at 120 ℃ with the set power of 1000w in a microwave oven, then dropwise adding 100g of 5% ammonia water solution at 100 ℃ with the power of 600w (the dropwise adding speed is 10 g/min), and continuously drying the mixture for 4 hours at 180 ℃ by using 800w power microwaves. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst. The main components of the catalyst are as follows: 50 parts of molecular sieve, 50 parts of kaolin and 4.3 parts of metal oxide in total.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.22 mmol/g.
Reforming in an aromatic hydrocarbon combined device with bromine index of 1200mgBr/100g in 9h-1The catalyst life evaluation reaction was carried out at a temperature of 220 ℃ under 3.6MPa, until the life of the catalyst was evaluated at 120 hours at an exit of 100mgBr/100g bromine index.
Then, the catalyst was calcined at 600 ℃ for 2 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 112 hours under the same conditions and requirements as described above. The same was repeated four more times, and the catalyst lives were 106 hours each.
Example 8
Taking 30g of beta molecular sieve, 50g of USY molecular sieve and 31.0g of pseudo-boehmite (the content of alumina is 65 percent), adding 7g of sesbania powder, kneading, drying, roasting for 3 hours at 550 ℃ to obtain a roasted product, and performing NH treatment on the roasted product3TPD characterization gave a medium strong acid content of 0.38 mmol/g.
40g of the roasted product is taken, mixed aqueous solutions of different amounts of magnesium nitrate solution containing nitric acid (1.0, 2.0, 3.0, 4.0g of nitric acid and 1.0g of magnesium oxide in terms of total weight) are respectively added into the mixed aqueous solutions under the condition of a liquid-solid ratio of 5), the mixed aqueous solutions are treated in a microwave oven at a set power of 800w and a temperature of 90 ℃ for 1 hour, 30g of 5% ammonium carbonate solution is dropwise added under the power of 600w and the temperature of 100 ℃ (the dropping speed is 10 g/min), and the drying treatment is carried out for 7 hours under the condition of 110 ℃ by continuing the microwave with the power of 800 w. Then, the reaction mixture was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain catalyst A, B, C, D. The main components of the catalyst A are as follows: 80 parts of molecular sieve, 20 parts of alumina and 2.9 parts of total metal oxide; the main components of the catalyst B are as follows: 80 parts of molecular sieve, 20 parts of alumina and 5.8 parts of total metal oxide; the main components of the catalyst C are as follows: 80 parts of molecular sieve, 20 parts of alumina and 8.7 parts of total metal oxide; the main components of the catalyst D are as follows: 80 parts of molecular sieve, 20 parts of alumina and 11.6 parts of total metal oxide.
The catalyst A is subjected to NH3TPD characterization gave a medium strong acid content of 0.37 mmol/g. Reforming in an aromatic hydrocarbon combined device with bromine index of 1000mgBr/100g in 8h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.8MPa, until the life of the catalyst was evaluated at an exit index of 100mgBr/100g of bromine for 102 hours. Then, the catalyst was calcined at 550 ℃ for 2.5 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 98 hours under the same conditions and requirements as above. The same was repeated four more times, and the catalyst lives were 96 hours each.
The catalyst B is subjected to NH3TPD characterization gave a medium strong acid content of 0.36 mmol/g. Reforming in an aromatic hydrocarbon combined device with bromine index of 1000mgBr/100g in 8h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.8MPa, until the life of the catalyst was evaluated at 108 hours at an exit of 100mgBr/100g bromine index. Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 104 hours under the same conditions and requirements as above. The same was repeated four more times, with catalyst lifetimes of 99 hours each.
The catalyst C is subjected to NH3TPD characterization gave a medium strong acid content of 0.36 mmol/g. Reforming in an aromatic hydrocarbon combined device with bromine index of 1000mgBr/100g in 8h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.8MPa, until the life of the catalyst was evaluated at 120 hours at an exit of 100mgBr/100g bromine index. Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 116 hours under the same conditions and requirements as above. The same was repeated four more times, with catalyst lifetimes of 108 hours each.
The catalyst D is passed over NH3TPD characterization gave a medium strong acid content of 0.35 mmol/g. At bromine indexIs 1000mgBr/100g of arene combined device reforming material in 8h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.8MPa, until the life of the catalyst was evaluated at 110 hours at an exit of 100mgBr/100g bromine index. Then, the catalyst was calcined at 550 ℃ for 2.5 hours in an air atmosphere to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 98 hours under the same conditions and requirements as above. The same was repeated four more times, and the catalyst lives were 102 hours each.
Comparative example 1
The procedure of example 1 was repeated, except that no microwaves were used, and equal-volume isothermal impregnation was carried out:
mixing USY molecular sieve 100g and pseudoboehmite 40g (alumina content 65%), adding sesbania powder 8g, kneading, drying, calcining at 600 deg.C for 3 hr to obtain the calcined product, and treating with NH3TPD characterization gave a medium strong acid content of 0.4 mmol/g.
10g of the roasted product is taken, added into a mixed aqueous solution of lanthanum nitrate, gallium nitrate and magnesium nitrate (the molar ratio is 1:1:1, and the total weight of oxides is 0.5g) at the liquid-solid ratio of 0.2, soaked for 2 hours at the temperature of 120 ℃, then 10g of 10 percent ammonium carbonate solution is dripped at the temperature of 120 ℃ (the dripping speed is 2 g/min), and dried for 6 hours at the temperature of 120 ℃. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.30 mmol/g.
At a bromine index of 1500mg/100g of reformate, at 18h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.9MPa, until the life of the catalyst was evaluated at a bromine index of 100mg/100g at the outlet for 65 hours.
Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 56 hours under the same conditions and requirements as described above. The catalyst life after four more iterations was 50 hours.
Comparative example 2
Mixing USY molecular sieve 100g and pseudoboehmite 40g (alumina content 65%), adding sesbania powder 8g, kneading, drying, and calcining at 600 deg.C for 3 hrWhile obtaining a calcined product which is passed over NH3TPD characterization gave a medium strong acid content of 0.4 mmol/g.
10g of the roasted product is taken, added into a mixed aqueous solution of lanthanum nitrate, zinc nitrate and magnesium nitrate (the molar ratio is 1:1:1 and the total weight of oxides is 0.5g) at the liquid-solid ratio of 0.2, soaked for 2 hours, then 10g of 10% ammonium carbonate solution is dropwise added (the dropping speed is 2 g/min), and dried for 20 hours at the temperature of 120 ℃. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.26 mmol/g.
At a bromine index of 1500mg/100g of reformate, at 18h-1The catalyst life evaluation reaction was carried out at a temperature of 180 ℃ under 1.9MPa, until the life of the catalyst was evaluated at an exit index of 100mg/100g of bromine for 62 hours.
Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the life of the regenerated catalyst was 4 hours under the same conditions and requirements as above. The catalyst life was 48 hours after four more iterations.
Comparative example 3
The procedure of example 1 was repeated except that no precipitant was added:
mixing USY molecular sieve 100g and pseudoboehmite 40g (alumina content 65%), adding sesbania powder 8g, kneading, drying, calcining at 600 deg.C for 3 hr to obtain the calcined product, and treating with NH3TPD characterization gave a medium strong acid content of 0.4 mmol/g.
10g of the roasted product is taken, added into a mixed aqueous solution of lanthanum nitrate, zinc nitrate and magnesium nitrate (the molar ratio is 1:1:1 and the total weight of oxides is 0.5g) at the liquid-solid ratio of 0.2, treated for 2 hours at the temperature of 120 ℃ in a microwave oven with the set power of 300w, and dried for 2 hours at the temperature of 100 ℃ by continuing to use microwaves with the power of 200 w. Then, the catalyst was calcined at 550 ℃ for 3 hours in an air atmosphere to obtain a catalyst.
The catalyst is passed over NH3TPD characterization gave a medium strong acid content of 0.20 mmol/g.
At a bromine index of 1500mg/100g of reformate, at 18h-11.9MPa at a temperature of 180 DEG CThe catalyst life evaluation reaction was carried out until the life of the catalyst was evaluated at an exit of 100mg/100g bromine index for 58 hours.
Then, the catalyst was calcined at 550 ℃ under an air atmosphere for 2.5 hours to regenerate the catalyst, and then the lifetime of the regenerated catalyst was 54 hours under the same conditions and requirements as described above. The catalyst life after four more iterations was 49 hours.
Claims (11)
1. The catalyst comprises a molecular sieve, a binder and a metal oxide, wherein the medium-strong acid content of the catalyst is more than 80 percent calculated by 100 percent of the medium-strong acid content of a roasted product after the molecular sieve and the binder are combined, and the medium-strong acid content is NH3TPD/Desorption peak area result meter above 350 ℃.
2. The catalyst for removing olefin from aromatic hydrocarbon according to claim 1, wherein the catalyst comprises the following components in parts by weight:
50-100 parts of molecular sieve, preferably 65-90 parts;
4.99-50 parts of binder, preferably 10-34 parts;
0.01 to 16 parts of metal oxide, preferably 0.01 to 10 parts.
3. The catalyst for removing olefins from aromatic hydrocarbons according to claim 1 or 2,
the molecular sieve is selected from at least one of Y-type molecular sieve, ZSM-5 type molecular sieve, ZSM-12 type molecular sieve, beta type molecular sieve, MCM-22 type molecular sieve and MCM-56 type molecular sieve, and is preferably selected from Y-type molecular sieve, beta type molecular sieve and MCM-22 type molecular sieve; and/or
The binder is selected from at least one of alumina, kaolin, attapulgite, bentonite, diatomite and silicon dioxide, and is preferably selected from alumina and/or silicon oxide; and/or
The metal oxide is selected from at least one oxide of Cr, Mg, Cu, Zn, Ga, rare earth metal, Sr, Ba and Bi, and is preferably selected from at least one oxide of rare earth metal, Mg and Ga.
4. The method for preparing the catalyst for removing olefin from aromatic hydrocarbon according to any one of claims 1 to 3, comprising the steps of:
step 1, mixing the components including the molecular sieve and the binder and then roasting;
step 2, placing the roasted product in the step 1 into a metal compound solution, and performing microwave treatment;
step 3, dripping a precipitator solution into the solution under microwave;
and 4, continuously utilizing the microwave to carry out drying treatment, and then roasting to obtain the catalyst.
5. The method according to claim 4, wherein the temperature of the calcination in step 1 and step 4 is 400 to 800 ℃, preferably 450 to 650 ℃.
6. The method according to claim 4, wherein in step 2, the metal compound is at least one selected from the group consisting of a metal chloride, a metal nitrate, and a metal acetate.
7. The method according to claim 4, wherein in step 2, the liquid-solid ratio of the calcined product to the metal compound solution is 0.1 to 15, preferably 1 to 7.
8. The production method according to claim 4,
in step 2 and step 3, the microwave conditions were as follows: the temperature is 40-180 ℃, the power is more than 2 w/g of roasted product, and the treatment time is 0.2-20 h; and/or
In step 4, the microwave conditions were as follows: the temperature is 40-180 ℃, the power is more than 1 w/g of roasted product, and the processing time is 0.2-20 h.
9. The production method according to any one of claims 4 to 8, wherein, in step 3,
the precipitant is selected from at least one of ammonium carbonate, ammonia, urea, 8-hydroxyquinoline and dimethylglyoxime; and/or
The concentration of the precipitant solution is 0.2-30%, preferably 0.5-15%; and/or
The dripping speed of the precipitant solution is 0.1-100 g/min, preferably 1-20 g/min.
10. The catalyst for removing olefin from aromatic hydrocarbon according to any one of claims 4 to 9.
11. Use of a catalyst according to any one of claims 1 to 3 or a catalyst according to claim 10 for the deolefination of aromatics.
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