CN112657549B - Regenerated catalyst and preparation method and application thereof - Google Patents
Regenerated catalyst and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a regenerated catalyst prepared from a burnt molecular sieve catalyst, and a preparation method and application thereof. The regenerated catalyst comprises the following components: 60 to 99.8 parts of burnt molecular sieve catalyst, 0.1 to 39.9 parts of titanium and 0.1 to 39.9 parts of zirconium. According to the invention, the burnt aromatic hydrocarbon non-hydro-dealkening molecular sieve catalyst is modified by combining the supported titanium and zirconium elements, so that the obtained regenerated catalyst has high activity and good regeneration performance, and the problems of low activity and poor regeneration performance of the regenerated industrial catalyst in the past are mainly solved.
Description
Technical Field
The invention relates to the field of aromatic hydrocarbon olefin removal catalysts, in particular to a regenerated catalyst and a preparation method and application thereof.
Background
Aromatic hydrocarbons are produced by an aromatic hydrocarbon combination device or an ethylene device and an oil refining device, and a certain amount of olefin impurities are inevitably generated in the production process of aromatic hydrocarbon raw material products. These olefinic impurities are relatively reactive in chemical nature and the presence of olefinic impurities can have a very detrimental effect on subsequent processes, particularly in aromatics complex such as xylene adsorption separation where olefins are particularly sensitive to adsorbents. After reforming, aromatics extraction, isomerization, toluene disproportionation processes, trace amounts of olefin impurities are removed.
Early aromatic hydrocarbon refining processes used clay as a deolefination catalyst. The clay has low activity, short service life, large dosage, non-regeneration, large influence on environment and high environmental protection cost. Later developed a molecular sieve olefin removal refining technology and hydrogenation technology to replace industrial clay. Although the hydrogenation technology has longer service life of the catalyst, the hydrogenation technology has the advantages of high catalyst cost in hydrogenation, high aromatic hydrocarbon loss in operation and high operation cost. Molecular sieve catalysts achieve longer single pass service life with their relatively large surface area and acid content, and are renewable. However, the catalyst needs to be regenerated in an ex-situ way after each deactivation, and needs to be removed from the reactor for regeneration, so that the activity of the molecular sieve catalyst is easy to change and even greatly reduced in the molecular sieve regeneration process. The waste can be discarded after several regenerations, and is used as a dangerous waste treatment. The Chinese patent CN102008976A, CN103041841A, CN102039160A, CN104907090A adopts molecular sieve as main active component, and the catalyst performance is improved by modifying through various methods, but the problem of activity change is not solved.
Chinese patents CN102039160a and CN102041035A describe a catalyst for removing olefins from reformate, which comprises 20-90 parts of molecular sieve and 10-80 parts of at least one material selected from SiO 2 、Al 2 O 3 Or a mixture thereof, and a catalyst containing at least one metal selected from Mo, zr and Nb or an oxide thereof, at least one element selected from Cl, br and S or an oxide thereof, and at least one element selected from F, P or an oxide thereof in terms of elements, effectively prolongs the catalyst regeneration period, but cannot be regenerated due to the inclusion of F.
The catalyst adopts the molecular sieve as a main catalytic activity source, the active center of the molecular sieve is easy to change irreversibly in the regeneration process of the molecular sieve, and the overall performance of the regenerated catalyst is reduced and cannot be controlled.
CN103041841a is formed by crushing a cracking waste catalyst and is used as a catalyst for removing olefins from reformate, but the service life of the catalyst cannot be guaranteed due to the low molecular sieve content.
CN103495435a adopts a method of impregnating lewis acid to prolong the regeneration period, but the halide must be impregnated after each regeneration to ensure the presence of the halide, and the requirement of environmental protection is high during regeneration, which is not suitable for large-scale industrial application.
At present, after the arene olefin-removing catalyst is regenerated for a plurality of times, the activity of the catalyst is greatly reduced, the single cycle life is greatly reduced, the catalyst cannot be continuously used for industrial production, and the catalyst can only be used as hazardous waste treatment.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a catalyst prepared from a burnt molecular sieve catalyst, and a preparation method and application thereof.
The invention aims to provide a regenerated catalyst which comprises the following components in parts by weight:
60 to 99.8 portions of burnt molecular sieve catalyst; preferably 70-95 parts;
0.1 to 39.9 parts of titanium; preferably 1 to 20 parts;
0.1 to 39.9 parts of zirconium; preferably 1.5 to 29 parts;
the weight parts of the components are based on 100 parts of the total weight of the components, wherein the contents of titanium and zirconium are calculated by the weight of oxides.
Wherein the molecular sieve catalyst is a catalyst taking molecular sieve as one of the active components of the catalyst or the main active components, and contains the molecular sieve; the invention preferably refers to an aromatic hydrocarbon non-hydrodeolefine molecular sieve catalyst.
The aromatic hydrocarbon non-hydrodeolefine molecular sieve can be selected from non-hydrodeolefine catalysts commonly used in industry in the field, wherein the catalyst takes the molecular sieve as an active component or one of main active components.
The aromatic hydrocarbon non-hydro-dealkenation molecular sieve can contain components such as a conventional carrier, a modified element and the like besides the molecular sieve; the content of each component is also the usual content, such as about 70wt% of molecular sieve, about 30wt% of carrier and proper amount of modifying element. Specifically, the molecular sieve can be at least one of a Y molecular sieve and MCM-22; the carrier is at least one of alumina and silicon dioxide; the modifying element may be at least one of a rare earth element and a second main group element.
According to a preferred embodiment of the present invention, the burned molecular sieve catalyst in the regenerated catalyst according to the present invention:
the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve after being burnt is less than 50 percent calculated by XRD and calculated with the standard Y-type molecular sieve as 100 percent;
the crystallinity of the molecular sieve catalyst containing the MCM-22 molecular sieve after being burnt is less than 60 percent calculated by XRD and calculated with the crystallinity of the standard MCM-22 molecular sieve as 100 percent;
the XRD calculation is calculated to be 100% of the standard Y-type molecular sieve crystallinity and the standard MCM-22 molecular sieve, wherein the sum of the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve and the MCM-22 molecular sieve after being burnt is less than 50%.
According to a preferred embodiment of the present invention, the regenerated catalyst of the present invention, wherein the pore volume of the molecular sieve catalyst after the scorch is 0.2 to 0.6cm 3 Per gram, specific surface area of 300-650 m 2 /g。
According to a preferred embodiment of the present invention, the regenerated catalyst of the present invention, wherein the acid amount of the molecular sieve catalyst after scorch is 0.6mmol/g or less, preferably 0.3 to 0.6mmol/g.
The second object of the present invention is to provide a process for preparing the regenerated catalyst.
The preparation method of the regenerated catalyst comprises the steps of burning the used molecular sieve catalyst, then carrying out alkali treatment, loading the titanium and zirconium and then roasting.
Preferably, the preparation method comprises the following steps:
(1) The used molecular sieve catalyst is burnt by an oxygen-containing gas source, and the burning temperature is 450-800 ℃, preferably 500-600 ℃;
(2) The burnt molecular sieve catalyst obtained in the step (1) is placed in an aqueous solution containing ammonia or an amino-containing compound and having a pH of 8-13 for treatment, wherein the weight ratio of liquid to solid is 0.4-15, preferably 2-10;
(3) And (3) modifying the material obtained in the step (2) by titanium and zirconium, and roasting to obtain the regenerated catalyst.
Wherein in the step (1), the heating time of the scorch is 3-6 hours, preferably 1-20 hours; the constant temperature time is 0.1 to 20 hours, preferably 1 to 5 hours.
In the step (1), after the used molecular sieve catalyst containing the Y-type molecular sieve is burnt, the crystallinity of the molecular sieve catalyst is less than 50 percent calculated by XRD and calculated to be 100 percent of the standard Y-type molecular sieve crystallinity;
the crystallinity of the used molecular sieve catalyst containing the MCM-22 molecular sieve is calculated to be 100% with the standard MCM-22 molecular sieve by XRD after the molecular sieve catalyst is burnt, and the crystallinity is below 60%;
the molecular sieve catalyst containing the Y-type molecular sieve and the MCM-22 molecular sieve after being used is burnt, and calculated by XRD, the crystallinity of the molecular sieve catalyst is calculated to be 100% with that of the standard Y-type molecular sieve and that of the standard MCM-22 molecular sieve, wherein the sum of the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve and that of the molecular sieve catalyst containing the MCM-22 molecular sieve is less than 50%.
In the invention, the crystallinity of the standard Y-type molecular sieve is measured according to the national standard SH/T0340-92.
Adopts Chinese standard: SH/T0339-92 (unit cell parameter), SH/T0340-92 (crystallinity), calculate relative crystallinity in XRD (331), (511, 333), (440), (533), (642), (862, 660), (555, 751), (664) relative crystallinity calculated by taking NaY molecular sieve as standard.
In the invention, the crystallinity of the standard MCM-22 molecular sieve is synthesized into the peak intensity contrast of 25.9-26.1 calculated as 100% according to the standard method provided by the world molecular sieve society, and the components are as followsNa 0.08 [Al 4 Si 68 O 144 ]The synthesis starting material was a commercially available analytically pure sample and the silicon source was Degussa white carbon black Aerosil 200 supplied by standard methods.
In the step (1) of the method, the pore volume of the molecular sieve catalyst after being burnt is 0.2-0.6 cm 3 /g; specific surface area of 300-650 m 2 /g；
The acid amount of the molecular sieve catalyst after the scorch is less than 0.6mmol/g, preferably 0.3-0.6 mmol/g.
In the method, the used molecular sieve catalyst is burnt, the cokes covered on the active center are burnt out, and the pore canal of the catalyst is recovered.
In the step (2), the ammonia-containing or amine-containing compound is at least one of inorganic ammonium, organic amine, amino acid, urea, such as ammonium acetate, ammonium sulfate, ammonium nitrate, propylamine, glycine, etc. The concentration of the compounds is from 0.1 to 18% by weight, preferably from 1 to 8% by weight.
In step (2), the treatment is carried out at room temperature to 190℃for 0.5 to 30 hours, preferably at room temperature to 100℃for 1 to 10 hours.
In the step (2), steps such as filtering, washing and the like can be carried out after the treatment is finished, and then drying is carried out.
In the step (3), the titanium modification mode comprises one or more of titanium salt impregnation and vapor deposition, wherein the titanium salt is preferably at least one of titanate (such as methyl titanate), titanium nitrate and titanium chloride;
the zirconium modification mode comprises one or more of zirconium salt impregnation and vapor deposition, wherein the zirconium salt is preferably at least one of zirconium sulfate, zirconium hypochlorite, zirconium nitrate, zirconyl nitrate and zirconium chloride.
In the step (3), the concentration of the solution of the titanium salt or the zirconium salt is preferably 0.1 to 12% by weight, more preferably 1 to 8% by weight. The solvent is organic solvent or water with the salt dissolving capability, such as ethanol and aliphatic hydrocarbon solvent.
In the titanium salt impregnation or zirconium salt impregnation, the impregnation temperature is preferably kept at a constant temperature of from room temperature to 100 ℃ for 1 to 20 hours, and more preferably kept at a constant temperature of from room temperature to 65 ℃ for 1 to 6 hours.
In the titanium salt impregnation or the vapor deposition treatment of the zirconium salt, the treatment is preferably carried out at a temperature of from room temperature to 600 ℃ for 0.5 to 20 hours under an inert atmosphere, and more preferably at a temperature of from 100 to 500 ℃ for 1 to 6 hours.
In the step (3), the modified elements may be dried at an elevated temperature under vacuum or under an inert atmosphere, preferably at 50 to 200 ℃ under nitrogen atmosphere for 1 to 40 hours.
In the step (3), the roasting temperature is preferably 350-800 ℃, more preferably 450-650 ℃; the calcination time is preferably 0.2 to 20 hours, more preferably 2 to 6 hours.
The invention further provides an application of the catalyst preparation method in regenerating an aromatic hydrocarbon non-hydrodeolefine molecular sieve catalyst.
The fourth purpose of the invention is to provide the catalyst prepared by the preparation method.
According to the technical scheme, through the scorching treatment and the effective modification treatment of titanium and zirconium, the uniformity of the acid strength distribution of the catalyst is better, so that the performance of the regenerated catalyst is greatly improved.
The regenerated catalyst has low preparation cost, and the prepared catalyst has better regeneration performance, thereby solving the environmental protection pressure problem of catalyst post-treatment.
The regenerated catalyst of the invention is treated for 3 hours at 700 ℃ under 100% water vapor, the catalyst is subjected to front-back comparison, the total pore volume is reduced by less than 10%, the activity evaluation service life is more than 90%, and the acid loss is less than 20%. The service life of the coked catalyst baked for 4 hours at 500 ℃ is more than 95% before the reaction.
Detailed Description
The present invention is described in detail below with reference to specific embodiments, and it should be noted that the following embodiments are only for further description of the present invention and should not be construed as limiting the scope of the present invention, and some insubstantial modifications and adjustments of the present invention by those skilled in the art from the present disclosure are still within the scope of the present invention.
Wherein the reagents other than the catalyst are commercially available (reagent grade).
The non-hydrodeolefination molecular sieve catalyst of aromatic hydrocarbon as a raw material mentioned in the detailed description of the invention is derived from an industrially used non-hydrodeolefination molecular sieve catalyst of aromatic hydrocarbon.
Method for determining catalyst composition:
si, al, ti, zr, etc.: obtained by ICP (inductively coupled plasma) analysis. ICP test conditions were: varian 700-ES series XPS instrument.
The modified content variometer load is calculated by the weight difference before and after modification. Namely, the weight of the catalyst before modification after weighing and burning (titanium and zirconium) and the weight of the catalyst obtained after modification and roasting are weighed, and the difference between the two is compared to obtain the modified weight ratio. XRF (X-ray fluorescence) or ICP methods can also be used for characterization. XRF test conditions were: rigaku ZSX 100e type XRF instrument. The method uses parts of catalyst before modification except two element oxides.
Ammonia temperature programming desorption instrument (NH) for characterizing catalyst solid acidity 3 TPD) is Tianjin pre-claim TP-5000 type multipurpose adsorption instrument. Carrier gas (N) 2 ) The flow rate is 40 mL/min -1 Keeping the temperature at 600 ℃ for 30min, cooling to 120 ℃ to keep constant, absorbing ammonia for 30min, and purging with nitrogen for 2h. The temperature rising interval is 50-600 ℃, and the temperature rising rate is 10 ℃ min -1 . Acid adsorption is then used, and then acid-base titration is used to determine the amount of acid.
Measuring specific surface and pore volume of sample by using TriStar-3000 physical adsorption instrument of Micromeritics company, N 2 As an adsorbate, the adsorption temperature was 77K and the sample was 7X 10 before testing -2 And (3) under Pa, vacuumizing and activating for more than 10 hours at 350 ℃, wherein the specific surface of the sample is calculated by a BET method, the micropore volume is calculated by an H-K method and the pore distribution is calculated by a BJH method.
Bromine index determination method of reaction product activity: the olefin content in the raw materials and the products is expressed in the form of bromine index by adopting a microcoulometric titration method.
[ example 1 ]
The used industrial Y molecular sieve catalyst for non-hydro-dealkylation of aromatic hydrocarbon is carried out at the temperature of 600℃,Heating time is 3h, and the coke is burnt at constant temperature for 5 hours. Taking a decoking industrial Y molecular sieve catalyst A (pore volume of 0.2 cm) 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.4mmol/g; crystallinity 40%) in an aqueous solution containing ammonia at pH 11 (containing 2% mass concentration of ammonium acetate); treating at the weight ratio of liquid to solid of 5 and 90 ℃ for 5 hours, filtering, washing and drying at 120 ℃ for 6 hours. 100g of the treated material was subjected to isovolumetric impregnation modification with 45.0g of an ethanol solution of methyl titanate (containing 7.5% by mass of methyl titanate) at 60℃for 6 hours. Then drying for 5 hours under nitrogen atmosphere at 200 ℃ to obtain a catalyst, then taking 70g of material, carrying out isovolumetric impregnation by adopting 35g of zirconium sulfate aqueous solution (containing 10.0% of zirconium sulfate by mass concentration), and roasting for 3 hours at 650 ℃ under other conditions which are the same as the impregnation conditions of methyl titanate to obtain the catalyst B. 5g of each catalyst A, B is taken, and the bromine index of the reformate is 1200mg/100g in 5h -1 The reaction was evaluated at a temperature of 170℃under 1.9MPa and at an outlet bromine index of 150mg/100g for 65 and 90 hours, respectively. The deactivated catalyst was repeatedly subjected to three times of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 82 hours. The catalyst composition is shown in Table 1.
[ examples 2 to 6 ]
The preparation method of the novel catalyst prepared by the used aromatic hydrocarbon olefin removal catalyst comprises the following steps:
the used industrial Y molecular sieve catalyst for removing olefin is burnt at 550 ℃ for 3 hours and at constant temperature for 3 hours. The industrial Y molecular sieve catalyst C (pore volume of 0.35 cm) for removing olefin after use after scorch is taken 3 /g; specific surface area of 520m 2 /g; the acid amount is 0.42mmol/g; crystallinity 50%) was placed in an aqueous solution containing ammonia at pH 10 (containing 4% by mass of ammonium sulfate), treated at a liquid-solid weight ratio of 4, 60 ℃ for 5 hours, filtered, washed, and dried at 100 ℃ for 9 hours. 100g of the treated material was subjected to impregnation modification with an ethanol solution of titanium chloride (titanium in terms of titanium dioxide weight content, see Table 1). Drying at 120deg.C under nitrogen atmosphere for 7 hr to obtain catalyst, and soaking with zirconyl nitrate water solution (zirconium weight content based on zirconium oxide is shown in Table 1), under other conditionsAnd (3) under the same titanium salt impregnation condition, roasting for 3 hours at 650 ℃ to obtain the catalysts D2-D6. Taking 5g of each of the catalysts C, D2-D6, and obtaining reformate with bromine index of 1200mg/100g for 10h -1 The reaction was evaluated at 1.9MPa and 180℃for a lifetime of 200mg/100g bromine index at the outlet, respectively, as shown in Table 2. The catalyst life after three regeneration (regeneration conditions: 550 ℃ C., 3 hours, air atmosphere) was repeatedly evaluated for the deactivated catalyst, and the catalyst life was as shown in Table 2. The catalyst composition is shown in Table 1 and the life results are shown in Table 2.
Examples 7 to 11
The used aromatic hydrocarbon non-hydro-dealkening industrial Y molecular sieve catalyst is burnt under the conditions of 1 (temperature 450 ℃, heating time 1h and constant temperature 20 h), 2 (temperature 500 ℃, heating time 1.5h and constant temperature 10 h), 3 (temperature 560 ℃, heating time 20h and constant temperature 0.1 h), 4 (temperature 670 ℃, heating time 8h and constant temperature 0.5 h), and 5 (temperature 780 ℃, heating time 7h and constant temperature 0.1 h). The spent de-olefination industrial Y molecular sieve catalysts E1-E5 (which are E1 (pore volume of 0.3 cm) 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.6mmol/g; crystallinity 50%), E2 (pore volume 0.35cm 3 /g; specific surface area of 630m 2 /g; the acid amount is 0.6mmol/g; crystallinity 50%) E3 (pore volume 0.6cm 3 /g; specific surface area of 450m 2 /g; the acid amount is 0.55mmol/g; crystallinity 50%), E4 (pore volume 0.5cm 3 /g; specific surface area of 400m 2 /g; the acid amount is 0.45mmol/g; crystallinity 50%), E5 (pore volume 0.2cm 3 /g; specific surface area of 300m 2 /g; the acid amount is 0.3mmol/g; crystallinity 50%). The burnt catalyst is placed in an aqueous solution containing urea with pH of 11 (urea solution with mass concentration of 6 percent); treating at 3-90 deg.c for 5 hr, filtering, washing and stoving at 100 deg.c for 10 hr. After the treatment, 100g of the material was subjected to impregnation modification with 100g of an ethanol solution of methyl titanate (titanium is shown in Table 1 in terms of titanium dioxide, the concentration of which is 1.5 times the amount to be impregnated), and the material was immersed at room temperature for 20 hours. Then drying under nitrogen atmosphere at 200deg.C for 5 hr to obtain catalyst, and collecting 70g of material, and adding 35g of zirconium sulfate aqueous solution (zirconium is oxidizedThe zirconium content by weight is shown in Table 1) was subjected to isovolumetric impregnation under the same conditions as the titanium salt impregnation, and then calcined at 550℃for 3 hours to prepare catalysts F1 to F5. Taking 5g of each catalyst, and obtaining reformate with bromine index of 1200mg/100g in 5h -1 The reaction was evaluated at 1.9MPa and at 170℃and the lifetime at 150mg/100g bromine index at the outlet, respectively, is given in Table 2. The catalyst life after three repeated evaluations of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) of the deactivated catalyst is shown in Table 2. The catalyst composition is shown in Table 1.
Examples 12 to 16
The used industrial Y molecular sieve catalyst for non-hydro-dealkylation of aromatic hydrocarbon is burnt under the condition of temperature 550 ℃ and heating time of 3h and constant temperature of 3 h. The burnt industrial Y molecular sieve catalyst G (pore volume of 0.5 cm) for removing olefin after use is taken 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.5mmol/g; crystallinity 50%), placed under condition 1 (aqueous solution containing pH 8 (containing 0.1% by mass concentration of ammonium sulfate solution); treating for 30 hours at a liquid-solid weight ratio of 0.4 and at room temperature) under conditions of 2 (aqueous solution containing pH 9 (ammonium nitrate solution containing 3% by mass); treating for 12 hours at a liquid-solid weight ratio of 2 and 50 ℃, and 3 (aqueous solution containing pH 11 (solution containing propylamine and ammonium sulfate with mass concentration of 0.1%); treating for 5 hours at a liquid-solid weight ratio of 3 and 180 ℃, and under conditions of 4 (an aqueous solution containing ammonia and having a pH of 11 (glycine solution containing 18% by mass); treating for 5 hours at a liquid-solid weight ratio of 15 and 90 ℃, and under conditions of 5 (aqueous solution containing ammonia and pH of 13 (glycine solution containing 6% mass concentration); treating for 5h at the liquid-solid weight ratio of 15 and 60 ℃, filtering, washing and drying for 10h at the temperature of 100 ℃. 100g of the treated material was subjected to impregnation modification with 150g of an ethanol solution of methyl titanate (titanium in terms of titanium dioxide, weight content is shown in Table 1, concentration thereof is 2.2 times the amount to be impregnated)) at 100℃for 2 hours. Then drying for 5 hours under nitrogen atmosphere at 200 ℃ to obtain a catalyst, then taking 70g of material, impregnating with 90g of zirconium sulfate aqueous solution (zirconium is shown in table 1 in terms of zirconium dioxide, the weight content is 1.9 times of the required impregnation amount), and roasting at 550 ℃ for 3 hours under other conditions which are the same as the titanium salt impregnation conditions to obtain the catalyst H1-H5. Taking each catalyst5g of each of the catalyst was obtained in a reformate with a bromine index of 620mg/100g for 16 hours -1 The reaction was evaluated at 1.9MPa and at 170℃and the lifetime at 20mg/100g bromine index at the outlet, respectively, is shown in Table 2. The catalyst life after three repeated evaluations of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) of the deactivated catalyst is shown in Table 2. The catalyst composition is shown in Table 1.
Examples 17 to 21
The used industrial Y molecular sieve catalyst for non-hydro-dealkylation of aromatic hydrocarbon is burnt under the condition of the temperature of 570 ℃ and the temperature rising time of 4 hours and the constant temperature of 2 hours). The industrial Y molecular sieve catalyst I (pore volume of 0.6 cm) for removing olefin after use after scorch is taken 3 /g; specific surface area of 550m 2 /g; the acid amount is 0.6mmol/g; crystallinity 50%), and is placed in an aqueous solution containing pH 10 (containing 4% by mass concentration of ammonium nitrate solution) at a liquid-solid weight ratio of 5, 90℃for 8 hours, filtered, washed, and dried at 190℃for 8 hours. 100g of the treated material was subjected to isovolumetric impregnation modification with 50g of a methyl titanate ethanol solution (titanium in terms of titanium dioxide, weight content is shown in Table 1, concentration of which is 1.0 times of the amount to be impregnated), at 30℃for 3 hours. Then drying under nitrogen atmosphere at 120 ℃ for 12 hours to obtain a catalyst, then taking 70g of the catalyst, carrying out isovolumetric impregnation on the 70g of the catalyst by adopting 35g of zirconium hypochlorite aqueous solution (zirconium is calculated by zirconium dioxide, the weight content is shown in table 1, and the concentration is 1.0 times of the required impregnation amount), and carrying out other conditions under the same titanium salt impregnation conditions, and then preparing the catalysts J1-J5 under the conditions of respectively 1 (roasting at 350 ℃ for 20 hours), 2 (roasting at 500 ℃ for 8 hours), 3 (roasting at 600 ℃ for 4 hours), 4 (roasting at 700 ℃ for 2 hours) and 5 (roasting at 800 ℃ for 0.5 hours). Taking 5g of each catalyst, and adding an aromatic hydrocarbon carbon octaisomeride material with bromine index of 300mg/100g into the catalyst for 28h -1 The reaction was evaluated at 1.9MPa and at 170℃and the lifetime at 20mg/100g bromine index at the outlet, respectively, is shown in Table 2. The catalyst life after three repeated evaluations of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) of the deactivated catalyst is shown in Table 2. The catalyst composition is shown in Table 1.
Examples 22 to 26
The used industrial Y molecular sieve catalyst for non-hydro-dealkening of aromatic hydrocarbon is carried outThe scorching condition is that the temperature is 550 ℃, the temperature rising time is 6 hours, and the constant temperature is 2 hours). Industrial Y molecular sieve catalyst K I (pore volume of 0.4 cm) for removing olefin after use after scorch 3 /g; specific surface area of 650m 2 /g; the acid amount is 0.6mmol/g; crystallinity 50%). Respectively adopting titanium chloride and zirconium chloride (the weight content of titanium is shown in table 1 in terms of titanium dioxide, and the weight content of zirconium is shown in table 1 in terms of zirconium oxide) to carry out vapor deposition treatment at 400 ℃ and 550 ℃ respectively under nitrogen in an inert atmosphere; then, the mixture was calcined at 550℃for 2 hours to prepare catalysts L1-L2. Respectively adopting titanium chloride and zirconium chloride (the weight content of titanium is shown in table 1 in terms of titanium dioxide, and the weight content of zirconium is shown in table 1 in terms of zirconium oxide) to carry out vapor deposition treatment under nitrogen in an inert atmosphere at 400 ℃; then roasting for 3 hours under the water vapor treatment at 200, 350 and 600 ℃ and finally roasting for 4 hours at 550 ℃ to obtain the catalyst L3-L5. Taking 5g of each catalyst, extracting oil from aromatic hydrocarbon with bromine index of 500mg/100g for 15h -1 The reaction was evaluated at 1.9MPa and at 170℃and the lifetime at 50mg/100g bromine index at the outlet, respectively, is shown in Table 2. The catalyst life after three repeated evaluations of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) of the deactivated catalyst is shown in Table 2. The catalyst composition is shown in Table 1.
[ example 27 ]
The used aromatic hydrocarbon non-hydro-dealkening MCM-22 molecular sieve catalyst is burnt at the temperature of 600 ℃ for 3 hours and the constant temperature of 5 hours. Taking a dealkened MCM-22 molecular sieve catalyst M (pore volume of 0.4 cm) after being burnt 3 /g; specific surface area of 630m 2 /g; the acid amount is 0.5mmol/g, the crystallinity is 40%) is put into an aqueous solution (containing 2% mass concentration of ammonium acetate) with ammonia pH of 11; treating at the weight ratio of liquid to solid of 5 and 90 ℃ for 5 hours, filtering, washing and drying at 120 ℃ for 6 hours. 100g of the treated material was subjected to isovolumetric impregnation modification with 45.0g of an ethanol solution of methyl titanate (7.5% by mass concentration of methyl titanate) at 60℃for 6 hours. Drying at 200deg.C under nitrogen atmosphere for 5 hr to obtain catalyst, soaking 70g of the catalyst in 35g of zirconium sulfate aqueous solution (10.0% zirconium sulfate) under the same volume as methyl titanate soaking conditions, and calcining at 650deg.CCatalyst N was obtained 3 hours. 5g of each catalyst M, N is taken, and the bromine index of the catalyst is 200mg/100g of carbon octaarene material is taken for 32 hours -1 The reaction was evaluated at a temperature of 170℃under 1.9MPa and at an outlet bromine index of 20mg/100g for 66 and 103 hours, respectively. The deactivated catalyst was repeatedly subjected to three regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 95 hours. The catalyst composition is shown in Table 1 and the evaluation data is shown in Table 2.
[ example 28 ]
The used arene non-hydro-dealkened MCM-22 molecular sieve and USY molecular sieve catalyst (the content ratio of the MCM-22 molecular sieve to the USY content is 1:2) are burnt at the temperature of 600 ℃ for 3h and at the constant temperature of 5 hours. Mixing the burnt olefin-removed molecular sieve catalyst 1 (pore volume of 0.5 cm) 3 /g; specific surface area of 550m 2 /g; the acid amount was 0.4mmol/g and the crystallinity was 40%) was placed in an aqueous solution containing ammonia at pH 11 (containing 2% by mass of ammonium carbonate); treating at the weight ratio of liquid to solid of 5 and 90 ℃ for 5 hours, filtering, washing and drying at 120 ℃ for 6 hours. 100g of the treated material was subjected to impregnation modification with 35.0g of an ethanol solution of methyl titanate (9.6% by mass concentration of methyl titanate) at 90℃for 3 hours. Then drying for 4 hours at 1500 ℃ under nitrogen atmosphere to obtain a catalyst, then taking 70g of material, impregnating with 32g of zirconium sulfate aqueous solution (10.9% zirconium sulfate by mass concentration), and roasting for 3 hours at 650 ℃ under other conditions similar to the methyl titanate impregnating condition to obtain a new catalyst mixture 1. Taking 5g of catalyst, reforming into oil material with bromine index of 600mg/100g for 15h -1 The reaction was evaluated at a temperature of 180℃under 1.9MPa, respectively, and at an outlet bromine index of 100mg/100g, the evaluation time was 90 hours, respectively. The deactivated catalyst was repeatedly subjected to three regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 86 hours.
The used arene non-hydro-dealkened MCM-22 molecular sieve and USY molecular sieve catalyst (the content ratio of the MCM-22 molecular sieve to the USY is 2:1) are burnt at the temperature of 600 ℃ for 3h and at the constant temperature of 5 hours. Mixing the burnt olefin-removed molecular sieve catalyst with 2 (pore volume of 0.55 cm) 3 /g; specific surface area of 500m 2 /g; the catalyst mixture 2 obtained by treating the catalyst mixture with an acid amount of 0.35mmol/g and a crystallinity of 45%) in the same manner as described above was evaluated by the same method. Taking 5g of catalyst, reforming into oil material with bromine index of 1200mg/100g for 10h -1 The reaction was evaluated at a temperature of 180℃under 1.9MPa, respectively, and at an outlet bromine index of 150mg/100g, the evaluation time was 98 hours, respectively. The deactivated catalyst was repeatedly subjected to three regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 89 hours.
Comparative example 1
The used non-hydrodeolefine industrial Y molecular sieve catalyst (the same as the non-hydrodeolefine industrial Y molecular sieve catalyst of the aromatic hydrocarbon in example 1) is burnt at 600 ℃ for 3h and 5h at constant temperature. Taking a decoking industrial Y molecular sieve catalyst A (pore volume of 0.2 cm) 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.4mmol/g; crystallinity 40%) was placed in an aqueous solution containing ammonia at pH 11 (containing 2% mass concentration of ammonium acetate) and treated at a liquid-to-solid weight ratio of 5, 90 ℃ for 5h. Filtering, washing and drying at 120 ℃ for 6 hours. 100g of the treated material was subjected to isovolumetric impregnation modification with 45.0g of an ethanol solution of methyl titanate (7.5% by mass concentration of methyl titanate) at 60℃for 6 hours. Then dried under nitrogen atmosphere at 200℃for 5 hours and then calcined at 650℃for 3 hours to give catalyst B1. Taking 5g of catalyst B1 and reformate with bromine index of 1200mg/100g for 5h -1 The reaction was evaluated at a temperature of 170℃under 1.9MPa and at an outlet bromine index of 150mg/100g for 65 and 66 hours, respectively. The deactivated catalyst was repeatedly subjected to three regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 63 hours. The catalyst composition is shown in Table 1.
Comparative example 2
The used non-hydrodeolefine industrial Y molecular sieve catalyst (the same as the non-hydrodeolefine industrial Y molecular sieve catalyst of the aromatic hydrocarbon in example 1) is burnt at 600 ℃ for 3h and 5h at constant temperature. Taking a decoking industrial Y molecular sieve catalyst A (pore volume of 0.2 cm) 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.4mmol/g; crystallinity 40%) in an aqueous solution containing ammonia at pH 11 (containing 2% mass concentration of ammonium acetate); treating at a liquid-solid weight ratio of 5 and 90 ℃ for 5 hours. Filtering, washing and drying at 120 ℃ for 6 hours. 70g of the treated material was subjected to isovolumetric impregnation with 35g of an aqueous zirconium sulfate solution (10.0% by mass of zirconium sulfate) at 60℃for 6 hours. Then dried under nitrogen atmosphere at 200℃for 5 hours and then calcined at 650℃for 3 hours to give catalyst B2. Taking 5g of the catalyst, and adding reformate with bromine index of 1200mg/100g for 5h -1 The reaction was evaluated at a temperature of 170℃under 1.9MPa and at an outlet bromine index of 150mg/100g for 65 and 68 hours, respectively. The deactivated catalyst was repeatedly subjected to three regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 66 hours. The catalyst composition is shown in Table 1 and the evaluation data is shown in Table 2.
[ comparative example 3 ]
The used non-hydrodeolefine industrial Y molecular sieve catalyst (the same as the non-hydrodeolefine industrial Y molecular sieve catalyst of the aromatic hydrocarbon in example 1) is burnt at 600 ℃ for 3h and 5h at constant temperature. 100g of a coked deolefinated industrial Y molecular sieve catalyst A (pore volume of 0.2 cm) was taken 3 /g; specific surface area of 500m 2 /g; the acid amount is 0.4mmol/g; crystallinity 40%) was modified by isovolumetric infusion using 45.0g of an ethanol solution of methyl titanate (7.5% strength by mass methyl titanate) and immersed at 60℃for 6 hours. Then drying for 5 hours at 200 ℃ under nitrogen atmosphere to obtain a catalyst, then taking 70g of material, carrying out isovolumetric impregnation by adopting 35g of zirconium sulfate aqueous solution (10.0% zirconium sulfate by mass concentration), and roasting for 3 hours at 650 ℃ under other conditions which are the same as the methyl titanate impregnation conditions to obtain a catalyst B3. Taking reformate with the weight of catalyst B3 of 5g and bromine index of 1200mg/100g for 5h -1 The reaction was evaluated at a temperature of 170℃under 1.9MPa and at an outlet bromine index of 150mg/100g for 65 and 72 hours, respectively. The deactivated catalyst was repeatedly subjected to three times of regeneration (regeneration conditions: 600 ℃ C., 2 hours, air atmosphere) and the catalyst life was 65 hours. The catalyst composition is shown in Table 1 and the evaluation data is shown in Table 2.
Table 1 catalyst compositions (content in parts by weight) prepared in examples and comparative examples
Table 2 performance results for the operation of the example catalysts
| Project | Catalyst | Life, h | Catalyst | Life, h | Life after three regenerations, h |
| Example 1 | A | 65 | B | 90 | 82 |
| Example 2 | C | 40 | D2 | 70 | 64 |
| Example 3 | C | 40 | D3 | 50 | 47 |
| Example 4 | C | 40 | D4 | 49 | 46 |
| Example 5 | C | 40 | D5 | 72 | 65 |
| Example 6 | C | 40 | D6 | 70 | 65 |
| Example 7 | E1 | 69 | F1 | 98 | 91 |
| Example 8 | E2 | 65 | F2 | 102 | 97 |
| Example 9 | E3 | 63 | F3 | 107 | 96 |
| Example 10 | E4 | 60 | F4 | 98 | 92 |
| Example 11 | E5 | 40 | F5 | 90 | 85 |
| Example 12 | G | 63 | H1 | 103 | 95 |
| Example 13 | G | 63 | H2 | 102 | 94 |
| Example 14 | G | 63 | H3 | 100 | 94 |
| Example 15 | G | 63 | H4 | 102 | 93 |
| Example 16 | G | 63 | H5 | 103 | 92 |
| Example 17 | I | 65 | J1 | 102 | 90 |
| Example 18 | I | 65 | J2 | 101 | 91 |
| Example 19 | I | 65 | J3 | 100 | 93 |
| Example 20 | I | 65 | J4 | 101 | 92 |
| Example 21 | I | 65 | J5 | 99 | 90 |
| Example 22 | K | 63 | L1 | 98 | 94 |
| Example 23 | K | 63 | L2 | 98 | 93 |
| Example 24 | K | 63 | L3 | 99 | 95 |
| Example 25 | K | 63 | L4 | 97 | 93 |
| Example 26 | K | 63 | L5 | 98 | 93 |
| Example 27 | M | 66 | N | 103 | 95 |
| Example 28 | Mix 1 | 67 | Mix 1 | 90 | 86 |
| Example 28 | Mix 2 | 67 | Mix 2 | 98 | 89 |
| Comparative example 1 | A | 65 | B1 | 66 | 63 |
| Comparative example 2 | A | 65 | B2 | 68 | 66 |
| Comparative example 3 | A | 65 | B3 | 72 | 65 |
Claims (22)
1. The regenerated catalyst comprises the following components in parts by weight:
60-99.8 parts of burnt molecular sieve catalyst;
0.1-39.9 parts of titanium;
0.1-39.9 parts of zirconium;
the molecular sieve catalyst comprises a molecular sieve, and the molecular sieve comprises at least one of a Y-type molecular sieve and MCM-22;
wherein the titanium and zirconium content is calculated as their oxide weight;
the regenerated catalyst is prepared by the following steps: burning the used molecular sieve catalyst, then carrying out alkali treatment, loading the titanium and zirconium, and then roasting;
the pore volume of the molecular sieve catalyst after the scorching is 0.2-0.6 cm 3 Per gram, a specific surface area of 300 to 650m 2 /g; the acid amount of the burnt molecular sieve catalyst is below 0.6mmol/g; the base is an ammonia-containing or amine-containing compound.
2. The regenerated catalyst according to claim 1, characterized in that:
70-95 parts of a burnt molecular sieve catalyst;
1-20 parts of titanium;
1.5-29 parts of zirconium.
3. The regenerated catalyst according to claim 1, characterized in that:
the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve after being burnt is less than 50 percent calculated by XRD and calculated with the standard Y-type molecular sieve as 100 percent;
the crystallinity of the molecular sieve catalyst containing the MCM-22 molecular sieve after being burnt is less than 60 percent calculated by XRD and calculated with the crystallinity of the standard MCM-22 molecular sieve as 100 percent;
the XRD calculation is calculated to be 100% of the standard Y-type molecular sieve crystallinity and the standard MCM-22 molecular sieve, wherein the sum of the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve and the MCM-22 molecular sieve after being burnt is less than 50%.
4. The regenerated catalyst according to claim 1, characterized in that:
the acid amount of the burnt molecular sieve catalyst is 0.3-0.6 mmol/g.
5. A method for producing a regenerated catalyst according to any one of claims 1 to 4, comprising the steps of burning a used molecular sieve catalyst, then alkali-treating, and post-calcining the supported titanium and zirconium.
6. The preparation method according to claim 5, characterized by comprising the steps of:
(1) The used molecular sieve catalyst is burnt by an oxygen-containing source, and the burning temperature is 450-800 ℃;
(2) Placing the burnt molecular sieve catalyst obtained in the step (1) into an aqueous solution containing ammonia or an amino-containing compound and having a pH of 8-13 for treatment, wherein the weight ratio of liquid to solid is 0.4-15;
(3) And (3) modifying the material obtained in the step (2) by titanium and zirconium, and roasting to obtain the regenerated catalyst.
7. The preparation method according to claim 6, characterized by comprising the steps of:
the scorching temperature is 500-600 ℃;
the weight ratio of liquid to solid is 2-10.
8. The method for producing a catalyst according to claim 6 or 7, characterized in that:
in the step (1), the crystallinity of the used molecular sieve catalyst containing the Y-type molecular sieve is calculated to be 100% with the standard Y-type molecular sieve by XRD after being burnt, and the crystallinity is below 50%;
the crystallinity of the used molecular sieve catalyst containing the MCM-22 molecular sieve is calculated to be 100% with the standard MCM-22 molecular sieve by XRD after the molecular sieve catalyst is burnt, and the crystallinity is below 60%;
the molecular sieve catalyst containing the Y-type molecular sieve and the MCM-22 molecular sieve after being used is burnt, and calculated by XRD, the crystallinity of the molecular sieve catalyst is calculated to be 100% with that of the standard Y-type molecular sieve and that of the standard MCM-22 molecular sieve, wherein the sum of the crystallinity of the molecular sieve catalyst containing the Y-type molecular sieve and that of the molecular sieve catalyst containing the MCM-22 molecular sieve is less than 50%.
9. The method for preparing a catalyst according to claim 5 or 6, characterized in that:
the pore volume of the molecular sieve catalyst after the scorching is 0.2-0.6 cm 3 Per gram, a specific surface area of 300 to 650m 2 /g; and/or the number of the groups of groups,
the acid amount of the molecular sieve catalyst after the scorch is below 0.6mmol/g.
10. The method for preparing a catalyst according to claim 9, wherein:
the acid amount of the burnt molecular sieve catalyst is 0.3-0.6 mmol/g.
11. The method for preparing a catalyst according to claim 6, wherein:
in the step (1), the heating time of the coke is 3-6 hours; the constant temperature time is 0.1-20 h.
12. The method for preparing a catalyst according to claim 11, wherein:
the heating time of the burning is 1-20 h; the constant temperature time is 1-5 h.
13. The method for preparing a catalyst according to claim 6, wherein:
in the step (2), the ammonia-containing or amine-containing compound is at least one of inorganic ammonium, organic amine, amino acid and urea; the concentration of the compound is 0.1-18wt%.
14. The method for preparing a catalyst according to claim 13, wherein:
the concentration of the compound is 1-8wt%.
15. The method for preparing a catalyst according to claim 6, wherein:
in the step (2), the treatment is carried out for 0.5 to 30 hours at the temperature of between room temperature and 190 ℃.
16. The method for preparing a catalyst according to claim 15, wherein:
and (3) treating for 1-10 h at the room temperature to 100 ℃.
17. The method for preparing a catalyst according to claim 6, wherein:
in the step (3), the titanium modification mode comprises one or more of titanium salt impregnation and vapor deposition;
the zirconium modification mode comprises one or more of zirconium salt impregnation and vapor deposition.
18. The method for preparing a catalyst according to claim 17, wherein:
the titanium salt is at least one selected from titanate, titanium nitrate and titanium chloride;
the zirconium salt is at least one selected from zirconium sulfate, zirconium hypochlorite, zirconium nitrate, zirconyl nitrate and zirconium chloride.
19. The method for preparing a catalyst according to claim 6, wherein:
in the step (3), the roasting temperature is 350-800 ℃; and/or the number of the groups of groups,
in the step (3), the roasting time is 0.2-20 h.
20. The method for preparing a catalyst according to claim 19, wherein:
the roasting temperature is 450-650 ℃; and/or the number of the groups of groups,
the roasting time is 2-6 hours.
21. Use of the catalyst prepared by the method of any one of claims 5 to 20 in a non-hydrodeolefination reaction of regenerated aromatic hydrocarbons.
22. A catalyst prepared by the method of any one of claims 5-20.
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