CN109701623B - Hydroisomerization catalyst and hydrotreating method of hydrocracking tail oil - Google Patents
Hydroisomerization catalyst and hydrotreating method of hydrocracking tail oil Download PDFInfo
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Abstract
The invention relates to the field of hydrotreatment of hydrocracking tail oil, in particular to a hydroisomerization catalyst, a preparation method thereof and a hydrotreatment method of hydrocracking tail oil. The catalyst contains two ten-membered ring silicon-aluminum molecular sieves, wherein at least one ten-membered ring silicon-aluminum molecular sieve has the following characteristics: the molar ratio of silicon oxide to aluminum oxide is 120-300; contains a mesoporous structure and has a closed hysteresis loop at a low-temperature nitrogen adsorption-desorption curve P/P0-0.4-0.99, and the starting position of the closed hysteresis loop is at a position P/P0-0.4-0.7. The hydroisomerization catalyst provided by the invention is used for carrying out hydrotreating on hydrocracking tail oil, and the obtained target product has the advantages of higher viscosity index, lower pour point and higher yield.
Description
Technical Field
The invention relates to the field of hydrotreatment of hydrocracking tail oil, in particular to a hydroisomerization catalyst and a hydrotreatment method of hydrocracking tail oil.
Background
The molecular sieve material has high acidity and high specific surface area, and is an excellent acidic catalyst. Meanwhile, the molecular sieve material has strong chemical stability and hydrothermal stability, and is difficult to be corroded and dissolved by reactants to be damaged. Compared with the commonly used homogeneous catalyst, the molecular sieve material catalyst can be directly recycled without separation, and simultaneously, the environmental pollution and the product pollution are avoided. The specific surface area and other pore structure parameters of the molecular sieve material have important influence on the catalytic performance of the molecular sieve, so that the preparation of the molecular sieve with special pores is an important research direction in the chemical field.
CN104353484A discloses a preparation method of a cheap strong-acid hierarchical pore Beta zeolite, relating to a preparation method of a hierarchical pore Beta zeolite. The invention aims to solve the problem of acidity weakening of the existing desilication post-treatment hierarchical pore Beta zeolite molecular sieve. The method comprises the following steps: (1) calcining Beta zeolite to obtain microporous hydrogen type Beta zeolite; (2) adding the microporous hydrogen type Beta zeolite into an alkaline solution, stirring, washing and drying to obtain sodium type desiliconized hierarchical porous Beta zeolite; (3) adding the sodium desiliconized hierarchical pore Beta zeolite into an ammonium nitrate aqueous solution for exchange, and calcining to obtain hydrogen desiliconized hierarchical pore Beta zeolite; (4) and (3) adding the hydrogen-type desiliconized hierarchical pore Beta zeolite into an acid solution, stirring, washing, drying, and then repeating the step (3) to obtain the strong-acid hierarchical pore Beta zeolite.
CN103073020A discloses a hierarchical pore zeolite molecular sieve and a preparation method and application thereof. The preparation method specifically comprises the following steps: the method for preparing the hierarchical zeolite molecular sieve by assembling silanized zeolite seed crystals under hydrothermal conditions by using a cationic surfactant as a template. The method overcomes the problem that the multistage pore zeolite cannot be prepared due to the mismatching between the conventional cationic surfactant and the zeolite template. The prepared material realizes the composition of micropores and mesopores, and is a highly crystallized multi-level pore channel zeolite molecular sieve. In the method, substantially, organosilane is grafted to a seed crystal by utilizing a specific functional group reaction, and is matched with a cationic surfactant to prepare a mesoporous molecular sieve, wherein mesopores are formed by guiding the cationic surfactant, and the mesopores with the aperture of about 2.4nm are formed by utilizing the hard template action of the organosilane. The seed crystal selected in the invention is microporous molecular sieve, which is added into a preparation system after silanization, the hydrophobic property of the seed crystal is utilized to increase the effect of the seed crystal on the hydrophobic end of a surfactant micelle so as to reduce the interaction between two guiding agents, but the formed mesopores still do not have a regular structure, and whether the addition of the seed crystal reduces the dosage of a template agent is not reported.
CN104891526A discloses a preparation method of a mesoporous molecular sieve with high hydrothermal stability. The method comprises the following steps: (1) preparing a first Y-type molecular sieve precursor: (2) and (3) crystallization: adding seed crystals into a first Y-type molecular sieve precursor, adjusting the pH value to 0.5-5, stirring at 20-50 ℃ for 10-24 h, aging at 20-50 ℃ for 2-24 h to obtain an assembled product, transferring the assembled product into a microreactor with a polytetrafluoroethylene lining, transferring the assembled product and the reactor into an autoclave, crystallizing at 100-200 ℃ for 10-48 h, filtering, washing and drying to obtain the high-stability mesoporous molecular sieve. Firstly, a precursor of the microporous molecular sieve is prepared, the mesoporous-microporous molecular sieve is used for preparing the mesoporous molecular sieve as a seed crystal, two methods of molecular sieve precursor assembly and seed crystal are combined, and the mesoporous molecular sieve with high stability is obtained under the condition of not using an organic template agent. Not only greatly reduces the preparation cost of the molecular sieve, but also saves the process of calcining the template agent and reduces the energy consumption.
CN102050459A discloses a method for preparing a high-silicon molecular sieve, wherein the method comprises flowing the molecular sieve with an inert carrier gas under the carrying of the inert carrier gas flow, and mixing with gas-phase SiCl4Contacting molecular sieve with gas-phase SiCl in a flowing state4The contact time of (a) is from 10 seconds to 100 minutes. The method for preparing the high-silicon molecular sieve can realize the molecular sieve and SiCl4The contact reaction of (2) is continuously carried out, and the molecular sieve and SiCl can be controlled by controlling the flow rate of the carrier gas and the length of the tubular reactor4The time of contact, thereby enabling the molecular sieve to be contacted with SiCl4The contact reaction of (2) is sufficiently carried out in the tubular reactor.
CN1703490A discloses a catalyst combination method for producing lube base oil. The invention relates to a process for converting waxes containing heavy components to high quality lube basestocks by using a linear mesoporous molecular sieve having a near circular pore structure with an average diameter of 0.50nm to 0.65nm, wherein the difference between the maximum and minimum diameters is 0.05nm or less, followed by a molecular sieve beta zeolite catalyst. Both catalysts comprise one or more group VIII metals. For example, a cascaded two-bed catalyst system consisting of a first bed Pt/ZSM-48 catalyst followed by a second bed Pt/beta catalyst facilitates the treatment of heavy lube oils.
CN1803998A discloses a dewaxing catalyst containing a composite molecular sieve, which contains a molecular sieve with a one-dimensional mesoporous structure and a molecular sieve with a macroporous structure, wherein the weight ratio of the molecular sieve with the one-dimensional mesoporous structure to the molecular sieve with the macroporous structure is 80-99: 1-20, the molecular sieve with the macroporous structure contains non-framework silicon, and the content of the silicon is 1-20 wt% calculated by oxide and based on the molecular sieve.
Disclosure of Invention
The invention aims to provide a hydroisomerization catalyst and a hydrotreating method of hydrocracking tail oil.
The invention provides a hydroisomerization catalyst, which contains two ten-membered ring silicon-aluminum molecular sieves, wherein at least one ten-membered ring silicon-aluminum molecular sieve has the following characteristics: the molar ratio of silicon oxide to aluminum oxide is 120-300; contains a mesoporous structure and has a closed hysteresis loop at a low-temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the starting position of the closed hysteresis loop is at P/P0= 0.4-0.7.
The invention also provides a hydrotreating method of hydrocracking tail oil, which comprises the following steps: under the condition of hydroisomerization reaction, contacting hydrocracking tail oil with a catalyst for reaction, wherein the catalyst is the hydroisomerization catalyst.
In the hydroisomerization catalyst, two ten-membered ring silica-alumina molecular sieves (particularly a ZSM-22 molecular sieve and a ZSM-48 molecular sieve) are combined for use, and at least one of the two molecular sieves has special physicochemical properties, so that the catalyst can obtain a remarkably good pour point depression effect when being applied to a hydrotreating production process of hydrocracking tail oil, and an obtained target product has a high viscosity index, a low pour point and a high yield.
Detailed Description
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The hydroisomerization catalyst contains two ten-membered ring silicon-aluminum molecular sieves. At least one ten-membered ring silicoaluminophosphate molecular sieve has the characteristics of high silicon and containing mesopores. Preferably, both of the ten-membered ring aluminosilicate molecular sieves have the characteristics of high silicon content and mesoporous content.
Preferably, the ten-membered ring molecular sieve has a high silicon content. Ten-membered ring molecular sieves prepared according to methods conventional in the art typically have a silica to alumina mole ratio of less than 100. The ten-membered ring molecular sieve of the present invention has a silica/alumina molar ratio of 120 to 300, and specifically, may have any value in a range of, for example, 120, 130, 140, 150, 160, 170, 180, 190, 200, 210, 220, 230, 240, 250, 260, 270, 280, 290, 300, or any two of these values. Preferably, the ten-membered ring molecular sieve has a silica/alumina molar ratio of 150 to 200.
Preferably, the ten-membered ring molecular sieve of the present invention has a mesoporous structure. The ten-membered ring molecular sieves prepared according to conventional methods in the art are generally microporous molecular sieves and do not contain a mesoporous structure. On the low temperature nitrogen adsorption-desorption curve of the ten-membered ring molecular sieve of the present invention, the adsorption branch and desorption branch show a closed hysteresis loop at P/P0=0.4-0.99, and the start position of the closed hysteresis loop is at P/P0=0.4-0.7, whereas the ten-membered ring molecular sieve prepared by the prior art does not have this feature, i.e., no hysteresis loop or the start position of the hysteresis loop appears at higher partial pressure in this interval (typically at P/P0> 0.7). Preferably, the start position of the closed hysteresis loop is at P/P0= 0.4-0.6.
Preferably, the ten-membered ring molecular sieve is characterized by a nitrogen adsorption BET (Brunner-Emmet-Teller) method, the mesoporous area in the molecular sieve can be 50m 2/g-250 m2/g, the specific surface area of the molecular sieve can be 150m 2/g-400 m2/g, and the proportion of the mesoporous area to the specific surface area can be 20-70%, preferably 25-65%.
Preferably, the precursors of the ten-membered ring molecular sieves of the present invention are enriched in penta-coordinated aluminum, while the finished molecular sieve contains little to no penta-coordinated aluminum. Specifically, the content of the penta-coordinated aluminum in the precursor of the ten-membered ring molecular sieve is 4 to 30% by weight, preferably 10 to 30% by weight; and the penta-coordinated aluminum content in the finished molecular sieve is 3% by weight or less, preferably 2.5% by weight or less, more preferably 2% by weight or less, even more preferably 1.5% by weight or less, even more preferably 0.5% by weight or less, and most preferably no penta-coordinated aluminum is contained.
Generally, the preparation of the aluminum-containing molecular sieve can be divided into steps of colloid formation, crystallization, post-treatment and the like. In order to obtain a ten-membered ring molecular sieve having high silicon content and containing mesopores, a post-treatment step in the synthesis process of the aluminum-containing molecular sieve needs to be specially treated. Preferably, the ten-membered ring molecular sieve is prepared according to the following steps:
(1) filtering the crystallized mother liquor to form a filter cake with the dry basis content of 5-30 wt%;
(2) directly roasting the filter cake to obtain a molecular sieve precursor;
(3) subjecting the molecular sieve precursor to a hydrothermal treatment;
(4) and filtering, washing and drying the hydrothermal treatment product.
In the step (1), the mother liquor after crystallization is filtered for the purpose of removing the synthesis mother liquor. The invention is particularly limited with respect to the dry content of the filter cake formed by filtration. In particular, the filter cake has a dry content of 5 to 30% by weight, preferably 6 to 15% by weight. When the dry basis content in the filter cake is out of the above range, the physicochemical properties of the prepared molecular sieve are out of the range defined by the present invention. In the present invention, "dry basis" is defined as: the mass percentage of the material after roasting at 600 ℃ for 4 hours to the mass of the material before roasting.
In the step (2), the filter cake formed in the step (1) is directly roasted at a high temperature without being dried. In the present invention, the temperature of the calcination may be 400-600 ℃, preferably 450-550 ℃. The heating rate during the calcination may be 10 to 100 ℃/min, preferably 20 to 50 ℃/min. The calcination time may be 1 to 12 hours, preferably 2 to 6 hours. The roasting environment can be a natural environment, namely oxygen-containing gas is not required to be specially introduced during roasting. Even if the calcination is carried out in the natural environment, the water in the filter cake can oxidize the template agent and can react with the aluminum in the molecular sieve to form non-framework aluminum. In particular, the product treated by step (2) in the present invention (i.e., the molecular sieve precursor) contains a significant amount of penta-coordinated non-framework aluminum (i.e., penta-coordinated aluminum). The penta-coordinated non-framework aluminum is defined as a peak having a chemical shift, Sigma, of 15 to 40ppm in a 27Al NMR spectrum. 27Al NMR spectroscopic measurement conditions can be found in publications such as Guoling Zhao et Al, Applied Catalysis A: General 299 (2006) 167-.
In the present invention, the amount of penta-coordinated aluminum in the product treated in step (2) (i.e., the molecular sieve precursor) is from 40 to 80% by weight, preferably from 50 to 70% by weight; in the step (2), the sample after the roasting treatment can be naturally cooled, and the target temperature is preferably room temperature.
In step (3), the medium for the hydrothermal treatment is preferably acidic water. In the present invention, the acidic water refers to a H2O solution containing H +. Among them, H2O is a liquid substance called "water" obtained by a conventional method. H + is ions released by the dissociation of organic acid and/or inorganic acid. To obtain the acidic water, at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid and malic acid, preferably hydrochloric acid and/or citric acid, may be added to the "water". The content of the inorganic acid and/or the organic acid in the acidic water may be 0.1 to 5M, preferably 0.2 to 2M.
In step (3), the liquid-solid volume ratio of the hydrothermal treatment may be 5 to 200, preferably 20 to 100; in the step (3), the temperature of the hydrothermal treatment can be 100-300 ℃, and preferably 100-200 ℃; in the step (3), the hydrothermal treatment may be performed for 0.5 to 24 hours, preferably for 1 to 12 hours, and more preferably for 1 to 4 hours; in step (3), the hydrothermal treatment is preferably carried out in a closed vessel, and the pressure of the hydrothermal treatment is preferably the autogenous pressure of the closed vessel under hydrothermal conditions.
In the step (4), the molecular sieve is required to be filtered and washed after being treated in the step (3). Among them, the filtration method may be a method known to those skilled in the art. The washing process can be water washing with deionized water, and the water washing is completed until the pH value of the filtrate is 6-8, preferably 6-7. The pH measurement of the solution may be performed using pH paper or a pH meter, and the measurement method is well known to those skilled in the art.
In the step (4), the drying treatment of the molecular sieve is not particularly limited, and may be carried out, for example, by drying at 120 ℃ for 6 hours in accordance with a conventional method.
In the present invention, the mother liquid after crystallization can be prepared according to the conventional method in the art, for example, when the ten-membered ring aluminosilicate molecular sieve is ZSM-22 molecular sieve, the mother liquid after crystallization can be prepared according to the method disclosed in the document O.Muraza et al, Microporous and Mesoporous Materials 206 (2015) 136-143. In one embodiment, the process for preparing the crystallized mother liquor comprises: preparing silicon-containing solution, aluminum-containing solution and alkaline liquid, mixing the above-mentioned liquids, making colloid, then making crystallization at a certain temperature.
In the hydroisomerization catalyst of the present invention, the ten-membered ring molecular sieve is not particularly limited in type, and may be, for example, at least one of a ZSM-22 molecular sieve, a ZSM-23 molecular sieve, a ZSM-48 molecular sieve, a ZSM-5 molecular sieve, an SSZ-32 molecular sieve, and an Eu-1 molecular sieve. Preferably, the ten-membered ring molecular sieve is a ZSM-22 molecular sieve and/or a ZSM-48 molecular sieve.
In the hydroisomerization catalyst of the present invention, in order to further improve the hydrotreating effect, it is preferable that the ten-membered ring molecular sieve has a difference in silica/alumina molar ratio of not more than 60, and specifically, the difference may be, for example, any value in the range of 0, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60 and any two of these values. More preferably, the difference is 20-40.
In the hydroisomerization catalyst of the present invention, preferably, the mass ratio of the two ten-membered ring silicoaluminophosphate molecular sieves is 10: 90-30: 70. one of the ten-membered ring molecular sieves may be present in an amount of 20 to 50 wt%, preferably 25 to 45 wt%, more preferably 30 to 45 wt%, based on the total weight of the two ten-membered ring molecular sieves; the content of the other ten-membered ring molecular sieve is 50 to 80% by weight, preferably 55 to 75% by weight, more preferably 55 to 70% by weight.
In the present invention, the hydroisomerization catalyst may be a supported catalyst, and the preparation process thereof may include: the ten-membered ring molecular sieve and the refractory inorganic oxide are mixed, formed, and then loaded with an active metal component, for example, by impregnation, followed by activation and reduction.
In the present invention, the heat-resistant inorganic oxide is preferably alumina.
In the present invention, the active metal component may be a group VIII metal component. Group VIII metals such as Ru, Os, Rh, Ir, Pd and Pt. Preferably, the group VIII metal is selected from Pd and Pt.
In the present invention, the active metal component may be provided from an active metal component precursor. The active metal component precursor is selected from group VIII noble metal element-containing compounds. The group VIII noble metal element-containing compound may be selected from one or more of group VIII noble metal element-containing nitrates, chlorides, sulfates, formates, acetates, phosphates, citrates, oxalates, carbonates, hydroxycarbonates, hydroxides, phosphates, phosphides, sulfides, aluminates, molybdates, tungstates and water-soluble oxides.
In the present invention, the content of the molecular sieve in the hydroisomerization catalyst may be 20 to 60% by weight, preferably 25 to 55% by weight, based on the total weight of the catalyst; the content of the heat-resistant inorganic oxide (such as alumina) is 35 to 80 wt%, preferably 42 to 72 wt%; the content of the active metal component is 0.1 to 5% by weight, preferably 0.2 to 3% by weight, more preferably 0.4 to 1% by weight.
The invention also provides a hydrotreating method of hydrocracking tail oil, which comprises the following steps: under the condition of hydroisomerization reaction, contacting hydrocracking tail oil with a catalyst for reaction, wherein the catalyst is the hydroisomerization catalyst provided by the invention or the hydroisomerization catalyst prepared according to the method.
In the present invention, the distillation range of the hydrocracking tail oil can be generally 350-.
In the present invention, the hydroisomerization reaction conditions are not particularly limited as long as sufficient hydroisomerization reaction of the hydrocracking tail oil is performed. Generally, the hydroisomerization reaction conditions may include: the temperature is 200-500 ℃, preferably 250-400 ℃, and more preferably 300-350 ℃; a pressure of 1 to 30MPa, preferably 2 to 20MPa, more preferably 5 to 20MPa, the pressure referred to herein being an absolute pressure; the space velocity is 0.1-5h-1, preferably 0.1-3h-1, more preferably 0.5-2 h-1; the volume ratio of the hydrogen to the oil is 50-3000, preferably 300-3000, more preferably 400-600.
According to the method, the hydrocracking tail oil is contacted with the hydroisomerization catalyst to carry out hydroisomerization reaction, so that higher yield of an isomerization product can be obtained; and the isomerized product has a lower pour point while having a higher viscosity index, and is suitable for being used as lubricating oil base oil.
The present invention will be described in detail with reference to examples, but the scope of the present invention is not limited thereto.
In the following examples and comparative examples, the content of each element in the measurement sample was analyzed and measured by a 3271E type X-ray fluorescence spectrometer commercially available from Nippon chemical and electric machines industries, and the sample was baked at 600 ℃ for 3 hours before the measurement.
In the following examples and comparative examples, the specific surface area and the external surface area of the sample were measured by using an automatic adsorption apparatus model DIGISORB 2500 of Micromeritics, USA, and the sample was baked at 600 ℃ for 3 hours before the test, and the measurement method was performed according to the ASTM D4222-98 standard method.
In the following examples and comparative examples, dry basis means the percentage of the weight of the product obtained after calcination of a certain amount of material in a muffle furnace at 600 ℃ for 4 hours in an air atmosphere, to the weight of the material before calcination. I.e. dry basis (weight of product obtained after calcination ÷ weight of material before calcination) × 100%.
Preparation example 1
(1) Preparation of crystallized mother liquor
36.3 g of a silica sol containing 40% by weight of SiO2, 1.77 g of analytically pure Al2(SO4) 3.18H 2O, 3.94 g of analytically pure KOH and 8.44 g of hexamethylenediamine are taken for use. Hexamethylenediamine was mixed with silica sol, KOH and Al2(SO4) 3.18H 2O were mixed with 89.4 g of deionized water, and the two solutions were mixed, stirred for 1 hour, transferred to a reaction vessel and crystallized at 160 ℃ for 72 hours.
(2) Preparation of the Filter cake
Filtering the crystallized mother liquor prepared in the step (1), and continuing to pump and filter for 5 minutes when no filtrate exists on a filter cake to obtain a filter cake F-1, wherein the dry content of the filter cake F-1 is 11.2 wt%, and the molar ratio of silicon oxide to aluminum oxide is 60.
(3) Preparation of molecular Sieve precursors
The filter cake F-1 was warmed from room temperature to 450 ℃ at a temperature rise rate of 25 ℃ per minute and held at that temperature for 4 hours. And in the temperature rising process, the roasting furnace is a closed roasting furnace, and the molecular sieve precursor C-1 is obtained.
(4) Preparation of molecular sieve finished product
Putting the molecular sieve precursor C-1 into a HCl solution with the concentration of 1M for closed hydrothermal treatment. Wherein the liquid-solid ratio is 50, the temperature of the hydrothermal treatment is 180 ℃, the time of the hydrothermal treatment is 3 hours, after the hydrothermal treatment is finished, the product is filtered and washed until the pH value of the filtrate is 7, and after drying for 4 hours at 120 ℃, the product is roasted for 4 hours at 550 ℃, and the finished product H-1 of the ZSM-22 molecular sieve is obtained. As can be seen from the nitrogen adsorption-desorption curve of the molecular sieve, the ZSM-22 molecular sieve exhibits a closed hysteresis loop at the low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the start position of said closed hysteresis loop is at P/P0= 0.4-0.5.
Preparation of comparative example 1
A mother liquor after crystallization was prepared according to procedure (1) in preparation example 1, followed by filtration, and the filter cake obtained after filtration was dried at 120 ℃ for 6 hours and then calcined at 550 ℃ for 4 hours to obtain a solid product and NH4Exchanging Cl for 3 times, and drying to form the ammonium molecular sieve finished product DH-1.
Preparation example 2
(1) Preparation of crystallized mother liquor
45 g of white carbon black, 1.25 g of analytically pure Al2(SO4) 3.18H 2O, 1.88 g of analytically pure NaOH and 39.3 g of hexamethylenediamine are taken for use. Mixing hexamethylenediamine with white carbon black and 200 g of deionized water, mixing NaOH with Al2(SO4)3 & 18H2O and 272 g of deionized water, mixing the two solutions, stirring for 1H, transferring the mixture into a reaction kettle, and crystallizing for 72 hours at 160 ℃.
(2) Preparation of the Filter cake
Filtering the crystallized mother liquor prepared in the step (1), and continuing to pump and filter for 5 minutes when no filtrate exists on a filter cake to obtain a filter cake F-2, wherein the dry content of the filter cake F-2 is 11.2 weight percent, and the molar ratio of silicon oxide to aluminum oxide is 60.
(3) Preparation of molecular Sieve precursors
The filter cake F-2 was warmed from room temperature to 450 ℃ at a temperature rise rate of 25 ℃/min and held at that temperature for 4 hours. And in the temperature rising process, the roasting furnace is a closed roasting furnace, and the molecular sieve precursor C-2 is obtained.
(4) Preparation of molecular sieve finished product
And putting the molecular sieve precursor C-2 into a citric acid solution with the concentration of 1M for closed hydrothermal treatment. Wherein the liquid-solid ratio is 100, the temperature of the hydrothermal treatment is 180 ℃, the time of the hydrothermal treatment is 2 hours, after the hydrothermal treatment is finished, the product is filtered and washed until the pH value of the filtrate is 7, and after drying for 4 hours at 120 ℃, the product is roasted for 4 hours at 550 ℃, and the finished product H-2 of the ZSM-48 molecular sieve is obtained. As can be seen from the nitrogen adsorption-desorption curve of the molecular sieve, the ZSM-48 molecular sieve exhibits a closed hysteresis loop at the low temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the start position of said closed hysteresis loop is at P/P0= 0.4-0.5.
Preparation of comparative example 2
The mother liquor after crystallization was prepared according to procedure (1) in preparation example 2, followed by filtration, and the filter cake obtained after filtration was dried at 120 ℃ for 6 hours and then calcined at 550 ℃ for 4 hours to obtain a solid product and NH4Exchanging Cl for 3 times, and drying to form the ammonium molecular sieve finished product DH-2.
Test example 1
(1) The mesoporous area and the specific surface area of the molecular sieve finished products prepared in the above examples and comparative examples were measured by using an automatic adsorption apparatus model DIGISORB 2500 of Micromeritics, usa, and the ratio of the mesoporous area to the specific surface area was calculated, and the results are shown in table 1 below.
(2) The contents of the respective elements in the molecular sieve precursors and the molecular sieve finished products prepared in the above examples and comparative examples were analyzed and measured by a 3271E type X-ray fluorescence spectrometer commercially available from japan physical and electrical machines industries, and the silicon-aluminum ratio and the content of penta-coordinated aluminum were determined, and the results are shown in table 1 below.
TABLE 1
Example 1
5 g (dry basis) of the molecular sieve H-1 and 20g (dry basis) of the molecular sieve H-2 are respectively ground into 120 meshes, mixed, then mixed with 75 g (dry basis) of alumina, molded, and loaded with 0.4 weight percent of metal Pt after being roasted at 560 ℃. Activating for 3h at 400 ℃, and reducing for 3h at 400 ℃ to prepare the catalyst, which is named as Cat-1.
Example 2
A catalyst was prepared according to the method of example 1, except that 10g (dry basis) of molecular sieve H-1 and 24g (dry basis) of molecular sieve H-2 were used, to thereby prepare catalyst Cat-2.
Example 3
A catalyst was prepared according to the method of example 1, except that 28g (dry basis) of molecular sieve H-1 and 28g (dry basis) of molecular sieve H-2 were used, to thereby prepare catalyst Cat-3.
The catalysts prepared in the above examples were respectively loaded in a high-pressure hydrogenation reactor for evaluation, and the properties of the raw oil used are shown in table 2, and the evaluation conditions are shown in table 3. After the reaction is finished, the product is distilled to cut off light components at the temperature of less than 370 ℃. Pour point, viscosity index analysis and yield calculations were performed on the components above 370 c and the results are shown in table 4. The yield is defined as: yield = mass of greater than 370 ℃ component in product/mass of feed.
TABLE 2
TABLE 3
TABLE 4
As can be seen from the data in Table 4, the method for producing the lubricating base oil by hydrocracking the tail oil can obtain better pour point depressing effect, and the lubricating base oil has high yield and high viscosity index.
The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including combinations of various technical features in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.
Claims (25)
1. A hydroisomerization catalyst is characterized by comprising two ten-membered ring silicoaluminophosphate molecular sieves, wherein the two ten-membered ring silicoaluminophosphate molecular sieves are a ZSM-22 molecular sieve and a ZSM-48 molecular sieve respectively, and both the two ten-membered ring silicoaluminophosphate molecular sieves have the following characteristics: the molar ratio of silicon oxide to aluminum oxide is 120-300; contains a mesoporous structure and has a closed hysteresis loop at a low-temperature nitrogen adsorption-desorption curve P/P0=0.4-0.99, and the starting position of the closed hysteresis loop is at P/P0= 0.4-0.7;
the ten-membered ring silicoaluminophosphate molecular sieve is prepared according to the following steps:
(1) filtering the crystallized mother liquor to form a filter cake with the dry basis content of 5-30%;
(2) directly roasting the filter cake to obtain a molecular sieve precursor;
(3) subjecting the molecular sieve precursor to a hydrothermal treatment;
(4) filtering, washing and drying the hydrothermal treatment product;
in the step (3), the medium for the hydrothermal treatment is acidic water.
2. The hydroisomerization catalyst of claim 1, wherein in the at least one ten-membered ring silica alumina molecular sieve, the molecular sieve has a silica to alumina molar ratio of from 150 to 200.
3. The hydroisomerization catalyst of claim 1, wherein in the at least one ten-membered ring silicoaluminophosphate molecular sieve, the mesopore area of the molecular sieve is 50m2/g～250m2The proportion of the mesoporous area in the specific surface area is 20-70 percent.
4. The hydroisomerization catalyst of claim 3, wherein the proportion of mesopore area to specific surface area in the at least one ten-membered ring aluminosilicate molecular sieve is from 25% to 65%.
5. The hydroisomerization catalyst of any of claims 1-4, wherein the closed hysteresis loop begins at a position P/P0=0.4-0.6 in the at least one ten-membered ring aluminosilicate.
6. The hydroisomerization catalyst of any of claims 1-4, wherein the at least one ten-membered ring aluminosilicate has a penta-coordinated aluminum content in the precursor of the molecular sieve in the range of from 4 to 30 wt.%, calculated as oxide and based on the total alumina content of the molecular sieve.
7. The hydroisomerization catalyst recited in claim 6, wherein the at least one ten-member ring silica alumina molecular sieve has a penta-coordinated aluminum content in its precursor in the range of from 10 to 30 weight percent, calculated as oxide and based on the total alumina content of the molecular sieve.
8. The hydroisomerization catalyst of any of claims 1-4, wherein the amount of penta-coordinated aluminum in the at least one ten-membered ring aluminosilicate is 3 wt.% or less, calculated as oxide and based on the total alumina content of the molecular sieve, in the finished molecular sieve.
9. The hydroisomerization catalyst of claim 8, wherein the amount of penta-coordinated aluminum in the at least one ten-membered ring aluminosilicate is less than 1 weight percent, calculated as oxide and based on the total alumina content of the molecular sieve.
10. The hydroisomerization catalyst of claim 9, wherein the at least one ten-membered ring aluminosilicate molecular sieve is free of penta-coordinated aluminum in the finished molecular sieve, calculated as oxide and based on the total alumina content of the molecular sieve.
11. The hydroisomerization catalyst of claim 1, wherein, in step (1), the dry content of the filter cake formed by said filtering is from 6 to 15%.
12. The hydroisomerization catalyst according to claim 1 or 11, wherein, in step (2), the calcination temperature is 400-600 ℃.
13. The hydroisomerization catalyst according to claim 12, wherein, in step (2), the calcination temperature is 450-550 ℃.
14. The hydroisomerization catalyst according to claim 1 or 11, wherein the acidic water contains an inorganic acid and/or an organic acid, and the content of the inorganic acid and/or the organic acid is 0.1M to 5M.
15. The hydroisomerization catalyst according to claim 14, wherein the content of the inorganic acid and/or organic acid is 0.2M to 2M.
16. The hydroisomerization catalyst of claim 14, wherein the acidic water comprises at least one of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, citric acid, acetic acid, maleic acid, oxalic acid, nitrilotriacetic acid, 1, 2-cyclohexanediaminetetraacetic acid, citric acid, tartaric acid, and malic acid.
17. The hydroisomerization catalyst according to claim 1 or 11, wherein, in step (3), the liquid-solid volume ratio of the hydrothermal treatment is 5-200; the temperature of the hydrothermal treatment is 100-300 ℃; the time of the hydrothermal treatment is 0.5 to 24 hours.
18. The hydroisomerization catalyst of claim 17, wherein, in step (3), the liquid-to-solid volume ratio of the hydrothermal treatment is from 20 to 100; the temperature of the hydrothermal treatment is 100-200 ℃; the time of the hydrothermal treatment is 1-12 hours.
19. The hydroisomerization catalyst of claim 17, wherein, in step (3), the hydrothermal treatment is performed for a time ranging from 1 hour to 4 hours; the hydrothermal treatment is carried out in a closed container, and the pressure of the hydrothermal treatment is the autogenous pressure of the closed container under the hydrothermal condition.
20. The hydroisomerization catalyst according to claim 1 or 11, wherein in the step (4), the washing is performed by washing with deionized water, and the washing is completed until the pH of the filtrate is 6-8.
21. The hydroisomerization catalyst according to claim 20, wherein in the step (4), the washing process is finished until the filtrate has a pH value of 6 to 7.
22. The hydroisomerization catalyst of any of claims 1-4, 7, 9-10, 11, 13, 15-16, 18-19, and 21, wherein the two ten-membered ring silica alumina molecular sieves have molar ratios of silica to alumina that differ by no more than 60.
23. The hydroisomerization catalyst of claim 22, wherein the two ten-member ring silica alumina molecular sieves have a difference in silica to alumina molar ratios ranging from 20 to 40.
24. The hydroisomerization catalyst of claim 22, wherein the ZSM-22 molecular sieve is present in an amount of 10 to 30 wt% and the ZSM-48 molecular sieve is present in an amount of 70 to 90 wt%, based on the total weight of the ZSM-22 molecular sieve and the ZSM-48 molecular sieve.
25. A method for hydrotreating a hydrocracked tail oil, the method comprising: contacting and reacting hydrocracking tail oil with a catalyst under hydroisomerization reaction conditions, wherein the catalyst is the hydroisomerization catalyst according to any one of claims 1 to 24.
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