CN109110778B - Hierarchical pore MTT structure molecular sieve prepared by controlling dealkalized lignin, preparation method and application - Google Patents

Hierarchical pore MTT structure molecular sieve prepared by controlling dealkalized lignin, preparation method and application Download PDF

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CN109110778B
CN109110778B CN201811254095.4A CN201811254095A CN109110778B CN 109110778 B CN109110778 B CN 109110778B CN 201811254095 A CN201811254095 A CN 201811254095A CN 109110778 B CN109110778 B CN 109110778B
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张香文
王庆法
刘林林
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Tianjin University
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Abstract

The invention discloses a molecular sieve with a hierarchical pore MTT structure, which contains mesopores and micropores, and the specific surface area of the molecular sieve is 400m2The pore diameter of the mesopores is 2-20nm, and the pore size of the micropores is 0.52nm multiplied by 0.45 nm. The invention also discloses a preparation method of the molecular sieve with the hierarchical pore MTT structure, which is regulated and controlled by dealkalized lignin, and application of the molecular sieve to a catalyst carrier in improving the yield of a single-branched chain isomerized product in a normal alkane hydroisomerization reaction.

Description

Hierarchical pore MTT structure molecular sieve prepared by controlling dealkalized lignin, preparation method and application
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a hierarchical pore MTT structure molecular sieve prepared by controlling dealkalized lignin, a preparation method and application thereof.
Background
In petroleum products, lubricating oil, jet fuel and the like are all focused on various properties at low temperature, particularly on a condensation point, a freezing point and the like. In recent years, hydrocarbon products obtained from coal by the fischer-tropsch synthesis method are cleaner, have the characteristics of no sulfur, no nitrogen, and low aromatic hydrocarbons, and have attracted attention as feedstock oils for producing fuels, lubricant base oils, and the like. For lowering the pour point of a lubricant, it is not desirable to form isomers with many branches, and isomerization of waxes to form less branched isomers, especially at lower pour points with a single branch in the center.
For the isomerization dewaxing reaction of the lubricant base oil, a catalyst prepared by loading metal active components Pt, Pd and other group VIII elements on a microporous MTT structure molecular sieve is generally used. The size of a pore channel of the MTT structure molecular sieve is generally about 0.52nm multiplied by 0.45nm, the structure limits the generation and diffusion of a multi-branched chain isomeric product, so that the isomeric product generates a secondary reaction, namely a cracking reaction, the cracking product promotes the generation of carbon deposition, and the pore channel of a catalyst is easy to block; and only the active sites located near the molecular sieve openings contribute to the formation of the double-branched isomers. The isomerization reaction of long-chain normal alkane (carbon atom number is more than 15) mainly takes place at the pore opening of the catalyst, and only the active site near the pore opening of the molecular sieve can play a role. Thus, the high activity catalyst for isomerization of long paraffins requires the use of a molecular sieve having a relatively large number of openings. There are generally two methods for increasing the number of molecular sieve openings: 1. preparing a molecular sieve with small crystal grains, and 2, synthesizing the molecular sieve with the hierarchical pore structure.
Patent US 7390763B 2 discloses a method for preparing a small-grain MTT-structure molecular sieve and its use in the preparation of molecular sieves C10+The application of the normal paraffin in the isomerization and pour point depression can improve the yield of the target product by 7.14 percent by using the small-grain MTT structure molecular sieve. Patent CN 103153860 a proposes a method for preparing a small-grain molecular sieve in the absence of an amine component, but the formation and diffusion limitation of a multi-branched isomeric product by the pore structure of the molecular sieve with an MTT structure lead to a secondary reaction, i.e. a cracking reaction, of the isomeric product; the cracking products promote the generation of carbon deposition and easily block catalyst pore channels.
Patent CN 105645428A describes a preparation method of SSZ-32 molecular sieve with mesoporous-microporous hierarchical structure, which comprises the steps of homogenizing and mixing raw materials, adding starch, aging, crystallizing, calcining, etc. to obtain SSZ-32 molecular sieve with hierarchical structure, wherein the molecular sieve can improve the content of multi-branched isomers in the isomerized product in the hydroisomerization reaction of straight-chain alkane, but the content of single-branched chain isomerized product is still low. Patent CN 105640607 a describes a preparation method of SSZ-23 molecular sieve with mesoporous-microporous hierarchical structure, which is also to prepare SSZ-32 molecular sieve with hierarchical structure by homogenizing and mixing raw materials, adding starch, aging, crystallizing, calcining and other processes, wherein the molecular sieve can also improve the content of multi-branched isomers in the isomerized product in the hydroisomerization reaction of straight-chain alkane, but the content of single-branched isomeric product is still low.
The molecular sieve uses a catalyst carrier, so the activity, selectivity and stability of the molecular sieve in the hydroisomerization reaction are not ideal, and particularly the specific surface area of the molecular sieve is still small; when the method is used for normal alkane hydroisomerization reaction, the content of single-branched chain isomerization products in the product is still low.
The lignin is a multi-stereo net-shaped high molecular organic matter rich in negative charge groups, and functional groups such as phenolic hydroxyl, alcoholic hydroxyl, carboxyl and the like exist on molecules, so that modification of a high molecular structure is facilitated. In nature, the reserves of lignin are second only to cellulose, and are cheap, easily available and renewable resources. The dealkalized lignin is a product obtained by neutralizing and precipitating alkaline lignin with acid.
The invention firstly adds dealkalized lignin in situ on the basis of the molecular sieve with the microporous structure to prepare mesopores in a crystal and among the crystals so as to obtain the molecular sieve with the hierarchical pore MTT structure. The molecular sieve with the multi-level pore MTT structure has larger specific surface area of 400m2More than g, the N-alkane hydroisomerization compound is used for normal alkane hydroisomerization reaction, shows excellent activity, selectivity and stability, and can obviously improve the yield of single-branched chain isomerization products in the product.
Disclosure of Invention
The invention discloses a hierarchical pore MTT structure molecular sieve, which contains mesopores and micropores, and the specific surface area of the molecular sieve is 400m2The pore diameter of the mesopores is 2-20nm, and the pore size of the micropores is 0.52nm multiplied by 0.45 nm.
The second aspect of the invention discloses a preparation method of the molecular sieve with the hierarchical pore MTT structure, which comprises the following steps:
(1) adding a template agent, alkali liquor, a silicon source and an aluminum source into water, and uniformly mixing;
(2) adding dealkalized lignin into the mixed solution obtained in the step (1) and reacting at a certain temperature;
(3) and (3) washing the solid product obtained in the step (2) to be neutral, drying, calcining, and cooling to room temperature to obtain the hierarchical pore MTT structure molecular sieve.
Preferably, the template agent in the step (1) is one or more of imidazolium salt, isobutylamine and 1, 7-heptanediamine; the aluminum source is one or more of octadecanoic water, aluminum sulfate, aluminum sol and silicon-aluminum sol; the silicon source is silica sol; the alkali liquor is NaOH or KOH aqueous solution.
Preferably, the molar ratio of the template agent to the alkali liquor to the silicon source to the aluminum source to the lignin to the water is: SiO 22/Al2O315-100; templating agent/SiO2，0.01-0.3；H2O/SiO2，10-80；OH-/SiO20.05 to 0.7; Lignin/SiO2，0.05-1.5。
Preferably, the reaction conditions in step (2) are: the temperature is 150-180 ℃, and the reaction time is 3-10 days.
Preferably, the calcining condition in the step (3) is that the temperature is more than 600 ℃, and the calcining time is 3-5 hours.
The third aspect of the invention discloses the application of the molecular sieve with the hierarchical pore MTT structure on a catalyst carrier.
Preferably, the hierarchical pore MTT structure molecular sieve increases the yield of single-branched isomeric products in the normal alkane hydroisomerization reaction.
The invention has the beneficial effects that:
1. the hierarchical pore MTT structure molecular sieve is a hierarchical pore structure molecular sieve, has micropores and mesopores, has a large number of orifices, a large specific surface area and pore volume and large accessibility of active sites, can be used as a catalyst carrier to load VIII group elements such as metal active components Pt and Pd, can optimize the pore property and the reasonable configuration of the active sites of a porous catalyst, and has a wide application prospect in reactions requiring acid sites such as hydroisomerization and the like. The catalyst is especially used for the isomerization and pour point depression reaction of long-chain normal paraffin containing wax, shows higher activity and isomerization selectivity, and can obviously improve the yield of single-branched chain isomerization products in the products.
2. The invention obtains the specific surface area of 400m for the first time2The molecular sieve with the concentration of more than g is used for normal alkane hydroisomerization reaction, shows excellent activity and selectivity, has the mole ratio of single-branch products to multi-branch products of more than 12, and obviously improves the quality of lubricating oil.
3. In order to make up the defects of small aperture, limited diffusion of reactants and products, poor catalytic activity and the like of a microporous molecular sieve, the preparation method of the molecular sieve with the hierarchical pore MTT structure firstly introduces dealkalized lignin as a co-template agent in situ, and functional groups such as phenolic hydroxyl, alcoholic hydroxyl, carboxyl and the like exist on dealkalized lignin molecules, so that modification of a high molecular structure is facilitated. The self-formed sponge structure at the aging temperature, and the interaction of the hydroxyl and the silicon-aluminum structure realize the one-step synthesis of the MTT molecular sieve with the micropore-mesopore hierarchical structure, and the in-situ preparation of the rich mesopores in and among crystals on the basis of the micropore structure has higher specific surface area and pore volume. On one hand, the introduction of the dealkalized lignin can be used as a mesoporous guiding agent to generate mesopores on the basis of micropores, so that the pore property and the reasonable configuration of active sites of the porous catalyst are optimized, and the number of orifices and the specific surface area of the molecular sieve are increased; and secondly, the use of an organic template agent can be reduced, the environmental pollution is reduced, the preparation cost of the catalyst is reduced, and the large-scale application of the hierarchical pore MTT molecular sieve is facilitated. And the ratio of mesopores in the hierarchical pore molecular sieve can be regulated and controlled by regulating the adding ratio of the dealkalized lignin. The effect of the present invention is not achieved by using ordinary lignin.
Drawings
Fig. 1 is a powder XRD pattern of the multi-pore MTT structure molecular sieves prepared in comparative example and example 1.
FIG. 2 is a graph showing N of the multi-stage pore MTT structure molecular sieves prepared in comparative example and example 12Adsorption-desorption isotherm curve.
FIG. 3 is a graph comparing the selectivity of the microporous MTT structure molecular sieve prepared in the comparative example and the multi-stage pore MTT structure molecular sieve prepared in example 1 to n-hexadecane hydroisomerization.
FIG. 4 is a graph comparing the molar ratios of single-branched isomeric product to multi-branched isomeric product for a microporous MTT structure molecular sieve prepared in the comparative example and a multi-stage pore MTT structure molecular sieve prepared in example 1 versus n-hexadecane hydroisomerate.
Detailed Description
The technical solution of the present invention will now be described in detail below in order to more clearly understand the technical features, objects and advantages of the present invention, and the following examples illustrate the processes of the present invention, but the present invention is not limited to these examples.
Example 1:
1.53g of an imidazolium salt, 22.5g of high purity water and 12.0g of a potassium hydroxide solution (1mol/L) were weighed out and added to a polytetrafluoroethylene liner, followed by stirring. Then, 7.62g of silica sol having a silica-alumina molar ratio of 50, 2.5g of silica-alumina sol and 0.9g of isobutylamine were added to the above-mentioned alkaline solution and stirred uniformly. Finally adding dealkalized lignin, wherein the molar weight of the dealkalized lignin is lignin/SiO2Stirring the mixture evenly, putting the reactant gel into a hydrothermal synthesis kettle with a polytetrafluoroethylene lining, sealing the kettle, and crystallizing the product for 8 days at the self-generated pressure of 175 ℃.
Taking out the crystallized product, cooling, centrifugally separating, washing with deionized water to neutrality, and drying in a 120 deg.c oven; and then placing the molecular sieve in a muffle furnace, and calcining for 6 hours at 650 ℃ to obtain the hierarchical pore MTT structure molecular sieve.
The XRD diffraction pattern of the obtained hierarchical pore MTT structure molecular sieve is shown as a curve in figure 1, and N is2The adsorption-desorption isotherms are shown in the graph of fig. 2. As can be seen from FIG. 1, the crystal form of the molecular sieve product obtained after in-situ addition of the dealkalized lignin is not changed and is still the molecular sieve with the MTT structure; as can be seen from fig. 2, the molecular sieve obtained in example 1 has mesopores.
The specific surface area of the obtained multi-stage pore MTT molecular sieve is 410m2The mesoporous aperture range is 2-20 nm.
Example 2:
the specific synthesis conditions were similar to example 1, except that the dealkalized lignin was added in a molar amount of dealkalized lignin/SiO20.05. The specific surface area of the obtained multi-stage pore MTT molecular sieve is 420m2The mesoporous aperture range is 2-20 nm.
Example 3:
the specific synthesis conditions were similar to example 1, except that the dealkalized lignin was added in a molar amount of dealkalized lignin/SiO21.5. The specific surface area of the obtained multi-stage pore MTT molecular sieve is 430m2The mesoporous aperture range is 2-20 nm.
Example 4
The specific synthesis conditions were similar to those of example 1, except that the aluminum source was an aluminum sol and the silica to alumina ratio was 65. The specific surface area of the obtained multi-stage pore MTT molecular sieve is 420m2The mesoporous aperture range is 2-20 nm.
Example 5:
the specific synthesis conditions were similar to those of example 1, the calcination temperature being 700 ℃. The specific surface area of the obtained multi-stage pore MTT molecular sieve is 156m2The mesoporous aperture range is 2-20 nm.
Comparative example:
the starting materials and synthesis conditions were the same as in example 1, except that no dealkalized lignin was added. The XRD diffraction pattern of the obtained microporous MTT structure molecular sieve is shown as a curve in figure 1, and N2The adsorption-desorption isotherms are shown in the graph of fig. 2.
Example 6: n-hexadecane hydroisomerization
The hierarchical pore MTT molecular sieve obtained in example 1 and the microporous MTT structure molecular sieve obtained in the comparative example were used as carriers, respectively, loaded with noble metal Pt at a loading of 0.5 wt%, and applied to the hydroisomerization reaction of n-hexadecane at a reaction pressure of 5MPa, with the product analysis results shown in table 1. From the table 1, it can be seen that, at the same reaction temperature, the conversion rate and the isomerization amount of the Pt/hierarchical pore MTT structure molecular sieve catalyst are greatly improved compared with the conversion rate and the isomerization amount of the Pt/microporous MTT structure molecular sieve, the single-branched chain isomerization product in the product is remarkably improved, and the molar ratio of the single-branched chain product to the multi-branched chain product is improved to more than 15 from less than 4 at 270 ℃; the molecular sieve with the multi-level pore MTT structure, which is prepared by the invention, is applied to the isomerization and pour point depression reaction of normal paraffin, so that an isoparaffin mixture can be prepared with high activity and high selectivity, and the molar ratio of a single-branched chain isomerized product to a multi-branched chain isomerized product in the product is obviously improved.
The isomerization selectivity is shown in FIG. 3, and the ratio of the single-branched isomeric product to the multi-branched isomeric product in the isomeric product is shown in FIG. 4.
TABLE 1 evaluation results of catalytic Properties
Figure BDA0001842314450000061
[ notes ] in Table 1, "< C ≦ C15The "% by weight" represents the total mass fraction of substances having a carbon number of 15 or less in the product; "isomeric C16%/wt% "represents the total mass fraction of n-hexadecane isomers in the product; "isomerization selectivity/%" means the percentage of reactant selectivity to the n-hexadecane isomer; single-branched product/multi-branched product means the molar ratio of single-branched product to multi-branched product in the product.
Example 7: isodewaxing of normal paraffins
The hierarchical porous MTT molecular sieve obtained in the example 1 and the microporous MTT molecular sieve obtained in the comparative example are respectively used as carriers to load noble metal Pt with the load of 0.5 wt%, and are applied to n-C20～n-C60Isodewaxing of mixed normal paraffins produces lubricant base oils.
The results were: the yield of III-type plus lubricating oil base oil obtained by catalyzing the hierarchical pore MTT molecular sieve loaded with noble metal Pt in the embodiment 1 is over 50 percent; under the same conditions, the yield of the III-type plus lubricating oil base oil obtained by using the microporous MTT-structure molecular sieve obtained in the comparative example as a carrier to load noble metal Pt is about 30%. And the viscosity index of the III-type + lubricating oil base oil obtained by the multistage pore MTT molecular sieve loaded with the noble metal Pt in the embodiment 1 can reach more than 140, and the pour point can be reduced by more than 15% compared with the III-type + lubricating oil base oil obtained by the microporous MTT molecular sieve with the structure obtained by a comparative ratio and used as a carrier loaded with the noble metal Pt. The isodewaxing reaction of the normal paraffin of the molecular sieve with the hierarchical pore MTT structure and the supported noble metal Pt catalyst can prepare the lubricant base oil with high activity and high selectivity.

Claims (5)

1. The preparation method of the molecular sieve with the hierarchical pore MTT structure is characterized in that the molecular sieve with the hierarchical pore MTT structure contains mesopores and micropores, and the specific surface area of the molecular sieve is 400m2More than g, the aperture of the mesopores is 2-20nm, and the pore size of the micropores is 0.52nm multiplied by 0.45 nm;
the preparation method of the molecular sieve with the hierarchical pore MTT structure comprises the following steps:
(1) adding a template agent, alkali liquor, a silicon source and an aluminum source into water, and uniformly mixing; the template agent is imidazolium salt; the aluminum source is one or more of aluminum sulfate octadecahydrate, aluminum sol and silicon-aluminum sol; the silicon source is silica sol; the alkali liquor is NaOH or KOH aqueous solution;
(2) adding dealkalized lignin into the mixed solution obtained in the step (1) and reacting at a certain temperature;
(3) washing the solid product obtained in the step (2) to be neutral, drying, calcining, and cooling to room temperature to obtain the hierarchical pore MTT structure molecular sieve;
the molar ratio of the template agent, the alkali liquor, the silicon source, the aluminum source, the dealkalized lignin and the water is as follows: SiO 22/Al2O315-100; templating agent/SiO2，0.01-0.3；H2O/SiO2，10-80；OH-/SiO20.05 to 0.7; dealkalized lignin/SiO2，0.05-1.5。
2. The method according to claim 1, wherein the reaction conditions in step (2) are as follows: the temperature is 150-180 ℃, and the reaction time is 3-10 days.
3. The method according to claim 1, wherein the calcination in the step (3) is carried out at a temperature of 600 ℃ or higher for 3 to 5 hours.
4. Use of the hierarchical pore MTT structure molecular sieve obtained by the preparation method according to any one of claims 1 to 3 for a catalyst support.
5. Use according to claim 4, wherein the multi-pore MTT structure molecular sieve increases the yield of single-branched isomerate product in n-alkane hydroisomerization reactions.
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