CN115025811A - Synthesis method of ZSM-5 molecular sieve and preparation method of deethylation type carbon eight aromatic hydrocarbon isomerization catalyst - Google Patents
Synthesis method of ZSM-5 molecular sieve and preparation method of deethylation type carbon eight aromatic hydrocarbon isomerization catalyst Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
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- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
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- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
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- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention provides a synthesis method of a ZSM-5 molecular sieve and a preparation method of a deethylation type carbon eight-aromatic isomerization catalyst, belonging to the technical field of molecular sieve catalyst preparation; the method comprises the following steps: mixing water, a silicon source, an aluminum source, an organic template agent, a second organic matter and an alkali source according to a certain molar ratio to prepare initial gel; the second organic matter is saccharide; aging the initial gel followed by crystallization; after crystallization is finished, cooling, separating and drying to obtain the ZSM-5 molecular sieve; due to the size limitation of molecules, the second organic matter introduced by the invention can only be filled at the pore channel intersection of the ZSM-5 and has a competition effect with the organic template agent for balancing charges, so that the aluminum atoms at the pore channel intersection can be reduced, and the falling position of the aluminum atoms in the pore channel is increased; the increase of aluminum atoms in the pore channels can increase the cracking capability, thereby improving the ethylbenzene dealkylation activity of the ZSM-5 molecular sieve.
Description
Technical Field
The invention belongs to the technical field of catalyst preparation, and relates to a synthesis method of a ZSM-5 molecular sieve for regulating and controlling an acid center of a deethyl type C eight aromatic hydrocarbon isomerization catalyst, and a preparation method of the deethyl type C eight aromatic hydrocarbon isomerization catalyst.
Background
The p-xylene is an important basic chemical raw material, the import quantity of the p-xylene in China is more than 1000 ten thousand tons every year in recent years, and the p-xylene is in a short-supply and short-demand state for a long time. The current method for increasing the yield of p-xylene is mainly to isomerize carbon octa-aromatic hydrocarbon (such as o-xylene and m-xylene) into a target product. However, the carbon octaarene also comprises ethylbenzene. Because the chemical property of ethylbenzene is similar to that of other dimethylbenzene, the later separation is difficult, so that ethylbenzene needs to be subjected to deethylation to be converted into benzene in the isomerization process. Currently, the de-ethylated C-octa-aromatics isomerization catalyst is a bi-functional catalyst in which the common metal center is Pt (hydrogenation/dehydrogenation) and the acid center is ZSM-5 molecular sieve (cracking/isomerization).
Since alundum is electronegative in ZSM-5 molecular sieves and is the active center in acid catalysis, the distribution of framework aluminum atoms in ZSM-5 molecular sieves changes the catalytic performance. The ZSM-5 molecular sieve is a two-dimensional structure (see figure 1) composed of a ten-membered ring straight channel and a ten-membered ring sinusoidal channel, the size of the straight channel is 0.53X 0.56nm, and the size of the sinusoidal channel is 0.51X 0.55 nm. Obviously, the positions of the framework aluminum atoms can be distributed in three cases ( positions 1, 2 and 3 in fig. 1) in the straight channel, in the sinusoidal channel and at the intersection between the two. There are studies showing (Journal of catalysis. 2011, 283, 98): the protonation rate of framework aluminum atoms of the ZSM-5 molecular sieve in spatial small channels is 5 times that in large channels. Therefore, increasing the aluminum atom content in the straight and sinusoidal channels, and decreasing the aluminum atom content at the intersections increases the protonation rate, which will increase the de-ethylation activity of the catalyst. In addition, The aluminum atoms at The intersections are prone to macromolecular reactions due to their large spatial positions (The Journal of Physical Chemistry C, 2019, 123, 15637; Angewandte Chemistry International Edition, 2022, e 202205413), which in most catalytic reactions are more prone to carbon deposition, thereby affecting The catalyst life.
In recent decades, researchers have modulated the distribution of framework aluminum atoms in a ZSM-5 Molecular sieve from angles such as a silicon source (ACS Catalysis, 2016, 6, 731), an aluminum source (Molecular Systems Design & Engineering, 2018, 3, 159), and a templating agent (Catalysis Today, 2018, 303, 64) synthesized from the ZSM-5 Molecular sieve. However, these aluminum atoms of the framework inevitably fall at the intersection of the channels no matter how the synthesis factor is changed. In particular, when tetrapropylammonium hydroxide is used as a template, researchers found that: the molecular size of the tetrapropyl cation is far larger than that of a straight channel and a sinusoidal channel, so that the tetrapropyl cation can only be positioned at the channel crossing position of the ZSM-5 molecular sieve. To balance the positive charge of the tetrapropyl cation, there must be one aluminum atom at the channel intersection. It is known that the template mainly has two functions of framework filling and charge balancing in the synthesis process of the molecular sieve.
Disclosure of Invention
The invention overcomes the defects of the prior art and provides a synthesis method of a ZSM-5 molecular sieve and a preparation method of a deethylation type carbon eight aromatic isomerization catalyst; the invention adopts saccharides as a second organic matter, fills the pore channels in the synthesis process of the molecular sieve, competes with a template agent such as tetrapropylammonium hydroxide, and reduces aluminum atoms at the intersection of the pore channels; as the aluminum atoms at the intersection of the pore channels are reduced, more aluminum atoms can be positioned in the pore channels, thereby improving the deethylation activity of the ZSM-5 molecular sieve.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a synthesis method of a ZSM-5 molecular sieve comprises the following steps:
a) mixing water, a silicon source, an aluminum source, an organic template agent, a second organic matter and an alkali source according to a certain molar ratio to prepare initial gel; the second type of organic substance is a saccharide. The second type of organic matter exists in a synthesis system in a molecular form in the process of hydrothermal synthesis of the molecular sieve, so that the second type of organic matter only plays a role in framework filling in the synthesis process of the ZSM-5 molecular sieve.
b) The initial gel is aged and subsequently crystallized.
c) After crystallization, the ZSM-5 molecular sieve is obtained by cooling, separating and drying.
Preferably, the silicon source is one or any combination of white carbon black, silica sol, silica gel, water glass, ethyl orthosilicate and methyl orthosilicate. The more preferred silicon source is silica gel or silica white.
Preferably, the aluminum source is one or any combination of sodium metaaluminate, aluminum oxide, aluminum nitrate, aluminum hydroxide and aluminum isopropoxide. More preferred aluminum sources are sodium metaaluminate or alumina.
Preferably, the template agent is one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide and n-butylamine. A more preferred templating agent is tetrapropylammonium hydroxide.
Preferably, the second organic substance is one of glucose, fructose, maltose, lactose and sucrose. More preferred is sucrose or maltose.
Preferably, the alkali source is sodium hydroxide or potassium hydroxide. More preferred is sodium hydroxide.
Preferably, the molar ratio of the initial gel is H 2 O: SiO 2 : Al 2 O 3 : TPAOH: R: NaOH =(5~300):1: (0.05~0.0001): (0.1~0.5)：(0.01~0.1)：(0.1~0.3)。
Preferably, the molar ratio of the initial gel is H 2 O: SiO 2 : Al 2 O 3 : TPAOH: R: NaOH =(10~20):1: (0.05~0.001): (0.2~0.3)：(0.01~0.02)：(0.2~0.3)。
Preferably, the initial gel is aged at room temperature for 2h and subsequently crystallized at 140-200 ℃ for 5-100 h. The crystallization temperature is more preferably 170 ℃. The crystallization time is more preferably 48 hours.
The method for preparing the deethylation type carbon eight aromatic hydrocarbon isomerization catalyst by using the ZSM-5 molecular sieve comprises the steps of mixing the ZSM-5 molecular sieve with pseudo-boehmite, adding 3.0 wt% of hydrochloric acid solution, kneading, molding and loading 0.1 wt% of noble metal Pt to prepare the deethylation type carbon eight aromatic hydrocarbon isomerization catalyst.
Compared with the prior art, the invention has the beneficial effects that.
In the synthesis process of the ZSM-5 molecular sieve, the second organic matter is introduced, and the second organic matter only plays a role in skeleton filling in the synthesis process of the molecular sieve, competes with the traditional tetrahydro ammonium hydroxide, occupies the position of the cross of the pore canal in advance, reduces aluminum atoms at the cross of the pore canal, and has the advantages of two aspects:
(1) from a material perspective: due to the large molecular size of the second organic material, it can only be located at the intersection of the channels. And because the substance does not ionize in a molecular sieve synthesis system and exists in a molecular form in a molecular sieve framework, aluminum atoms do not exist at the intersection of the pore channels. However, tetrapropylammonium hydroxide, the most commonly used organic templating agent, is located at the channel intersections in the framework of the molecular sieve, and must have an aluminum atom to balance the charge. Thus, the introduction of the second organic may reduce aluminum atoms at the intersection of the channels. The increase of aluminum atoms in the pore channels can increase the cracking capability, thereby improving the ethylbenzene dealkylation activity of the ZSM-5 molecular sieve. The invention relates to a method for improving the ethyl removal activity of a ZSM-5 molecular sieve by micro-regulating and controlling aluminum distribution.
(2) From the point of view of catalytic performance: because the cracking activity of the aluminum atoms at the intersection of the pore channels is weaker than that of the aluminum atoms in the pore channels, the dealkylation activity of the ZSM-5 molecular sieve in ethylbenzene can be improved after the second organic matter is introduced. In addition, the carbon deposition amount at the cross part of the pore channels is easier than that in the pore channels, and the carbon deposition amount of the ZSM-5 molecular sieve can be reduced in the same reaction time.
Drawings
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly understood, the following drawings are taken for illustration:
FIG. 1 is a channel structure of a ZSM-5 molecular sieve; in the figure, 1 is the straight channel position; 2 is the position of a sine channel; and 3 is the crossing position of the straight channel and the sine channel.
FIG. 2 is an XRD spectrum of a sample of comparative example 1 and samples of examples 1 to 5; the sample of comparative example 1 was designated as P, and the samples of examples 1 to 5 were designated as S1 to S5.
FIG. 3 is an SEM photograph of a sample of comparative example 1 and samples of examples 1 to 5; the sample of comparative example 1 was designated as P, and the samples of examples 1 to 5 were designated as S1 to S5.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. The technical solutions of the present invention are described in detail below with reference to examples, but the scope of protection is not limited thereto.
Comparative example 1
6.25 g of sodium hydroxide (96 wt%) is dissolved in 90.0 g of deionized water, 29 g of tetrapropylammonium hydroxide solution (35%) is added, after stirring for 5min, 3.10 g of sodium metaaluminate (41 wt% in terms of alumina) is added, after stirring until clarification, 31.25g of silica gel (solid content: 96 wt%) is added, the mixture is aged for 2h at room temperature, and after the aging is finished, the mixture is put into a polytetrafluoroethylene crystallization reaction kettle and crystallized for 48h at 170 ℃. After the reaction is finished, quenching, centrifugal separation and drying are carried out to obtain a sample P.
Example 1
6.25 g of sodium hydroxide (96 wt%) is dissolved in 90.0 g of deionized water, 29 g of tetrapropylammonium hydroxide solution (35%) and 1.71 g of sucrose are added, stirred for 5min, then 3.10 g of sodium metaaluminate (41% in terms of alumina) is added, stirred until the mixture is clear, 31.25g of silica gel (96 wt% of solid content) is added, the mixture is aged for 2h at room temperature, and then the mixture is put into a polytetrafluoroethylene crystallization reaction kettle after the aging is finished, and crystallized for 48h at 170 ℃. After the reaction, the reaction mixture was quenched, centrifuged, and dried to obtain sample S1.
Example 2
6.25 g of sodium hydroxide (96 wt%) is dissolved in 90.0 g of deionized water, 29 g of tetrapropylammonium hydroxide solution (35%) and 2.9 g of sucrose are added, stirred for 5min, then 1.25g of sodium metaaluminate (41% in terms of alumina) is added, after stirring to be clear, 33.33 g of white carbon black (solid content: 90 wt%) is added, the mixture is aged for 2h at room temperature, and after the aging is finished, the mixture is put into a polytetrafluoroethylene crystallization reaction kettle and crystallized for 48h at 170 ℃. After the reaction, the reaction mixture was quenched, centrifuged, and dried to obtain sample S2.
Example 3
Dissolving 12.0 g of sodium hydroxide (96%) in 180 g of deionized water, adding 60 g of tetrapropylammonium hydroxide solution (35%) and 5.8 g of sucrose, stirring for 5min, adding 2.79 g of alumina (70% of alumina), stirring until the mixture is clear, adding 31.25g of silica gel (solid content: 96%), aging for 2h at room temperature, filling the mixture into a polytetrafluoroethylene crystallization reaction kettle after aging is finished, and crystallizing for 48h at 170 ℃. After the reaction, the reaction mixture was quenched, centrifuged, and dried to obtain sample S3.
Example 4
Dissolving 12.0 g of sodium hydroxide (96%) in 100 g of deionized water, adding 40 g of tetrapropylammonium hydroxide solution (35%) and 1.9 g of maltose, stirring for 5min, adding 1.25g of sodium metaaluminate (41% in terms of alumina), stirring until the mixture is clear, adding 31.25g of silica gel (solid content: 96%), aging for 2h at room temperature, filling the mixture into a polytetrafluoroethylene crystallization reaction kettle after the aging is finished, and crystallizing for 48h at 170 ℃. After the reaction, the reaction mixture was quenched, centrifuged, and dried to obtain sample S4.
Example 5
Dissolving 12.0 g of sodium hydroxide (96%) in 130 g of deionized water, adding 40 g of tetrapropylammonium hydroxide solution (35%) and 3.2 g of maltose, stirring for 5min, adding 2.5 g of sodium metaaluminate (41% in terms of alumina), stirring until the mixture is clear, adding 31.25g of silica gel (solid content: 96%), aging for 2h at room temperature, filling the mixture into a polytetrafluoroethylene crystallization reaction kettle after the aging is finished, and crystallizing for 48h at 170 ℃. After the reaction, the sample was quenched, centrifuged, and dried to obtain sample S5.
FIG. 1 is a schematic diagram of the channel structure of a ZSM-5 molecular sieve, and three possible positions of aluminum atoms can be seen from the diagram.
FIG. 2 is an XRD pattern of a sample of comparative example 1 and samples of examples 1 to 5; the sample of comparative example 1 was designated as P, and the samples of examples 1 to 5 were designated as S1 to S5. It can be seen from FIG. 1 that the comparative example and the example both are pure phase ZSM-5 molecular sieves, with good crystallinity and no heterocrystal phase. Indicating that the introduction of the second organic in the present invention does not change the crystal type of the sample.
FIG. 3 is SEM pictures of comparative example 1 samples and example samples S1-S5.
Application example 1
In order to confirm the catalytic performance of the ZSM-5 molecular sieve, 50% of the molecular sieve and 50% of alumina are mixed, kneaded with a proper amount of hydrochloric acid solution (the mass fraction is 3.0%), molded, and loaded with 0.1% of Pt to prepare an isomerization catalyst. Next, the comparative example 1 sample, example samples S1 to S5 were subjected to catalytic performance tests using 7.0 mass% of ethylbenzene and 93.0 mass% of meta-xylene as reaction raw materials, and the catalytic results are shown in table 1.
The reaction conditions are as follows: the reaction temperature, 370 ℃; the reaction pressure is 0.8 MPa; space velocity =8.0 h -1 (ii) a The hydrogen/hydrocarbon molar ratio was 2.0, and after 24 hours of reaction, a sample was taken and analyzed by gas chromatography. Wherein the catalytic performance parameter is ethylbenzene conversion rate X EB Isomerization activity of S PX The calculation is made according to the following formula: x EB =（1-w EB /w EB,0 ）×100 %，S PX =w PX /w ΣX X 100% of formula (II), w EB ，w PX And w ΣX Respectively represents the mass fractions of ethylbenzene, paraxylene and total xylene in the product, w EB,0 The mass fraction of ethylbenzene in the feed oil is shown. As can be seen from table 1: the ethylbenzene conversion of the synthesized sample of the present invention was higher than that of comparative example 1 because the aluminum distribution was changed after the introduction of the second organic substance, thereby increasing the removal rate of ethylbenzene. In addition, the isomerization activity of the invention is not reduced and is close to the thermodynamic equilibrium value (-24.0) under the reaction condition. The improvement of the ethylbenzene conversion rate without greatly reducing the activity of xylene isomerization is illustrated, and the improvement of the ethylbenzene conversion rate by changing the aluminum distribution is feasible.
TABLE 1
The above is a further detailed description of the present invention, which is given in connection with specific preferred embodiments thereof, and it is not intended that the present invention be limited thereto, and that several simple deductions or substitutions may be made by a person skilled in the art without departing from the invention, which should be considered as falling within the scope of the invention as defined by the appended claims.
Claims (10)
1. A synthetic method of a ZSM-5 molecular sieve is characterized by comprising the following steps:
a) mixing water, a silicon source, an aluminum source, an organic template agent, a second organic matter and an alkali source according to a certain molar ratio to prepare initial gel; the second type of organic matter is a saccharide;
b) aging and subsequently crystallizing said initial gel;
c) after crystallization, the ZSM-5 molecular sieve is obtained by cooling, separating and drying.
2. The method for synthesizing the ZSM-5 molecular sieve according to claim 1, wherein the silicon source is one or any combination of white carbon black, silica sol, silica gel, water glass, tetraethoxysilane and methyl orthosilicate.
3. The method of synthesizing a ZSM-5 molecular sieve as claimed in claim 1, wherein the aluminum source is one or any combination of sodium metaaluminate, alumina, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide.
4. The method of synthesizing a ZSM-5 molecular sieve according to claim 1, wherein the templating agent is one of tetraethylammonium hydroxide, tetrapropylammonium hydroxide, n-butylamine.
5. The method of synthesizing a ZSM-5 molecular sieve as claimed in claim 1, wherein the second organic material is one of glucose, fructose, maltose, lactose, sucrose.
6. The method of synthesizing a ZSM-5 molecular sieve as claimed in claim 1, wherein the alkali source is sodium hydroxide or potassium hydroxide.
7. The method of synthesizing a ZSM-5 molecular sieve as claimed in claim 1, wherein the molar ratio of the initial gel is H 2 O: SiO 2 : Al 2 O 3 : TPAOH: R: NaOH =(5~300):1: (0.05~0.0001): (0.1~0.5)：(0.01~0.1)：(0.1~0.3)。
8. The synthesis method of ZSM-5 molecular sieve as claimed in claim 7, wherein the molar ratio of the initial gel is H 2 O: SiO 2 : Al 2 O 3 : TPAOH: R: NaOH =(10~20):1: (0.05~0.001): (0.2~0.3)：(0.01~0.02)：(0.2~0.3)。
9. The method as set forth in claim 1, wherein the initial gel is aged at room temperature for 2h and then crystallized at 140-200 ℃ for 5-100 h.
10. A method for preparing a catalyst for the isomerization of carbon octa-aromatics in the deethylation type by using the ZSM-5 molecular sieve as claimed in any of claims 1 to 9, wherein the catalyst for the isomerization of carbon octa-aromatics in the deethylation type is prepared by mixing the ZSM-5 molecular sieve with pseudo-boehmite, adding a 3.0 wt% hydrochloric acid solution, and then kneading, molding and supporting 0.1 wt% of noble metal Pt.
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