CN111939967A - Catalyst for synthesizing exo-tetrahydrodicyclopentadiene and preparation method and application method thereof - Google Patents
Catalyst for synthesizing exo-tetrahydrodicyclopentadiene and preparation method and application method thereof Download PDFInfo
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Abstract
The invention relates to synthesis of exo-tetrahydrodicyclopentadiene, and in particular relates to a catalyst for synthesizing exo-tetrahydrodicyclopentadiene as well as a preparation method and an application method thereof. The catalyst contains an H-type molecular sieve and a metal element as an active component, wherein the metal element is at least one selected from Pt element, Pd element and Au element, the H-type molecular sieve is at least one selected from HY, USY, SSY, NTY and ReY molecular sieves, and the sodium content in the H-type molecular sieve is less than 0.5 wt%. The catalyst of the invention can effectively improve the conversion rate of bridge type tetrahydrodicyclopentadiene and simultaneously improve the yield of hanging type tetrahydrodicyclopentadiene.
Description
Technical Field
The invention relates to synthesis of exo-tetrahydrodicyclopentadiene, in particular to a catalyst for synthesizing exo-tetrahydrodicyclopentadiene through hydroisomerization and a preparation method thereof, and a method for synthesizing exo-tetrahydrodicyclopentadiene.
Background
The exo-THDCPD is an isomeric product of the bridge type tetrahydrodicyclopentadiene (exo-THDCPD), has higher volume heat value (39.6MJ/L), lower freezing point (-79 ℃), proper flash point (55 ℃) and good oxidation stability, is a high-density hydrocarbon fuel with good low-temperature performance and high volume heat value, and is widely used as a propellant of aircrafts such as missiles, rockets, airplanes and the like.
The exo-THDCPD is prepared by isomerizing endo-THDCPD by adopting traditional strong L acid anhydrous aluminum chloride, solid-supported aluminum chloride, solid super acid, heteropoly acid and molecular sieve catalyst. The anhydrous aluminum chloride catalyst has high activity, good selectivity and mild reaction conditions, but is easy to generate high polymers, large in catalyst dosage and short in service life, only can be used for intermittent reaction, and in the reaction process, the anhydrous aluminum chloride and heavy components generated by the reaction can generate a complex compound to generate a large amount of waste, the catalyst cannot be recycled, the post-treatment needs alkali neutralization, the product separation and refining process is complex, and acidic wastewater generated by the subsequent treatment pollutes the environment. Although the problem of product separation does not exist in the immobilized aluminum chloride catalyst, the preparation process is complicated, sensitive to water and high in requirement on raw materials, and chlorine needs to be continuously supplemented in the reaction process, so that the development of the method is greatly limited.
The exo-THDCPD is prepared by catalyzing endo-THDCPD isomerization by a fixed bed reactor and a molecular sieve, which is an effective way for solving the problems and has better industrial application prospect. However, the molecular sieve catalyst has the problems of higher reaction temperature, lower conversion rate, poorer selectivity and easy coking and inactivation, and the industrial application of the molecular sieve catalyst is limited.
In the prior art, molecular sieves such as NH4Y, NaY, ReY, NH4-USY, NH4-SSY, H-beta, HZSM-5 and the like catalyze endo-THDCPD to isomerize in a kettle type batch reactor to prepare exo-THDCPD, wherein the H-USY effect is best, the conversion rate of endo-THDCPD is 94.93%, the yield of exo-THDCPD is 89.69% and the yield of adamantane is 3.03% at the reaction temperature of 195 ℃.
CN101786936A discloses a process method for synthesizing exo-THDCPD by catalyzing endo-THDCPD gas phase isomerization by using molecular sieves such as Y, Beta, mordenite, Al-MCM-41, Al-MCM-48, Al-SBA-15 and the like, although the process is simple and the yield of hydroisomerization is high, the catalyst is inactivated quickly, a large amount of carrier gas is needed, and the industrial application potential is limited.
CN106699499A discloses a method for improving endo-THDCPD isomerization selectivity by using an ultrastable Y-type molecular sieve with high sodium content as a catalyst, wherein chlorine-containing organic matters are added into raw materials to ensure that the single-pass conversion rate of bridge type tetrahydro dicyclopentadiene isomerization is more than 95% and the yield is more than 90%.
Therefore, a simple, efficient, safe and stable catalyst and method for the hydroisomerization of exo-tetrahydrodicyclopentadiene synthesized from bridge-type tetrahydrodicyclopentadiene is needed.
Disclosure of Invention
The invention aims to provide a novel catalyst for synthesizing exo-tetrahydrodicyclopentadiene through hydroisomerization so as to obtain the effect of obviously improving the conversion rate of bridge-type tetrahydrodicyclopentadiene and simultaneously improving the yield of exo-tetrahydrodicyclopentadiene on the premise of avoiding using substances which are commonly used in the prior art and are unsafe in industrial application, such as chlorine-containing compounds and the like.
In order to achieve the above object, a first aspect of the present invention provides a catalyst for hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene, which contains an H-type molecular sieve and a metal element as an active component, wherein the metal element is at least one selected from Pt element, Pd element and Au element, the H-type molecular sieve is at least one selected from HY, USY, SSY, NTY and ReY molecular sieves, and the sodium content in the H-type molecular sieve is less than 0.5 wt%, wherein the active component content in terms of element in the catalyst is (0.1 to 5) wt%.
A second aspect of the invention provides a process for preparing a catalyst according to the first aspect of the invention, the process comprising: the method comprises the steps of contacting a solution I containing metal elements as active components with an H-type molecular sieve by adopting an impregnation method, and drying and roasting intermediates obtained after the contact in sequence.
The third invention of the present invention provides a method for synthesizing exo-tetrahydrodicyclopentadiene, which comprises: in the presence of a solvent, bridge type tetrahydro-dicyclopentadiene is contacted with a catalyst for hydroisomerization reaction, wherein the catalyst is the catalyst for synthesizing hanging type tetrahydro-dicyclopentadiene in the hydroisomerization reaction in the first aspect of the invention.
The method adopts the catalyst containing the H-type molecular sieve and the active component with specific types and proportions to be used in the reaction of synthesizing the exo-tetrahydrodicyclopentadiene by hydroisomerization, can obtain excellent raw material conversion rate and product yield, and can avoid chloride which is necessary to be used in the method in the prior art so as to overcome the defects of corrosion of a device or potential safety hazard of operation caused by application of the chloride in catalyst industrial application.
Specifically, in the method for synthesizing the exo-tetrahydrodicyclopentadiene by using the catalyst of the first aspect of the present invention to catalyze the hydroisomerization reaction of the bridge-type tetrahydrodicyclopentadiene, for example, a chlorine-containing compound commonly used in the prior art can be avoided, and the conversion rate of the bridge-type tetrahydrodicyclopentadiene and the yield of the exo-tetrahydrodicyclopentadiene can be significantly increased.
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.
As described above, the first aspect of the present invention provides a catalyst for hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene, which contains an H-type molecular sieve and a metal element as an active component, wherein the metal element is at least one selected from Pt element, Pd element and Au element, the H-type molecular sieve is at least one selected from HY, USY, SSY, NTY and ReY molecular sieves, and the sodium content in the H-type molecular sieve is less than 0.5 wt%, wherein the active component content in terms of element in the catalyst is (0.1 to 5) wt%.
Particularly preferably, the metal element is Pt element.
According to a particularly preferred embodiment, the H-type molecular sieve is a ReY molecular sieve and/or a USY molecular sieve in order to obtain a higher conversion when the catalyst is used for catalytic synthesis of exo-tetrahydrodicyclopentadiene.
The Re (rare earth element) element in the ReY molecular sieve of the present invention may be, for example, at least one of La and Ce.
The following provides several preferred technical features of the catalyst for hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene.
Preferably, the active component is present in the catalyst in an amount of (0.3 to 0.5) wt.% on an elemental basis. The inventor of the invention finds that when the sodium content in the H-type molecular sieve is controlled to be less than 0.3 wt%, the obtained catalyst can obviously improve the product yield in the reaction of catalytically synthesizing the exo-tetrahydrodicyclopentadiene.
According to a preferred embodiment, the sodium content in the H-type molecular sieve of the invention is less than 0.4 wt%, more preferably the sodium content is less than 0.3 wt%. The inventor of the invention finds that when the sodium content in the H-type molecular sieve is controlled to be less than 0.3 wt%, the obtained catalyst can enable the conversion rate of raw materials to be higher and the product yield to be higher in the reaction of catalytically synthesizing the exo-tetrahydrodicyclopentadiene.
The catalyst of the present invention may further comprise a carrier such as alumina, silica-containing alumina, etc., which is conventionally used in the art, and the specific content of the carrier such as alumina, silica-containing alumina, etc., is not particularly limited in the present invention, and a person skilled in the art can determine the appropriate content according to the conventional application and operation practice in the art.
The method for preparing the catalyst for the hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene is not particularly limited, and those skilled in the art can adopt the conventional method for preparing the catalyst in the art, but in order to obtain a catalyst with higher bridge-type tetrahydrodicyclopentadiene conversion rate and exo-tetrahydrodicyclopentadiene yield, as described above, the second aspect of the present invention provides a method for preparing the catalyst for the hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene.
Preferably, the conditions for contacting the solution I with the type H molecular sieve include: the temperature is 0-50 ℃ and the time is 0.5-24 h.
Preferably, the drying conditions include: the temperature is 80-150 ℃ and the time is 3-16 h. More preferably, the drying conditions include: the temperature is 100 ℃ and 130 ℃, and the time is 8-12 h.
Preferably, the conditions of the calcination include: the temperature is 400 ℃ and 600 ℃, and the time is 1-6 h. More preferably, the firing conditions include: the temperature is 400 ℃ and 500 ℃, and the time is 2-5 h.
The impregnation method of the present invention may be, for example, an equal-volume impregnation method or an excess impregnation method.
In the present invention, the solution I containing the metal element as an active component can be obtained by various methods conventionally used in the art, and the substance forming the solution I can be any soluble substance containing the metal element as an active component, and for example, can be a soluble salt containing an active metal component, and for example, can be tetraammonium platinum chloride, chloroplatinic acid-hydrochloric acid, a palladium chloride solution, chloroauric acid-hydrochloric acid, or the like. The concentration of the impregnation liquid can be adjusted as required.
In the method of the present invention, before the immersion contact, the water absorption of the H-type molecular sieve may be tested, and the H-type molecular sieve may be dried.
In the method of the present invention, when the metal element as an active component is Pt, preferably, Pt is supported by an equal volume impregnation method; when the active component is Pd and/or Au, preferably, the Pd and/or Au is supported by an equal volume impregnation or excess impregnation method. And drying, roasting, tabletting and screening the solid-liquid mixture obtained after loading to obtain the catalyst with the mesh number of 20-40.
As described above, the third aspect of the present invention provides a method for synthesizing exo-tetrahydrodicyclopentadiene.
In the method for synthesizing exo-tetrahydrodicyclopentadiene of the present invention, it is preferable that the solvent is at least one selected from the group consisting of methylcyclohexane, n-hexane, petroleum ether, C8 paraffin, and exo-tetrahydrodicyclopentadiene.
Particularly preferably, in the method for synthesizing exo-tetrahydrodicyclopentadiene of the present invention, the solvent is methylcyclohexane. The inventor of the invention finds that by adopting methylcyclohexane as the solvent in the method for synthesizing exo-tetrahydrodicyclopentadiene, obviously higher exo-tetrahydrodicyclopentadiene yield can be obtained, and the conversion rate of raw materials is higher.
Preferably, the weight ratio of the solvent to the bridged tetrahydrodicyclopentadiene is (0.6-20): 1.
according to a preferred embodiment, the hydroisomerization reaction conditions comprise: the reaction temperature is 120-180 ℃, the reaction pressure is 0-3MPa, and the mass space velocity is 0.2-10h-1The hydrogen-hydrocarbon volume ratio is 300-3000.
According to a more preferred embodiment, the hydroisomerization reaction conditions comprise: the reaction temperature is 140-170 ℃, the reaction pressure is 0.5-1.5MPa, and the mass space velocity is 1-5h-1The hydrogen-hydrocarbon volume ratio is 600-.
In the present invention, unless otherwise specified, the pressures are gauge pressures.
In addition, the catalyst disclosed by the invention is non-corrosive and has better catalytic stability, no harmful substances to a human body are required to be added in the reaction process, the step of separating the catalyst from a product is not required, and the operation process is simple.
The present invention will be described in detail below by way of examples. Unless otherwise specified, the various starting materials used are commercially available or prepared by methods available in the literature.
The bridged tetrahydrodicyclopentadiene conversion and the product yield in the following examples were respectively obtained by the following formulas.
The percent conversion of bridged tetrahydrodicyclopentadiene (%) × 100% (mass of bridged tetrahydrodicyclopentadiene in 1-reaction product/mass of bridged tetrahydrodicyclopentadiene in reaction raw material)
The yield (%) of the exo-tetrahydrodicyclopentadiene is equal to the mass of exo-tetrahydrodicyclopentadiene in the reaction product/mass of bridged tetrahydrodicyclopentadiene in the reaction raw material x 100%
Preparation example 1
ReY1 molecular sieve: calculated as oxides and by weight, the composition of the ReY1 molecular sieve before ammonium exchange is: na (Na)2O is 1.28%, Al2O320.50% of SiO265.00% of La2O39.80% of CeO20.38%, the balance being impurities; and its sodium content was reduced to 0.05% by ammonium exchange.
(1) A solution of tetraammonium platinum chloride (i.e., solution I) was prepared.
(2) And (2) contacting the solution I with a ReY1 molecular sieve by adopting an isometric impregnation method, wherein the temperature is 20 ℃, the time is 8 hours, drying the impregnated solid substance at 120 ℃ for 10 hours, then roasting at 500 ℃ for 3 hours, and tabletting and screening to obtain the Pt-ReY1 catalyst loaded with 20-40 meshes of Pt, which is named as catalyst A.
Wherein, in the catalyst A, the content of Pt element is 0.5 wt%.
Preparation example 2
ReY2 molecular sieve: calculated as oxides and by weight, the composition of the ReY2 molecular sieve before ammonium exchange is: na (Na)2O is 1.08%, Al2O319.10% of SiO259.20% of La2O313.20% of CeO21.52 percent, and the balance of impurities; and the sodium content was reduced to 0.25% by ammonium exchange.
(1) A solution of tetraammonium platinum chloride (i.e., solution I) was prepared.
(2) And (2) contacting the solution I with a ReY2 molecular sieve by adopting an isometric impregnation method, wherein the temperature is 30 ℃, the time is 6 hours, drying the impregnated solid substance at 100 ℃ for 14 hours, then roasting at 450 ℃ for 4 hours, and tabletting and screening to obtain the Pt-ReY2 catalyst with the supported Pt of 20-40 meshes, wherein the catalyst is named as catalyst B.
Wherein, in the catalyst B, the content of Pt element is 0.5 wt%.
Preparation example 3
ReY3 molecular sieve: calculated as oxides and by weight, the composition of the ReY3 molecular sieve before ammonium exchange is: na (Na)2O is 1.28%, Al2O320.50% of SiO265.00% of La2O39.80% of CeO20.38%, the balance being impurities; and its sodium content was reduced to 0.35% by ammonium exchange.
(1) A solution of tetraammonium platinum chloride (i.e., solution I) was prepared.
(2) And (2) contacting the solution I with a ReY3 molecular sieve by adopting an isometric impregnation method, wherein the temperature is 20 ℃, the time is 8 hours, drying the impregnated solid substance at 120 ℃ for 10 hours, then roasting at 500 ℃ for 3 hours, and tabletting and screening to obtain the Pt-ReY3 catalyst loaded with 20-40 meshes of Pt, which is named as catalyst C.
Wherein, in the catalyst C, the content of Pt element is 0.5 wt%.
Preparation example 4
This preparation example was carried out in a similar manner to preparation example 1, except that the solution I was a palladium chloride solution and the Pd-ReY1 catalyst (designated as catalyst D) supporting Pd obtained in this preparation example was such that the content of the Pd element was 0.3% by weight.
Preparation example 5
This production example was carried out in a similar manner to production example 1, except that the concentration of tetraammonium platinum chloride in the solution I was adjusted so that the Pt-ReY 1-supported Pt catalyst (designated as catalyst E) obtained in this production example had a Pt element content of 0.8 wt%.
Preparation example 6
USY molecular sieves: the USY molecular sieve is prepared by carrying out ammonium exchange and hydrothermal roasting treatment on a NaY molecular sieve, and the composition of the NaY molecular sieve before ammonium exchange is as follows by oxide and weight content: na (Na)2O is 3.93%, Al2O322.9% of SiO272.8 percent, and the balance being impurities; the sodium content of the NaY molecular sieve is reduced to 0.25 percent through ammonium exchange.
(1) A chloroplatinic acid-hydrochloric acid solution (i.e., solution I) was prepared.
(2) And (2) contacting the solution I with a USY molecular sieve by adopting an isometric impregnation method, drying the impregnated solid substance at 100 ℃ for 12h, then roasting at 500 ℃ for 3h, tabletting and screening to obtain the Pt-USY catalyst loaded with Pt of 20-40 meshes, wherein the temperature is 20 ℃, and the time is 8h, and the catalyst is named as catalyst F.
Wherein, in the catalyst F, the content of Pt element is 0.5 wt%.
Preparation example 7
HY molecular sieve: the composition of the NaY molecular sieve prior to ammonium exchange, calculated as oxides and by weight, is: na (Na)2O is 3.93%, Al2O322.9% of SiO272.8%, the balance beingImpurities; and reducing the sodium content to 0.35 percent through ammonium exchange, and further preparing the HY molecular sieve through roasting treatment.
(1) A solution of tetraammonium platinum chloride (i.e., solution I) was prepared.
(2) And (2) contacting the solution I with an HY molecular sieve by an isometric impregnation method at the temperature of 20 ℃ for 8 hours, drying the impregnated solid matter at 120 ℃ for 10 hours, then roasting at 500 ℃ for 3 hours, tabletting and screening to obtain the Pt-HY catalyst loaded with 20-40 meshes, and naming the catalyst as catalyst G.
Wherein, in the catalyst G, the content of Pt element is 0.5 wt%.
Comparative preparation example 1
This comparative preparation example was conducted in a similar manner to preparation example 1, except that the solution I was a nickel nitrate solution, and the Ni element content in the Ni-ReY 1-supported Ni-catalyst (designated as catalyst D-Cat1) obtained in this comparative preparation example was made 0.5 wt%.
Comparative preparation example 2
This comparative preparation example was carried out in a similar manner to preparation example 1, except that the concentration of platinum tetraammonium chloride in the solution I was adjusted so that the content of Pt element in the Pt-ReY 1-supported catalyst (designated as catalyst D-Cat2) obtained in this comparative preparation example was 5.5 wt%.
Comparative preparation example 3
This comparative preparation was carried out in a similar manner to preparation 1, except that the sodium content of the ReY1 molecular sieve was reduced to 0.5% by ammonium exchange in this comparative preparation.
In the Pt-ReY 1-supported catalyst (named catalyst D-Cat3) obtained in this comparative preparation example, the content of Pt element was 0.5% by weight.
Test example 1
5g of the catalyst shown in Table 1 were charged in a fixed bed reactor for bridge tetrahydrodicyclopentadiene hydroisomerization with methylcyclohexane as the solvent, and the molar ratio of methylcyclohexane: the weight ratio of the bridge type tetrahydrodicyclopentadiene is 1: 1. the method is carried out in a fixed bed reaction mode under the hydrogen condition, and the hydrogen isomerization reaction condition is as follows:the reaction temperature is 150 ℃, the reaction pressure is 0.5MPa, the volume ratio of hydrogen to hydrocarbon is 1300, and the mass space velocity is 2h-1And feeding the liquid phase by a plunger pump, and starting reaction after the reaction raw materials enter a catalyst bed layer.
As a result: after the reaction was stably operated, the conversion of the bridged tetrahydrodicyclopentadiene (indicated as "conversion" in the following table) and the yield of the exo-tetrahydrodicyclopentadiene (indicated as "yield" in the following table) were as shown in table 1.
TABLE 1
| Catalyst and process for preparing same | Conversion rate/% | Yield/% |
| A | 98.2 | 95.8 |
| B | 98.5 | 95.6 |
| C | 94.5 | 92.2 |
| D | 98.3 | 94.9 |
| E | 98.0 | 93.8 |
| F | 98.5 | 95.4 |
| G | 96.8 | 94.0 |
| D-Cat1 | 92.8 | 89.2 |
| D-Cat2 | 70.5 | 63.5 |
| D-Cat3 | 75.0 | 72.0 |
Test example 2
The test example was carried out in a similar manner to test example 1, except that the hydroisomerization reaction conditions in this test example were as follows: the reaction temperature is 170 ℃, the reaction pressure is 0.5MPa, the volume ratio of hydrogen to hydrocarbon is 1300, and the mass space velocity is 1h-1。
The rest is the same as in test example 1.
As a result: after the reaction was stably operated, the conversion of the bridged tetrahydrodicyclopentadiene and the yield of the exo-tetrahydrodicyclopentadiene are shown in Table 2.
TABLE 2
| Catalyst and process for preparing same | Conversion rate/% | Yield/% |
| A | 98.5 | 95.5 |
| B | 98.3 | 95.2 |
| C | 95.8 | 91.5 |
| D | 98.4 | 95.2 |
| E | 98.3 | 92.8 |
| F | 98.5 | 95.3 |
| G | 97.6 | 94.2 |
| D-Cat1 | 93.0 | 87.0 |
| D-Cat2 | 71.2 | 60.7 |
| D-Cat3 | 76.7 | 70.5 |
Test example 3
This test example was conducted in a similar manner to test example 1, except that the hydroisomerization reaction solvent was n-hexane.
The rest is the same as in test example 1.
As a result: after the reaction was stably operated, the conversion of the bridged tetrahydrodicyclopentadiene and the yield of the exo-tetrahydrodicyclopentadiene are shown in Table 3.
TABLE 3
From the results, when the catalyst for synthesizing the exo-tetrahydrodicyclopentadiene through hydroisomerization provided by the invention is used for synthesizing the exo-tetrahydrodicyclopentadiene, the conversion rate of the bridge-type tetrahydrodicyclopentadiene can reach more than 93% under various flexible reaction conditions, and the yield of the exo-tetrahydrodicyclopentadiene can reach more than 91%.
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 (10)
1. A catalyst for synthesizing hanging type tetrahydro dicyclopentadiene by hydroisomerization, which contains an H-type molecular sieve and a metal element as an active component, wherein the metal element is at least one selected from Pt element, Pd element and Au element, the H-type molecular sieve is at least one selected from HY, USY, SSY, NTY and ReY molecular sieves, and the sodium content in the H-type molecular sieve is less than 0.5 wt%, and the content of the active component calculated by the element in the catalyst is (0.1-5) wt%.
2. The catalyst according to claim 1, wherein the active component is contained in the catalyst in an amount of (0.3-0.5) wt% on an elemental basis.
3. The catalyst of claim 1 or 2, wherein the sodium content in the H-type molecular sieve is less than 0.4 wt%; it is further preferred that the sodium content is less than 0.3 wt%.
4. A process for preparing a catalyst for the hydroisomerization synthesis of exo-tetrahydrodicyclopentadiene as claimed in any of claims 1 to 3, which process comprises: the method comprises the steps of contacting a solution I containing metal elements as active components with an H-type molecular sieve by adopting an impregnation method, and drying and roasting intermediates obtained after the contact in sequence.
5. The method of claim 4, wherein the conditions under which solution I is contacted with the type H molecular sieve comprise: the temperature is 0-50 ℃ and the time is 0.5-24 h.
6. A method for synthesizing exo-tetrahydrodicyclopentadiene, the method comprising: in the presence of a solvent, bridge type tetrahydro-dicyclopentadiene is contacted with a catalyst for hydroisomerization reaction, wherein the catalyst is the catalyst for hydroisomerization synthesis of hanging type tetrahydro-dicyclopentadiene according to any one of claims 1 to 3.
7. The method of claim 6, wherein the solvent is selected from at least one of methylcyclohexane, n-hexane, petroleum ether, and C8 paraffin;
preferably, the solvent is methylcyclohexane.
8. The process according to claim 6 or 7, wherein the weight ratio of the solvent to the bridged tetrahydrodicyclopentadiene is (0.6-20): 1.
9. the process of any one of claims 6 to 8, wherein the hydroisomerization reaction conditions comprise: the reaction temperature is 120-180 ℃, the reaction pressure is 0-3MPa, and the mass space velocity is 0.2-10h-1The hydrogen-hydrocarbon volume ratio is 300-3000.
10. The process of claim 9, wherein the hydroisomerization reaction conditions comprise: the reaction temperature is 140-170 ℃, the reaction pressure is 0.5-1.5MPa, and the mass space velocity is 1-5h-1The hydrogen-hydrocarbon volume ratio is 600-.
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| WO2023046050A1 (en) * | 2021-09-24 | 2023-03-30 | 中国石油化工股份有限公司 | Continuous method for preparing exo-tetrahydrodicyclopentadiene |
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| CN106669777A (en) * | 2016-12-27 | 2017-05-17 | 中央军委后勤保障部油料研究所 | Preparation method of endo-tetrahydrodicyclotadiene isomerization catalyst |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
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| CN103100399A (en) * | 2011-11-11 | 2013-05-15 | 中国石油化工股份有限公司 | Preparation method of mesoporous-microporous composite molecular sieve |
| CN106669777A (en) * | 2016-12-27 | 2017-05-17 | 中央军委后勤保障部油料研究所 | Preparation method of endo-tetrahydrodicyclotadiene isomerization catalyst |
| CN106699499A (en) * | 2016-12-27 | 2017-05-24 | 中央军委后勤保障部油料研究所 | Method for improving isomeric selectivity of endo-tetrahydrodicyclotadiene |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| WO2023046050A1 (en) * | 2021-09-24 | 2023-03-30 | 中国石油化工股份有限公司 | Continuous method for preparing exo-tetrahydrodicyclopentadiene |
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