A method and system for the production of a pendant tetrahydrodicyclopentadiene and the pendant tetrahydrodicyclopentadiene obtained

Abstract

The application discloses a method and system for preparing a hanging tetrahydrodicyclopentadiene and the obtained hanging tetrahydrodicyclopentadiene, and the method comprises the following steps: in the presence of hydrogen, heavy aromatic hydrocarbon is sequentially subjected to a first reaction, a second reaction and rectification treatment, and in the rectification treatment, a rich bridge type tetrahydrodicyclopentadiene fraction is taken out from a side line; in the presence of hydrogen, the bridge type tetrahydrodicyclopentadiene in the rich bridge type tetrahydrodicyclopentadiene fraction is subjected to a conversion reaction to obtain the hanging tetrahydrodicyclopentadiene. The system comprises a first reactor, a second reactor, a rectification tower and a re-reactor which are sequentially connected. The application takes heavy aromatic hydrocarbon as a raw material, and after the first reaction and the second reaction, a rich tetrahydrodicyclopentadiene fraction is taken out from a side line through rectification, the tetrahydrodicyclopentadiene is a bridge type tetrahydrodicyclopentadiene, the purity of the bridge type tetrahydrodicyclopentadiene in the fraction is greater than 96%, and the content of sulfur and nitrogen is less than 1 ppm, the fraction has high cleanliness and can be directly used for isomerization to prepare the hanging tetrahydrodicyclopentadiene.

Description

TECHNICAL FIELD

[0001] The present application belongs to the preparation of exo-tetrahydrodicyclopentadiene, and particularly relates to a method and system for preparing exo-tetrahydrodicyclopentadiene and the obtained exo-tetrahydrodicyclopentadiene. BACKGROUND

[0002] The exo-tetrahydrodicyclopentadiene has a low freezing point (-79℃), a suitable flash point (55℃), a high volumetric heat value (39.6 MJ / L) and low toxicity, and is a high-density liquid hydrocarbon fuel with excellent performance, which can be directly used as a high-density carbon-hydrogen fuel or used as a solvent or additive mixed with other high-density carbon-hydrogen fuels, and is widely used as a propellant for missiles, rockets, torpedoes and other aircraft, and is the most widely used and the best high-density carbon-hydrogen fuel in terms of comprehensive performance. Meanwhile, the exo-tetrahydrodicyclopentadiene can also be used as a solvent or diluent for paints and surfactants and lubricating oil.

[0003] In the prior art, the preparation method of the exo-tetrahydrodicyclopentadiene mainly comprises the following steps: first, obtaining endo-tetrahydrodicyclopentadiene (endo-THDCPD) by hydrogenating dicyclopentadiene (DCPD); and then, synthesizing the exo-tetrahydrodicyclopentadiene (exo-THDCPD) by isomerization of the endo-tetrahydrodicyclopentadiene through an acidic catalyst.

[0004] At present, the dicyclopentadiene is mainly obtained from by-product carbon five and by-product carbon nine in cracking. Due to different compositions and separation processes, the purity of the dicyclopentadiene obtained from the by-product carbon five is generally about 80%, and the purity of the dicyclopentadiene obtained from the by-product carbon nine is generally above 93%. Although they are both dicyclopentadiene, the purity of the dicyclopentadiene obtained from the by-product carbon five is obviously lower, and the cost of obtaining dicyclopentadiene with the same purity is higher.

[0005] On the one hand, the dicyclopentadiene has particular chemical activity and flammable and explosive hazards, and strict safety measures must be taken in the production process of the dicyclopentadiene, which greatly increases the production cost and the loss. Moreover, the obtained dicyclopentadiene must be polymerized to obtain dicyclopentadiene dimers, and then the dicyclopentadiene dimers are used to prepare endo-tetrahydrodicyclopentadiene by hydrogenation, and the exo-tetrahydrodicyclopentadiene is prepared by isomerization of the endo-tetrahydrodicyclopentadiene through a catalyst.

[0006] On the other hand, the hydrogenation of the dicyclopentadiene is mostly carried out in a batch reaction kettle, and the product endo-tetrahydrodicyclopentadiene can also be obtained through a continuous catalytic hydrogenation device. In the hydrogenation process of the dicyclopentadiene, the catalysts mostly used are noble metal catalysts or metal catalysts, and the catalytic effect is good. Representative catalysts are palladium-carbon catalyst and Raney nickel catalyst, but the palladium-carbon catalyst is relatively expensive, and the preparation process of the Raney nickel catalyst is relatively complex, and the reaction pressure required is relatively high.

[0007] For example, CN101134707A discloses a method for preparing a hanging type tetrahydrodicyclopentadiene, which comprises the following steps: preparing a metal salt aqueous solution, preparing a supported catalyst, catalyzing a reaction, and separating and purifying, etc. The reaction catalyst is a noble metal supported catalyst, and the selectivity of the hanging type tetrahydrodicyclopentadiene is up to 65.68% at a low space velocity.

[0008] Therefore, it is necessary to prepare the hanging type tetrahydrodicyclopentadiene by using cleaner and cheaper raw materials and a simpler process. SUMMARY

[0009] In order to overcome the problems in the prior art, the present application provides a method and system for preparing a hanging type tetrahydrodicyclopentadiene and the obtained hanging type tetrahydrodicyclopentadiene, wherein the method uses heavy aromatic hydrocarbons as raw materials, and the heavy aromatic hydrocarbons are subjected to two-stage reactions (preferably hydrogenation reactions) and rectification treatment to obtain a bridge type tetrahydrodicyclopentadiene, and then the bridge type tetrahydrodicyclopentadiene is used to prepare the hanging type tetrahydrodicyclopentadiene. In the method, the hanging type tetrahydrodicyclopentadiene can be directly obtained without extracting or preparing dicyclopentadiene in the intermediate process, and the by-products can be directly used for oil blending or returned to the device for utilization. The process route has high raw material cleanliness and low cost.

[0010] One of the purposes of the present application is to provide a method for preparing a hanging type tetrahydrodicyclopentadiene, which comprises:

[0011] (1) sequentially performing a first-stage reaction, a second-stage reaction and rectification treatment on heavy aromatic hydrocarbons in the presence of hydrogen, and in the rectification treatment, a bridge type tetrahydrodicyclopentadiene-rich fraction is taken out from a side line of a product rectification column;

[0012] (2) in the presence of hydrogen, the bridge type tetrahydrodicyclopentadiene-rich fraction is subjected to a reaction to obtain a hanging type tetrahydrodicyclopentadiene.

[0013] In step (1), a fraction segment is taken out from a side line of a product rectification column on the basis of an existing industrial device, and the fraction segment is rich in the bridge type tetrahydrodicyclopentadiene. The fraction segment has low impurity content, high cleanliness, and sulfur and nitrogen contents of less than 1 ppm, and meets the technical requirements for producing the hanging type tetrahydrodicyclopentadiene.

[0014] In a preferred embodiment, in step (1), the conditions of the first-stage reaction include: a temperature of 30-180 ℃; and / or, a pressure of 1-6 MPa; and / or, a hydrogen / oil volume ratio of (200-1200):1; and / or, a volume space velocity of 0.1-2.0 h -1 .

[0015] In a further preferred embodiment, in step (1), the conditions of the first-stage reaction comprise: a temperature of 40-170°C; and / or, a pressure of 2-5 MPa; and / or, a hydrogen to oil volume ratio of (300-800): 1; and / or, a volume space velocity of 0.3-1.5 h -1 .

[0016] For example, the conditions of the first-stage reaction comprise: a temperature of 40°C, 50°C, 60°C, 70°C, 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C or 170°C; and / or, a pressure of 2 MPa, 3 MPa, 4 MPa or 5 MPa; and / or, a hydrogen to oil volume ratio of 300: 1, 400: 1, 500: 1, 600: 1, 700: 1 or 800: 1; and / or, a volume space velocity of 0.3 h -1 , 0.5 h -1 , 0.8 h -1 , 1 h -1 , 1.2 h -1 or 1.5 h -1 .

[0017] In a preferred embodiment, in step (1), the conditions of the second-stage reaction comprise: a temperature of 100-500°C; and / or, a pressure of 1-7 MPa; and / or, a hydrogen to oil volume ratio of (900-3000): 1; and / or, a volume space velocity of 0.1-2.0 h -1 .

[0018] In a further preferred embodiment, in step (1), the conditions of the second-stage reaction comprise: a temperature of 200-350°C; and / or, a pressure of 2-5 MPa; and / or, a hydrogen to oil volume ratio of (1000-2000): 1; and / or, a volume space velocity of 0.3-1.5 h -1 .

[0019] For example, the conditions of the second-stage reaction comprise: a temperature of 200°C, 250°C, 300°C or 350°C; and / or, a pressure of 2 MPa, 2.5 MPa, 3 MPa, 3.5 MPa, 4 MPa, 4.5 MPa or 5 MPa; and / or, a hydrogen to oil volume ratio of 1000: 1, 1100: 1, 1200: 1, 1300: 1, 1400: 1, 1500: 1, 1600: 1, 1700: 1, 1800: 1, 1900: 1 or 2000: 1; and / or, a volume space velocity of 0.3 h -1 , 0.5 h -1 , 0.8 h -1 , 1 h -1 , 1.2 h -1 or 1.5 h -1 .

[0020] In a preferred embodiment, the first reaction is carried out in the presence of a catalyst I, said catalyst I comprising a support I selected from one or a combination of two of alumina, silica, and an active component I selected from at least one of Mo, Ni, Co, W.

[0021] Preferably, the active component I is supported on the support I. Catalyst I is prepared by conventional methods for preparing hydrogenation catalysts, the support I is prepared by kneading and extruding, and the active component I is prepared by incipient wetness impregnation.

[0022] In a further preferred embodiment, the support I is alumina; and / or, the active component I is Ni.

[0023] In a still further preferred embodiment, in the catalyst I, the support I is present in an amount of 75 to 95 wt%, preferably 81 to 92 wt%; and / or, the active component I is present in an amount of 5 to 25 wt%, preferably 8 to 19 wt%.

[0024] For example, in the catalyst I, the support I is present in an amount of 75 wt%, 80 wt%, 85 wt%, 90 wt%, or 95 wt%; and / or, the active component I is present in an amount of 5 wt%, 10 wt%, 15 wt%, 20 wt%, or 25 wt%.

[0025] In a preferred embodiment, the second reaction is carried out in the presence of a catalyst II, said catalyst II comprising a support II selected from at least one of alumina, silica, titania (e.g. a combination of one or two or a combination of three), and an active component II selected from at least one of Mo, Ni, Co, W (e.g. a combination of one or two or a combination of three or a combination of four). Preferably, the active component II is supported on the support II.

[0026] Catalyst II is prepared by conventional methods for preparing hydrogenation catalysts, the support II is prepared by kneading and extruding, and the active component II is prepared by incipient wetness impregnation,

[0027] In a further preferred embodiment, the support II is selected from alumina, silica, a combination of silica-alumina or a combination of alumina-silica-titania, preferably a combination of alumina-silica-titania; and / or, the active component II is selected from at least two of Mo, Ni, Co, W, preferably two, three or four of Mo, Ni, Co, W, more preferably Mo, Ni, Co, and W.

[0028] The inventors have found through a large number of experiments that the effect is better when using a combination of carriers than when using a single carrier, most preferably the effect is better when using two or three carriers in combination, and the effect is best when using three carriers; the effect is better when using a combination of active components than when using a single active component, most preferably the effect is better when using four or three or two active components, and the effect is best when using four or three active components.

[0029] In a further preferred embodiment, in the catalyst II, the content of the carrier II is 60-85 wt%, preferably 65-82 wt%; and / or, the content of the active component II is 15-40 wt%, preferably 18-35 wt%.

[0030] For example, in the catalyst II, the content of the carrier II is 60 wt%, 65 wt%, 70 wt%, 75 wt%, 80 wt% or 85 wt%; and / or, the content of the active component II is 15 wt%, 20 wt%, 25 wt%, 30 wt%, 35 wt% or 40 wt%.

[0031] In a most preferred embodiment, when the carrier II is selected from a combination of silica-alumina or titania-alumina, the content of silica or titania is 2-15 wt% and the content of alumina is 85-98 wt%, based on 100 wt% of the carrier II.

[0032] For example, when the carrier II is selected from a combination of silica-alumina or titania-alumina, the content of silica or titania is 2 wt%, 5 wt%, 8 wt%, 10 wt%, 12 wt% or 15 wt% and the content of alumina is 85 wt%, 88 wt%, 90 wt%, 92 wt%, 95 wt% or 98 wt%, based on 100 wt% of the carrier II.

[0033] In another most preferred embodiment, when the carrier II is selected from a combination of alumina-silica-titania, the content of silica is 2-8 wt%, the content of titania is 1-5 wt%, and the content of alumina is 87-97 wt%, based on 100 wt% of the catalyst II.

[0034] In a preferred embodiment, the pore volume of the carrier II is 0.3-0.8 mL / g; and / or, the specific surface area is 150-300 m 2 / g; and / or, the average pore diameter is 7-14 nm.

[0035] For example, the catalyst II has a pore volume of 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 mL / g; and / or, a specific surface area of 150, 180, 200, 220, 250, 280 or 300 m 2 / g; and / or, an average pore diameter of 7, 8, 9, 11, 12, 13 or 14 nm.

[0036] In a preferred embodiment, in step (1), the rectification is carried out in a rectification column, wherein the overhead temperature is 80-150°C, the bottom temperature is 150-250°C, and the overhead pressure is -120 to -50 KPa.

[0037] In a further preferred embodiment, in step (1), the rectification is carried out in a rectification column, wherein the overhead temperature is 110-135°C, the bottom temperature is 170-195°C, and the overhead pressure is -90 to -75 KPa.

[0038] For example, the overhead temperature is 110°C, 115°C, 120°C, 125°C, 130°C or 135°C, the bottom temperature is 170°C, 175°C, 180°C, 185°C, 190°C or 195°C, and the overhead pressure is -90, -85, -80 or -75 KPa.

[0039] In a still further preferred embodiment, the rectification column is a plate column.

[0040] In a preferred embodiment, in step (1), the side draw is carried out at 183-200°C, and the fraction segment is a rich-bridged tetrahydrodicyclopentadiene fraction.

[0041] In a further preferred embodiment, in step (1), the side draw is carried out at 183-200°C, or 190-200°C, or 190-195°C, or 190-193°C (preferably 191-193°C), and the fraction segment is a rich-bridged tetrahydrodicyclopentadiene fraction.

[0042] Since the boiling point of bridged tetrahydrodicyclopentadiene is 192°C, the side draw at 183-200°C (preferably 190-195°C, more preferably 191-193°C) is a rich-bridged tetrahydrodicyclopentadiene fraction. Thus, in the present application, a single side draw of a rectification column can achieve the requirement of obtaining a rich-bridged tetrahydrodicyclopentadiene fraction segment, which has the advantages of shortening the process, saving cost and improving efficiency.

[0043] The inventors have found through a large number of experiments that a single rectification column combined with a side draw can obtain a rich-bridged tetrahydrodicyclopentadiene fraction, which is completely not involved in the prior art.

[0044] In a preferred embodiment, in the bridge-type tetrahydrodicyclopentadiene-rich fraction segment, the bridge-type tetrahydrodicyclopentadiene content is greater than 96%, and the sulfur and nitrogen contents are both less than 1 ppm, and the purity is high.

[0045] In a preferred embodiment, step (2) is carried out in the presence of catalyst III, which is selected from any catalyst for preparing the hanging-type tetrahydrodicyclopentadiene from the bridge-type tetrahydrodicyclopentadiene disclosed in the prior art, preferably but not limited to at least one selected from the group consisting of aluminum trichloride, aluminum tribromide, and iron trichloride.

[0046] In a further preferred embodiment, the amount of catalyst III used is 0.1 wt% to 10 wt%, based on 100 wt% of the bridge-type tetrahydrodicyclopentadiene-rich fraction.

[0047] For example, the amount of catalyst III used is 0.1 wt%, 0.5 wt%, 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, or 10 wt%, based on 100 wt% of the bridge-type tetrahydrodicyclopentadiene-rich fraction.

[0048] In a preferred embodiment, the reaction conditions of step (2) include a temperature of 20 to 150°C, preferably 60 to 130°C; and / or a pressure of normal pressure to 3 MPa; and / or a time of 1 to 5 h.

[0049] For example, the conversion conditions of step (2) include a temperature of 60°C, 80°C, 90°C, 100°C, 120°C, or 150°C; and / or a pressure of normal pressure, 0.5 MPa, 1 MPa, 1.5 MPa, 2 MPa, 2.5 MPa, or 3 MPa; and / or a time of 1 h, 2 h, 3 h, 4 h, or 5 h.

[0050] In the present application, the yield of the hanging-type tetrahydrodicyclopentadiene is greater than 95% by using the method of the present application.

[0051] In the present application, the heavy aromatic hydrocarbon is a mixed aromatic hydrocarbon with carbon nine aromatic hydrocarbon as the main component, which is mainly derived from ethylene tar and cracking C9, and the distillation range of the heavy aromatic hydrocarbon mixed raw material is 138°C to 234°C; wherein the bromine value is 80 gBr / 100 g oil, the S content is 230 ppm, and the N content is 36 ppm.

[0052] The second object of the present application is to provide a system for preparing the hanging-type tetrahydrodicyclopentadiene, which is preferably used for carrying out the method of the first object of the present application, and the system comprises a reactor segment, a second reactor segment, a rectifying column, and a re-reaction reactor connected in sequence.

[0053] In a preferred embodiment, the catalyst I is loaded in the first reactor, the catalyst I comprising a support I selected from one or a combination of alumina, silica and an active component I selected from at least one of Mo, Ni, Co, W.

[0054] In a further preferred embodiment, the support I is alumina; and / or, the active component I is Ni.

[0055] Preferably, the active component I is supported on the support I, the catalyst being prepared by a conventional hydroprocessing catalyst preparation method, the support being kneaded and extruded, and the active component being impregnated by volume.

[0056] In a still further preferred embodiment, in the catalyst I, the support I is present in an amount of 75-95 wt%, preferably 81-92 wt%, and the active component I is present in an amount of 5-25 wt%, preferably 8-19 wt%.

[0057] In a preferred embodiment, the catalyst II is loaded in the second reactor, the catalyst II comprising a support II selected from at least one of alumina, silica, titania (e.g. one or a combination of two or a combination of three) and an active component II selected from at least one of Mo, Ni, Co, W (e.g. one or a combination of two or a combination of three or a combination of four).

[0058] In a further preferred embodiment, the support II is selected from alumina, silica, a combination of silica-alumina or a combination of alumina-silica-titania, preferably a combination of alumina-silica-titania; and / or, the active component II is selected from at least two of Mo, Ni, Co, W, preferably two, three or four of Mo, Ni, Co, W, more preferably Mo, Ni, Co and W.

[0059] Preferably, the catalyst II is prepared by a conventional hydroprocessing catalyst preparation method, the support being kneaded and extruded, and the active component being impregnated by volume.

[0060] In a still further preferred embodiment, in the catalyst II, the support II is present in an amount of 60-85 wt%, preferably 65-82 wt%, and the active component II is present in an amount of 15-40 wt%, preferably 18-35 wt%.

[0061] In a preferred embodiment, the support II has a pore volume of 0.3-0.8 mL / g; and / or, a specific surface area of 120-300 m 2 / g; and / or, an average pore diameter of 7-14 nm.

[0062] For example, the pore volume of the carrier II is 0.3, 0.4, 0.5, 0.6, 0.7 or 0.8 mL / g; and / or, the specific surface area is 120, 150, 180, 200, 220, 250, 280 or 300 m 2 / g; and / or, the average pore diameter is 7, 8, 9, 10, 11, 12, 13 or 14 nm.

[0063] In a preferred embodiment, a side draw outlet is provided in the rectification column at a fraction of 183-200°C, which is the fraction rich in endo-tetrahydrodicyclopentadiene.

[0064] In a further preferred embodiment, a side draw outlet is provided in the rectification column at a fraction of 183-193°C or 190-200°C or 190-195°C or 190-193°C, which is the fraction rich in endo-tetrahydrodicyclopentadiene.

[0065] For example, the feed position is 42-48% and the side draw outlet is 69-81%, in terms of the rectification column from top to bottom position of 0-100%; for example, the feed position is 42%, 43%, 44%, 45%, 46%, 47% or 48%, and the side draw outlet is 72%, 73%, 74%, 75%, 76%, 77%, 78%, 79%, 80% or 81% or a range between any two values thereof, for example 74-75%, 73-76%, 73-80% or 69-75%.

[0066] Wherein, the rectification column is provided with a feed position and a side draw outlet, and is also provided with a top outlet and a bottom outlet.

[0067] In a preferred embodiment, the re-reactor is a stirred tank, preferably a magnetic stirred tank.

[0068] Wherein, the (magnetic) stirred tank can be charged with materials for reaction.

[0069] The third object of the present application is to provide a hanging tetrahydrodicyclopentadiene obtained by the method of the first object of the present application or the system of the second object of the present application.

[0070] The endpoints of the ranges and any values described herein are not limited to the precise values stated. The endpoints of the ranges are provided as a separate matter from the values within the ranges. The range endpoints are solely useful as a separate matter for indicating that a range of values will be encompassed. For values which are less than or greater than a stated range, the range is intended to encompass values which are both less than and greater than the stated range. The same is true for ranges which are stated to be between two values. These ranges are simply used as a separate matter from the actual values which will be encompassed. In the following, the individual technical solutions can in principle be combined with each other to give new technical solutions, which should also be considered to be specifically disclosed herein.

[0071] Compared with the prior art, the present application has the following beneficial effects: the present application takes heavy aromatic hydrocarbon as raw material, after one-stage hydrogenation reaction and two-stage hydrogenation reaction, a four-hydrogen dicyclopentadiene-rich fraction is obtained by rectification side line, the four-hydrogen dicyclopentadiene is bridge-type four-hydrogen dicyclopentadiene, the purity of the bridge-type four-hydrogen dicyclopentadiene in the fraction is greater than 96%, and the sulfur and nitrogen are both less than 1 ppm, the fraction has high cleanliness and can be used for directly isomerizing to prepare hanging-type four-hydrogen dicyclopentadiene. BRIEF DESCRIPTION OF DRAWINGS

[0072] Figure 1 A flowchart of the method of the present application is shown. DETAILED DESCRIPTION

[0073] The present application will be described in detail below with reference to specific examples. It is necessary to point out that the following examples are only used to further illustrate the present application and cannot be understood as limiting the protection scope of the present application. Some non-essential improvements and adjustments of the present application made by those skilled in the art according to the content of the present application still fall within the protection scope of the present application.

[0074] In addition, it should be noted that the various specific technical features described in the following specific embodiments can be combined in any appropriate manner without contradiction. In order to avoid unnecessary repetition, various possible combinations are not described again in the present application.

[0075] Furthermore, various different embodiments of the present application can also be combined in any appropriate manner, as long as it does not deviate from the idea of the present application, and the technical solutions thus formed are part of the original disclosure of the present specification and also fall within the protection scope of the present application.

[0076] The raw materials used in the examples and comparative examples are all disclosed in the prior art if not particularly limited, for example, can be directly purchased or prepared according to the preparation method disclosed in the prior art.

[0077] Heavy aromatic hydrocarbon is a mixed aromatic hydrocarbon with carbon nine aromatic hydrocarbon as main component, which is mainly derived from ethylene tar and cracking C9. The distillation range of the heavy aromatic hydrocarbon mixed raw material is 138-254℃, the bromine value is 80gBr / 100g oil, the S content is 230ppm, and the N content is 36ppm.

[0078] The yield of the hanging type tetrahydrodicyclopentadiene is % = (the generated amount of the hanging type tetrahydrodicyclopentadiene / the added amount of the bridge type tetrahydrodicyclopentadiene) × 100%.

[0079] Example 1

[0080] The heavy aromatic hydrocarbon mixed raw material is sequentially subjected to one-stage hydrogenation reaction and two-stage hydrogenation reaction. The one-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component contains 15% nickel oxide and the rest is alumina, based on weight. The two-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component contains 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, and 2wt% titanium oxide, and the rest is alumina. The pore volume of the two-stage hydrogenation catalyst carrier is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0081] The temperature of the one-stage hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 The temperature of the two-stage hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0082] Then, rectification is performed. The feed position is 44% and the side line sampling outlet is 74-75% in the rectification tower from top to bottom in a position of 0-100%. The rectification tower top temperature is 126℃, the tower bottom temperature is 185℃, the tower top pressure is -80KPa, and the side line sampling outlet is 191℃-193℃ fraction. A rich tetrahydrodicyclopentadiene fraction is obtained, in which the content of the bridge type tetrahydrodicyclopentadiene fraction is 97%. The sulfur and nitrogen contents of the fraction are both less than 1ppm.

[0083] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen gas protection is performed, normal pressure, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, and after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography. The yield of the hanging type tetrahydrodicyclopentadiene is 96.8%.

[0084] Example 2

[0085] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation in sequence; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the remainder is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, 2wt% titanium oxide, and the remainder is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0086] The temperature of the first stage of hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 The temperature of the second stage of hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0087] Then, rectification is performed, the feed position is 44% and the side line extraction position is 73-76% based on the position of 0-100% from top to bottom of the rectification tower, the rectification tower top temperature is 126℃, the tower kettle temperature is 185℃, the tower top pressure is -80KPa, the side line extraction temperature is 190℃-195℃, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of tetrahydrodicyclopentadiene fraction is 93.2%. The sulfur and nitrogen contents of the fraction are both less than 1ppm.

[0088] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen gas protection is performed, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of exo-tetrahydrodicyclopentadiene is 92.2%.

[0089]

Example 3

[0090] The heavy aromatic hydrocarbon mixture is subjected to a first-stage hydrogenation reaction and a second-stage hydrogenation reaction in sequence; the first-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component comprises 15% nickel oxide and the balance is alumina, based on weight; the second-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component comprises 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, and 2wt% titanium oxide, and the balance is alumina, the pore volume of the carrier of the second-stage hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0091] The temperature of the first-stage hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 ; the temperature of the second-stage hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0092] Then, rectification is performed, the feed position is 44% and the side line extraction position is 73-80% in the rectification column from top to bottom in a position of 0-100%, the rectification column top temperature is 126℃, the column bottom temperature is 185℃, the column top pressure is -80KPa, the side line extraction is a fraction of 190℃-200℃, and a tetrahydrodicyclopentadiene-rich fraction is obtained, wherein the content of tetrahydrodicyclopentadiene is 76.6%. The sulfur and nitrogen contents of the fraction are both less than 1ppm.

[0093] 40g of the obtained tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of exo-tetrahydrodicyclopentadiene is 74.3%.

[0094]

Example 4

[0095] The heavy aromatic hydrocarbon mixture is subjected to a first-stage hydrogenation reaction and a second-stage hydrogenation reaction in sequence; the first-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component comprises 15% nickel oxide and the balance is alumina, based on weight; the second-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component comprises 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, and 2wt% titanium oxide, and the balance is alumina, the pore volume of the carrier of the second-stage hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0096] The temperature of the first-stage hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 ; the temperature of the second-stage hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0097] Then, rectification is performed, the feed position is 44% and the side line take-off position is 69-75% in the rectification column from top to bottom in a position of 0-100%, the rectification column top temperature is 126℃, the column bottom temperature is 185℃, the column top pressure is -80KPa, the side line take-off temperature is 183℃-193℃, and a tetrahydrodicyclopentadiene-rich fraction is obtained, wherein the content of tetrahydrodicyclopentadiene is 82.3%. The sulfur and nitrogen contents of the fraction are both less than 1ppm.

[0098] 40g of the obtained tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, the reaction temperature is 100℃, the stirring speed is 400r / min, the reaction time is 3 hours, and after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of exo-tetrahydrodicyclopentadiene is 80.5%.

[0099]

Example 5

[0100] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the remainder is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 7wt% silicon oxide, and the remainder is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.66mL / g, the specific surface area is 249m 2 / g, and the average pore diameter is 8.43nm.

[0101] The temperature of the first stage of hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 ; the temperature of the second stage of hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0102] Then, rectification is performed, the feed position is 44% based on the 0-100% position from top to bottom of the rectification tower, the side line extraction outlet is 74-75%, the rectification tower top temperature is 126℃, the tower kettle temperature is 185℃, the tower top pressure is -80KPa, the side line extraction outlet is 191℃-193℃, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of the bridged tetrahydrodicyclopentadiene fraction is 96.5%. The sulfur and nitrogen content of the fraction is less than 2ppm.

[0103] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen gas protection is performed, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of the bridged tetrahydrodicyclopentadiene is 96.3%.

[0104]

Example 6

[0105] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation in sequence; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the remainder is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, and the remainder is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.65mL / g, the specific surface area is 210m 2 / g, and the average pore diameter is 8.25nm.

[0106] The first stage of hydrogenation is carried out at a temperature of 80℃, a pressure of 3MPa, a hydrogen to oil volume ratio of 600:1, and a volume space velocity of 0.8h -1 ; the second stage of hydrogenation is carried out at a temperature of 280℃, a pressure of 3.2MPa, a hydrogen to oil volume ratio of 1250:1, and a volume space velocity of 1h -1 .

[0107] The product is then subjected to rectification, and based on the rectification column from top to bottom, the feed position is 44%, the side line extraction outlet is 74-75%, the rectification column top temperature is 126℃, the column bottom temperature is 185℃, the column top pressure is -80KPa, the side line extraction outlet is 191℃-193℃, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of bridged tetrahydrodicyclopentadiene is 95.8%. The sulfur and nitrogen content of the fraction is less than 2ppm.

[0108] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled, the reaction is carried out at normal pressure, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of bridged tetrahydrodicyclopentadiene is 93.9%.

[0109]

Example 7

[0110] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation in sequence; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the remainder is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, and the remainder is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.65mL / g, the specific surface area is 210m2 The average pore diameter is 11.3 nm.

[0111] The temperature of the first-stage hydrogenation is 80°C, the pressure is 3 MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8 h -1 The temperature of the second-stage hydrogenation is 280°C, the pressure is 3.2 MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1 h -1 .

[0112] Then, rectification is performed, the feed position is 44%, the side line take-out position is 74-75%, the rectification tower top temperature is 126°C, the tower bottom temperature is 185°C, the tower top pressure is -80 KPa, the side line takes out a 191°C-193°C fraction, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of the bridged tetrahydrodicyclopentadiene fraction is 96.6%. The sulfur and nitrogen contents of the fraction are both less than 2 ppm.

[0113] The 40 g of the obtained rich tetrahydrodicyclopentadiene fraction is added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, the reaction temperature is 100°C, the stirring rate is 400 r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography. The yield of the bridged tetrahydrodicyclopentadiene is 96.4%.

[0114]

Example 8

[0115] The heavy aromatic hydrocarbon mixture raw material is sequentially subjected to first-stage hydrogenation and second-stage hydrogenation. The first-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is equal-volume impregnated, and based on weight, 15% nickel oxide and the balance of aluminum oxide are included. The second-stage hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is equal-volume impregnated, and based on weight, 14 wt% molybdenum oxide, 13 wt% nickel oxide, 5 wt% silicon oxide, and 2 wt% titanium oxide are included, and the balance is aluminum oxide. The pore volume of the second-stage hydrogenation catalyst carrier is 0.64 mL / g, the specific surface area is 223 m 2 / g, and the average pore diameter is 11.3 nm.

[0116] The temperature of the first-stage hydrogenation is 80°C, the pressure is 3 MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8 h -1 The temperature of the second-stage hydrogenation is 280°C, the pressure is 3.2 MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1 h -1 .

[0117] Then, rectification is performed, with the rectification column from top to bottom position being 0-100%, feed position being 44%, side line taking out position being 74-75%, rectification column top temperature being 126°C, column bottom temperature being 185°C, column top pressure being -80KPa, side line taking out 191-193°C fraction, to obtain a rich tetrahydrodicyclopentadiene fraction, wherein the content of bridged tetrahydrodicyclopentadiene fraction is 95.2%. The sulfur and nitrogen content of the fraction is less than 3ppm.

[0118] Then, rectification is performed, with the rectification column from top to bottom position being 0-100%, feed position being 44%, side line taking out position being 74-75%, rectification column top temperature being 126°C, column bottom temperature being 185°C, column top pressure being -80KPa, side line taking out 191-193°C fraction, to obtain a rich tetrahydrodicyclopentadiene fraction, wherein the content of bridged tetrahydrodicyclopentadiene fraction is 95.2%. The sulfur and nitrogen content of the fraction is less than 3ppm.

[0119]

Example 9

[0120] The heavy aromatic hydrocarbon mixture raw material is subjected to primary hydrogenation reaction and secondary hydrogenation reaction in sequence; wherein the primary hydrogenation catalyst is prepared by conventional catalyst preparation method, the carrier is kneaded extrusion, and the active component is equal volume impregnation, and based on weight, it contains 15% nickel oxide and the rest is alumina; the secondary hydrogenation catalyst is prepared by conventional catalyst preparation method, the carrier is kneaded extrusion, and the active component is equal volume impregnation, and based on weight, it contains 27wt% nickel oxide, 5wt% silicon oxide, 2wt% titanium oxide, and the rest is alumina, the pore volume of the carrier of the secondary hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0121] The temperature of the primary hydrogenation is 80°C, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 ; the temperature of the secondary hydrogenation is 280°C, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0122] Then, rectification is performed, with the rectification column from top to bottom position being 0-100%, feed position being 44%, side line taking out position being 74-75%, rectification column top temperature being 126°C, column bottom temperature being 185°C, column top pressure being -80KPa, side line taking out 191-193°C fraction, to obtain a rich tetrahydrodicyclopentadiene fraction, wherein the content of bridged tetrahydrodicyclopentadiene fraction is 95.2%. The sulfur and nitrogen content of the fraction is less than 3ppm.

[0123] The 40 g of the obtained tetrahydrodicyclopentadiene-rich fraction is added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, normal pressure, reaction temperature is 100°C, stirring rate is 400 r / min, reaction time is 3 hours, after the reaction, the product is weighed, the product components are analyzed by gas chromatography, the yield of the hanging type tetrahydrodicyclopentadiene is 81.7%.

[0124]

Example 10

[0125] The heavy aromatic hydrocarbon mixture raw material is subjected to primary hydrogenation reaction and secondary hydrogenation reaction in sequence; the primary hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component includes 15% nickel oxide and the rest is alumina by weight; the secondary hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in an equal volume, and the active component includes 5 wt% molybdenum oxide, 4 wt% nickel oxide, 3 wt% cobalt oxide, 15 wt% tungsten oxide, 5 wt% silicon oxide, and 2 wt% titanium oxide, and the rest is alumina, the pore volume of the carrier of the secondary hydrogenation catalyst is 0.64 mL / g, the specific surface area is 223 m 2 / g, and the average pore diameter is 11.3 nm.

[0126] The temperature of the primary hydrogenation is 50°C, the pressure is 2 MPa, the hydrogen / oil volume ratio is 400:1, the volume space velocity is 0.4 h -1 ; the temperature of the secondary hydrogenation is 210°C, the pressure is 2.2 MPa, the hydrogen / oil volume ratio is 1000:1, and the volume space velocity is 0.5 h -1 .

[0127] Then, rectification is performed, the feeding position is 44% in the rectification column from top to bottom, the side line sampling outlet is 74-75%, the rectification column top temperature is 126°C, the column bottom temperature is 185°C, the column top pressure is -80 KPa, the side line sampling outlet is 191°C-193°C fraction, and the tetrahydrodicyclopentadiene-rich fraction is obtained, wherein the content of the bridged tetrahydrodicyclopentadiene fraction is 96.7%. It is measured that the sulfur and nitrogen contents of the fraction are both less than 1 ppm.

[0128] The 40 g of the obtained tetrahydrodicyclopentadiene-rich fraction is added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, normal pressure, reaction temperature is 100°C, stirring rate is 400 r / min, reaction time is 3 hours, after the reaction, the product is weighed, the product components are analyzed by gas chromatography, the yield of the hanging type tetrahydrodicyclopentadiene is 81.7%.

[0129]

Example 11

[0130] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the remainder is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, 2wt% titanium oxide, and the remainder is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0131] The temperature of the first stage of hydrogenation is 160℃, the pressure is 4.6MPa, the hydrogen / oil volume ratio is 800:1, and the volume space velocity is 1.4h -1 ; the temperature of the second stage of hydrogenation is 330℃, the pressure is 4.5MPa, the hydrogen / oil volume ratio is 2000:1, and the volume space velocity is 1.5h -1 .

[0132] Then, rectification is performed, the feed position is 44% and the side line extraction position is 74-75% based on the rectification tower from top to bottom, the rectification tower top temperature is 126℃, the tower kettle temperature is 185℃, the tower top pressure is -80KPa, the side line extraction temperature is 191℃-193℃, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of the bridged tetrahydrodicyclopentadiene fraction is 95.4%. The sulfur and nitrogen contents of the fraction are both less than 1ppm.

[0133] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen gas protection is performed, the reaction temperature is 100℃, the stirring rate is 400r / min, the reaction time is 3 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of the bridged tetrahydrodicyclopentadiene is 94.8%.

[0134]

Example 12

[0135] The heavy aromatic hydrocarbon mixture is subjected to a first stage of hydrogenation and a second stage of hydrogenation; the first stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 15% nickel oxide and the rest is alumina; the second stage of hydrogenation catalyst is prepared by a conventional catalyst preparation method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume, and based on weight, 5wt% molybdenum oxide, 4wt% nickel oxide, 3wt% cobalt oxide, 15wt% tungsten oxide, 5wt% silicon oxide, 2wt% titanium oxide, and the rest is alumina, the pore volume of the carrier of the second stage of hydrogenation catalyst is 0.64mL / g, the specific surface area is 223m 2 / g, and the average pore diameter is 11.3nm.

[0136] The temperature of the first stage of hydrogenation is 80℃, the pressure is 3MPa, the hydrogen / oil volume ratio is 600:1, and the volume space velocity is 0.8h -1 ; the temperature of the second stage of hydrogenation is 280℃, the pressure is 3.2MPa, the hydrogen / oil volume ratio is 1250:1, and the volume space velocity is 1h -1 .

[0137] Then, rectification is performed, the feed position is 44% and the side line extraction position is 74-75% based on the 0-100% position of the rectification tower from top to bottom, the rectification tower top temperature is 110℃, the tower kettle temperature is 170℃, the tower top pressure is -90KPa, the side line extraction temperature is 191℃-193℃, and a rich tetrahydrodicyclopentadiene fraction is obtained, wherein the content of the bridged tetrahydrodicyclopentadiene fraction is 96.6%. The sulfur and nitrogen content of the fraction is less than 1ppm.

[0138] 40g of the obtained rich tetrahydrodicyclopentadiene fraction is added to a 100ml magnetic stirring kettle, 1.2g of anhydrous aluminum chloride (catalyst) is added, hydrogen is filled for protection, the reaction pressure is 2MPa, the reaction temperature is 60℃, the stirring speed is 400r / min, the reaction time is 5 hours, after the reaction is completed, the product is weighed, and the product components are analyzed by gas chromatography, and the yield of the bridged tetrahydrodicyclopentadiene is 96.1%.

[0139]

Example 13

[0140] The heavy aromatic hydrocarbon mixture is subjected to first-stage hydrogenation and second-stage hydrogenation in sequence. The first-stage hydrogenation catalyst is prepared by a conventional method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume. The active component comprises 15% nickel oxide and the balance is alumina, based on weight. The second-stage hydrogenation catalyst is prepared by a conventional method, the carrier is kneaded and extruded, and the active component is impregnated in equal volume. The active component comprises 5% molybdenum oxide, 4% nickel oxide, 3% cobalt oxide, 15% tungsten oxide, 5% silicon oxide and 2% titanium oxide, based on weight, and the balance is alumina. The pore volume of the carrier of the second-stage hydrogenation catalyst is 0.64 mL / g, the specific surface area is 223 m 2 / g, and the average pore diameter is 11.3 nm.

[0141] The first-stage hydrogenation is carried out at a temperature of 80°C, a pressure of 3 MPa, a hydrogen / oil volume ratio of 600:1 and a volume space velocity of 0.8 h -1 .

[0142] The second-stage hydrogenation is carried out at a temperature of 280°C, a pressure of 3.2 MPa, a hydrogen / oil volume ratio of 1250:1 and a volume space velocity of 1 h -1 .

[0143] The distillation is then carried out at a feed position of 44% and a side line take-off position of 74-75% in the distillation column, a column top temperature of 135°C, a column bottom temperature of 195°C, a column top pressure of -75 KPa, and a side line take-off temperature of 191°C-193°C, to obtain a rich tetrahydrodicyclopentadiene fraction, wherein the content of bridged tetrahydrodicyclopentadiene is 96.2%. The sulfur and nitrogen contents of the fraction are both less than 1 ppm.

[0144]

Comparative Example 1

[0145] The tetrahydrodicyclopentadiene fraction obtained by hydrogenation of dicyclopentadiene has a dicyclopentadiene content of 82% and a sulfur and nitrogen content of more than 5 ppm. The specific operation is as follows:

[0146] The 40 g of the obtained tetrahydrodicyclopentadiene fraction was added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) was added, hydrogen was filled for protection, normal pressure, the reaction temperature was 100°C, the stirring rate was 400 r / min, the reaction time was 2 hours, after the reaction was completed, the product was weighed, and the product components were analyzed by gas chromatography, the yield of the hanging type tetrahydrodicyclopentadiene was 81.1%.

[0147] Comparative Example 2

[0148] The tetrahydrodicyclopentadiene fraction obtained by hydrogenation of the carbon five dicyclopentadiene was used, the fraction was composed of 79.8% of tetrahydrodicyclopentadiene, and the sulfur and nitrogen content of the fraction was greater than 8 ppm. The specific operation was as follows:

[0149] The 40 g of the obtained tetrahydrodicyclopentadiene fraction was added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) was added, hydrogen was filled for protection, normal pressure, the reaction temperature was 100°C, the stirring rate was 400 r / min, the reaction time was 2 hours, after the reaction was completed, the product was weighed, and the product components were analyzed by gas chromatography, the yield of the hanging type tetrahydrodicyclopentadiene was 81.1%.

[0150] Comparative Example 3

[0151] The process of Example 1 was repeated, except that the overhead material was directly taken out. The content of the hanging type tetrahydrodicyclopentadiene fraction was 43.6%. The sulfur and nitrogen content of the fraction was less than 1 ppm.

[0152] The 40 g of the obtained tetrahydrodicyclopentadiene fraction was added into a 100 ml magnetic stirring kettle, 1.2 g of anhydrous aluminum chloride (catalyst) was added, hydrogen was filled for protection, normal pressure, the reaction temperature was 100°C, the stirring rate was 400 r / min, the reaction time was 2 hours, after the reaction was completed, the product was weighed, and the product components were analyzed by gas chromatography, the yield of the hanging type tetrahydrodicyclopentadiene was 81.1%.

[0153] Comparative Example 4

[0154] The process of Example 1 was repeated, except that two rectification towers were used for rectification, the first rectification tower was a packed tower, operated at normal pressure, the overhead temperature was 190°C, and the column bottom temperature was 230°C, the column bottom material of the first rectification tower entered the second rectification tower, the second rectification tower was a plate tower, the overhead temperature was 115°C, the column bottom temperature was 165°C, and the overhead pressure was -95 KPa, the overhead obtained a fraction with a normal pressure distillation range of 190-193°C, and a tetrahydrodicyclopentadiene-rich fraction was obtained, wherein the content of the hanging type tetrahydrodicyclopentadiene was 96.9%. The sulfur and nitrogen content of the fraction was less than 1 ppm.

[0155] The 40 g of the obtained tetrahydrodicyclopentadiene fraction was added into a 100 ml magnetic stirring tank reactor, 1.2 g of anhydrous aluminum chloride (catalyst) was added, hydrogen was filled for protection, the reaction temperature was 100 ℃, the stirring speed was 400 r / min, the reaction time was 2 hours, after the reaction was completed, the product was weighed, and the product components were analyzed by gas chromatography. The yield of the hanging tetrahydrodicyclopentadiene was 96.6%.

[0156] Compared with Example 1, the comparative example 4 needs to use two rectifying towers, which increases the cost, and the process is more complex and the flow is more complicated. The Example 1 uses one rectifying tower to achieve the technical effect of two rectifying towers in the comparative example 4.

[0157] The above detailed description of the present application is made in combination with the specific implementation and the exemplary examples, but these descriptions cannot be understood as the limitation of the present application. Those skilled in the art understand that the technical solutions and the implementation of the present application can be variously replaced, modified or improved without deviating from the spirit and scope of the present application, and these all fall within the scope of the present application. The protection scope of the present application is subject to the appended claims.

Claims

1. A method for preparing exo-tetrahydrodicyclopentadiene, comprising: (1) sequentially subjecting heavy aromatic hydrocarbons to a first reaction, a second reaction and a rectification treatment in the presence of hydrogen, in which a rich exo-tetrahydrodicyclopentadiene fraction is side-drawn in the rectification treatment, wherein the side-draw outlet is 74-75% or 73-76% of the rectification column from top to bottom; (2) subjecting the rich exo-tetrahydrodicyclopentadiene fraction to a reaction in the presence of hydrogen to obtain exo-tetrahydrodicyclopentadiene; the first reaction is carried out in the presence of catalyst I, which comprises carrier I and active component I, the carrier I is selected from alumina, and the active component I is selected from at least one of Mo, Ni, Co and W; the second reaction is carried out in the presence of catalyst II, which comprises carrier II and active component II, the carrier II is selected from an alumina-silica-titania combination, and the active component II is Mo, Ni, Co and W; in the catalyst I, the content of the carrier I is 75-95 wt%, and the content of the active component I is 5-25 wt%; in the catalyst II, the content of the carrier II is 60-85 wt%, and the content of the active component II is 15-40 wt%.

2. The method of claim 1, wherein, The conditions of the one-stage reaction include: a temperature of 30-180℃; and / or, a pressure of 1-6 MPa; and / or, a hydrogen / oil volume ratio of (200-1200):1; and / or, a volume space velocity of 0.1-2.0 h -1 .

3. The method of claim 1, wherein, The conditions of the second reaction include: a temperature of 100-500℃; and / or, a pressure of 1-7 MPa; and / or, a hydrogen / oil volume ratio of (900-3000):1; and / or, a volume space velocity of 0.1-2.0 h -1 .

4. The method according to claim 1, characterized in that: the rectification treatment is carried out in a rectification column, in which the overhead temperature is 80-150°C, the bottom temperature is 150-250°C, and the overhead pressure is -120 to -50 KPa.

5. The method according to one of claims 1 to 4, characterized in that Step (2) is carried out in the presence of catalyst III, which is selected from at least one of aluminum trichloride, aluminum tribromide and ferric trichloride.

6. The method of claim 5, wherein, Based on 100 wt% of the rich exo-tetrahydrodicyclopentadiene fraction, the amount of catalyst III used is 0.1 wt% to 10 wt%.

7. The method of claim 5, wherein, The reaction in step (2) is carried out under conditions including: a temperature of 20-150°C; and / or a pressure of normal pressure to 3 MPa; and / or a time of 1-5 h.

8. A system for preparing a hanging type of tetrahydrodicyclopentadiene, for carrying out the method according to any one of claims 1 to 7, said system comprising, in sequence, a first reactor, a second reactor, a rectifying column and a re-reactor, the side line take-off being between 74 and 75% or between 73 and 76% of the rectifying column, in terms of the position from top to bottom of the rectifying column, said first reactor being loaded with a catalyst I, said catalyst I comprising a support I selected from one of alumina, silica and an active component I selected from at least one of Mo, Ni, Co, W, said second reactor being loaded with a catalyst II, said catalyst II comprising a support II selected from an alumina-silica-titania combination and an active component II being Mo, Ni, Co and W, the content of the support I in the catalyst I being between 75 and 95% by weight and the content of the active component I being between 5 and 25% by weight, the content of the support II in the catalyst II being between 60 and 85% by weight and the content of the active component II being between 15 and 40% by weight.

9. The system according to claim 8, characterized in that, said re-reactor is a stirred tank.

10. The system according to claim 8, characterized in that, said re-reactor is a magnetically stirred tank. ​ ​

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