A production process, device and method of cyclopentanol

Abstract

The present application includes a production process, device and method of cyclopentanol. The process includes pyrolyzing a raw material containing dicyclopentadiene to obtain a material A containing cyclopentadiene, mixing it with hydrogen and contacting it with a bimetallic catalyst to undergo a hydrogenation reaction to obtain a material B containing cyclopentene, cyclopentadiene and cyclopentane, mixing it with an acid and a solid acid catalyst to undergo a catalytic esterification reaction to obtain a material C containing fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester, and mixing the material C with hydrogen and then mixing it with a copper-based hydrogenation catalyst to undergo a hydrogenation reaction to obtain a product containing cyclopentanol. The device includes a pyrolysis unit, a selective hydrogenation unit, a catalytic distillation unit and a catalytic hydrogenation unit connected in series in a pipeline; the route has low raw material cost, mild reaction conditions, simple operation, low separation energy consumption, and is suitable for continuous and stable large-scale production. Adding an inhibitor prolongs the life of the catalyst and improves the yield. The yield of cyclopentanol is more than 95% based on cyclic olefins as raw materials.

Description

Technical Field

[0001] The present application relates to a production process, device and method of cyclopentanol, and belongs to the new technical field of chemical production and manufacturing. Background Art

[0002] Cyclopentanol is an important organic chemical raw material and intermediate, mainly used in the production of flavors and fragrances, dyes, medicines and other chemical products. At present, the main synthesis methods are: 1) cyclopentanone reduction; 2) cyclopentene direct hydration; 3) cyclopentene indirect hydration.

[0003]

[0004] There are three catalysts and reaction processes used in the cyclopentanone reduction method: 1) cyclopentanone is hydrogenated with lithium aluminum tetrahydride in ether; 2) catalytic hydrogenation is carried out at 150°C and 15MPa in the presence of a chromium copper catalyst; 3) catalytic hydrogenation is carried out at 0.2-0.3MPa in the presence of a Pt catalyst.

[0005] US2414646 et al. reported the indirect hydration of cyclopentene, which mainly involves firstly carrying out an esterification reaction between cyclopentene and sulfuric acid, obtaining the corresponding sulfate ester and then hydrolyzing it:

[0006]

[0007] JP2001181222 reports that the direct hydration route of cyclopentene is that cyclopentene directly reacts with water in the presence of a solid acid catalyst, the reaction conditions are between 100-300° C., and the reaction pressure is between 0.1 MPa-30 MPa.

[0008]

[0009] CN108069819 reported the addition reaction of cyclopentene and acetic acid to generate cyclopentyl acetate, and then hydrolyzing cyclopentyl acetate to obtain cyclopentanol.

[0010] In the above routes: 1) More than 90% of the cyclopentanone raw materials in the cyclopentanone reduction route come from the decomposition process of adipic acid. Due to the high raw material cost, long process route and serious pollution of this route, the cyclopentanone raw material is expensive, and the technical and economic feasibility of the cyclopentanone hydrogenation route is affected; 2) The cyclopentene direct hydration route has obvious advantages in process operation and equipment corrosion resistance, but there are still the following problems: a) High requirements for the purity of cyclopentene and water raw materials. Since the solubility of cyclopentene and upstream materials such as cyclopentane in water is similar, the content of cyclopentane impurities in the cyclopentene raw material must be reduced as much as possible to reduce the negative impact of the dissolution effect of cyclopentane impurities on the reaction rate; b) The hydration reaction rate is slow. Due to the difference in polarity, the solubility of cyclopentene in water is very small, resulting in the limitation of the reaction rate by the reaction concentration; c) The single-pass conversion rate is low. The cyclopentene hydration reaction is a thermodynamic equilibrium-limited reaction, and the cyclopentene single-pass reaction conversion rate can usually only reach about 3%. d) The reaction operation and subsequent separation and circulation costs are high. Since the reaction system is a three-phase complex system of "oil phase (cyclohexene) - water phase - solid phase acid". Strong stirring is required to form an emulsified system to improve the mass transfer of the reaction; the catalyst produces corresponding wear and consumption during the stirring process, and the fine catalyst produced by wear brings difficulties to the subsequent material separation; in addition, due to the low single-pass conversion rate of cyclopentene, a large amount of unreacted cyclopentene material needs to be recycled. 3) The conversion rate of cyclopentene to cyclopentyl carboxylate in the indirect hydration route of cyclopentene can reach about 70%, and cyclopentanol can be subsequently generated by hydrolysis, ester exchange or hydrogenation. Among them, the hydrolysis and ester exchange methods are equilibrium reactions, so they have the disadvantages of low conversion rate and high separation energy consumption.

[0011] Usually, cyclopentene is obtained by depolymerization and hydrogenation of dicyclopentadiene in the C5 component during the petroleum refining process. However, the depolymerization and hydrogenation of dicyclopentadiene causes the cyclopentadiene to polymerize again, the hydrogenation selectivity is not high, and the yield of cyclopentadiene after the reaction is not high. The boiling points of cyclopentadiene, cyclopentene and cyclopentane obtained after the hydrogenation reaction are 42.5°C, 44.2°C and 49.2°C respectively, and they are not easy to separate. This results in high costs for cyclopentene and cyclopentanol produced from cyclopentene.

[0012] Therefore, based on the current technological status, there is still a need to develop a new process for preparing cyclopentanol using dicyclopentadiene in the C5 component as raw material to improve its process economy and make it have the characteristics of safe process operating conditions, high reaction efficiency, low energy consumption and high atomic utilization. Summary of the invention

[0013] According to one aspect of the present application, a production process of cyclopentanol is provided, comprising the following steps:

[0014] The raw material containing dicyclopentadiene is pyrolyzed to obtain material A containing cyclopentadiene; material A is mixed with hydrogen and then contacted with a bimetallic hydrogenation catalyst for a selective hydrogenation reaction to obtain material B containing cyclopentene, cyclopentadiene and cyclopentane; material B is mixed with an acid and a solid acid catalyst for a catalytic esterification reaction to obtain material C containing fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester; material C is mixed with hydrogen and then mixed with a copper-based hydrogenation catalyst for a hydrogenation reaction to obtain a product containing cyclopentanol. The pyrolysis temperature is 200-500°C;

[0015] The active components of the bimetallic hydrogenation catalyst are metal I and metal II; the metal I is Pd; the metal II is selected from one of Pt, Ru, W, and Mo, and the carrier is selected from at least one of Al2O3, SiO2, TiO2, and amorphous silicon-aluminum composite oxide;

[0016] The temperature of the selective hydrogenation is 40-180°C; the pressure is 0.1-1.0 MPa;

[0017] The acid is a fatty acid, selected from at least one of the compounds represented by formula I;

[0018]

[0019] Wherein, R1 is selected from H, C1-C3 hydrocarbon group or C1-C3 halogenated hydrocarbon group;

[0020] Preferably, the C1-C3 hydrocarbon group is selected from C1-C3 alkyl groups;

[0021] Preferably, the C1-C3 halogenated hydrocarbon group is selected from C1-C3 halogenated alkyl groups;

[0022] The polymerization inhibitor is selected from at least one of hydroquinone, p-nitrophenol and p-methoxyphenol;

[0023] The solid acid catalyst is selected from at least one of a modified macroporous strongly acidic ion exchange resin or a modified molecular sieve;

[0024] Preferably, the modification is to load 0.1-1.0% of rare earth elements on a macroporous strongly acidic ion exchange resin or a molecular sieve by impregnation; the rare earth element includes one of La, Ce, Pr, and Nd;

[0025] Preferably, the macroporous strongly acidic ion exchange resin is selected from at least one of Amberlyst15, Amberlyst16, Amberlyst35, Amberlyst36, Amberlyst39 and Amberlyst45;

[0026] Preferably, the molecular sieve is at least one selected from ZSM-5, Beta, Y, MCM-22, and ZSM-35;

[0027] The catalytic distillation pressure is 0.1-1.0 MPa; the temperature is 50-150°C;

[0028] The copper-based hydrogenation catalyst is a copper-based supported catalyst; the copper-based supported catalyst comprises an active component, an additive and a carrier;

[0029] The active component of the copper-based supported catalyst is Cu; preferably, the mass content of copper is 20-50%, calculated as the mass of copper oxide;

[0030] Preferably, the additive is selected from noble metals and transition metals, and the mass content is 0.1 to 1.0%, calculated on the basis of the mass of the metal;

[0031] Preferably, the auxiliary agent is selected from at least one of Au, Ag, Pt, Pd, Zn, Cr, Mo, and W;

[0032] The carrier is selected from at least one of SiO2, Al2O3, amorphous silicon-aluminum composite oxide, and TiO2;

[0033] The hydrogenation reaction temperature is 150-300° C. and the pressure is 2.0-6.0 MPa.

[0034] According to another aspect of the present application, a cyclopentanol production device is provided, the cyclopentanol production device comprising a pyrolysis unit, a selective hydrogenation unit, a catalytic distillation unit and a catalytic hydrogenation unit connected in series through pipelines;

[0035] The pyrolysis unit comprises a pyrolyzer and a gas-liquid separator I which are connected in sequence via pipelines;

[0036] The selective hydrogenation unit comprises a gasification chamber, a first reactor and a gas-liquid separator II;

[0037] The catalytic distillation unit includes a catalytic distillation tower and a gas-liquid separator III;

[0038] The catalytic hydrogenation unit includes a second reactor and a gas-liquid separator IV.

[0039] The top outlet of the separator I in the pyrolysis unit is connected to the feed inlet pipeline of the gasification chamber in the selective hydrogenation unit;

[0040] The middle outlet of the gas-liquid separator II in the selective hydrogenation unit is connected to the feed inlet pipeline of the catalytic distillation tower in the catalytic distillation unit;

[0041] The middle outlet of the gas-liquid separator III in the catalytic distillation unit is communicated with the feed inlet pipeline of the second reactor in the catalytic hydrogenation unit.

[0042] In the pyrolysis unit, the pyrolyzer is connected to the feed inlet pipeline of the gas-liquid separator I;

[0043] In the selective hydrogenation unit, the gasification chamber is connected to the feed inlet pipeline of the first reactor; the discharge port of the first reactor is connected to the feed inlet pipeline of the gas-liquid separator II; the top outlet of the gas-liquid separator II is connected to the gas inlet pipeline of the gasification chamber;

[0044] In the catalytic distillation unit, the bottom outlet of the catalytic distillation tower is connected to the feed inlet pipeline of the gas-liquid separator III; the top outlet of the gas-liquid separator III is connected to the feed inlet of the catalytic distillation tower through a pipeline;

[0045] In the catalytic hydrogenation unit, the discharge port of the second reactor is connected to the feed port pipeline of the gas-liquid separator IV; the top outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the bottom outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the gas-liquid separator II is also provided with a middle product outlet.

[0046] According to another aspect of the present application, a method for producing cyclopentanol is provided, which is produced by the above-mentioned production process and the above-mentioned production device;

[0047] The following steps are involved:

[0048] (1) A raw material containing dicyclopentadiene enters a pyrolyzer, and after pyrolysis, is fractionated in a gas-liquid separator I to obtain a material A containing cyclopentadiene with a boiling point between 40 and 45° C.;

[0049] (2) Material A and hydrogen enter the gasification chamber to mix, then enter the first reactor to contact and react with the bimetallic catalyst, and then pass through the gas-liquid separator II to obtain separated hydrogen and material B containing cyclopentene, cyclopentadiene and cyclopentane with a boiling point between 40 and 50° C.; the separated hydrogen is returned to the gasification chamber through the pipeline from the top outlet of the gas-liquid separator II to continue to participate in the reaction;

[0050] (3) Material B is mixed with an excess of acid and then enters a catalytic distillation tower to contact and react with a solid acid catalyst. The bottom flow of the catalytic distillation tower passes through a gas-liquid separator III to obtain a material C containing fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester with a boiling point between 130 and 180° C. and unreacted acid. The unreacted acid is returned to the catalytic distillation tower through a pipeline from the top outlet of the gas-liquid separator III to continue to participate in the reaction.

[0051] The overhead product of the catalytic distillation tower contains cyclopentane and trace amounts of cyclopentene and cyclopentadiene that have not been completely reacted;

[0052] (4) Material C and hydrogen are mixed and then enter the second reactor to contact and react with the hydrogenation catalyst, and then pass through the gas-liquid separator IV to obtain separated hydrogen, products, unreacted fatty acid cyclopentyl esters and unreacted fatty acid cyclopentenyl esters; the separated hydrogen is returned to the second reactor through the top outlet of the gas-liquid separator IV via a pipeline to continue to participate in the reaction; the unreacted fatty acid cyclopentyl esters and unreacted fatty acid cyclopentenyl esters are returned to the second reactor through the bottom outlet of the gas-liquid separator IV via a pipeline to continue to participate in the reaction;

[0053] The boiling point of the product is between 140 and 141°C; the product contains cyclopentanol;

[0054] Preferably, the product further contains fatty alcohol; the fatty alcohol is a compound having a structure shown in Formula II;

[0055] R1——OH

[0056] Formula II.

[0057] The content of dicyclopentadiene in the raw material is 60.0-99.0wt%;

[0058] The content of cyclopentadiene in material A is 99.0-99.8wt%.

[0059] The temperature of the gasification chamber is 100-500°C;

[0060] The hydrogen gas and material A are mixed at a molar ratio of 1.0 to 1.5, based on the molar amount of cyclopentadiene in material A;

[0061] The space velocity after mixing is 0.6~15g·g -1 ·h -1 , measured by the space velocity of cyclopentadiene in material A;

[0062] The composition of the material B is 94.0-98.0 wt % of cyclopentene, 0.1-2.0 wt % of cyclopentadiene, and 0.1-5.0 wt % of cyclopentane.

[0063] The substances entering the catalytic distillation tower also include a polymerization inhibitor; the polymerization inhibitor is selected from at least one of hydroquinone, p-nitrophenol, and p-methoxyphenol; the content of the polymerization inhibitor is less than 150 ppm;

[0064] The molar ratio of the acid to the cyclopentene in material B is 0.5 to 10.0;

[0065] The space velocity of the material B is 0.6-3.0 g·g -1 ·h-1 , measured by the space velocity of cyclopentene in material B;

[0066] The total content of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in the material C is more than 99.5wt%;

[0067] The mass ratio of the overhead distillate of the catalytic distillation tower to the bottom effluent of the catalytic distillation tower is 1:40-400.

[0068] The molar ratio of hydrogen to material C is 2:1 to 10:1, based on the total molar amount of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C;

[0069] The space velocity of the material C is 0.5 to 2.0 g·g -1 ·h -1 , measured by the space velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C.

[0070] The beneficial effects of this application include:

[0071] 1) In the process route for preparing cyclopentanol by pyrolysis-hydrogenation-addition-hydrogenation of dicyclopentadiene provided in the present application, the starting raw materials are abundant in source and low in price, which can reduce the raw material cost of producing cyclopentanol; and the conversion rate and selectivity of the four process steps in the process route are both above 97%, and the yield of cyclopentanol calculated on the basis of cyclic olefins can reach above 95%, which has outstanding economic efficiency.

[0072] 2) The process for preparing cyclopentanol provided in the present application solves the disadvantage that the separation energy consumption of the mixture of cyclopentadiene, cyclopentene and cyclopentane obtained after the hydrogenation reaction of cyclopentadiene is high due to the similar boiling points, reduces energy consumption, and improves the economy of the overall process. The mixture of cyclopentene, cyclopentadiene and cyclopentane generated after the hydrogenation of cyclopentadiene in the present process does not need to be separated, and can directly enter the catalytic distillation tower to react with monocarboxylic acid for addition reaction. Cyclopentene and cyclopentadiene form carboxylic acid cyclopentyl ester and carboxylic acid cyclopentenyl ester with carboxylic acid, respectively. The conversion rate of cyclopentene and cyclopentadiene can reach more than 99.0%. Therefore, cyclopentene and cyclopentadiene generate ester products through addition reaction and are separated from cyclopentane, saving separation energy consumption.

[0073] 3) The process for preparing cyclopentanol provided by the present application can use the reaction raw materials containing cyclopentadiene to carry out the addition reaction in the addition reaction, thereby avoiding the energy consumption generated by the separation and circulation of cyclopentadiene. The catalyst life is extended by catalyst modification or the addition of inhibitor, and the process also increases the yield of the cyclopentanol product.

[0074] 4) The catalyst prepared by adding a noble metal additive to an ester hydrogenation catalyst in the present application not only has an extremely high conversion rate and selectivity for the hydrogenation of cyclopentyl acetate in the reaction of catalyzing the hydrogenation of a mixture of cyclopentyl acetate and cyclopentenyl acetate to produce cyclopentanol and ethanol, but the added noble metal additive can also promote the hydrogenation saturation of the double bonds of cyclopentenyl acetate and the hydrogenation of the ester bonds, so that cyclopentenyl acetate can also produce cyclopentanol and ethanol with high conversion rate and high selectivity.

[0075] 5) The process route provided in this application is a continuous reaction route with mild reaction conditions and simple operation, which is suitable for continuous and stable large-scale production. BRIEF DESCRIPTION OF THE DRAWINGS

[0076] Figure 1 This is a schematic diagram of a process in one implementation of the present application.

[0077] List of parts and reference numerals:

[0078] a: pyrolysis unit;

[0079] b: Selective hydrogenation unit;

[0080] c: catalytic distillation unit;

[0081] d: Catalytic hydrogenation unit:

[0082] 1: Raw material; 2: Pyrolyzer; 3: Gas-liquid separator I; 4: Material A;

[0083] 5: gasification chamber; 6: first reactor; 7: gas-liquid separator II; 8: hydrogen; 9: material B;

[0084] 10: acid, inhibitor; 11: catalytic distillation tower; 12: gas-liquid separator III; 13: unreacted acid; 14: material C;

[0085] 15: second reactor; 16: gas-liquid separator IV; 17: unreacted fatty acid cyclic ester; 18: product I (fatty alcohol); 19: product II (cyclopentanol). DETAILED DESCRIPTION

[0086] The present invention is further described below in conjunction with the examples, but the present application is not limited to these examples. Unless otherwise specified, the raw materials and addition catalysts in the examples of the present application are purchased through commercial channels. The olefin hydrogenation catalysts and ester hydrogenation catalysts used in the examples of the present application are all prepared in this laboratory.

[0087] The compositions of raw materials and products in this application were measured by gas chromatography.

[0088] The conversion rate and selectivity of the reaction are calculated as follows:

[0089] Cyclopentadiene hydrogenation reaction:

[0090]

[0091]

[0092] Addition reaction:

[0093]

[0094]

[0095]

[0096]

[0097] Cyclopentyl acetate / cyclopentenyl acetate hydrogenation reaction:

[0098]

[0099]

[0100]

[0101]

[0102] The modification method of the solid acid catalyst is to load 0.1-1.0% of rare earth elements on a macroporous strong acid ion exchange resin or a molecular sieve by impregnation; the rare earth element includes one of La, Ce, Pr and Nd.

[0103] Device example 1

[0104] An embodiment of a cyclopentanol production device described in the present application is as follows: the cyclopentanol production device comprises a pyrolysis unit, a selective hydrogenation unit, a catalytic distillation unit and a catalytic hydrogenation unit which are sequentially connected in series through pipelines;

[0105] The pyrolysis unit comprises a pyrolyzer and a gas-liquid separator I which are connected in sequence via pipelines;

[0106] The selective hydrogenation unit comprises a gasification chamber, a first reactor and a gas-liquid separator II;

[0107] The catalytic distillation unit includes a catalytic distillation tower and a gas-liquid separator III;

[0108] The catalytic hydrogenation unit includes a second reactor and a gas-liquid separator IV.

[0109] The top outlet of the separator I in the pyrolysis unit is connected to the feed inlet pipeline of the gasification chamber in the selective hydrogenation unit;

[0110] The middle outlet of the gas-liquid separator II in the selective hydrogenation unit is connected to the feed inlet pipeline of the catalytic distillation tower in the catalytic distillation unit;

[0111] The middle outlet of the gas-liquid separator III in the catalytic distillation unit is communicated with the feed inlet pipeline of the second reactor in the catalytic hydrogenation unit.

[0112] In the pyrolysis unit, the pyrolyzer is connected to the feed inlet pipeline of the gas-liquid separator I;

[0113] In the selective hydrogenation unit, the gasification chamber is connected to the feed inlet pipeline of the first reactor; the discharge port of the first reactor is connected to the feed inlet pipeline of the gas-liquid separator II; the top outlet of the gas-liquid separator II is connected to the gas inlet pipeline of the gasification chamber;

[0114] In the catalytic distillation unit, the bottom outlet of the catalytic distillation tower is connected to the feed inlet pipeline of the gas-liquid separator III; the top outlet of the gas-liquid separator III is connected to the feed inlet of the catalytic distillation tower through a pipeline;

[0115] In the catalytic hydrogenation unit, the discharge port of the second reactor is connected to the feed port pipeline of the gas-liquid separator IV; the top outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the bottom outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the gas-liquid separator IV is also provided with a middle product outlet.

[0116] The following embodiments all use the above-mentioned device to produce cyclopentanol.

[0117] Example 1

[0118] After the raw material 1 with a dicyclopentadiene content of 70wt% enters the pyrolyzer 2 (temperature 300°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0119] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 300°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, they enter the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 6.0g·g -1 ·h -1Based on the cyclopentadiene in material A, the reaction temperature is 90°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.9%, the cyclopentadiene selectivity is 97.5wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 95.9wt% of cyclopentene, 1.1wt% of cyclopentadiene and 2.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0120] 100 ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixture was 2:1. The mixture entered the catalytic distillation tower 11, which was filled with 0.5% La-modified Amberlyst 15 ion exchange resin catalyst. The reaction conditions were pressure 1.0 MPa, reaction temperature 120°C, and feed space velocity 0.6 g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:68. The composition of the catalytic distillation tower top material is 0.4wt% cyclopentadiene, 7.2wt% cyclopentene, and 92.4wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.8% and 99.1%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.5% and 95.2%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0121] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-0.1% Au / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 10:1, and the feed space velocity is 2.0 g·g -1 ·h -1 The reaction temperature is 250 ℃ and the reaction pressure is 6.0 MPa based on the air velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.5% and 97.5% respectively, the ethanol selectivity is 34.5wt%, and the cyclopentanol selectivity is 64.9wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% through gas-liquid separator IV16, and the yield of cyclopentanol calculated based on cyclopentadiene is 96.4%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0122] Example 2

[0123] After the raw material 1 with a dicyclopentadiene content of 85wt% enters the pyrolyzer 2 (temperature 350°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.7wt%.

[0124] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 100°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, they enter the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.5% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 6.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 60°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.4%, the cyclopentene selectivity is 99.5wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 97.4wt% of cyclopentene, 1.6wt% of cyclopentadiene and 0.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0125] 80 ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixed material was 4:1. The mixed material entered the catalytic distillation tower 11, which was filled with 0.5% Ce-modified Amberlyst16 ion exchange resin catalyst. The reaction conditions were pressure 0.5 MPa, reaction temperature 80°C, and feed space velocity 2.0 g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:186. The composition of the catalytic distillation tower top material is 1.4wt% cyclopentadiene, 49.2wt% cyclopentene, and 49.4wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.5% and 99.1%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.2% and 96.7%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0126] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-0.5% Au / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 5:1, and the feed space velocity is 1.0 g·g -1 ·h -1The reaction temperature is 200 ℃ and the reaction pressure is 4.0MPa. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.7% and 97.5% respectively, the ethanol selectivity is 34.1wt%, and the cyclopentanol selectivity is 65.0wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 97.9%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0127] Example 3

[0128] After the raw material 1 with a dicyclopentadiene content of 60wt% enters the pyrolyzer 2 (temperature 350°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0129] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 500°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.5:1, based on the molar amount of cyclopentadiene in material A. After mixing, they enter the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 6.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 150° C. and the reaction pressure is 1.0 MPa. After the reaction, the cyclopentadiene conversion rate is 99.8%, the cyclopentadiene selectivity is 96.4wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50° C., which mainly contains 96.1wt% of cyclopentene, 0.2wt% of cyclopentadiene and 3.6wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0130] Material B is mixed with acetic acid, and the total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixed material is 4:1. The mixed material enters the catalytic distillation tower 11, which is filled with 0.5% Pr modified Amberlyst35 ion exchange resin catalyst. The reaction conditions are pressure 1.0 MPa, reaction temperature 150°C, and feed space velocity 3.0 g·g -1 ·h -1Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:49. The composition of the catalytic distillation tower top material is 0.02wt% cyclopentadiene, 2.6wt% cyclopentene, and 97.4wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.9% and 99.6%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 98.9% and 95.0%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0131] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-1.0% Au / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 2:1, and the feed space velocity is 0.5 g·g -1 ·h -1 The reaction temperature is 200 ℃ and the reaction pressure is 2.0MPa based on the air velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.1% and 97.5% respectively, the ethanol selectivity is 34.3wt%, and the cyclopentanol selectivity is 64.8wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 94.8%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0132] Example 4

[0133] After the raw material 1 with a dicyclopentadiene content of 90wt% enters the pyrolyzer 2 (temperature 350°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0134] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 400°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, they enter the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 0.6g·g -1 ·h -1Based on the cyclopentadiene in material A, the reaction temperature is 50°C and the reaction pressure is 1.0MPa. After the reaction, the cyclopentadiene conversion rate is 99.1%, the cyclopentadiene selectivity is 98.5wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 97.5wt% of cyclopentene, 0.6wt% of cyclopentadiene and 1.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0135] 50 ppm of hydroquinone and 100 ppm of p-nitrophenol were added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixture was 6:1. The mixture entered the catalytic distillation tower 11, which was filled with 0.5% Nd-modified Amberlyst 36 ion exchange resin catalyst. The reaction conditions were pressure 0.1 MPa, reaction temperature 60°C, and feed space velocity 1.0 g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:103. The composition of the catalytic distillation tower top material is 0.4wt% cyclopentadiene, 16.4wt% cyclopentene, and 83.2wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.7% and 99.2%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.4% and 95.7%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0136] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 25% CuO-1.0% Ag / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 10:1, and the feed space velocity is 0.5 g·g -1 ·h -1 The reaction temperature is 150 ℃ and the reaction pressure is 6.0 MPa. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 97.8% and 97.5% respectively, the ethanol selectivity is 34.2wt%, and the cyclopentanol selectivity is 64.9wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 97.2%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0137] Example 5

[0138] After the raw material 1 with a dicyclopentadiene content of 99wt% enters the pyrolyzer 2 (temperature 350°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0139] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 350°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, the mixture enters the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 15.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 150°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.3%, the cyclopentene selectivity is 97.5wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 95.7wt% of cyclopentene, 1.7wt% of cyclopentadiene and 2.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0140] 150ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixed material was 10:1. The mixed material entered the catalytic distillation tower 11, which was filled with 0.1% La modified Amberlyst39 ion exchange resin catalyst. The reaction conditions were pressure 0.1MPa, reaction temperature 50°C, and feed space velocity 1.0g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:66. The composition of the catalytic distillation tower top material is 0.6wt% cyclopentadiene, 10.4wt% cyclopentene, and 89.0wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.7% and 99.1%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.1% and 96.2%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0141] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 35% CuO-0.5% Pt / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 10:1, and the feed space velocity is 1.0 g·g -1 ·h-1 The reaction temperature is 180 ℃ and the reaction pressure is 6.0MPa. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.0% and 97.5% respectively, the ethanol selectivity is 34.1wt%, and the cyclopentanol selectivity is 64.6wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 95.5%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0142] Example 6

[0143] After the raw material 1 with a dicyclopentadiene content of 85wt% enters the pyrolyzer 2 (temperature 200°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.3wt%.

[0144] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 200°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, they enter the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Ru / TO2 olefin hydrogenation catalyst particles, and the feed space velocity is 6.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 80°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.8%, the cyclopentene selectivity is 98.4wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 97.1wt% of cyclopentene, 1.2wt% of cyclopentadiene and 1.6wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0145] 100 ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixed material was 5:1. The mixed material entered the catalytic distillation tower 11, which was filled with 0.1% La modified Amberlyst45 ion exchange resin catalyst. The reaction conditions were pressure 0.5 MPa, reaction temperature 90°C, and feed space velocity 1.0 g·g -1 ·h -1Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:88. The composition of the catalytic distillation tower top material is 0.5wt% cyclopentadiene, 23.3wt% cyclopentene, and 76.1wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.5% and 99.1%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.4% and 96.7%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0146] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-0.1% Pt / Al2O3 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 10:1, and the feed space velocity is 0.5 g·g -1 ·h -1 The reaction temperature is 200 ℃ and the reaction pressure is 4.0MPa. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.2% and 97.5% respectively, the ethanol selectivity is 34.1wt%, and the cyclopentanol selectivity is 64.7wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 96.7%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0147] Example 7

[0148] After the raw material 1 with a dicyclopentadiene content of 80wt% enters the pyrolyzer 2 (temperature 500°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.6wt%.

[0149] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 250°C). After mixing, the molar ratio of hydrogen to cyclopentadiene is 1.2:1, based on the molar amount of cyclopentadiene in material A. After mixing, the mixture enters the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% W / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 3.0g·g -1 ·h -1Based on the cyclopentadiene in material A, the reaction temperature is 120°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 99.1%, the cyclopentadiene selectivity is 96.4wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 95.1wt% of cyclopentene, 0.9wt% of cyclopentadiene and 3.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0150] 100 ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixture was 3:1. The mixture entered the catalytic distillation tower 11, which was filled with 0.1% La-modified ZSM-5 molecular sieve catalyst. The reaction conditions were pressure 1.0 MPa, reaction temperature 150°C, and feed space velocity 0.6 g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:44. The composition of the catalytic distillation tower top material is 0.2wt% cyclopentadiene, 11.8wt% cyclopentene, and 88.0wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.5% and 99.0%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 99.1% and 95.8%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0151] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-0.1% Pd / SiO2 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 10:1, and the feed space velocity is 1.0 g·g -1 ·h -1 The reaction temperature is 300 ℃ and the reaction pressure is 6.0MPa based on the air velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 99.2% and 97.5% respectively, the ethanol selectivity is 34.1wt%, and the cyclopentanol selectivity is 64.9wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% through gas-liquid separator IV16, and the yield of cyclopentanol calculated based on cyclopentadiene is 94.7%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0152] Example 8

[0153] After the raw material 1 with a dicyclopentadiene content of 90wt% enters the pyrolyzer 2 (temperature 250°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0154] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 300°C). The molar ratio of hydrogen to cyclopentadiene is 3.0:1, based on the molar amount of cyclopentadiene in material A. After mixing, the mixture enters the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.1% Mo / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 3.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 90°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.6%, the cyclopentene selectivity is 98.8wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 97.3wt% of cyclopentene, 1.4wt% of cyclopentadiene and 1.2wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0155] 100 ppm of hydroquinone was added to material B, and then mixed with trifluoroacetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixture was 2:1. The mixture entered the catalytic distillation tower 11, which was filled with 1.0% La-modified Amberlyst 15 ion exchange resin catalyst. The reaction conditions were a pressure of 0.5 MPa, a reaction temperature of 100°C, and a feed space velocity of 1.0 g·g -1 ·h -1 Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:116. The composition of the catalytic distillation tower top material is 0.7wt% cyclopentadiene, 24.6wt% cyclopentene, and 74.7wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl trifluoroacetate and cyclopentenyl trifluoroacetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.6% and 99.2%, respectively, and the selectivities of cyclopentyl trifluoroacetate and cyclopentenyl trifluoroacetate are 98.5% and 95.7%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0156] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 35% CuO-0.1% Pd / Al2O3 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl trifluoroacetate and cyclopentenyl trifluoroacetate is 6:1, and the feed space velocity is 0.5 g·g -1 ·h-1 The reaction temperature is 180 ℃ and the reaction pressure is 2.0 MPa. The conversion rates of cyclopentyl trifluoroacetate and cyclopentenyl trifluoroacetate are 98.4% and 97.5% respectively, the ethanol selectivity is 34.5wt%, and the cyclopentanol selectivity is 64.7wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% by gas-liquid separator IV16, and the yield of cyclopentanol calculated by cyclopentadiene is 96.2%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0157] Example 9

[0158] After the raw material 1 with a dicyclopentadiene content of 90wt% enters the pyrolyzer 2 (temperature 250°C), it is separated by the gas-liquid separator I3 to obtain material A with a boiling point between 40 and 45°C and a cyclopentadiene purity of 99.5wt%.

[0159] The hydrogen and material A are mixed and enter the gasification chamber 5 (temperature 3500°C). The molar ratio of hydrogen to cyclopentadiene is 1.5:1, based on the molar amount of cyclopentadiene in material A. After mixing, the mixture enters the first reactor 6 for hydrogenation reaction; the first reactor 6 is filled with 1.0% Pd-0.5% Pt / Al2O3 olefin hydrogenation catalyst particles, and the feed space velocity is 6.0g·g -1 ·h -1 Based on the cyclopentadiene in material A, the reaction temperature is 60°C and the reaction pressure is 0.1MPa. After the reaction, the cyclopentadiene conversion rate is 98.3%, the cyclopentadiene selectivity is 99.5wt%, and the main by-product is cyclopentane. The product after the reaction is separated by gas-liquid separator II7 to obtain hydrogen and material B with a boiling point between 40 and 50°C, which mainly contains 97.7wt% of cyclopentene, 1.7wt% of cyclopentadiene and 0.5wt% of cyclopentane. The hydrogen returns to the gasification chamber 5 to continue the reaction.

[0160] 100 ppm of hydroquinone was added to material B, and then mixed with acetic acid. The total molar ratio of acetic acid to (cyclopentene and cyclopentadiene) in the mixture was 3:1. The mixture entered the catalytic distillation tower 11, which was filled with 0.1% Ce-modified Amberlyst15 ion exchange resin catalyst. The reaction conditions were a pressure of 0.5 MPa, a reaction temperature of 80°C, and a feed space velocity of 1.0 g·g -1 ·h -1Based on the cyclopentene in material B. The mass ratio of the catalytic distillation tower top material to the catalytic distillation tower bottom material is 1:265. The composition of the catalytic distillation tower top material is 2.2wt% cyclopentadiene, 27.8wt% cyclopentene, and 70.0wt% cyclopentane. The catalytic distillation tower bottom material is separated by gas-liquid separator III12 to obtain unreacted acid with an acetic acid content of 99.7% and material C with a total content of cyclopentyl acetate and cyclopentenyl acetate with a boiling point between 155 and 165°C. The conversion rates of cyclopentene and cyclopentadiene during the catalytic distillation process are 99.8% and 99.1%, respectively, and the selectivities of cyclopentyl acetate and cyclopentenyl acetate are 98.9% and 96.5%, respectively. The unreacted acid is returned to the catalytic distillation tower 11 to continue the reaction.

[0161] The material C is mixed with hydrogen and then introduced into the second reactor 15, in which the ester hydrogenation catalyst 30% CuO-0.1% Pd / Al2O3 is loaded. The reaction conditions are that the molar ratio of hydrogen to cyclopentyl acetate and cyclopentenyl acetate is 5:1, and the feed space velocity is 1.0 g·g -1 ·h -1 The reaction temperature is 220 ℃ and the reaction pressure is 5.0MPa based on the air velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C. The conversion rates of cyclopentyl acetate and cyclopentenyl acetate are 98.5% and 97.5% respectively, the ethanol selectivity is 34.3wt%, and the cyclopentanol selectivity is 64.9wt%. The product is separated into hydrogen, unreacted fatty acid cyclic ester, ethanol with a purity of 99.5wt%, and cyclopentanol with a purity of 99.5wt% through gas-liquid separator IV16, and the yield of cyclopentanol calculated based on cyclopentadiene is 97.8%. Hydrogen and unreacted fatty acid cyclic ester are returned to the second reactor 15 to continue the reaction.

[0162] The above are only a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application is disclosed as above with preferred embodiments, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.

Claims

1. A production process of cyclopentanol, characterized in that: The following steps are involved: The raw material containing dicyclopentadiene is pyrolyzed to obtain material A containing cyclopentadiene; the material A is mixed with hydrogen and then contacted with a bimetallic hydrogenation catalyst to undergo a selective hydrogenation reaction to obtain material B containing cyclopentene, cyclopentadiene and cyclopentane; the material B is mixed with an acid and a solid acid catalyst to undergo a catalytic esterification reaction to obtain material C containing fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester; the material C is mixed with hydrogen and then mixed with a copper-based hydrogenation catalyst to undergo a hydrogenation reaction to obtain a product containing cyclopentanol; The active components of the bimetallic hydrogenation catalyst are metal I and metal II; the metal I is Pd; the metal II is selected from one of Pt, Ru, W, and Mo, and the carrier is selected from at least one of Al2O3, SiO2, TiO2, and amorphous silicon-aluminum composite oxide; The solid acid catalyst is selected from at least one of a modified macroporous strongly acidic ion exchange resin or a modified molecular sieve; The modification method of the solid acid catalyst is to load 0.1-1.0% of the rare earth element on a macroporous strong acid ion exchange resin or a molecular sieve by impregnation; The rare earth element includes one of La, Ce, Pr and Nd; The copper-based hydrogenation catalyst is a copper-based supported catalyst; the copper-based supported catalyst comprises an active component, an additive and a carrier; The active component of the copper-based supported catalyst is Cu; The mass content of copper is 20-50%, calculated as the mass of copper oxide; The additive is selected from noble metals and transition metals, and the mass content is 0.1-1.0%, calculated on the basis of metal mass; The auxiliary agent is selected from at least one of Au, Ag, Pt, Pd, Zn, Cr, Mo, and W; The carrier is selected from at least one of SiO2, Al2O3, amorphous silicon-aluminum composite oxide, and TiO2.

2. The production process according to claim 1, characterized in that: The pyrolysis temperature is 200-500°C; The temperature of the selective hydrogenation is 40-180°C; the pressure is 0.1-1.0MPa; The acid is a fatty acid, selected from at least one of the compounds represented by formula I; Formula I Wherein, R1 is selected from H, C1~C3 hydrocarbon group or C1~C3 halogenated hydrocarbon group; The polymerization inhibitor is selected from at least one of hydroquinone, p-nitrophenol and p-methoxyphenol; The catalytic esterification reaction pressure is 0.1-1.0 MPa; the temperature is 50-150°C; The hydrogenation reaction temperature is 150-300°C; the pressure is 2.0-6.0MPa.

3. The production process according to claim 1, characterized in that: The macroporous strongly acidic ion exchange resin is selected from at least one of Amberlyst 15, Amberlyst 16, Amberlyst 35, Amberlyst 36, Amberlyst 39 and Amberlyst 45.

4. The production process according to claim 1, characterized in that: The molecular sieve is at least one selected from ZSM-5, Beta, Y, MCM-22, and ZSM-35.

5. The production process according to claim 2, characterized in that: The C1-C3 hydrocarbon group is selected from C1-C3 alkyl groups.

6. The production process according to claim 2, characterized in that: The C1-C3 halogenated hydrocarbon group is selected from C1-C3 halogenated alkyl groups.

7. A method for producing cyclopentanol, characterized in that: Produced by the production process described in any one of claims 1 to 6; The following steps are involved: (1) The raw material containing dicyclopentadiene enters the pyrolyzer, and after pyrolysis, it is fractionated in the gas-liquid separator I to obtain material A containing cyclopentadiene with a boiling point between 40 and 45°C; (2) Material A and hydrogen enter the gasification chamber to mix, then enter the first reactor to contact and react with the bimetallic catalyst, and then pass through the gas-liquid separator II to obtain separated hydrogen and material B containing cyclopentene, cyclopentadiene and cyclopentane with a boiling point between 40 and 50°C; the separated hydrogen returns to the gasification chamber through the pipeline from the top outlet of the gas-liquid separator II to continue to participate in the reaction; (3) Material B is mixed with excess acid and then enters a catalytic distillation tower to contact and react with a solid acid catalyst. The bottom effluent of the catalytic distillation tower passes through a gas-liquid separator III to obtain a material C containing fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester with a boiling point between 130 and 180° C. and unreacted acid. The unreacted acid is returned to the catalytic distillation tower through a pipeline from the top outlet of the gas-liquid separator III to continue to participate in the reaction. The overhead product of the catalytic distillation tower contains cyclopentane and trace amounts of cyclopentene and cyclopentadiene that have not been completely reacted; (4) Material C and hydrogen are mixed and then enter the second reactor to contact and react with the hydrogenation catalyst, and then pass through the gas-liquid separator IV to obtain separated hydrogen, products, unreacted fatty acid cyclopentyl esters and unreacted fatty acid cyclopentenyl esters; the separated hydrogen is returned to the second reactor through the top outlet of the gas-liquid separator IV via a pipeline to continue to participate in the reaction; the unreacted fatty acid cyclopentyl esters and unreacted fatty acid cyclopentenyl esters are returned to the second reactor through the bottom outlet of the gas-liquid separator IV via a pipeline to continue to participate in the reaction; The boiling point of the product is between 140 and 141°C; the product contains cyclopentanol; Produced using the following equipment: The device comprises a pyrolysis unit, a selective hydrogenation unit, a catalytic distillation unit and a catalytic hydrogenation unit which are sequentially connected in series through pipelines; The pyrolysis unit comprises a pyrolyzer and a gas-liquid separator I which are connected in sequence via pipelines; The selective hydrogenation unit comprises a gasification chamber, a first reactor and a gas-liquid separator II; The catalytic distillation unit includes a catalytic distillation tower and a gas-liquid separator III; The catalytic hydrogenation unit includes a second reactor and a gas-liquid separator IV; The top outlet of the separator I in the pyrolysis unit is connected to the feed inlet pipeline of the gasification chamber in the selective hydrogenation unit; The middle outlet of the gas-liquid separator II in the selective hydrogenation unit is connected to the feed inlet pipeline of the catalytic distillation tower in the catalytic distillation unit; The middle outlet of the gas-liquid separator III in the catalytic distillation unit is connected to the feed inlet pipeline of the second reactor in the catalytic hydrogenation unit; In the pyrolysis unit, the pyrolyzer is connected to the feed inlet pipeline of the gas-liquid separator I; In the selective hydrogenation unit, the gasification chamber is connected to the feed inlet pipeline of the first reactor; the discharge port of the first reactor is connected to the feed inlet pipeline of the gas-liquid separator II; the top outlet of the gas-liquid separator II is connected to the gas inlet pipeline of the gasification chamber; In the catalytic distillation unit, the bottom outlet of the catalytic distillation tower is connected to the feed inlet pipeline of the gas-liquid separator III; the top outlet of the gas-liquid separator III is connected to the feed inlet of the catalytic distillation tower through a pipeline; In the catalytic hydrogenation unit, the discharge port of the second reactor is connected to the feed port pipeline of the gas-liquid separator IV; the top outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the bottom outlet of the gas-liquid separator IV is connected to the feed port pipeline of the second reactor; the gas-liquid separator II is also provided with a middle product outlet.

8. The method according to claim 7, characterized in that The product also contains fatty alcohol; the fatty alcohol is a compound having a structure shown in Formula II; Formula II.

9. The method according to claim 7, characterized in that: (1): the content of dicyclopentadiene in the raw material is 60.0-99.0 wt %; The content of cyclopentadiene in material A is 99.0~99.8wt%.

10. The method according to claim 7, characterized in that (2) Medium: The temperature of the vaporization chamber is 100-500°C; The hydrogen gas and the material A are mixed at a molar ratio of 1.0 to 1.5, based on the molar amount of cyclopentadiene in the material A; The space velocity after mixing is 0.6~15 g . g -1. h -1 , measured by the space velocity of cyclopentadiene in material A; The composition of the material B is 94.0-98.0 wt % of cyclopentene, 0.1-2.0 wt % of cyclopentadiene, and 0.1-5.0 wt % of cyclopentane.

11. The method according to claim 7, characterized in that (3) In the step of: the substance entering the catalytic distillation tower further comprises a polymerization inhibitor; the polymerization inhibitor is selected from at least one of hydroquinone, p-nitrophenol and p-methoxyphenol; the content of the polymerization inhibitor is less than 150 ppm; The molar ratio of the acid to the cyclopentene in material B is 0.5 to 10.0; The space velocity of material B is 0.6~3.0 g . g -1. h -1 , measured by the space velocity of cyclopentene in material B; The total content of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in the material C is more than 99.5wt%; The mass ratio of the overhead distillate of the catalytic distillation tower to the bottom effluent of the catalytic distillation tower is 1:40-400.

12. The method according to claim 7, characterized in that (4) wherein the molar ratio of hydrogen to material C is 2:1 to 10:1, based on the total molar amount of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C; The space velocity of the material C is 0.5~2.0 g . g -1. h -1 , measured by the space velocity of fatty acid cyclopentyl ester and fatty acid cyclopentenyl ester in material C.

Images