Cyclopentadiene dimerization using shell and tube heat exchangers

Abstract

A system and method for producing dicyclopentadiene by thermal dimerization of cyclopentadiene. A feed stream containing cyclopentadiene flows through four shell-and-tube heat exchangers connected in series. Each shell-and-tube heat exchanger comprises a shell and one or more tubes disposed in the shell. A heat transfer medium flows in the shell while the feed stream flows in the tubes to absorb the exothermic heat released by the dimerization of cyclopentadiene in the tubes. In this way, the temperature in the tubes is controlled at a level wherein the conversion of cyclopentadiene is above 99% and the occurrence of a runaway reaction is substantially prevented.

Description

[0001] CROSS-REFERENCE TO RELATED APPLICATIONS

[0002] This application claims priority to and the benefit of U.S. Provisional Application No. 62 / 778,568, filed on December 12, 2018, the contents of which are incorporated herein by reference in their entirety. Technical Field

[0003] The present invention generally relates to systems and methods for producing dicyclopentadiene. More specifically, the present invention relates to systems and methods for producing dicyclopentadiene by thermal dimerization of cyclopentadiene in a reaction system comprising one or more shell and tube heat exchangers. Background Art

[0004] Dicyclopentadiene is used as a highly reactive intermediate in the production of resins such as unsaturated polyesters and aromatics. Typically, dicyclopentadiene is formed by dimerization of cyclopentadiene, a component of pyrolysis gasoline produced by steam cracking of naphtha. In conventional processes for dimerization of cyclopentadiene, tubular reactors are used to provide relatively long residence times sufficient to achieve high conversions. Tubular reactors are often surrounded by large heat dissipation media because cyclopentadiene dimerization is highly exothermic. Some systems include large tanks with one or more impellers to quickly mix the liquids and dissipate the heat generated during the dimerization reaction.

[0005] However, the economic feasibility of conventional cyclopentadiene dimerization processes is relatively limited. First, for conventional methods that achieve a cyclopentadiene conversion greater than 50%, the energy demand is relatively high because the reactor must be kept at an elevated reaction temperature for a long time to achieve the required long residence time. In addition, high reaction temperatures can cause the highly exothermic dimerization reaction to release a large amount of heat, resulting in a runaway reaction in the reaction system. Therefore, in general, the energy consumption of conventional dimerization methods is high. Meanwhile, for stirred tank reactors with impellers, running the impeller requires a large amount of energy. In addition, the impeller cannot fully mix the liquid in the cyclopentadiene dimerization reactor, and such mixing forms hot spots in the liquid in the reactor. These hot spots not only limit the conversion of cyclopentadiene, but also trigger side reactions of cyclopentadiene to form higher polymers other than dimers.

[0006] In general, despite the existence of systems and methods for producing dicyclopentadiene via dimerization, there remains a need in the art for improvements, at least in light of the above-mentioned shortcomings of conventional systems and methods. Summary of the invention

[0007] A solution to at least some of the above problems associated with a system and method for producing dicyclopentadiene by thermal dimerization has been found. The solution is a method for producing dicyclopentadiene in four shell-and-tube heat exchangers in series, the heat exchangers providing a large heat exchange area and a large volume ratio of heat exchange medium to reaction mixture in four reaction stages. In particular, the heat exchange medium can be controlled to a temperature that results in a high conversion rate of cyclopentadiene. In addition, the temperature control mechanism and the configuration of the shell-and-tube heat exchanger can effectively mitigate the temperature rise caused by the large amount of heat released by the dimerization reaction, thereby preventing a runaway reaction from occurring in the reaction system. Therefore, the method of the present invention provides a technical solution to solve at least some of the problems associated with the above-mentioned currently available methods for producing dicyclopentadiene.

[0008] Embodiments of the present invention include a method for producing dicyclopentadiene. The method comprises a first stage, which comprises passing a feed stream comprising cyclopentadiene monomer through a first tube of a first shell-and-tube heat exchanger. The temperature of the feed stream when it enters the first tube is in the range of 40 to 60°C. The first tube comprises fins. The first stage also comprises passing a heat transfer medium through the first shell of the first shell-and-tube heat exchanger in the same direction as the flow of the feed stream. The temperature of the heat transfer medium when it enters the first shell is in the range of 65 to 80°C. The first stage also comprises subjecting the feed stream in the first tube to reaction conditions sufficient to dimerize the cyclopentadiene monomer to form dicyclopentadiene. The temperature of the first stage effluent when it leaves the first tube is in the range of 80 to 90°C. The method also comprises a second stage, which comprises cooling the first stage effluent at a temperature of 90 to 100°C to produce a second stage effluent. The process further comprises a third stage comprising cooling the second stage effluent at a temperature of 110 to 120° C. to produce a third stage effluent. The process further comprises a fourth stage comprising cooling the third stage effluent at a temperature of 120 to 130° C. to produce a fourth stage effluent. Each of the first stage, the second stage, the third stage and the fourth stage is performed in a different shell and tube heat exchanger.

[0009] Embodiments of the present invention include a method for producing dicyclopentadiene. The method comprises a first stage, which comprises passing a feed stream comprising cyclopentadiene monomer through a first tube of a first shell-and-tube heat exchanger. The temperature of the feed stream when it enters the first tube is in the range of 40 to 60°C. The first tube comprises fins. The first stage also comprises passing a heat transfer medium through the first shell of the first shell-and-tube heat exchanger in the same direction as the flow of the feed stream. The temperature of the heat transfer medium when it enters the first shell is in the range of 65 to 80°C. The first stage further comprises subjecting the feed stream in the first tube to reaction conditions sufficient to dimerize the cyclopentadiene monomer to form dicyclopentadiene, wherein the temperature of the first stage effluent when it leaves the first tube is in the range of 80 to 90°C. The temperature of the heat transfer medium when it leaves the first shell is in the range of 70 to 80°C. The method also comprises a second stage, which comprises cooling the first stage effluent at a temperature of 90 to 100°C to produce a second stage effluent. The method further comprises a third stage comprising cooling the second stage effluent at a temperature of 110 to 120° C. to produce a third stage effluent. The method further comprises a fourth stage comprising cooling the third stage effluent at a temperature of 120 to 130° C. to produce a fourth stage effluent. Each of the first stage, the second stage, the third stage and the fourth stage is performed in a different horizontal shell and tube heat exchanger.

[0010] Included below are definitions of various terms and phrases used throughout this specification.

[0011] The term "about" or "approximately" is defined as close to, as understood by one of ordinary skill in the art. In a non-limiting embodiment, these terms are defined as within 10%, preferably within 5%, more preferably within 1%, and most preferably within 0.5%.

[0012] The terms "wt. %, "vol. %" or "mol. %" refer to the weight, volume or mole percentage of a component, respectively, based on the total weight, total volume or total moles of the material including the component. In a non-limiting example, 10 moles of a component in 100 moles of a material is 10 mol.% of the component.

[0013] The term "substantially" and variations thereof are defined to include ranges within 10%, within 5%, within 1% or within 0.5%.

[0014] When used in the claims and / or specification, the terms "inhibit" or "reduce" or "prevent" or "avoid" or any variation of these terms include any measurable amount of reduction or complete inhibition to achieve the desired result.

[0015] The term "effective," as that term is used in the specification and / or claims, means sufficient to achieve a desired, expected, or intended result.

[0016] The term "runaway reaction" as used in the specification and / or claims refers to a thermally unstable reaction system that exhibits an uncontrolled accelerated reaction rate, which results in a rapid increase in temperature and / or pressure.

[0017] The use of the word "a" or "an" when used in conjunction with the terms "comprising," "including," "containing," or "having" in the claims or the specification can mean "one," but it is also consistent with the meaning of "one or more," "at least one," and "one or more than one."

[0018] The terms "comprising" (and any form of comprising, such as "comprise" and "comprises"), "having" (and any form of having, such as "have" and "has"), "including" (and any form of including, such as "includes" and "include"), or "containing" (and any form of containing, such as "contains" and "contain") are inclusive or open-ended, and do not exclude additional, unrecited elements or method steps.

[0019] The methods of the present invention may "comprise," "consist essentially of," or "consist of" a particular ingredient, component, composition, etc. disclosed throughout the specification.

[0020] The term "mainly", as used in the specification and / or claims, means greater than any one of 50 wt.%, 50 mol.%, and 50 vol.%. For example, "mainly" may include 50.1 wt.% to 100 wt.% and all values ​​and ranges therebetween, 50.1 mol.% to 100 mol.% and all values ​​and ranges therebetween, or 50.1 vol.% to 100 vol.% and all values ​​and ranges therebetween.

[0021] Other objects, features and advantages of the present invention will become apparent from the following drawings, detailed descriptions and examples. However, it should be understood that although the drawings, detailed descriptions and examples show specific embodiments of the present invention, they are only given by way of illustration and are not meant to be limiting. In addition, it is expected that changes and modifications within the spirit and scope of the present invention will become apparent to those skilled in the art through this detailed description. In other embodiments, features from a specific embodiment can be combined with features from other embodiments. For example, features from an embodiment can be combined with features from any other embodiment. In other embodiments, additional features can be added to the specific embodiments described herein. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] For a more comprehensive understanding, reference is now made to the following description in conjunction with the accompanying drawings, in which:

[0023] Figure 1 A schematic diagram of a system for producing dicyclopentadiene according to an embodiment of the present invention is shown;

[0024] Figure 2 A schematic flow chart showing a method for producing dicyclopentadiene according to an embodiment of the present invention; and

[0025] Figure 3A and Figure 3B Simulation results are shown for the conversion of cyclopentadiene and the temperature of the reaction mixture versus the length of the tubes in a shell and tube heat exchanger. Figure 3A shows the results of a simulation performed on a shell and tube heat exchanger comprising tubes with 8 fins; Figure 3B Results of simulations performed on a shell and tube heat exchanger comprising tubes without fins are shown. DETAILED DESCRIPTION

[0026] At present, the method for producing dicyclopentadiene by dimerization of cyclopentadiene has several problems such as low conversion rate and runaway reaction in the production system. The low conversion rate of cyclopentadiene can significantly increase the production cost of dicyclopentadiene. The occurrence of runaway reaction can cause the production system to stop completely. The present invention provides a solution for at least some of these problems. The premise of this solution is a method for producing dicyclopentadiene, which comprises four stages, each of which is carried out in a shell and tube heat exchanger, and the shell and tube heat exchanger comprises fins on the tube. The method provides a large heat transfer surface area and a large volume ratio of heat transfer medium to reaction mixture to absorb the exothermic heat released by the dimerization reaction of cyclopentadiene. In addition, the temperature of the heat transfer medium is controlled at a higher temperature than the conventional method to achieve a higher conversion rate and prevent runaway reaction from occurring in the production system. Therefore, the method of the present invention can improve the production efficiency of dicyclopentadiene. These and other non-limiting aspects of the present invention are further discussed in detail in the following sections.

[0027] A. Systems for the production of dicyclopentadiene

[0028] In an embodiment of the present invention, a system for producing dicyclopentadiene by dimerization of cyclopentadiene may include four shell and tube heat exchangers connected in series. Figure 1 , a schematic diagram of a system 100 capable of producing dicyclopentadiene with improved production efficiency and minimized runaway reaction is shown. According to an embodiment of the present invention, the system 100 includes a first shell and tube heat exchanger 101 suitable for receiving a feed stream 11 and a heat transfer medium stream 12. In an embodiment of the present invention, the feed stream 11 contains cyclopentadiene. The heat transfer medium stream 12 may contain water. According to an embodiment of the present invention, the water in the heat transfer medium stream 12 may be chemically treated water or filtered water.

[0029] In an embodiment of the present invention, the first shell and tube heat exchanger 101 includes a shell 102 and one or more first tubes 103 disposed within the first shell 102. According to an embodiment of the present invention, the first shell and tube heat exchanger 101 also includes a first feed inlet 104 disposed on one end of the shell and tube heat exchanger 101. The first feed inlet 104 may be adapted to receive a feed stream 11 into the one or more first tubes 103. The first shell and tube heat exchanger 101 may also include a medium inlet 105 disposed on the same end of the shell and tube heat exchanger 101. The first medium outlet 105 may be adapted to receive a heat transfer medium stream 12 into the first shell 102.

[0030] In an embodiment of the present invention, each of the one or more first tubes 103 includes fins for additional heat exchange surface area. Each tube 103 may include 6 to 10 fins and all ranges and values ​​therebetween, including 7, 8, and 9 fins. The surface area to volume ratio of the one or more first tubes 103 may be 50 to 150 m 2 / m 3 and all ranges and values ​​therebetween, inclusive, from 50 to 55 m 2 / m 3 , 55 to 60m 2 / m 3 , 60 to 65m 2 / m 3 , 65 to 70m 2 / m 3 , 70 to 75m 2 / m 3 , 75 to 80m 2 / m 3 , 80 to 85m 2 / m 3 , 85 to 90m 2 / m 3, 90 to 95m 2 / m 3 , 95 to 100m 2 / m 3 100 to 105m 2 / m 3 , 105 to 110m 2 / m 3 , 110 to 115m 2 / m 3 , 115 to 120m 2 / m 3 120 to 125m 2 / m 3 , 125 to 130m 2 / m 3 130 to 135m 2 / m 3 , 135 to 140m 2 / m 3 140 to 145m 2 / m 3 and 145 to 150m 2 / m 3 In an embodiment of the present invention, the one or more first tubes 103 may have a substantially circular cross-section with a diameter to length ratio in the range of 0.0010 to 0.0020 and all ranges and values ​​therebetween, including 0.0011, 0.0012, 0.0013, 0.0014, 0.0015, 0.0016, 0.0017, 0.0018, and 0.0019. In an embodiment of the present invention, the heat transfer coefficient of the first tube 103 may be in the range of 250 to 1000 kJ m -2 hr -1 K -1 and all ranges and values ​​therebetween, inclusive, from 250 to 300 kJ m -2 hr -1 K -1 300 to 350 kJ m -2 hr -1 K -1 , 350 to 400 kJ m -2 hr -1 K -1 400 to 450 kJ m -2 hr -1 K -1 450 to 500 kJ m -2 hr -1 K -1 500 to 550 kJ m -2 hr -1 K -1, 550 to 600 kJ m - 2 hr -1 K -1 , 600 to 650 kJ m -2 hr -1 K -1 , 650 to 700 kJ m -2 hr -1 K -1 , 700 to 750 kJ m -2 hr -1 K -1 , 750 to 800 kJm -2 hr -1 K -1 , 800 to 850 kJ m -2 hr -1 K -1 , 850 to 900 kJ m -2 hr -1 K -1 , 900 to 950 kJ m -2 hr -1 K -1 , and 950 to 1000 kJ m -2 hr -1 K -1 According to an embodiment of the present invention, one or more tubes 103 may include fins disposed on their outer peripheries. One or more first tubes 103 may be made of a material comprising stainless steel, carbon steel, or a combination thereof. In an embodiment of the present invention, the ratio of the volume of the first shell 102 to the combined volume of the first tubes 103 may be in the range of 5 to 20 and all ranges and values ​​therebetween, including 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 11, 11 to 12, 12 to 13, 13 to 14, 14 to 15, 15 to 16, 16 to 17, 17 to 18, 18 to 19, and 19 to 20. According to an embodiment of the present invention, the first shell and tube heat exchanger 101 may include a first medium outlet 106 disposed on an end of the first shell and tube heat exchanger 101 away from the first medium outlet 106. The first medium outlet 106 may be suitable for releasing a heat transfer medium from the first shell 102. The first shell and tube heat exchanger 101 may further include a first reaction mixture outlet 107 disposed on an end of the first shell and tube heat exchanger 101 away from the first feed inlet 104 .

[0031] In an embodiment of the present invention, the medium outlet 106 of the first shell and tube heat exchanger 101 is in fluid communication with the second medium inlet 108 of the second shell and tube heat exchanger 109, so that the heat transfer medium flows from the first shell and tube heat exchanger 101 to the second shell 110 of the second shell and tube heat exchanger 109. The second shell and tube heat exchanger 109 may also include a second reaction mixture inlet 111, which is suitable for receiving the reaction mixture from the one or more tubes 103 of the first shell and tube heat exchanger 101 to the one or more second tubes 112 of the second shell and tube heat exchanger 109. According to an embodiment of the present invention, the second shell and tube heat exchanger 109 includes a second medium outlet 113 suitable for releasing the heat transfer medium from the shell 112. The second shell and tube heat exchanger 109 may include a second reaction mixture outlet 114, which is suitable for releasing the reaction medium from the one or more tubes 112 of the second shell and tube heat exchanger 109.

[0032] According to an embodiment of the present invention, the surface area to volume ratio of the one or more second tubes 112 of the second shell and tube heat exchanger 109 may be 50 to 150 m 2 / m 3 and all ranges and values ​​therebetween, inclusive, from 50 to 55 m 2 / m 3 , 55 to 60m 2 / m 3 , 60 to 65m 2 / m 3 , 65 to 70m 2 / m 3 , 70 to 75m 2 / m 3 , 75 to 80m 2 / m 3 , 80 to 85m 2 / m 3 , 85 to 90m 2 / m 3 , 90 to 95m 2 / m 3 , 95 to 100m 2 / m 3 100 to 105m 2 / m 3 , 105 to 110m 2 / m 3 , 110 to 115m 2 / m 3 , 115 to 120m 2 / m 3 120 to 125m 2 / m 3 , 125 to 130m 2 / m 3 130 to 135m2 / m 3 , 135 to 140m 2 / m 3 140 to 145m 2 / m 3 and 145 to 150m 2 / m 3 In an embodiment of the present invention, each second tube 112 of the second shell and tube heat exchanger 109 may have a substantially circular cross-section with a diameter to length ratio in the range of 0.0010 to 0.0020 and all ranges and values ​​therebetween, including 0.0011, 0.0012, 0.0013, 0.0014, 0.0015, 0.0016, 0.0017, 0.0018, and 0.0019. In an embodiment of the present invention, the heat transfer coefficient of the one or more second tubes 112 of the second shell and tube heat exchanger 109 may be in the range of 250 to 1000 kJ m -2 hr -1 K -1 and all ranges and values ​​therebetween, inclusive, from 250 to 300 kJ m -2 hr -1 K -1 300 to 350 kJ m -2 hr -1 K -1 , 350 to 400 kJ m -2 hr -1 K -1 400 to 450 kJ m -2 hr -1 K -1 450 to 500 kJ m -2 hr -1 K -1 500 to 550 kJ m -2 hr -1 K -1 , 550 to 600 kJ m -2 hr -1 K -1 , 600 to 650 kJ m -2 hr -1 K -1 , 650 to 700 kJ m -2 hr -1 K -1 , 700 to 750 kJ m -2 hr - 1 K -1 , 750 to 800 kJ m -2 hr -1 K-1 , 800 to 850 kJ m -2 hr -1 K -1 , 850 to 900 kJ m -2 hr -1 K -1 , 900 to 950 kJ m - 2 hr -1 K -1 , and 950 to 1000 kJ m -2 hr -1 K -1 . In an embodiment of the present invention, one or more second tubes 112 of the second shell and tube heat exchanger 109 may include fins surrounding them. The one or more tubes 112 of the second shell and tube heat exchanger 109 may be constructed of a material comprising stainless steel, carbon steel, or a combination thereof. In an embodiment of the present invention, the ratio of the volume of the second shell 110 to the combined volume of the second tubes 112 of the second shell and tube heat exchanger 109 may be in the range of 5 to 20 and all ranges and values ​​therebetween, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 11, 11 to 12, 12 to 13, 13 to 14, 14 to 15, 15 to 16, 16 to 17, 17 to 18, 18 to 19, and 19 to 20. In an embodiment of the present invention, the second shell and tube heat exchanger 101 may be substantially the same as or different from the first shell and tube heat exchanger 109.

[0033] In an embodiment of the present invention, the system 100 may further include a third shell and tube heat exchanger 115 and a fourth shell and tube heat exchanger 116. According to an embodiment of the present invention, the second shell and tube heat exchanger 109 may be in fluid communication with the third shell and tube heat exchanger 115, so that the reaction mixture from the second tube 112 of the second shell and tube heat exchanger 109 flows to the third tube 117 of the third shell and tube heat exchanger 115, and the heat transfer medium flows from the second shell 110 of the second shell and tube heat exchanger 109 to the third shell 118 of the third shell and tube heat exchanger 115.

[0034] Similarly, the third shell and tube heat exchanger 115 can be in fluid communication with the fourth shell and tube heat exchanger 116, so that the reaction mixture from the third tube 117 of the third shell and tube heat exchanger 115 flows to the fourth tube 119 of the fourth shell and tube heat exchanger 116, and the heat transfer medium flows from the third shell 118 of the third shell and tube heat exchanger 115 to the fourth shell 120 of the fourth shell and tube heat exchanger 116. In an embodiment of the present invention, the fourth shell and tube heat exchanger 116 can include a product outlet 122, which is suitable for releasing the reaction mixture (fourth stage effluent) from the tube 119 of the fourth shell and tube heat exchanger 116. The fourth shell and tube heat exchanger 116 can include a fourth medium outlet 123, which is suitable for releasing the heat transfer medium from the shell 120 of the fourth shell and tube heat exchanger 116.

[0035] According to an embodiment of the present invention, each of the third shell and tube heat exchanger 115 and the fourth shell and tube heat exchanger 116 may be substantially the same as or different from the first shell and tube heat exchanger 101 and / or the second shell and tube heat exchanger 109. In an embodiment of the present invention, the surface area to volume ratio of each of the third tube 117 of the third shell and tube heat exchanger 115 and the fourth tube 119 of the fourth shell and tube heat exchanger 116 may be 50 to 150 m 2 / m 3 and all ranges and values ​​therebetween, inclusive, from 50 to 55 m 2 / m 3 , 55 to 60m 2 / m 3 , 60 to 65m 2 / m 3 , 65 to 70m 2 / m 3 , 70 to 75m 2 / m 3 , 75 to 80m 2 / m 3 , 80 to 85m 2 / m 3 , 85 to 90m 2 / m 3 , 90 to 95m 2 / m 3 , 95 to 100m 2 / m 3 100 to 105m 2 / m 3 , 105 to 110m 2 / m 3 , 110 to 115m 2 / m 3 , 115 to 120m 2 / m 3 120 to 125m 2 / m3 , 125 to 130m 2 / m 3 130 to 135m 2 / m 3 , 135 to 140m 2 / m 3 140 to 145m 2 / m 3 and 145 to 150m 2 / m 3 In an embodiment of the present invention, each of the tubes 117 of the third shell and tube heat exchanger 115 and the tubes 119 of the fourth shell and tube heat exchanger 116 may have a substantially circular cross-section with a diameter to length ratio in the range of 0.0010 to 0.0020 and all ranges and values ​​therebetween, including 0.0011, 0.0012, 0.0013, 0.0014, 0.0015, 0.0016, 0.0017, 0.0018, and 0.0019. In an embodiment of the present invention, each of the third tubes 117 of the third shell and tube heat exchanger 115 and the fourth tubes 119 of the fourth shell and tube heat exchanger 116 may have a heat transfer coefficient in the range of 250 to 1000 kJ m -2 hr -1 K -1 and all ranges and values ​​therebetween, inclusive, from 250 to 300 kJ m -2 hr -1 K -1 300 to 350 kJ m -2 hr -1 K -1 , 350 to 400 kJ m -2 hr -1 K -1 400 to 450 kJ m -2 hr -1 K -1 450 to 500 kJ m -2 hr -1 K -1 500 to 550 kJ m -2 hr -1 K -1 , 550 to 600 kJ m -2 hr -1 K -1 , 600 to 650 kJ m -2 hr -1 K -1 , 650 to 700 kJ m -2 hr - 1 K -1, 700 to 750 kJ m -2 hr -1 K -1 , 750 to 800 kJ m -2 hr -1 K -1 , 800 to 850 kJ m -2 hr -1 K -1 , 850 to 900 kJ m - 2 hr -1 K -1 , 900 to 950 kJ m -2 hr -1 K -1 , and 950 to 1000 kJ m -2 hr -1 K -1 In an embodiment of the present invention, the shell and tube volume ratio of each of the third shell and tube heat exchanger 115 and the fourth shell and tube heat exchanger 116 can be in the range of 5 to 20 and all ranges and values ​​therebetween, 5 to 6, 6 to 7, 7 to 8, 8 to 9, 9 to 10, 10 to 11, 11 to 12, 12 to 13, 13 to 14, 14 to 15, 15 to 16, 16 to 17, 17 to 18, 18 to 19, and 19 to 20. In an embodiment of the present invention, each of the third tube 117 of the third shell and tube heat exchanger 115 and the fourth tube 119 of the fourth shell and tube heat exchanger 116 may comprise stainless steel, carbon steel, or a combination thereof. In an embodiment of the present invention, the first shell and tube heat exchanger 101, the second shell and tube heat exchanger 109, the third shell and tube heat exchanger 115, and the fourth shell and tube heat exchanger 116 are horizontal heat exchangers. In each shell and tube heat exchanger, the reaction mixture and the heat transfer medium may flow in substantially the same direction.

[0036] According to an embodiment of the present invention, the system 100 also includes a temperature control system, which is suitable for maintaining the reaction temperature in the first tube 102, the second tube 112, the third tube 117 and the fourth tube 119 in the range of 40 to 130°C and all ranges and values ​​therebetween, including the ranges of 40 to 45°C, 45 to 50°C, 50 to 55°C, 55 to 60°C, 60 to 65°C, 65 to 70°C, 70 to 75°C, 75 to 80°C, 80 to 85°C, 85 to 90°C, 90 to 95°C, 95 to 100°C, 100 to 105°C, 105 to 110°C, 110 to 115°C, 115 to 120°C, 120 to 125°C and 125 to 130°C. In an embodiment of the present invention, the temperature control system is suitable for adjusting the flow rate of the heat transfer medium stream 12 and / or the flow rate of the feed stream 11 to control the reaction temperature in the first tube 103, the second tube 112, the third tube 117 and / or the fourth tube 119 to prevent a runaway reaction.

[0037] B. Method for producing dicyclopentadiene

[0038] A method for producing dicyclopentadiene from cyclopentadiene has been discovered. Compared with conventional methods, the method can increase the conversion rate of cyclopentadiene and substantially prevent the occurrence of runaway reactions. Figure 2 As shown, an embodiment of the present invention includes a method 200 for producing dicyclopentadiene by thermal dimerization. The method 200 can be implemented by the system 100, such as Figure 1 As shown. According to an embodiment of the present invention, the method 200 may include a first stage (as shown in box 201), a second stage (as shown in box 205), a third stage (as shown in box 206), and a fourth stage (as shown in box 207). In an embodiment of the present invention, as shown in box 202, the first stage of the method 200 includes flowing a feed stream 11 containing cyclopentadiene monomer through a first tube 103 of a first shell and tube heat exchanger 101. In an embodiment of the present invention, the temperature of the feed stream 11 when it enters the first tube is in the range of 40 to 60°C and all ranges and values ​​therebetween, including the ranges of 40 to 42°C, 42 to 44°C, 44 to 46°C, 46 to 48°C, 48 to 50°C, 50 to 52°C, 52 to 54°C, 54 to 56°C, 56 to 58°C, and 58 to 60°C. According to an embodiment of the present invention, each first tube 103 comprises 6 to 8 fins.

[0039] According to an embodiment of the present invention, as shown in box 203, the first stage of the method 200 also includes flowing the heat transfer medium stream 12 through the first shell and tube heat exchanger 101 in the same direction as the flow of the feed stream 11. The temperature of the heat transfer medium when it enters the first shell 102 can be in the range of 65 to 80° C. and all ranges and values ​​therebetween, including the ranges of 65 to 68° C., 68 to 71° C., 71 to 74° C., 74 to 77° C., and 77 to 80° C. In an embodiment of the present invention, the flow rate ratio of the feed stream 11 to the heat transfer medium is in the range of 0.01 to 0.05 and all ranges and values ​​therebetween, including 0.02, 0.03, and 0.04.

[0040] According to an embodiment of the present invention, the first stage of the method 200 further includes subjecting the feed stream 11 in the first tube 103 to reaction conditions sufficient to dimerize the cyclopentadiene monomer to form dicyclopentadiene, as shown in block 204. In an embodiment of the present invention, the reaction conditions include a reaction temperature in the range of 40 to 100° C. and all ranges and values ​​therebetween, including ranges of 40 to 45° C., 45 to 50° C., 50 to 55° C., 55 to 60° C., 60 to 65° C., 65 to 70° C., 70 to 75° C., 75 to 80° C., 80 to 85° C., 85 to 90° C., 90 to 95° C., and 95 to 100° C. The reaction conditions may also include a residence time in the first shell and tube heat exchanger 101 in the range of 0.3 to 0.6 minutes and all ranges and values ​​therebetween, including 0.3 to 0.35 minutes, 0.35 to 0.40 minutes, 0.40 to 0.45 minutes, 0.45 to 0.50 minutes, 0.50 to 0.55 minutes, and 0.55 to 0.60 minutes. In an embodiment of the present invention, the first stage effluent exiting the first reaction mixture outlet 107 contains 55 to 65 wt.% of dicyclopentadiene and all ranges and values ​​therebetween, including 55 to 56 wt.%, 56 to 57 wt.%, 57 to 58 wt.%, 58 to 59 wt.%, 59 to 60 wt.%, 60 to 61 wt.%, 61 to 62 wt.%, 62 to 63 wt.%, 63 to 64 wt.%, and 64 to 65 wt.%.

[0041] In an embodiment of the present invention, as shown in box 205, the method 200 includes a second stage, which includes cooling the first stage effluent in the second shell and tube heat exchanger 109 at the following temperature to produce a second stage effluent: 90 to 110°C and all ranges and values ​​therebetween, including the ranges of 90 to 92°C, 92 to 94°C, 94 to 96°C, 96 to 98°C, 98 to 100°C, 100 to 102°C, 102 to 104°C, 104 to 106°C, 106 to 108°C and 108 to 110°C. In an embodiment of the present invention, the reaction mixture in the second pipe 112 is maintained in the range of 80 to 125° C. and all ranges and values ​​therebetween, including the ranges of 80 to 85° C., 85 to 90° C., 90 to 95° C., 95 to 100° C., 100 to 105° C., 105 to 110° C., 110 to 115° C., 115 to 120° C., and 120 to 125° C. The second stage effluent exiting the second reaction mixture outlet 114 may contain 80 to 90 wt.% of dicyclopentadiene and all ranges and values ​​therebetween, including the ranges of 80 to 81 wt.%, 81 to 82 wt.%, 82 to 83 wt.%, 83 to 84 wt.%, 84 to 85 wt.%, 85 to 86 wt.%, 86 to 87 wt.%, 87 to 88 wt.%, 88 to 89 wt.%, and 89 to 90 wt.%. The temperature of the heat transfer medium in the second shell 110 of the second shell and tube heat exchanger 109 can be in the range of 90 to 100° C. and all ranges and values ​​therebetween, including the ranges of 90 to 92° C., 92 to 94° C., 94 to 96° C., 96 to 98° C., and 98 to 100° C. According to an embodiment of the present invention, the second shell and tube heat exchanger 109 is operated with a residence time in the range of 0.3 to 0.6 minutes and all ranges and values ​​therebetween, including the ranges of 0.3 to 0.35 minutes, 0.35 to 0.40 minutes, 0.40 to 0.45 minutes, 0.45 to 0.50 minutes, 0.50 to 0.55 minutes, and 0.55 to 0.60 minutes.

[0042] In an embodiment of the invention, as shown in block 206, the method 200 includes a third stage, which includes cooling the second stage effluent in the second shell and tube heat exchanger 109 at a temperature of 115 to 125° C. and all ranges and values ​​therebetween, including 115 to 116° C., 116 to 117° C., 117 to 118° C., 118 to 119° C., 119 to 120° C., 120 to 121° C., 121 to 122° C., 122 to 123° C., 123 to 124° C., and 124 to 125° C. In an embodiment of the invention, the reaction mixture in the third tube 117 may be maintained in the range of 100 to 125° C. and all ranges and values ​​therebetween, including the ranges of 100 to 105° C., 105 to 110° C., 110 to 115° C., 115 to 120° C., and 120 to 125° C. The third stage effluent exiting the third reaction mixture outlet 121 may contain 90 to 96 wt.% dicyclopentadiene and all ranges and values ​​therebetween, including 91 wt.%, 92 wt.%, 93 wt.%, 94 wt.%, and 95 wt.%. The temperature of the heat transfer medium in the third shell 118 of the third shell and tube heat exchanger 115 may be 110 to 120°C and all ranges and values ​​therebetween, including ranges of 110 to 111°C, 111 to 112°C, 112 to 113°C, 113 to 114°C, 114 to 115°C, 115 to 116°C, 116 to 117°C, 117 to 118°C, 118 to 119°C, and 119 to 120°C. According to an embodiment of the present invention, the third shell and tube heat exchanger 115 is operated with a residence time in the range of 0.3 to 0.6 minutes and all ranges and values ​​therebetween, including the ranges of 0.3 to 0.35 minutes, 0.35 to 0.40 minutes, 0.40 to 0.45 minutes, 0.45 to 0.50 minutes, 0.50 to 0.55 minutes and 0.55 to 0.60 minutes.

[0043] In an embodiment of the invention, the method 200 includes a fourth stage, as shown in block 207, which includes cooling the third stage effluent in the fourth shell and tube heat exchanger 116 to produce a fourth stage effluent. In an embodiment of the invention, the reaction mixture in the fourth tube 119 can be maintained in the range of 125 to 140° C. and all ranges and values ​​therebetween, including the ranges of 125 to 128° C., 128 to 131° C., 131 to 134° C., 134 to 137° C., and 137 to 140° C. The fourth stage effluent (product stream) exiting the fourth reaction mixture outlet 122 may contain 96 to 99.8 wt.% dicyclopentadiene and all ranges and values ​​therebetween, including 96 to 96.4 wt.%, 96.4 to 96.8 wt.%, 96.8 to 97.2 wt.%, 97.2 to 97.6 wt.%, 97.6 to 98 wt.%, 98 to 98.4 wt.%, 98.4 to 98.8 wt.%, 98.8 to 99.2 wt.%, 99.2 to 99.6 wt.%, and 99.6 to 99.8 wt.%. The temperature of the heat transfer medium in the fourth shell 120 of the fourth shell and tube heat exchanger 116 can be 120 to 140°C and all ranges and values ​​therebetween, including the ranges of 120 to 122°C, 122 to 124°C, 124 to 126°C, 126 to 128°C, 128 to 130°C, 130 to 132°C, 132 to 134°C, 134 to 136°C, 136 to 138°C and 138 to 140°C. According to an embodiment of the present invention, the residence time of the fourth shell and tube heat exchanger 116 is in the range of 0.3 to 0.6 minutes and all ranges and values ​​therebetween, including 0.3 to 0.6 minutes and all ranges and values ​​therebetween, including the ranges of 0.3 to 0.35 minutes, 0.35 to 0.40 minutes, 0.40 to 0.45 minutes, 0.45 to 0.50 minutes, 0.50 to 0.55 minutes and 0.55 to 0.60 minutes.

[0044] According to an embodiment of the present invention, method 200 can prevent a runaway reaction from occurring in system 100. In an embodiment of the present invention, the dimerization reaction of cyclopentadiene occurs in all tubes of the fourth shell and tube heat exchanger. In method 200, the total conversion rate of cyclopentadiene conversion can be 99.5% to 99.8% and all ranges and values ​​therebetween, including 99.6% and 99.7%.

[0045] Although referenced Figure 2 The blocks of the present invention describe the embodiments of the present invention, but it should be understood that the operation of the present invention is not limited to Figure 2 Therefore, embodiments of the present invention may use the same Figure 2 The various blocks in different orders are used to provide the functions described herein.

[0046] As part of the disclosure of the present invention, specific examples are included below. The examples are for illustrative purposes only and are not intended to limit the present invention. Those skilled in the art will readily recognize that parameters that may be changed or modified to produce substantially the same results.

[0047] Example

[0048] (Temperature simulation in a shell and tube heat exchanger)

[0049] The temperature inside the tubes of a shell and tube heat exchanger was simulated. In the simulation, the cyclopentadiene feed stream flows through the tubes at an initial temperature of 50°C, while the heat transfer medium flows in the shell at an initial temperature of 80°C. The initial flow rate of the feed stream is 2.44 m / s. 3 / hr, the initial flow rate of the heat transfer medium is 68.33m 3 / hr. Each tube in the shell and tube heat exchanger includes 8 fins, which increases the heat transfer area by 25% compared to tubes without fins.

[0050] For a device including a heat sink ( Figure 3A ) and without heat sink ( Figure 3B ) tubes, the heat exchanger medium (water) temperature, the reaction mixture temperature in the tubes (process temperature), and the conversion of cyclopentadiene along the length of the tubes are plotted. Figure 3A As shown, when the tube includes 8 fins, the temperature of the reaction mixture in the tube stabilizes and remains relatively stable from about the middle point to the end of the shell and tube heat exchanger. However, for the tube that does not include fins, the temperature of the reaction mixture in the tube increases sharply at the end of the shell and tube heat exchanger and drops rapidly, indicating that a runaway reaction may occur in the heat exchanger. Therefore, the shell and tube heat exchanger containing 8 fin tubes shows excellent temperature and conversion stability for conducting the thermal dimerization of cyclopentadiene.

[0051] In the context of the present invention, at least the following 15 embodiments are described. Embodiment 1 is a method for producing dicyclopentadiene. The method includes a first stage, the first stage including flowing a feed stream containing cyclopentadiene monomer through a first tube of a first shell and tube heat exchanger, wherein the temperature of the feed stream when it enters the first tube is in the range of 40 to 60°C, wherein the first tube includes a heat sink. The method also includes flowing a heat transfer medium through the first shell of the first shell and tube heat exchanger in the same direction as the flow of the feed stream, wherein the temperature of the heat transfer medium when it enters the first shell is in the range of 65 to 80°C. The method further includes subjecting the feed stream in the first tube to reaction conditions sufficient to dimerize the cyclopentadiene monomer to form dicyclopentadiene, wherein the temperature of the first stage effluent when it leaves the first tube is in the range of 80 to 90°C. The method also includes a second stage, the second stage including cooling the first stage effluent at a temperature of 90 to 110°C to produce a second stage effluent. In addition, the method includes a third stage, the third stage includes cooling the second stage effluent at a temperature of 110 to 120°C to produce a third stage effluent. The method also includes a fourth stage, the fourth stage includes cooling the third stage effluent at a temperature of 120 to 140°C to produce a fourth stage effluent, wherein each of the first stage, the second stage, the third stage and the fourth stage is carried out in a different shell and tube heat exchanger. Embodiment 2 is a method as described in embodiment 1, wherein the temperature of the heat transfer medium when it leaves the first shell is in the range of 65 to 80°C. Embodiment 3 is a method as described in any one of embodiments 1 or 2, wherein each shell and tube heat exchanger corresponding to the first stage, the second stage, the third stage and the fourth stage is a horizontal shell and tube heat exchanger. Embodiment 4 is a method as described in any one of embodiments 1 to 3, wherein the fourth stage effluent contains more than 99.5 to 99.9 wt.% of dicyclopentadiene. Embodiment 5 is a method as described in any one of embodiments 1 to 4, wherein each shell and tube heat exchanger used in the first stage, the second stage, the third stage, and the fourth stage is operated with a residence time of 0.3 to 0.6 minutes. Embodiment 6 is a method as described in any one of embodiments 1 to 5, wherein the shell and tube heat exchangers used in the first stage, the second stage, the third stage, and the fourth stage are adapted to provide a residence time of 0.7 to 1.1 m 2 / m 3. Embodiment 7 is a method as described in any one of Embodiments 1 to 6, wherein the heat exchange medium is selected from the group consisting of: water, brine, boiling water or a combination thereof. Embodiment 8 is a method as described in Embodiment 7, wherein the heat exchange medium containing water is maintained at a temperature below the boiling point of water. Embodiment 9 is a method as described in any one of Embodiments 7 or 8, wherein the heat exchange medium containing water is maintained at a temperature of 65 to 130°C. Embodiment 10 is a method as described in any one of Embodiments 1 to 9, wherein the fluid in the tubes of the heat exchanger is heated at a speed of 2 to 3 m 3 Embodiment 11 is a method as described in any one of embodiments 1 to 10, wherein the heat exchange medium in the shell of the heat exchanger flows at a flow rate of 3 to 75 m / hr. 3 / hr flow rate. Embodiment 12 is a method as described in any one of embodiments 1 to 11, wherein, in each heat exchanger, the fluid in the tube and the heat exchange medium in the shell have a volume ratio of 0.03 to 1.0. Embodiment 13 is a method as described in any one of embodiments 1 to 12, wherein the method is capable of substantially preventing a runaway reaction from occurring in the heat exchanger. Embodiment 14 is a method as described in any one of embodiments 1 to 13, wherein the temperature variation of the fluid in the tube of the heat exchanger is in the range of 20 to 50°C. Embodiment 15 is a method as described in any one of embodiments 1 to 14, wherein each of the first stage, the second stage, the third stage, and the fourth stage is configured such that its residence time and / or total heat exchanger tube length allow the reaction to proceed under control to achieve maximum conversion.

[0052] Although the embodiments and advantages thereof of the present application have been described in detail, it should be understood that various changes, substitutions and modifications can be made therein without departing from the spirit and scope of the embodiments defined by the appended claims. In addition, the scope of the present application is not limited to the specific embodiments of the processes, machines, manufactures, material compositions, devices, methods and steps described in the specification. As will be easily understood by those of ordinary skill in the art from the above disclosure, processes, machines, manufactures, material compositions, devices, methods or steps that currently exist or will be developed later to function substantially the same as the corresponding embodiments described herein or to achieve substantially the same results as the corresponding embodiments described herein can be utilized. Therefore, the appended claims are intended to include such processes, machines, manufactures, material compositions, devices, methods or steps within their scope.

Claims

1. A method for producing dicyclopentadiene, the method comprising: The first phase includes: passing a feed stream comprising cyclopentadiene monomer through a first tube of a first shell and tube heat exchanger, wherein the temperature of the feed stream as it enters the first tube is in the range of 40 to 60° C., wherein the first tube comprises fins; flowing a heat transfer medium through a first shell of the first shell and tube heat exchanger in the same direction as the flow of the feed stream, wherein the temperature of the heat transfer medium as it enters the first shell is in the range of 65 to 80° C.; and subjecting the feed stream in the first tube to reaction conditions sufficient to dimerize the cyclopentadiene monomer to form dicyclopentadiene, wherein the temperature of the first stage effluent as it exits the first tube is in the range of 80 to 90° C.; The second phase includes: flowing the first stage effluent through a second tube of a second shell and tube heat exchanger, wherein the second tube comprises fins; causing the heat transfer medium released from the first shell to flow through a second shell of a second shell and tube heat exchanger; and cooling the first stage effluent at a temperature of 90 to 110° C. to produce a second stage effluent; and The third stage includes: flowing the second stage effluent through a third tube of a third shell and tube heat exchanger, wherein the third tube includes fins; causing the heat transfer medium released from the second shell to flow through a third shell of a third shell and tube heat exchanger; and cooling the second stage effluent at a temperature of 110 to 120° C. to produce a third stage effluent; and The fourth stage includes: flowing the third stage effluent through a fourth tube of a fourth shell and tube heat exchanger, wherein the fourth tube includes fins; allowing the heat transfer medium released from the third shell to flow through a fourth shell of a fourth shell and tube heat exchanger; and cooling the third stage effluent at a temperature of 120 to 140° C. to produce a fourth stage effluent, wherein each shell and tube heat exchanger used in the first stage, the second stage, the third stage and the fourth stage is operated with a residence time of the respective feed stream or effluent of 0.3 to 0.6 minutes, wherein, in each heat exchanger, the feed stream or effluent in the tube and the heat exchange medium in the shell have a volume ratio of 0.03 to 1.0, and The temperature of the feed stream or effluent in the tubes of each heat exchanger varies within the range of 20 to 50°C.

2. The method of claim 1, wherein the temperature of the heat transfer medium as it leaves the first shell is in the range of 65 to 80°C.

3. The method of any one of claims 1 and 2, wherein each shell and tube heat exchanger corresponding to the first stage, the second stage, the third stage and the fourth stage is a horizontal shell and tube heat exchanger.

4. The process of any one of claims 1 and 2, wherein the fourth stage effluent comprises greater than 99.5 to 99.9 wt.% dicyclopentadiene.

5. The method according to any one of claims 1 and 2, wherein the shell and tube heat exchangers used in the first stage, the second stage, the third stage and the fourth stage are adapted to provide 0.7 to 1.1 m 2 / m 3 Heat exchange area within the range.

6. The method of any one of claims 1 and 2, wherein the heat exchange medium is selected from the group consisting of: water, brine, boiling water, or a combination thereof.

7. A method as claimed in claim 6, wherein the heat exchange medium comprising water is maintained at a temperature below the boiling point of water.

8. The method of claim 6, wherein the heat exchange medium comprising water is maintained at a temperature of 65 to 130°C.

9. The process of claim 1, wherein the feed stream in the tubes of the heat exchanger is 2 to 3 m 3 / hr flow rate.

10. The method according to any one of claims 1 to 2, wherein the heat exchange medium in the shell of the heat exchanger is 3 to 75 m 3 / hr flow rate.

11. The method of any one of claims 1 to 2, wherein the method is capable of substantially preventing a runaway reaction from occurring in a heat exchanger.

12. The process of any one of claims 1 to 2, wherein each of the first, second, third and fourth stages is configured such that its residence time and / or total heat exchanger tube length allows the reaction to proceed under control to achieve maximum conversion.

13. The process of claim 3, wherein each of the first stage, the second stage, the third stage, and the fourth stage is configured such that its residence time and / or total heat exchanger tube length allows the reaction to proceed under control to achieve maximum conversion.

14. The process of claim 4, wherein each of the first stage, the second stage, the third stage, and the fourth stage is configured such that its residence time and / or total heat exchanger tube length allows the reaction to proceed under control to achieve maximum conversion.

15. The process of claim 1 wherein each of the first stage, second stage, third stage and fourth stage is configured such that its residence time and / or total heat exchanger tube length allows the reaction to proceed under control to achieve maximum conversion.

16. The process of any one of claims 1 or 2, wherein each of the first stage, the second stage, the third stage, and the fourth stage is configured such that its residence time allows the reaction to proceed under control to achieve maximum conversion.

17. The process of any one of claims 1 or 2, wherein each of the first stage, the second stage, the third stage, and the fourth stage is configured such that its total heat exchanger tube length allows the reaction to proceed under control to achieve maximum conversion.

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