CN108349835A - Prepare the method and system of cyclopentadiene and/or dicyclopentadiene - Google Patents

Abstract

The method and system for preparing cyclopentadiene and/or dicyclopentadiene includes that acyclic C5 hydrocarbon is converted to CPD in first reactor, obtain product mixtures, in isolated subsystem, such as the product mixtures are detached in compression device group, it obtains containing CPD and the fraction of the rich C5 of substantially depleted hydrogen and C1 C4 hydrocarbon, in dipolymer reactor, the fraction of dimerization richness C5, the product effluent containing DCPD is obtained, the product effluent is then detached, obtains the fraction of richness DCPD.Multistage dimerization and separating step can be optionally used, the fraction of multiple richness DCPD of various purity and content is obtained.The fraction of rich C5 from each section of the technique can be recycled to first reactor, or after selective hydrogenation, convert it into motor petrol component.The fraction and motor petrol component of rich C5 can be optionally detached, the chemicals with added value is produced.

Description

Prepare the method and system of cyclopentadiene and/or dicyclopentadiene

Inventor：Larry L.Iaccino and Kevin C.P.Leung

The cross reference of related application

The present invention claims on 2 2nd, USSN 62/250,678 and 2016 Europe submitted submitted on November 4th, 2015 The priority and right of application 16153725.3.

Invention field

The present invention relates to the method and systems for preparing the cyclic annular C5 containing cyclopentadiene and/or dicyclopentadiene.Particularly, originally Invention is related to preparing the method and system of cyclopentadiene and dicyclopentadiene by acyclic C5 hydrocarbon.

Background of invention

Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are in entire chemical industry in very wide product example Such as polymer material, polyester resin, synthetic rubber, solvent, fuel, the high expectations used within the scope of fuel additive original Material.Typically, cyclopentadiene is as time in steam cracking (for example, naphtha and more heavy charge) method of liquid feedstock By-product is wanted to generate.As the process for steam cracking being converted to using relatively lightweight raw material (for example, ethane and propane feed), generate Less CPD, and the demand to CPD persistently rises.Pentamethylene and cyclopentene also have the high value as solvent, while cyclopentene It may be used as preparing the monomer of polymer and the starting material as other high value chemicals.

Therefore, it is still necessary to prepared by CPD specially, i.e. CPD is prepared as primary product by raw material, and with CPD as secondary By-product prepares opposite.US5,633,421 is generally disclosed C2-C5 paraffin dehydrogenations to obtain the side of corresponding alkene Method.Similarly, US2,982,798 generally disclose the dehydrogenation of aliphatic hydrocarbons containing 3-6 (including the two endpoints) a carbon atom Method.However, US5,633,421 and US2,982,798 all do not disclose by acyclic C5 hydrocarbon preparation CPD, the acyclic C5 hydrocarbon It is desirable as raw material, because they are abundant and low cost.In addition, in the CPD production methods of design specially There are many challenges.For example, the reaction that C5 hydrocarbon is converted to CPD is extremely absorbed heat and is promoted by low-pressure and high temperature, But the notable cracking of pentane and other C5 hydrocarbon may occur under compared with low temperature (for example, 450 DEG C -500 DEG C).Other challenge packets It includes loss of catalyst activity caused by the coking during preparation method and needs further processing to be removed from catalyst Coke, and oxygen-containing gas cannot be used directly to provide heat input without destroying catalyst to reactor.

From the point of view of storage and shipment, DCPD is easier to handle as the raw material ratio CPD for subsequent chemistry synthesis. DCPD and CPD is interchangeable in numerous applications.In some applications, DCPD is preferably directly used instead of CPD.For it The middle other application for needing CPD, DCPD when in use may be anti-via inverse diels-Alder (retro-diels-alder) Answer thermal depolymerization (aka crackings) at CPD.

The conventional method for preparing CPD is typically generated by intermediate concentration containing CPD, by notable concentration containing acyclic dienes and list The C5 hydrocarbon flows (one or more) of alkene.Because many C5 substances have close boiling point, azeotropic mixture is formed, and in distillation temperature It is reactive under degree, so it is industrially infeasible to recycle CPD from product mixtures via conventional distil-lation.In conventional recycling In scheme, CPD is recycled from other C5 hydrocarbon using process for dimerization (one or more), the process for dimerization makes CPD undergo diels- Alder reaction and generate the DCPD that can be easily detached with C5 hydrocarbon by conventional distil-lation.Lamentedly, CPD also can be with material Other two alkene reactions present in stream and generate codimerization object, the codimerization object pollutes DCPD.In addition, causing compared with higher oligomer The reaction of object (higer-order oligomer) also issues life in neutral temperature to high temperature.These side reactions generate undesirable Codimerization object and higher order oligomers, they make more down stream processing steps, for example, repeat, multistep cracking and dimerization become must It needs, to generate the DCPD having for the enough purity required by many applications.These methods are expensive, low yields, and may It is easy to fouling.

Therefore, it is still necessary to solve the method and system for preparing CPD and/or DCPD of above-mentioned challenge.

Summary of the invention

It has been found that by will wherein compare the acyclic C5 hydroconversion process of catalysis and it that acyclic dienes promotion CPD is generated Afterwards combine the method that efficiently separates that the Diels-Alder reaction between CPD and acyclic dienes minimizes, it can be by high yield Rate generates CPD, can thus generate high-purity DCPD.

The first aspect of the present invention is related to the method for preparing the cyclic annular C5 for including CPD and/or DCPD, and this method includes：(I) It will be in the C5 feedstocks to first reactor containing at least one acyclic C5 hydrocarbon；(II) make at least one acyclic C5 hydrocarbon and catalyst It contacts at conversion conditions, obtains first reactor hydrocarbon effluent comprising the C5 components containing CPD and acyclic dienes hydrocarbon；It is hydrogeneous The light components of gas and C1-C4 hydrocarbon；Monocyclic aromatics；And polynuclear aromatic compound；(III) detaches first reactor hydrocarbon Effluent, with the fraction of the fraction and the first richness C5 of (ii) containing CPD of the rich light components of production (i).It can be by dimerization, by that can contain There is the fraction of the first richness C5 of CPD to produce high-purity DCPD.

The second aspect of the present invention is related to the system for preparing cyclic annular C5 (including CPD and/or DCPD), the system packet It includes：(A) it is that reception is total to raw material containing at least one acyclic C5 hydrocarbon, non-essential hydrogen and non-essential C1-C4 hydrocarbon is total to the C5 of raw material Raw material and the first reactor constructed；(B) the acyclic C5 hydrocarbon that can be catalyzed at conversion conditions inside first reactor is loaded in turn Change to produce the catalyst of first reactor hydrocarbon, the first reactor hydrocarbon includes the C5 components containing CPD and acyclic dienes hydrocarbon；Contain The light components of hydrogen and C1-C4 hydrocarbon；Monocyclic aromatics；And polynuclear aromatic compound；(C) is to receive at least part First reactor hydrocarbon effluent and produce the first richness C5 of (i) containing CPD and depleted hydrogen and C1-C4 hydrocarbon fraction and (ii) it is hydrogeneous The fraction of the rich light components of gas and C1-C4 hydrocarbon and constructing detached with that first reactor is directly or indirectly in fluid communication first Subsystem.Additional equipment, such as dipolymer reactor and fractionating column can be added, to produce DCPD by the fraction of the first richness C5.

Brief description

Fig. 1 be the present invention prepare the illustrative methods of CPD and/or DCPD and the schematic diagram of system.

Fig. 2 is the schematic diagram of the details of the first isolated subsystem in Fig. 1.

Detailed description of the invention

In this disclosure, method is described as including at least one " step ".It should be appreciated that each step is can be One or many action or operation are carried out in method by continuously or discontinuously mode.It is unless otherwise specified otherwise or civilized up and down Really show difference, then each step in method can successively be carried out by the sequence listed by them, with and without with one or A number of other step overlappings, or carried out by any other order, it depends on the circumstances.In addition, it is one or more, or even all walk Suddenly it can simultaneously be carried out relative to the identical or different batch of material.For example, in a continuous process, although in method One step is carried out for just feeding the raw material of method starting point, but second step can exist simultaneously for by processing The intermediate product for feeding the raw material of the method in early stage in first step and generating carries out.Preferably, the step presses institute Sequence is stated to carry out.

Unless otherwise indicated, show that whole numerical value of quantity are interpreted as in all instances by term in present disclosure " about " it modifies.It should also be understood that the accurate numerical value used in description and claims constitutes specific embodiment. Through the precision for endeavouring to ensure data in embodiment.It will be appreciated, however, that the data of any measurement are due to the skill for measuring The limitation of art and/or equipment inherently contains a degree of error.

All numbers to periodic table of elements race and with reference to based on Chemical and Engineering News, 63 (5), the new annotation provided in 27 (1985), unless otherwise prescribed.

Definition

For this specification and the appended claims, following term is defined.

Term " cyclic annular C5 " or " cC5 " include but not limited to, pentamethylene, cyclopentene, cyclopentadiene and they in two kinds or More kinds of mixtures.Term " cyclic annular C5 " or " cC5 " further include alkylated analogs any in above-mentioned substance, such as first Cyclopentane, methyl cyclopentene and methyl cyclopentadiene.It should be recognized that for the object of the invention, cyclopentadiene with when Between within the scope of certain condition (including environment temperature and pressure) via the condensation of diels-Alder spontaneously dimerization and formed double Cyclopentadiene.

It includes but not limited to linear and branched saturate and unsaturation object that term is " acyclic ".

Term " aromatics " refers to the flat annular alkyl for having conjugated double bond, such as benzene.Term aromatic used herein above Compound covers the compound containing one or more aromatic rings, including but not limited to, benzene, toluene and dimethylbenzene and polynuclear aromatic Close object (PNA), including but not limited to, naphthalene, anthracene,With their alkylation pattern.Term " C6+ aromatic compounds " includes being based on The compound of aromatic ring containing six or more annular atoms, including but not limited to, benzene, toluene and dimethylbenzene and polynuclear aromatic chemical combination Object (PNA), including but not limited to, naphthalene, anthracene,With their alkylation pattern.

Term " BTX " includes but not limited to, benzene, toluene and dimethylbenzene (adjacent and/or and/or to) mixture.

Term " richness " used herein above, when the given mixture or material for describing to be prepared by aforementioned mixture or stream Group timesharing in stream refers to the component by the concentration that can not ignore more higher than its concentration in aforementioned mixture or stream It is present in the given mixture or stream.Therefore, it is by than in aforementioned stream by rich C5 fractions prepared by aforementioned stream The fraction of the higher concentration hydrocarbon containing C5 that can not ignore of C5 hydrocarbon concentration.

Term " depleted " used herein above, when for describing to be prepared by aforementioned mixture or stream given mixture or Group timesharing in stream refers to that (it may by concentration more lower than its concentration in aforementioned mixture or stream for the component It is insignificant) it is present in the given mixture or stream.Therefore, by depleted hydrogen fraction prepared by aforementioned stream be by The fraction of concentration (it can be insignificant) hydrogen more lower than density of hydrogen in aforementioned stream.

" wt% " used herein refers to weight percent, and " vol% " refers to percentage by volume, and " mol% " refers to rubbing That percentage.All ranges indicated herein should be including two endpoints as two specific embodiments, unless there are opposite Regulation indicates.

" top stream " used herein can be just in the top (very of container such as fractionating column or reactor Top) or side, with and without additional stream on it.It is preferred that top stream is taken out in the position of the near top of tower Go out.It is preferred that top stream is extracted out at the position above at least one raw material." bottom steam " used herein is less than institute State at the position of top stream, can just in the bottommost of container (very bottom) or side, and if in side, Then with and without additional stream below it.Preferably, bottom steam is extracted out at the position near the bottom of tower.It is excellent Choosing, bottom steam are extracted out at the position below at least one raw material." intermediate stream " used herein be top stream and Stream between bottom steam.

Term " light hydrocarbon " refers to the hydrocarbon containing 1-4 carbon atom in their molecular structure.Term " light components " is Refer to hydrogen and the hydrocarbon containing 1-4 carbon atom in their molecular structure.Term " hydrogen " refers to molecule H₂。

Term " normal boiling point " refers to the boiling point under 101 kPas of pressure.Term " steam " and " gas " all covering property Ground refers to the phase of the mixture of complete steam, ideal gas and gas and steam.

Term as used herein substantially free refers to such as≤0.8wt% by not higher than 1wt% ,≤ 0.6wt% ,≤0.5wt% ,≤0.1wt% ,≤0.01wt%, or the concentration of even≤0.001wt% include.

Term " motor petrol " refers to the mixed of the organic compound for the fuel for being suitable as using in gasoline internal combustion engine Close object.

Term " coke " includes but not limited to the low hydrogen content hydrocarbon being adsorbed on carbon monoxide-olefin polymeric.

Term " Cn " refers to hydrocarbon (one or more) of the per molecule containing n carbon atom, and wherein n is positive integer.Therefore, C5 hydrocarbon Therefore raw material contains one or more hydrocarbon of 5 carbon atoms, such as pentane, 2- methybutanes, 2,2- dimethyl comprising per molecule Pentane, 1- amylenes, 2- amylenes, 2- methyl-2-butenes, 3- methyl-2-butenes, 1,3- pentadienes, 1,4- pentadienes, 2- methyl- 1,3- butadiene, pentamethylene, cyclopentene etc..

Term " Cn+ " refers to the hydrocarbon (one or more) that per molecule contains at least n carbon atom.

Term " Cn- " refers to the hydrocarbon (one or more) that per molecule contains at most n carbon atom.

Term " hydrocarbon " refers to a kind of compound containing the hydrogen bonded with carbon, and covers (i) saturated hydrocarbon compound, (ii) insatiable hunger And hydrocarbon compound, and (iii) hydrocarbon compound (saturation and/or unsaturated) mixture, include the hydrocarbon compound with different n values Mixture.

Term " C5 raw materials " includes the raw material containing pentane, such as mainly pentane and/or isopentane (also referred to as methyl Butane) raw material, pentamethylene containing small percentage and/or neopentane (also referred to as 2,2- dimethylpropanes).

Term " monocyclic aromatics " refers to having the aromatic compounds there are one phenyl ring in its molecular structure and including It is alkylated pattern such as toluene, dimethylbenzene and ethylo benzene.

Term " polynuclear aromatic compound " refers to the aromatics with two or more aromatic rings in its molecular structure It closes object and includes that it is alkylated pattern.

Term " the 10th race's metal " refers to the element in the 10th race of the periodic table of elements and includes Ni, Pd and Pt.

Term " the 1st race's alkali metal " refer to the element in the 1st race of the periodic table of elements and include but not limited to, Li, Na, K, The mixture of Rb, Cs and two or more in them, and exclude hydrogen.

Term " the 2nd race's alkaline-earth metal " refer to the element in the 2nd race of the periodic table of elements and include but not limited to, Be, Mg, The mixture of Ca, Sr, Ba and two or more in them.

Term " the 11st race's metal " refer to the element in the 11st race of the periodic table of elements and include but not limited to, Cu, Ag, Au and The mixture of two or more in them.

Term " restricted index " is defined in US 3,972,832 and US 4,016,218, and this two documents pass through With reference to being incorporated herein.

Term as used herein " MCM-22 family molecular sieves " (or " material of MCM-22 races " or " MCM-22 races material " or " MCM-22 races zeolite ") include one or more in following substance：

The molecular sieve made of common first degree of crystal structure unit (building block) structure cell, the structure cell tool There are MWW matrix topologies.(structure cell is the space arrangement of atom, if tiled with three dimensions, describes crystal structure).Institute Crystal structure is stated at " Atlas of Zeolite Framework Types ", the 5th edition, is discussed in 2001, the text The entire content offered is incorporated herein by reference)；

The molecular sieve made of second degree of common structural unit is that the 2- dimensions of such MWW framework topology unit cells are flat Paving, forming tool, there are one the single layers of unit cell thickness, and preferably there are one c- unit cell thickness for tool；

The molecular sieve made of second degree of common structural unit is that have the unit cell thickness of one or more than one Layer, wherein with more than one unit cell thickness layer by by least two tool there are one unit cell thickness single layer stack, filling or In conjunction with and be made.This second degree of structural unit stack can by rule in the way of, irregular mode, random fashion or its Any combinations form；With

Divided made of any rule of the structure cell with MWW matrix topologies or random 2- dimensions or 3- dimension combinations Son sieve.

MCM-22 races include that there is those of such X-ray diffraction pattern molecular sieve, i.e., the described X-ray diffraction pattern to exist Include d spacing maximums at 12.4 ± 0.25,6.9 ± 0.15,3.57 ± 0.07 and 3.42 ± 0.07 angstroms.By using the K- of copper α bimodal (doublet) is as incident ray and the diffractometer equipped with scintillation counter and associated computer is as collection system Standard technique obtain X ray diffracting data for characterizing material.

Term as used herein " molecular sieve " is synonymously used with term " microporous crystalline material ".

Term as used herein " carbon selectivity " refers to the carbon being formed by corresponding ring-type C5, CPD, C1 and C2-4 The total mole number of molal quantity divided by the carbon in the C5 raw materials converted.Term " at least 30% carbon selectivity to cyclic annular C5 " is Refer in 100 moles of ring-type C5 for foring 30 moles for the carbon in converted C5 raw materials (such as pentane) Carbon.

Term as used herein " conversion ratio " refers to the carbon being converted in the acyclic C5 hydrocarbon (one or more) of product Molal quantity.Term " at least 70% conversion ratio of the acyclic C5 hydrocarbon (one or more) to product " refers to the acyclic C5 hydrocarbon At least the 70% of the molal quantity of (one or more) is converted to product.

Term as used herein " ferrosilicate " refers to that iron-containing iron content is micro- in skeleton structure and/or in pore canal system Permeability crystalline texture.

Term " alkylated naphthalene (one or more) " includes monoalkyl, dialkyl group, trialkyl and tetraalkyl naphthalene.

C5 raw materials

Here the useful C5 raw materials containing acyclic C5 hydrocarbon (one or more) can be obtained from crude oil or natural gas condensate, can To include straight run C5, and may include being split by refining and chemical method, such as fluid catalytic cracking (FCC), reformation plus hydrogen The cracking C5 that change, hydrotreating, coking and steam cracking generate is (with various degrees of unsaturation：Alkene, alkadienes, alkynes).

In one or more embodiments, can be used for the method for the present invention C5 raw materials include pentane, amylene, pentadiene and The mixture of two or more in them.Preferably, C5 raw materials include at least about 50wt% or 60wt% or 75wt%, Or 90wt% is saturated acyclic C5 hydrocarbon (one or more), it is desirable that pentane, or it is full comprising about 50wt%- about 100wt% With acyclic C5 hydrocarbon (one or more), it is desirable that pentane.Preferably, 2- methybutanes are pressed exists less than 10wt%.

C5 raw materials do not include C6 aromatic compounds, such as benzene optionally.Preferably, C6 aromatic compounds is by being less than 5wt% or less than 1wt% or less than 0.01wt%, or even 0wt% exist.

C5 raw materials are optionally not comprising one or more in toluene and/or dimethylbenzene (o-, m- and p-).Preferably, Toluene and dimethylbenzene it is (o-, m- and p-) by 5wt% is less than, preferably less than 1wt% is present in C5 raw materials, preferably by being less than 0.01wt% preferably presses 0wt% and exists.

C5 raw materials do not include C6+ aromatic compounds optionally, and preferably C6+ aromatic compounds, which is pressed, is less than 5wt%, preferably few Exist in 1wt%, preferably press and be less than 0.01wt%, preferably presses 0wt% and exist.

C5 raw materials do not include C6+ compounds optionally, and preferably C6+ compounds, which are pressed, is less than 5wt%, preferably less than 1wt% In the presence of preferably by 0.01wt% is less than, preferably by 0wt% presence, preferably any C6+ aromatic compounds is pressed less than 5wt%, preferably Exist less than 1wt%, preferably press and be less than 0.01wt%, preferably presses 0wt% and exist.

In the present invention, by (one or more) first fed equipped with catalyst of the acyclic C5 hydrocarbon included in C5 raw materials Reactor, wherein acyclic C5 hydrocarbon contacts the catalyst at conversion conditions, then the acyclic C5 hydrocarbon is (one or more) divides At least part of son is converted to CPD molecules, and containing CPD and optionally, other cyclic hydrocarbons are (for example, C5 cyclic hydrocarbons are for example Pentamethylene and cyclopentene) reaction product leave the first reactor as first reactor hydrocarbon effluent.Preferably, including Hydrogen and, and optionally the hydrogen of light hydrocarbon (such as C1-C4 hydrocarbon) is total to raw material and also feeds first reactor.Preferably, will Hydrogen is total at least part of raw material and at least part (preferably all) blending of C5 raw materials, then feeds first reactor. Hydrogen, which is present in the raw mixture at entry position (wherein raw material is contacted with catalyst first) and prevents or reduces coke, to exist Formation on catalyst granules.Carbon monoxide-olefin polymeric (will be described in more detail below) can include microporous crystalline metal Silicate (restricted index for preferably having less than 12), the 10th race's metal is together with the 1st race's alkali metal and/or the 2nd race's alkaline-earth metal； With optionally the 11st race's metal.Catalyst can be prepared by using the method being described more fully below.

First reactor can be plunger flow reactor or other reactor configurations.Catalyst can be used as fixed bed, urge The loadings such as catalyst particles fluid.Term as used herein " reactor " refers to any container (one wherein chemically reacted It is a or multiple).Reactor had not only included vivid reactor but also had included reaction zone in single reactor apparatus and when appropriate, The reaction zone of spanning multilevel reactor.In other words and as conventional, single reactor can have multiple reaction zones.Work as explanation When book is related to the first and second reactors, it includes two reactors that those of ordinary skill in the art, which will readily recognize such reference, And the single reactor with the first and second reaction zones.Equally, first reactor hydrocarbon effluent and second reactor outflow Object will be recognized including respectively from the first reaction zone of single reactor and the effluent of second reaction zone.

Term as used herein " moving bed " reactor refers to solid (for example, catalyst granules) and air flow contacts Region or container make superficial gas velocity (U) less than the rate required by the dilution phase pneumatic conveying of solid particle to maintain to have There is the Solid Bed of the voidage less than 95%.In moving-burden bed reactor, solid (for example, catalyst material) can slowly be worn It crosses reactor and can take out and be added to the top of the reactor from the bottom of the reactor.Moving-burden bed reactor can be with It works under some nowed formings (regime), including deposition or moving packed bed form (U<U_mf), be bubbled form (U_mf<U< U_mb), slug form (U_mb<U<U_c), transition and Turbulent Fluidization form (U_c<U<U_tr) and fast fluidization form (U>U_tr), Middle U_mfIt is minimum fluidization rate, U_mbIt is minimum bubbling rate, U_cRate when being pressure oscillation peak value, U_trIt is delivery rate.This A little difference mode of fluidization have been described in for example, Kunii, D., Levenspiel, O., Chapter 3of Fluidization Engineering,2^nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M., Chapter 6of Chemical Process Equipment,Revised 2^nd Edition,Butterworth-Heinemann, Boston, in 2010, they are incorporated by reference herein.

Term as used herein " deposition bed " reactor refers to that wherein the region of particle and air flow contacts or container meet Superficial gas velocity (U), which is less than, at least part of the reaction zone makes solid particle (for example, catalyst granules) fluidisation be wanted The minimum-rate asked, minimum fluidization rate (U_mf), U<U_mf, and/or work together under the rate higher than the minimum fluidization rate When by using inside reactor structure maintain along reactor beds gas axially upwards and/or solid performance (for example, temperature, Gas or solid composition etc.) gradient so that gas solids back-mixing minimize.The description of minimum fluidization rate for example, Kunii, D.,Levenspiel,O.,Chapter 3of Fluidization Engineering,2^nd Edition,Butterworth- Heinemann, Boston, 1991 and Walas, S.M., Chapter 6of Chemical Process Equipment, Revised 2^ndIt is provided in Edition, Butterworth-Heinemann, Boston, 2010.Deposition bed reactor can be " cyclic deposition bed reactor " refers to that there is solid (for example, catalyst material) to pass through the movement of the reactor and described The deposition bed of solid (for example, catalyst material) at least partly recycled.For example, solid (example can be removed from the reactor Such as, catalyst material), regeneration reheats and/or is detached with product stream, is then returned to reactor.

Term as used herein " fluid bed " reactor refers to having connecing for solid (for example, catalyst granules) and air-flow Tactile region or container meets superficial gas velocity (U) and is enough to make solid particle fluidisation (that is, being more than minimum fluidization rate U_mf) and be less than Rate required by the dilution phase pneumatic conveying of solid particle is to maintain the Solid Bed with the voidage less than 95%.Herein Used term " cascade liquid bed " refers to that the arranged in series satisfaction of each liquid bed may exist gas and/or solid performance The gradient of (for example, temperature, gas or solid composition, pressure etc.) is cascaded to separately just as the solid or gas from a fluid bed One fluid bed is such.The position of minimum fluidization rate is for example, Kunii, D., Levenspiel, O., Chapter 3of Fluidization Engineering,2^ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M.,Chapter6of Chemical Process Equipment,Revised 2^nd Edition,Butterworth- It is provided in Heinemann, Boston, 2010.Fluidized-bed reactor can be mobile fluidized-bed reactor, such as " ciculation fluidized Bed reactor ", refer to have solid (for example, catalyst material) pass through the reactor movement and the solid (for example, Catalyst material) the fluid bed at least partly recycled.For example, solid can be removed from the reactor (for example, catalyst material Material), regeneration reheats and/or is detached with product stream, is then returned to reactor.

Term as used herein " riser " reactor (also known as transport reactor) refers in fast fluidization or pneumatic defeated Send the region being delivered up only for being used for solid (for example, catalyst granules) in mode of fluidization or container (for example, right circular cylinder shape Pipe).Fast fluidization and pneumatic conveying flow form are characterized in that superficial gas rate (U) is more than transporting rate (U_tr).Soon Speed fluidisation and pneumatic conveying flow form are also described in Kunii, D., Levenspiel, O., Chapter 3of Fluidization Engineering,2^ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M.,Chapter 6of Chemical Process Equipment,Revised 2^nd Edition,Butterworth- In Heinemann, Boston, 2010.Fluidized-bed reactor, such as circulating fluid bed reactor can serve as promotion tube reaction Device.

Term as used herein " cocurrent " refers to two streams (for example, stream (a), stream (b)) along substantially the same Direction flowing.For example, if stream (a) flows to bottom and stream (b) from least one at the top of at least one reaction zone Bottom is flowed at the top of reaction zone, then the flowing of stream (a) will be considered and the flowing cocurrent of stream (b).In reaction zone On small-scale, there may be the regions that wherein flowing may not be cocurrent.

Term as used herein " adverse current " refers to two streams (for example, stream (a), stream (b)) along essentially the inverse Direction flowing.For example, if stream (a) flows to bottom and stream (b) from least one at the top of at least one reaction zone The bottom of reaction zone flows to top, then the flowing of stream (a) will be considered and the flowing of stream (b) adverse current.In reaction zone On small-scale, there may be the regions that wherein flowing may not be adverse current.

Acyclic C5 conversion process

The method that acyclic C5 hydrocarbon is converted to the product comprising ring-type C5 compounds includes making C5 raw materials and optionally hydrogen In one or more carbon monoxide-olefin polymerics (including but not limited to catalyst combination described herein under acyclic C5 conversion conditions Object) in the presence of contact to form the product.The product of the method for transformation of acyclic C5 raw materials includes ring-type C5 compounds.Cyclic annular C5 Compound can include one or more in pentamethylene, cyclopentene, cyclopentadiene, and include their mixture.

In one or more embodiments, acyclic C5 conversion conditions include at least temperature, partial pressure and weight (hourly) space velocity (WHSV) (WHSV).Temperature is at about 400 DEG C-about 700 DEG C, or about 450 DEG C-about 650 DEG C, and preferably approximately 500 DEG C-about 600 In the range of DEG C.It divides in about 3- about 100psi (21-689 kPas), or about 3- about 50psi (21-345 kPas), In the range of preferably approximately 3- about 20psi (21-138 kPas).Weight (hourly) space velocity (WHSV) is in about 1- about 50hr^-1, or about 1- is big About 20hr^-1In the range of.It is total that these conditions are included in the non-essential hydrogen in the range of about 0-3, or about 0.5- about 2 The molar ratio of raw material and acyclic C5 hydrocarbon.These conditions can also include total raw material C1-C4 hydrocarbon and acyclic C5 raw materials.

In one or more embodiments, the present invention relates to the methods that pentane is converted to cyclopentadiene, including with Lower step：Make pentane and optionally hydrogen (if it does, typically, H₂By the hydrogen of 0.01-3.0 and rubbing for pentane You are than existing) it is contacted with shape with one or more carbon monoxide-olefin polymerics (including but not limited to carbon monoxide-olefin polymeric described herein) At in 400 DEG C -700 DEG C of temperature, the partial pressure of 3- about 100psia and 1- about 50hr^-1Weight (hourly) space velocity (WHSV) under cyclopentadiene.

In the presence of a catalyst, many hope and undesirable side reaction may occur.The net effect of reaction is to generate hydrogen Gas and increase total volume (it is assumed that gross pressure is constant).One especially desirably overall reaction (that is, intermediate reaction step is not shown) is：

Pentane → CPD+3H₂。

Other overall reaction includes, but are not limited to：

Pentane → 1,3- pentadienes+2H₂,

Pentane → 1- amylenes+H₂,

Pentane → 2- amylenes+H₂,

Pentane → 2- methyl-2-butenes+H₂,

Pentane → pentamethylene+H₂,

Pentamethylene → cyclopentene+H₂, or

Cyclopentene → CPD+H₂。

Fluid inside first reactor is substantially in the gas phase.In the exit of first reactor, the first reaction is obtained Device hydrocarbon effluent, preferably in the gas phase.The first reactor hydrocarbon effluent can include the mixture of following hydrocarbon etc.：Including super Cross the heavy component such as polynuclear aromatic compound of 8 carbon atoms；C8, C7 and C6 hydrocarbon such as monocyclic aromatics；CPD (institutes Need product)；Unreacted C5 raw materials such as pentane；C5 by-products such as amylene (such as 1- amylenes, 2- amylenes), pentadiene (such as 1,3- pentadienes, 1,4- pentadienes), pentamethylene, cyclopentene, 2- methybutanes, 2-methyl-1-butene alkene, 3- methyl-1s- Butylene, 2- methyl-1s, 3- butadiene, 2,2- dimethylpropanes etc.；C4 by-products such as butane, 1- butylene, 2- butylene, 1,3- fourths Diene, 2- methylpropanes, 2- methyl-1-propylenes etc.；C3 by-products are such as propane, propylene；C2 by-products such as ethane and second Alkene, methane and hydrogen.

The first reactor hydrocarbon effluent can include CPD by the concentration of C (CPD) 1wt%, be reacted based on described first The total weight of C5 hydrocarbon in device hydrocarbon effluent；Can be independently 15,16,18 with a1≤C (CPD) 1≤a2, wherein a1 and a2, 20,22,24,25,26,28,30,32,34,35,36,38,40,45,50,55,60,65,70,75,80 or 85, as long as a1<a2.

The first reactor hydrocarbon effluent can include acyclic dienes by the total concentration of C (ADO) 1wt%, based on described The total weight of C5 hydrocarbon in first reactor hydrocarbon effluent；Can be independently with b1≤C (ADO) 1≤b2, wherein b1 and b2 20,18,16,15,14,12,10,8,6,5,4,3,2,1 or 0.5, as long as b1<b2.Preferably, 0.5≤C (ADO)≤10.It is preferred that Ground, acyclic dienes include 1,3-pentadiene by the concentration of C (PTD) 1wt%, based on the C5 in the first reactor hydrocarbon effluent The total weight of component；Can be independently 20,18,16,15,14,12,10,8 with c1≤C (PTD) 1≤c2, wherein c1 and c2, 6,5,4,3,2,1,0.5 or 0.3, as long as c1<c2.

As in the first reactor use catalyst and select reaction condition as a result, can be in the first reactor Reach high CPD and acyclic dienes molar ratio in hydrocarbon effluent, meets C (CPD) 1/C (ADO) 1 >=1.5, preferably 1.6,1.8, 2.0,2.2,2.4,2.5,2.6,2.8,3.0,3.2,3.4,3.5,3.6,3.8,4.0,5.0,6.0,8.0,10,12,14,15, 16,18 or 20.The high proportion of C (CPD) 1/C (ADO) 1 significantly decrease due to CPD in subsequent job step and acyclic dienes it Between Diels-Alder reaction caused by CPD lose, and therefore, allow the method for the present invention for the DCPD grades that then generate Divide and reaches high DCPD yields and high DCPD purity.

Desirably, it should total absolute pressure of the first reactor hydrocarbon effluent and temperature be maintained to be in such Level meets and substantially avoids the dimerization that CPD forms DCPD, and substantially inhibit the diels-between CPD and acyclic dienes Alder reaction.

Carbon monoxide-olefin polymeric

Here useful carbon monoxide-olefin polymeric includes microporous crystalline metal silicate, such as crystal aluminosilicate, crystallization Ferrosilicate or other silicates containing metallic crystal (such as wherein metal or metal-containing compound is dispersed in crystalline silicate structure It is interior and can be or can not be those of described crystalline framework part).It can be used as the micropore of carbon monoxide-olefin polymeric here Property crystalline metallosilicate framework types include, but are not limited to MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU.

Especially suitable microporosity metal silicate used herein above include framework types MWW, MFI, LTL, MOR, Those of BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU, one or more of which come from period of element Table the 8th, 11 and the metal (preferably one or more in Fe, Cu, Ag, Au, B, Al, Ga and/or In) of 13 races are being synthesized or are being soaked It is incorporated in crystal structure during being crystallized after profit.According to approval, metal silicate can have existing one or more metals and, For example, material is properly termed as ferrosilicate, but it will be likely to still contain a small amount of aluminium.

Microporous crystalline metal silicate preferably has less than the restricted index of 12 either 1-12 or 3-12.Here have Alumino-silicate have be less than 12, such as 1-12 or 3-12 restricted index, and including but not limited to zeolite beta, mercerising boiling Stone, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM- 58, the mixture of MCM-22 races material and two or more in them.In a preferred embodiment, microporous crystalline Alumino-silicate has the restricted index of about 3- about 12 and is ZSM-5.

ZSM-5 is described in US 3,702,886.ZSM-11 is described in US 3,709,979.ZSM-22 is described in US In 5,336,478.ZSM-23 is described in US 4,076,842.ZSM-35 is described in US 4,016,245.ZSM-48 is described In US 4,375,573, ZSM-50 is described in US 4,640,829, and ZSM-57 is described in US 4,873,067.ZSM-58 Description is in US 4,698,217.Restricted index and its assay method describe in US 4,016,218.It is every in the patent One entire content is incorporated by reference herein.

MCM-22 races material is selected from MCM-22, PSH-3, SSZ-25, MCM-36, MCM-49, MCM-56, ERB-1, EMM- 10, EMM-10-P, EMM-12, EMM-13, UZM-8, UZM-8HS, ITQ-1, ITQ-2, ITQ-30 and they in two or more The mixture of kind.

MCM-22 races material includes that MCM-22 (being described in US4,954,325), PSH-3 (are described in US4,439,409 In), SSZ-25 (being described in US4,826,667), ERB-1 (being described in EP293032), ITQ-1 (be described in US6,077, In 498) and ITQ-2 (being described in WO97/17290), MCM-36 (being described in US5,250,277), MCM-49 (be described in In US5,236,575), the mixture of MCM-56 (being described in US5,362,697) and two or more in them.It is to be included Related zeolite in MCM-22 races be UZM-8 (being described in US 6,756,030) and UZM-8HS (be described in US 7,713, In 513), the two is also suitable for the molecular sieve as MCM-22 races.

In one or more embodiments, microporous crystalline metal silicate, which has, is more than about 3, or more than about 25, or it is more than about 50, or it is more than about 100, or it is more than 400, or about 100- about 2,000, or about 100- about 1, 500, or about 50-2,000, or about 50-1,200 Si/M molar ratios.

In one or more embodiments, microporous crystalline alumino-silicate, which has, is more than about 3, or is more than about 25, Or it is more than about 50, or it is more than about 100, or it is more than 400, or about 100- about 400, or about 100- about 500, or it is big About 25-2,000, or about 50-1,500, or about 100-1,200, the SiO of about 100-1000₂/Al₂O₃Molar ratio.

In another embodiment of the present invention, by microporous crystalline metal silicate (such as alumino-silicate) and the 10th Race's metal or metallic compound and optionally one kind, two kinds, three kinds or more 1st, 2 or 11 race's metals or metallic compound knot It closes.

In one or more embodiments, the 10th race's metal includes, or is selected from Ni, Pd and Pt, preferably Pt.The catalysis 10th race's tenor of agent composition is at least 0.005wt%, the weight based on the carbon monoxide-olefin polymeric.At one or more In a embodiment, the 10th race's content is in about 0.005wt%- about 10wt%, or about 0.005wt% is to about In the range of 1.5wt%, the weight based on the carbon monoxide-olefin polymeric.

In one or more embodiments, the 1st race's alkali metal includes, or two in Li, Na, K, Rb, Cs and they The mixture of kind or more, preferably Na.

In one or more embodiments, the 2nd race's alkaline-earth metal in Be, Mg, Ca, Sr, Ba and they two kinds or More kinds of mixtures.

In one or more embodiments, the 1st race's alkali metal as oxide exist and the metal be selected from Li, The mixture of Na, K, Rb, Cs and two or more in them.In one or more embodiments, the 2nd race's alkaline-earth metal is made For oxide presence and mixture of the metal selected from Be, magnesium, calcium, Sr, Ba and two or more in them.At one Or in multiple embodiments, the 1st race's alkali metal exists as oxide and the metal is selected from Li, Na, K, Rb, Cs and they In the mixture of two or more；And the 2nd race's alkaline-earth metal as oxide exist and the metal be selected from Be, magnesium, The mixture of calcium, Sr, Ba and two or more in them.

In one or more embodiments, the 11st race's metal includes or selected from silver, gold, copper, preferably silver or copper.It is described to urge 11st race's tenor of agent composition is at least 0.005wt%, the weight based on the carbon monoxide-olefin polymeric.At one or In multiple embodiments, the 11st race's content is in about 0.005wt%- about 10wt%, or about 0.005wt% is to about In the range of 1.5wt%, the weight based on the carbon monoxide-olefin polymeric.

In one or more embodiments, carbon monoxide-olefin polymeric, which has, is less than 25, is either less than 15 or 1-25, or The α values (adding the 10th race's metal, preferably measured before platinum) of person 1.1-15.

In one or more embodiments of alumino-silicate, the molar ratio of the 1st race's alkali metal and Al are at least big About 0.5, or at least about 0.5 to about 3, preferably at least about 1, more preferably at least about 2.

In one or more embodiments of alumino-silicate, the molar ratio of the 2nd race's alkaline-earth metal and Al are at least About 0.5, or at least about 0.5 to about 3, preferably at least about 1, more preferably at least about 2.

In one or more embodiments, the molar ratio of the 11st race's metal and the 10th race's metal is at least about 0.1, or at least about 0.1 to about 10, preferably at least about 0.5, more preferably at least about 1.In one or more embodiment party In case, the 11st race's alkaline-earth metal exists as oxide and the metal is selected from gold, silver and copper and two or more in them The mixture of kind.

Preferably, useful carbon monoxide-olefin polymeric uses at conversion conditions here, and the conversion condition includes 400-800 DEG C temperature, the pressure and 1-100hr of 10-1,000 kPas of absolute pressure^-1WHSV.In one or more embodiments, this The use of invention carbon monoxide-olefin polymeric provides the acyclic C5 raw materials at least about 60% under acyclic C5 conversion conditions, or at least About 75%, or at least about 80%, or about 60%- about 80% conversion ratio, the acyclic C5 conversion conditions be with Equimolar H₂Raw material containing pentane, about 550 DEG C-about 600 DEG C of temperature, 3-10psia pentane partial pressure and 10- 20hr^-1Pentane weight (hourly) space velocity (WHSV).

Any use is provided in one or more embodiments, in inventive catalyst composition turns in acyclic C5 At least about 30% under the conditions of change, or at least about 40%, or at least about 50%, or about 30%- about 80% to ring The carbon selectivity of shape C5 compounds, the acyclic C5 conversion conditions include having equimolar H₂Pentane raw material, about 550 DEG C-about 600 DEG C of temperature, the pentane partial pressure of 3-10psia and 10-20hr^-1Pentane weight (hourly) space velocity (WHSV).

Any use is provided in one or more embodiments, in inventive catalyst composition turns in acyclic C5 At least about 30% under the conditions of change, or at least about 40%, or at least about 50%, or about 30%- about 80% to ring The carbon selectivity of pentadiene, the acyclic C5 conversion conditions include having equimolar H₂Pentane raw material, about 550 DEG C-big About 600 DEG C of temperature, the pentane partial pressure of 3-10psia and 10-20hr^-1Pentane weight (hourly) space velocity (WHSV).

The carbon monoxide-olefin polymeric of the present invention can be combined with matrix or binder material wear-resisting and more to assign them It is resistance to they in hydrocarbon Transformation Application during use by the severity of the condition of experience.The combining compositions can contain 1- The material of the present invention of 99wt%, the total weight of matrix (binder) and material based on the present invention.The phase of micro crystal material and matrix Comparative example can widely change, and wherein crystalline content is the about 1- about 90wt% and more generally of composite material, especially It is composite material when composite material forms the forms such as particle, spray-dried granules in bead, extrudate, pill, oil dripping to be prepared About 2- about 80wt%.

During use, coke may be deposited on the carbon monoxide-olefin polymeric to carbon monoxide-olefin polymeric in the methods of the invention On, thereby such carbon monoxide-olefin polymeric loses a part for its catalytic activity and becomes to be passivated.Can by routine techniques, including High pressure hydrogen process and with the coke on oxygen-containing gas combustion catalyst composition make catalyst deactivation composition regenerate.

Useful carbon monoxide-olefin polymeric includes crystal aluminosilicate or ferrosilicate, optionally with it is a kind of, two kinds or More kinds of other metals or metallic compound combine.Preferably conjugate includes：

1) it is combined with the 10th race's metal (such as Pt), the 1st race's alkali metal (such as sodium or potassium) and/or the 2nd race's alkaline-earth metal Crystal aluminosilicate (such as ZSM-5 or zeolite L)；

2) crystal aluminosilicate (example combined with the 10th race's metal (such as Pt) and the 1st race's alkali metal (such as sodium or potassium) Such as ZSM-5 or zeolite L)；

3) with the 10th race's metal (such as Pt), the 1st race's alkali metal (such as sodium or potassium) combine crystal aluminosilicate (such as Ferrosilicate or the ZSM-5 of iron processing)；

4) crystal aluminosilicate combined with the 10th race's metal (such as Pt) and the 1st race's alkali metal (such as potassium) (such as boils Stone L)；With

5) it is tied with the 10th race's metal (such as Pt), the 1st race's alkali metal (such as sodium) and the 11st race's metal (such as silver or copper) The crystal aluminosilicate (such as ZSM-5) of conjunction.

Another useful carbon monoxide-olefin polymeric is the 10th race's metal being supported on silica (for example, silica) (such as Ni, Pd and Pt, preferably Pt), the silica pass through the 1st race's alkali silicate (such as Li, Na, K, Rb and/or Cs Silicate) and/or the 2nd race's alkaline-earth-metal silicate (such as Mg, Ca, Sr and/or Ba silicate), preferably potassium silicate, sodium metasilicate, Calcium silicates and/or magnesium silicate, preferably potassium silicate and/or sodium metasilicate are modified.10th race's tenor of carbon monoxide-olefin polymeric be to Few 0.005wt%, based on the weight of the carbon monoxide-olefin polymeric, preferably approximately 0.005wt%- about 10wt%, or about 0.005wt% to about 1.5wt%, the weight based on the carbon monoxide-olefin polymeric.Silica (SiO₂) can typically use Make any silica of catalyst carrier, for example, with trade name DAVISIL 646 (Sigma Aldrich), DAVISON952, DAVISON 948 or DAVISON 955 (Davison Chemical Division of W.R.Grace and Company) Those of sale.

For the more information of useful carbon monoxide-olefin polymeric, the application of submission is referred to：

1) USSN 62/250,675 submitted on November 4th, 2015；

2) USSN 62/250,681 submitted on November 4th, 2015；

3) USSN 62/250,688 submitted on November 4th, 2015；

4) USSN 62/250,695 submitted on November 4th, 2015；With

5) USSN 62/250,689 submitted on November 4th, 2015；

They are incorporated by reference herein.

The cooling of first reactor hydrocarbon effluent

The condensation of undesirable side reaction such as thermal cracking, PNA and reactivity two olefinic substances, especially CPD in order to prevent Too early Diels-Alder reaction, once the first reactor hydrocarbon effluent leaves first reactor by it cool down be It is highly desirable to.For this purpose, the first reactor hydrocarbon effluent can be allowed to pass through at least one going out next to first reactor The heat exchanger of mouth setting, wherein in the range of its temperature is reduced to Tc1 DEG C-Tc2 DEG C, wherein Tc1 and Tc2 can be independently 20,50,80,150,200,250,300,350,400 or 450 DEG C, as long as Tc1<Tc2.Or or furthermore, it is possible to allow described first In the range of reactor hydrocarbon effluent is contacted with quenching liquid so that temperature is reduced to Tc1 DEG C-Tc2 DEG C, wherein Tc1 and Tc2 Can be independently 20,40,50,60,80,100,120,140,150,160,180,200,220,240,250,260,280, 300,320,340,350,360,380,400,420,440 or 450, as long as Tc1<Tc2.After the cooling period, it is anti-to come from described first Answer most of component of device hydrocarbon effluent still in gas or vapor phase.

Washing/quenching of first reactor hydrocarbon effluent

The first reactor hydrocarbon effluent includes the heavy component for the amount of can not ignore, including but not limited to：Polynuclear aromatic Substance (naphthalene and alkylated naphthalene, anthracene and alkylation anthracene, phenanthrene and alkylation are luxuriant and rich with fragrance), DCPD, due to not wishing between CPD and acyclic dienes The Diels-Alder reaction of prestige and the product formed.It is highly desirable to these heavy components, especially C8+ hydrocarbon at least It is partly removed from the first reactor hydrocarbon effluent so that them is avoided to pollute richness C5 fractions and subsequent contamination richness DCPD Fraction.For example, naphthalene is difficult to be removed from DCPD by distilling；Naphthalene and more heavy PNA, which can also condense formation, may make equipment scaling Solid.Therefore, naphthalene and more heavy PNA are hopefully before first reactor hydrocarbon effluent further processing from wherein removing It goes.

Advantageously, such heavy component effectively following in a reservoir can remove：The first reactor hydrocarbon stream is set to go out The stream of object contacts preferably after it is just partially cooled with washing oil.For this purpose, can be by the washing oil, it is desirable to which ground is in the operation phase Between in the liquid phase, as spray of small to washing container in, contact the first reactor hydrocarbon effluent at this time substantially The stream of steam.Additionally or in the alternative, the stream of the substantially steam of the first reactor hydrocarbon effluent can be sent to energy Enough suitable gas-liquid contact washing containers (for example, tower with grizzly bar and/or random packing) of processing fouling business.Described Enough contacts between one reactor hydrocarbon effluent and liquid washing oil cause heavy component (that is, C8+ hydrocarbon) anti-from described first The stream of the substantially steam of device hydrocarbon effluent is answered to be extracted into washing oil liquid.A small amount of washing oil may be entrained in low steam In the first reactor hydrocarbon effluent vapor stream of pressure.When necessary, the washing oil of the entrainment can then be removed.

In washing container, the first reactor hydrocarbon effluent vapor stream can be further quenched to 10-300 DEG C, It is preferred that 20-100 DEG C.Therefore, the washed of the first reactor hydrocarbon effluent and cooling vapor stream are obtained from washing container. Alternatively, it is also possible to obtain the washing oil liquid stream for including above-mentioned polynuclear aromatic compound.

Various washing oil can be used.The non-limiting examples of washing oil include：Hexamethylene；Monoalkyl, dialkyl group and trialkyl Hexamethylene；Benzene；Monoalkyl, dialkyl group and trialkyl benzene；Monoalkyl, dialkyl group, trialkyl and tetraalkyl naphthalene；Other alkylations are more Aromatic compound；Mixture with them and combination.Preferably washing oil is：Alkylbenzene and their mixture are (herein referred as Lightweight washing oil)；With alkylnaphthalene and their mixture (herein referred as heavy wash oil).It is further preferred that toluene, especially has at least The relatively pure toluene or alkylnaphthalene (one or more) of the purity of 50wt% especially have at least those of purity of 50wt% As washing oil.

In the fluid channel (including heat exchanger therebetween, if any) from first reactor to washing container, and Inside washing container, the dimerization between CPD molecules can occur, form DCPD；And CPD may with acyclic dienes hydrocarbon reaction, Form other C10+ hydrocarbon.These heavy components (if being formed) of major part are in the washing oil liquid material for leaving washing container It is distributed in stream.If washing oil liquid stream is transported to fuel disposition (fuel disposition) or to be delivered directly to other low In the disposition of value, then a part of CPD produced in the first reactor will degrade (downgrade) for low value.In order to subtract Few this non-required loss of yield in the container that people can operate under conditions of being conducive to reversed dimerization, and equally includes Together, Treatment of Washing oil liquid stream obtains tower top richness C5's to the stream that other downstreams of these heavy components and/or washing oil generate Stream and containing residual C8+ and washing oil bottom of tower richness washing oil stream.The stream of tower top richness C5 can be used as the fraction of the first richness C5 A part, be directly or indirectly fed in second reactor.Can further destilling tower bottom richness washing oil stream, to recycle at least It can directly or indirectly be recycled in washing container by a part of washing oil.This condition for being conducive to reversed dimerization includes for example Ranging from 150 to 350 DEG C, preferably 170 to 260 DEG C of temperature, ranging from 21 to 345kPa absolute pressure, preferably 21 to The absolute pressure of 138kPa and 0.01 to 10 hour, preferably 0.1 to 4 hour residence time.

The separation of first reactor hydrocarbon effluent

It then, will be preferably in the cooling of the exit of first reactor as described above and above by fluid interconnection channel The first reactor hydrocarbon effluent washed in the washing container is supplied in the first isolated subsystem, and in the first segregant It is processed in system, to obtain depleted C1-C4 hydrocarbon and hydrogen and the as needed rich C5 of depleted heavy component (such as C8+ hydrocarbon) Fraction.Since the property of the reaction occurred in first reactor leads in first reactor hydrocarbon effluent that there are notable volumes Hydrogen.Hydrogen and C1-C4 light hydrocarbons need the major part in view of C5 hydrocarbon that may make with efficiently separating for C5 hydrocarbon (including CPD) It is kept for the steam in hydrogen/lightweight hydrocarbon flow.Therefore, it is intended that ground, it can be advantageous to using with intermediate stage cooling and liquid The compression device group of body/steam separation is as the first isolated subsystem so that C5 hydrocarbon is to the damage in the hydrogen and lightweight hydrocarbon flow It loses and minimizes.

It includes pressing in at least 3- stages to be with the illustrative compression device group that intermediate stage cooling is detached with liquid/vapor The outlet pressure of the slave final stage at least 100psia (689 kPas of absolute pressures) of contracting/intermediate stage cooling that A bit.

Rich C5 hydrocarbon (the first C5 grades of richness can be obtained from multiple stages from the first isolated subsystem (such as compression device group) Point) one or more streams.It, can be by two of which or more when obtaining multiple streams of the first richness C5 fractions C5 grades of part-streams of single first richness are optionally merged into, is then followed by and processes together.The first richness C5 fractions generally comprise： (i)CPD；(ii) unreacted C5 hydrocarbon (one or more) such as pentane from C5 raw materials；(iii) pentamethylene and ring penta Alkene.

The first richness C5 fractions can further include a part for washing oil, especially if the washing oil contain C6 and C7 hydrocarbon, such as when hexamethylene and alkyl cyclohexane, benzene and alkylbenzene (for example, toluene).Such wash can be then removed when necessary Oil.Even if using higher boiling washing oil such as alkylnaphthalene, the first richness C5 fractions may also include C6 hydrocarbon by low concentration (as from the The by-product of one reactor) such as benzene.

It can be with from the first isolated subsystem (for example, first liquid/vapor separator in multistage compression device group) The non-essential stream containing heavy constituent is generated, at one especially in early stage, the stream includes washing oil and C8+ hydrocarbon (for example, DCPD and other products due to the Diels-Alder reaction generation between CPD and other diene) etc..If made With higher boiling washing oil such as methyl naphthalene (one or more), then such heavy stream may be the amount that can not ignore.If such Heavy stream is generated by compression device group, then can advantageously be combined it with the washing oil liquid stream generated by above-mentioned washing container, It is then followed by and processes together as described above.

From the first isolated subsystem (for example, compression device group), the rich light components for including hydrogen and C1-C4 hydrocarbon are also obtained Fraction.This richness light components fraction hopefully depleted C5 components, especially CPD, or at least minimize so that C5 molecules exist It is used in the method for the present invention and arrives top.

The cycle of the separation and hydrogen and/or light hydrocarbon of rich light components fraction

Rich light components fraction from the first isolated subsystem for detaching the first reactor hydrocarbon effluent is shown It is hydrogen to write component.C1-C4 hydrocarbon by C5 raw materials to be generated in the first reactor on a small quantity.Alternatively, in certain examples of the present invention It, can be by C1-C4 light hydrocarbons, such as CH in the method for property₄First reactor is supplied as total raw material, is caused from the first segregant The C1-C4 light hydrocarbons of higher concentration in the rich light components fraction that system obtains.

In view of a large amount of hydrogen generated in the method, rich light components fraction is detached to obtain the hydrogen of higher purity Air-flow is desirable, can use or sell as the industrial gas for having height to be worth.For this purpose, various methods and apparatus Can be used to recycle and concentrating hydrogen, for example, pressure-variable adsorption (PSA), Rapid Circulation pressure-variable adsorption (RCPSA), thermal swing adsorbent (TSA), Cryogenic method, UF membrane etc., wherein PSA or RCPSA are preferred.By using any one of these methods or their times What is combined, and can obtain three kinds of air-flows from rich light components fraction：Include the hydrogen-rich material of hydrogen by at least purity of 95mol% Stream, the total moles based on the hydrogen rich stream；Include the intermediate stream of hydrogen and C1-C4 hydrocarbon, the preferred C2+ hydrocarbon of C1-C4 hydrocarbon It is few；With can also containing the rich C1-C4 hydrocarbon flows of C5+ hydrocarbon, the C5+ hydrocarbon can then by washing or low-temperature fractionation (for example, Absorber) recycling.A part for hydrogen rich stream and/or a part for intermediate stream are (if it is anti-that C1-C4 hydrocarbon is fed to first jointly Answer device) it may loop to first reactor.Additionally or in the alternative, at least part of intermediate stream and/or C1-C4 hydrocarbon flows can It is required with the certain steps (such as method for transformation in first reactor) being produced as in the method for the present invention for use as fuel gas Thermal energy.Alternatively, richness C1-C4 hydrocarbon flows may be used as the raw material of other methods such as light olefin production and/or further add Work is to obtain LPG fractions.

As discussed above, it can be advantageous at least part of recycle hydrogen and C5 raw materials be blended, it is anti-then to feed first Device is answered to reduce the coke formation on catalyst granules, to increase the service life of the catalyst used in first reactor.In addition Or alternatively, recycle hydrogen can individually feed first reactor.Additionally or in the alternative, recycle hydrogen can be used for catalyst regeneration Or reduction.

The dimerization of first richness C5 fractions

It includes CPD that first richness C5 fractions, which advantageously press high concentration in the range of ca1wt%-ca2wt%, based on described The total weight of C5 hydrocarbon in first richness C5 fractions, wherein ca1 and ca2 can be independently 20,25,30,35,40,45,50,55, 60,65,70,75,80,85 or 90, as long as ca1<ca2.Such CPD can be directly used as being used to prepare such as norbornene, Vinyl norbornene, ethylidene norbornene, hydrocarbon resin adhesive or tackifier, unsaturated polyester resin, pentamethylene and/or The CPD raw materials of cyclopentene.

Additionally or in the alternative, at least part of the first richness C5 fractions can be supplied under the conditions of first group of dimerization The first dipolymer reactor (second reactor in the system) of work a, wherein part of the CPD is advantageously converted At DCPD.This may be highly desirable, because DCPD ratios CPD is more stable, and therefore can store and/or be transported to Different location, there, it is used as DCPD or is converted to CPD and is used to prepare value added product.

First dipolymer reactor (second reactor in the system) can advantageously plunger flow reactor, return Mixed reactor, continuous stirred tank reactor, boiling point reactors and/or baffled reactor；In addition, the reactor can contain Heat-transfer equipment such as coil.First dipolymer reactor can be by one or more in single container or in multiple containers A reaction zone constitutes and may include in the reaction zone or one or more heat transmission equipments between the reaction zone.

First group of dimerization condition in first dipolymer reactor can advantageously comprise：In Tb1 DEG C-Tb2 DEG C of model Interior temperature is enclosed, wherein Tb1 and Tb2 can be independently 30,50,60,80,100,120,140,150,160,180,200, 220,240 or 250, as long as Tb1<Tb2；Absolute pressure in the range of Pb1 kPas-Pb2 kPas, wherein Pb1 and Pb2 can be with It is independently 345,350,400,450,500,550,600,700,800,900,1000,1500,2000,2500,3000, 3500,4000,4500,5000,6000,6500,6894 or 7000, as long as Pb1<Pb2；With in-Tr2 minutes Tr1 minutes models The interior residence time is enclosed, wherein Tr1 and Tr2 can be independently 1,10,20,30,40,50,60,70,80,90,100,110, 120,130,140,150,160,170,180,190,200,210 or 220, as long as Tr1<Tr2.Preferably, if in the system Concatenated two dipolymer reactors are used in system, then first group of dimerization condition includes 70-130 DEG C of temperature, 689-3447 The residence time of the gross pressure and 20-200 minutes (such as 100-200 minutes) of kPa absolute pressure；Preferably, if described Concatenated three dipolymer reactors are used in system, then first group of dimerization condition includes 90-140 DEG C of temperature, 689- The gross pressure of 3447 kPas of absolute pressures and 1-30 minutes residence times.

A part of CPD included in the first richness C5 fractions for feeding the first dipolymer reactor is converted to DCPD. The exit of the second reactor (the first dipolymer reactor) obtains the first reactor effluent for including CPD and DCPD.It is excellent Selection of land limits the conversion degree in the second reactor and allows to generate high-purity DCPD；That is, the degree of limitation conversion ratio makes The amount of the CPD codimerization objects containing acyclic dienes and monoolefine must be maintained to make it possible to obtain required purity less than certain level DCPD.Advantageously, the first richness C5 fractions include the CPD of a concentration of C (CPD) 2wt%, based on the C5 components in the first richness C5 fractions Total weight；The first reactor effluent includes the DCPD of the CPD and a concentration of C (DCPD) 1 of a concentration of C (CPD) 3wt%, and two Person is based on the total weight of C5 hydrocarbon and C10 hydrocarbon in the first reactor effluent；And C (CPD) 3<C(CPD)2.

The separation of first richness DCPD fractions

Then at least part of the first reactor effluent is supplied into the second separation equipment, such as destilling tower, The first richness DCPD fractions (for example, bottoms effluent as bottom steam for example from the tower) of middle acquisition and the second C5 grades of richness Divide (for example, as top stream such as tower top effluent from the tower).Advantageously, the first richness DCPD fractions can have The DCPD concentration of C (DCPD) 1wt%；And x1≤C (DCPD) 1≤x2, wherein x1 and x2 can be independently 80,82,84, 85,86,88,90,91,92,93,94,95,96,97,98,99,99.2,99.4,99.5,99.6,99.8 or 100, as long as x1< x2.The ultra-high purity DCPD at least concentration of 98wt%, 99wt% or even 99.5wt% can be obtained (that is, UHP DCPD the first richness DCPD fractions) are used as.Optionally at least part of the first richness DCPD fractions can be supplied at least Another separation equipment, such as destilling tower, wherein the purity of the first richness DCPD fractions can be further increased.Second richness C5 CPD concentration in fraction is often below the first richness C5 fractions.Usual second richness C5 fractions include concentration range be 95.0wt% extremely The CPD of 99.9wt%, the total weight based on the second richness C5 fractions.

The dimerization of second richness C5 fractions

At least part of the second richness C5 fractions obtained from the second separation equipment can advantageously by High concentration in the range of ca3wt%-ca4wt% includes CPD, based on the total weight of the C5 hydrocarbon in the second richness C5 fractions, Wherein ca3 and ca4 can be independently 1,5,10,20,25,30,35,40,45,50,55 or 60, as long as ca3<ca4.Described Such CPD in two richness C5 fractions can be directly used as being used to prepare such as norbornene, vinyl norbornene, ethidine The CPD raw materials of norbornene, hydrocarbon resin adhesive or tackifier, unsaturated polyester resin, pentamethylene and/or cyclopentene.

Additionally or in the alternative, the second dimerization that the supply of the second richness C5 fractions can be worked under the conditions of second group of dimerization is anti- Device (the third reactor in the system) is answered, wherein a part of CPD is advantageously converted to DCPD, with the first dimerization reaction Operation in device (second reactor in the system) is similar, it is preferred that in higher temperature and/or longer stop Between lower operation can realize the satisfactory conversion ratio of lower concentration CPD.

Therefore, second group of dimerization condition in second dipolymer reactor can advantageously comprise：At Tb3 DEG C-Tb4 DEG C In the range of temperature, wherein Tb3 and Tb4 can be independently 30,50,60,80,100,120,140,150,160,180, 200,220,240 or 250, as long as Tb3<Tb4；Absolute pressure in the range of Pb3 kPas-Pb4 kPas, wherein Pb3 and Pb4 Can be independently 345,350,400,450,500,550,600,700,800,900,1000,1500,2000,2500,3000, 3500,4000,4500,5000,6000,6500,6894 or 7000, as long as Pb3<Pb4；With in-Tr4 minutes Tr3 minutes models The interior residence time is enclosed, wherein Tr3 and Tr4 can be independently 1,10,20,30,40,50,60,70,80,90,100,110, 120,130,140,150,160,170,180,190,200,210,220,230,240,250,260,270,280,290 or 300, As long as Tr3<Tr4.Preferably, if using concatenated two dipolymer reactors, second group of dimerization item in the system Part includes the temperature of 75-140 DEG C (such as 100-140 DEG C), the gross pressure of 689-3447 kPas of absolute pressure and 100-300 points The residence time of clock (such as 150-300 minutes)；Preferably, if using concatenated three dipolymer reactors in the system, Then second group of dimerization condition includes 100-140 DEG C of temperature, the gross pressure of 689-3447 kPas of absolute pressure and 1-30 points The residence time of clock.

Second dipolymer reactor (the third reactor in the system) can be and the first dipolymer reactor (system In second reactor) similar reactor.

A part of CPD included in the second richness C5 fractions for feeding the second dipolymer reactor is converted to DCPD. The exit of second dipolymer reactor obtains the third reactor effluent for including CPD and DCPD.Preferably, described the is limited Conversion degree in three reactors allows to generate high-purity DCPD；That is, the degree of limitation conversion ratio to maintain to contain acyclic two The amount of the CPD codimerization objects of alkene and monoolefine makes it possible to obtain the DCPD of required purity less than certain level.

The separation of second richness DCPD fractions

Then at least part of the third reactor effluent can be supplied third separation equipment, such as distilled Tower, wherein obtaining the second richness DCPD fractions (for example, bottoms effluent as bottom steam for example from the tower) and third Rich C5 fractions (for example, as top stream such as tower top effluent from the tower).Advantageously, the second richness DCPD fractions can With the DCPD concentration with C (DCPD) 2wt%；And x3≤C (DCPD) 2≤x4, wherein x3 and x4 can be independently 40, 50,60,65,70,75,80,82,84,85,86,88,90,91,92,93,94,95,96,97,98 or 99, as long as x3<x4.It is logical Often, the purity of the second richness DCPD fractions be less than the first richness DCPD fractions, reason be the second richness C5 fractions with it is described First richness C5 fractions are lower compared to the ratio between CPD therein and acyclic dienes.Nevertheless, can obtain at least 90wt%, Or the DCPD (HP DCPD) of the very high-purity of the concentration of 92wt% or 93wt% or even 95wt% is used as the second richness DCPD Fraction.Can be optionally by least part of richness DCPD fractions supply at least another separation equipment, such as distill Tower, wherein the purity of the second richness DCPD fractions can be further increased.Equally, the CPD in the third richness C5 fractions is dense Degree is often below the second richness C5 fractions.Usual third richness C5 fractions include the CPD of a concentration of 90.0wt% to 99.5wt%, are based on The total weight of third richness C5 fractions.

The dimerization of third richness C5 fractions

At least part of the third richness C5 fractions obtained from third separation equipment can advantageously by Concentration in the range of ca5wt%-ca6wt% includes CPD, based on the total weight of the C5 hydrocarbon in the third richness C5 fractions, Middle ca5 and ca6 can be independently 1,5,10,15,20,25,30,35,40,45,50,55 or 60, as long as ca5<ca6.It is described Such CPD in third richness C5 fractions can be directly used as being used to prepare such as norbornene, vinyl norbornene, ethylidene The CPD raw materials of base norbornene, hydrocarbon resin adhesive or tackifier, unsaturated polyester resin, pentamethylene and/or cyclopentene.

Additionally or in the alternative, at least part of the third richness C5 fractions can be supplied under the conditions of third group dimerization The third dipolymer reactor (the 4th reactor in the system) of operation a, wherein part of CPD is advantageously converted to DCPD, it is similar to the operation in first dipolymer reactor (second reactor in the system).

The third dipolymer reactor (the 4th reactor in the system) can be and first dipolymer reactor (second reactor in the system) similar reactor, it is preferred that in higher temperature and/or longer residence time Lower operation is can realize the satisfactory conversion ratio of the lower concentration CPD.

It is desirable that the major part of the CPD included in the third richness C5 fractions for feeding third dipolymer reactor is turned It is melted into DCPD.Additionally or in the alternative, make acyclic C5 diene (for example, 1,3-pentadiene；1,4- pentadienes, 1,2- pentadienes and/or 2- methyl-1s, 3- butadiene) to be reacted with CPD to prepare codimerization object in third dipolymer reactor be desirable.In addition Or it is alternatively possible to acyclic C5 diene will be contained (for example, steam cracking naphtha, light cat naphtha, heavy catalytic stone brain Oil) and/or other streams of C6 diene (for example, methyl cyclopentadiene and hexadiene) be added to supply third dipolymer reactor In charging.Furthermore, it is also possible to advantageously generate the trimer and tetramer of C5 the and C6 substances.In third dipolymer reactor Exit, it includes CPD and DCPD to obtain, anti-preferably together with the 4th of other C5 codimerization objects, total trimer and/or total tetramer the Answer device effluent.

Therefore, the third group dimerization condition in the third dipolymer reactor can advantageously comprise：At Tb5 DEG C-Tb6 DEG C In the range of temperature, wherein Tb5 and Tb6 can be independently 30,50,60,80,100,120,140,150,160,180, 200,220,240 or 250, as long as Tb5<Tb6；Absolute pressure in the range of Pb5 kPas-Pb6 kPas, wherein Pb5 and Pb6 Can be independently 345,350,400,450,500,550,600,700,800,900,1000,1500,2000,2500,3000, 3500,4000,4500,5000,6000,6500,6894 or 7000, as long as Pb5<Pb6；With in-Tr6 minutes Tr5 minutes models Enclose the interior residence time, wherein Tr5 and Tr6 can be independently 100,200,300,400,500,600,700,800,900 or 1000, as long as Tr5<Tr6.Preferably, the third group dimerization condition includes 80-150 DEG C, such as 100-150 DEG C of temperature, The gross pressure of 689-3447 kPas of absolute pressure and 150-300 minutes residence times.

The separation of third richness DCPD fractions

Then at least part of the 4th reactor effluent can be supplied the 4th separation equipment, such as distilled Tower, wherein obtaining third richness DCPD fractions (for example, as bottoms effluent from the tower) and the 4th richness C5 fraction (examples Such as, as the tower top effluent from the tower).Advantageously, the third richness DCPD fractions can have C (DCPD) 3wt% DCPD concentration；And x5≤C (DCPD) 3≤x6, wherein x5 and x6 can be independently 20,30,40,45,50,55,60, 65,70,75,80,82,84,85,86,88,90,91,92,93,94 or 95, as long as x5<x6.In general, DCPD grades of the third richness The purity divided is less than the second richness DCPD fractions, and reason is the third richness C5 fractions compared with the second richness C5 fractions wherein CPD it is lower with the ratio between acyclic dienes.Nevertheless, can obtain has at least 70wt%, 75wt%, 80wt%, 85wt% Or the moderate purity DCPD of the concentration of 90wt% is as third richness DCPD fractions.It can be optionally by DCPD grades of the third richness At least part divided supplies at least another separation equipment, such as destilling tower, wherein it is rich to further increase the third The purity of DCPD fractions.Equally, the CPD concentration in the 4th richness C5 fractions is often below the third richness C5 fractions.

Cycle of the rich C5 fractions to first reactor

At least part of above-mentioned first, second, third and fourth richness C5 fractions (if all generated in the methods of the invention Above-mentioned first reactor then) is may loop to, wherein can be by unreacted C5 hydrocarbon (one or more) and from the C5 raw materials The C5 hydrocarbon of Partial Conversion is further converted into CPD.

The first, second, third and fourth richness C5 fractions (if generating) can contain C6+ hydrocarbon, such as hexamethylene, Benzene, toluene etc..It is highly desirable to be for the accumulation for preventing in the reaction product of such C6+ components in the first reactor, Before being recycled to first reactor, by least part of the C6+ components with the richness C5 streams in separation equipment, such as It detaches and removes in destilling tower, to generate the 5th richness C5 streams and richness C6+ streams.Therefore, then by the 5th C5 grades of richness of purifying Divide and is recycled to first reactor.

Motor petrol blend components are formed by C5+ components

Motor petrol is comprising the C4 to C12 with about 35 DEG C of primary standard boiling point and about 200 DEG C of final boiling point The blended mixts of hydrocarbon.Motor petrol is mainly used as the fuel of automobile internal engine.In the presence of many via various locals, state Or the different motor petrol specifications that national governmental agencies require.One example is the Reid Vapour Pressure of final mogas production (RVP).The vapour pressure of motor petrol is its volatile measurement and high vapour pressure result in smog hydrocarbon high evaporation row It puts.

For the angle of performance, the important attribute of motor petrol is its octane number.Linear alkanes are (that is, linear saturation Molecule) often there is the octane number lower than other hydrocarbon such as aromatic compounds, alkene and branched paraffin.For this purpose, petroleum refining The many method of refining used in factory are designed to generate the hydrocarbon with these molecular configurations below.For example, catalytic reforming is to use In typically high-octane rating product liquid will be converted to the feed naphtha of low octane rating to manufacture for motor petrol The broad practice of commercial run of advanced blending stock.The method is by alkane and cycloalkanes at high-octane rating aromatic hydrocarbon. However, naphtha catalytic reforming is limited to C6+ raw materials.

Pentane, which is transformed into isopentane (a/k/a i- pentanes), can lead to the advantageous increase of octane, but RVP also has not The increase of profit.Pentane is converted to the substance (occurring in this first reactor in the present invention) of cyclopenta and internal olefinic Advantageously increase octane and advantageously reduces RVP.Rich DCPD streams can also add hydrogen partially or completely and generate low RVP/ more Higher octane blend components.

Therefore, additionally or in the alternative, above-mentioned first, second, third, fourth and fifth richness C5 fractions and richness C6+ streams It at least partially can be optionally with the additional stream containing diene (for example, steaming (if all generating in the methods of the invention) Vapour pressure naphtha, light cat gasoline fraction, heavy catalytic gasoline fraction) group merge can selectively plus hydrogen and generate vehicle Use gasoline component.Because the first, second, third, fourth and fifth richness C5 fractions contain the unsaturated C5 hydrocarbon of high concentration, packet CPD and cyclopentene are included, once so partial hydrogenation, they just often have than supply first reactor without ring filling C5 raw materials High octane number and low Reid Vapour Pressure (RVP)." selective hydrogenation " method used herein be simultaneously include diene and The mixture of monoolefine and processing of hydrogen in the presence of selective hydrocatalyst under the conditions of selective hydrogenation, the selection Property hydroconversion condition compare mono-olefins and to promote diene being converted to monoolefine at saturate.This selective hydrogenation can be at it In be mounted in the hydrogenation reactor of hydrogenation catalyst and carry out.It is highly desirable to, the motor petrol group of the selective hydrogenation Divide and presses not higher than 2.0wt%, is preferably no greater than 1.0wt%, not higher than 0.5wt% and ideally total dense not higher than 0.1wt% Degree includes diene, the total weight based on the motor petrol component.It in these areas, preferably will at least C5 grades of 25wt% thirds richness Divide and be recycled in first reactor, and at least 50wt% thirds richness C5 fractions are carried out to add hydrogen.It then can be by this automobile-used vapour Oil ingredient is blended with additional motor petrol component to obtain the motor petrol with required composition and performance.

Additionally or in the alternative, in above-mentioned first, second, third, fourth and fifth richness C5 fractions (if all in present invention side Generated in method) at least part and/or their hydrogenation products a part add hydrogen before or after, they can be detached To obtain separation of high-purity Cyclopentene, pentamethylene, 2- methyl-1s, 3- butadiene and/or 1,3-pentadiene, each of which can be with It uses or sells as valuable industrial materials.

The non-limiting examples of hydrogenation catalyst include：Palladium base or nickel-base catalyst.Illustratively hydroconversion condition includes： The pressure of 30-250 DEG C of temperature and 1,700-5,500 kPas of absolute pressure.

The present invention can be used for by low value C5 raw materials be converted to higher value CPD, DCPD, have high-octane rating and/or The motor petrol component of lower RVP, cyclopentene, pentamethylene, 1,3-pentadiene etc. and hydrogen.

Description with reference to the accompanying drawings

Attached drawing schematically illustrate an examples operation and is used for executing illustrative methods of the present invention (one or more) or its side The block flow diagram of the exemplary system of the present invention (one or more) and its subsystem (one or more) in face.It should be appreciated that Primary clustering is illustrated only in attached drawing.Ancillary equipment is such as control valve, pump, heat exchanger, reboiler, circulation loop (although not having Have and all show in all the appended drawings) stream and equipment thermodynamic condition are manipulated during entire method.

In system 101 shown in Fig. 1, the C5 raw material flows 103 and hydrogen of pentane will be included by for example, at least 50wt% Gas is total to raw material flow 105 and combines to form combination stream 107, then by the combination stream 107 and cycle third richness C5 streams 109 In conjunction with to form combination raw materials stream 111, the combination raw materials stream 111 is supplied into first reactor 113 (being also labeled as R1).Stream The molar ratio of hydrogen and C5 raw materials can be 0.1-3.0, preferably 0.3-2.0, more preferable 0.5-1.5 in 111.Co-feeding hydrogen It is mainly used for preventing the coke formation on catalyst, the hydrogen especially generated in situ wherein is in the position of low concentration Place.Reactor 113 can be the fixed bed reactors for the bed for being wherein loaded with catalyst 115.Catalyst 115 is selected from said combination Object.Reaction of C5 hydrocarbon in the presence of catalyst granules is highly endothermic.Therefore, reactor 113 is heated by outside heating To maintain 450 DEG C -800 DEG C of internal temperature.Weight (hourly) space velocity (WHSV) was at 1-100 hours^-1In the range of.By the C5 hydrocarbon in raw material 111 Signal portion by the pentane total conversion of 50%-99% be converted to CPD and by-product for example acyclic dienes, acyclic mono-olefin, Pentamethylene, cyclopentene；Light components including hydrogen and C1-C4 hydrocarbon；Monocyclic aromatics；And polynuclear aromatic compound. The exit of first reactor 113, total absolute pressure of the extraction in 500-800 DEG C of temperature and 20-700 kPas of absolute pressure First reactor hydrocarbon effluent 117.

The first reactor hydrocarbon effluent 117 can include CPD by the total concentration of 15wt%-80wt%, based on described The total weight of C5 hydrocarbon in first reactor hydrocarbon effluent 117.Once it leaves first reactor 113, just pass through one or more The first reactor hydrocarbon effluent stream 117 is quickly cooled down to obtain stream 121 to avoid undesirable by a heat exchanger 119 Side reaction such as thermal cracking, the too early Diels-Alder reaction of the condensation of PNA and reactive two olefinic substances (especially CPD). A certain amount of washing oil (not shown) can be added before heat exchanger 119 and/or in it to help prevent fouling.

Then cooled stream 121 and washing oil steam 125 are fed into washing container 123, wherein by the first reactor hydrocarbon Effluent is further quenched to obtain washed first reactor hydrocarbon effluent stream 129.It is used in Fig. 1 and 2 illustrated embodiments Washing oil by at least total concentration of 50wt% include alkylnaphthalene (one or more) and/or alkylbenzene, but can use above-mentioned Other washing oil.Stream 129 includes C5 components and light components from the first reactor hydrocarbon effluent.Stream 129 may be used also To contain C6, C7, C8 and the washing oil by the amount that can not ignore.Also obtained from washing container 123 comprising the washing oil, monocycle virtue The washing oil bottom steam 127 of compounds of group and polynuclear aromatic compound.

Then by top stream 129 as the first isolated subsystem 131 of cleaned first reactor hydrocarbon effluent supply ( Labeled as SD1), wherein obtain the first richness C5 streams 133, the additional richness C5 streams of one or more 134 one of (Fig. 1 show) with And the light component stream 161 comprising hydrogen and C1-C4 hydrocarbon.The advantageously depleted C1-C4 hydrocarbon of rich C5 streams 133 and 134.Stream 133 Can include one or more in C6, C7, C8+ and heavy wash oil by the amount that can not ignore.Stream 134 is hopefully pressed than stream 133 much lower concentration include C6, C7, C8+ and heavy wash oil.Preferably, stream 134 is washed substantially free of C10+ and heavy Oil.In view of the amount of the hydrogen generated in first reactor 113,161 total volume of stream is sizable.In order to recycle stream The C5 components of the amount of can not ignore present in 161 make stream 161 further (also referred to as " de- in container 163 with washing oil stream 165 Butane tower " or " debutanization tower section ") in contact with obtain include H₂With C1-C4 hydrocarbon and the stream 167 of depleted C5 components.Then will The washing oil stream 125 for leaving debutanizing tower container 163 is recycled to above-mentioned washing container 123.Can by using various equipment and (not shown), such as PSA, RCPSA, TSA, cryogenic method and UF membrane further detach stream 167 to method, following to obtain It is one or more in substance：(i) high-purity H₂Stream；(ii)H₂/ C1-C4 hydrocarbon mixture streams；(iii) richness C1-C4 hydrocarbon material Stream.

Stream 133 (can be washed by the concentration that can not ignore is (one or more) comprising C6, toluene, C8+ and heavy to it One or more degree in oil) together with above-mentioned stream 127 feed heavy wash oil (for example, alkylnaphthalene) removal column 135, The middle top stream 137 for obtaining richness C5 and depleted C10+, and the bottom steam 138 comprising C7 and C8+.It can be in subsequent destilling tower Stream 138 is purified in (not shown), is obtained the stream of rich alkylnaphthalene, can be recycled to above-described container 163 and/or wash It washs in container 123.Should make great efforts reduce heat exchanger 119, the CPD in 131 front end of container 123,135 and the first isolated subsystem and Reaction between acyclic dienes.Nevertheless, because these side reactions may be occurred by various degree, height caters to the need Be meet promote reversed dimerization reaction compared to dimerization under conditions of operational tower 135 so that by heavy component such as DCPD, Reaction product between DCPD and acyclic dienes is converted to CPD and other C5 components, and therefore recycles CPD at least partly and want Not so the other C5 components that can be lost in side reaction.For this purpose, the condition in tower 135 advantageously comprise 150-350 DEG C, preferably 170-260 DEG C of column bottom temperature and 3psia-50psia (21-345 kPas of absolute pressure), preferably 20psia-40psia (138- 276 kPas of absolute pressures) total absolute pressure and 0.01-10 hours, preferably 0.1-4 hours residence times.

Then the stream 137 obtained from the first isolated subsystem and stream 134 (all richness C5 and depleted C10+) one are acted as It is transported to the second reactor to work under the conditions of first group of dimerization for the first richness C5 fractions and (is also labeled as R2, and referred to as first Dipolymer reactor) 139 a part of the CPD wherein contained is converted to DCPD.First group of dimerization condition advantageously comprises： (345-6895 kPas absolutely for the temperature and 50psia-1000psia of 30-250 DEG C, preferably 70-140 DEG C (such as 90-130 DEG C) Pressure), total absolute pressure of preferably 100psia-500psia (689-3447 kPas of absolute pressure) and 1-220 minutes, preferably The residence time of 20-200 minutes (such as 100-200 minutes).By these condition optimizings to promote the dimerization between CPD molecules anti- The reaction between CPD and other diene should and be set to minimize.

Then the first reactor effluent 141 comprising CPD, other C5 hydrocarbon and DCPD is fed second from reactor 139 Separation equipment 143 (SD2) can be destilling tower.From tower 143, obtain extreme high purity DCPD bottom steams 147 and comprising The top stream of CPD and other C5 hydrocarbon.Stream 147 can be by least 95wt%, such as 96wt%, 98wt%, 99wt% or very Include DCPD, the total weight of the C10 hydrocarbon based on the stream 147 to higher concentration.Stream 147 can be in follow-up destilling tower In (not shown) purifying to obtain (1) extreme high purity DCPD, press at least 95wt%, such as 96wt%, 98wt%, 99wt% or Even higher concentration includes DCPD, the total weight based on the stream；(2) lightweight richness washing oil stream can be recycled to Said vesse 163 and/or washing 123 (not shown) of container.

Then top stream 145 (it is the second richness C5 fractions in the method for the present invention) is fed in second group of dimerization condition The second dipolymer reactor (third reactor of the invention, R3) 149 of lower work, wherein by the remaining parts CPD in stream 147 Ground is converted to DCPD.Second group of dimerization condition advantageously comprises：30-250 DEG C, preferably 100-140 DEG C of temperature, and 50psia-1000psia (345-6895 kPas of absolute pressure), preferably 100psia-500psia (689-3447 kPas of absolute pressure Power) total absolute pressure and 1-300 minutes, preferably 150-300 minutes residence times.By these condition optimizings so that residue The recycling of CPD maximizes, while reaching the conjunction specification production of follow-up DCPD fractions.

Then the third reactor effluent 151 comprising CPD, other C5 hydrocarbon and DCPD is fed into third from reactor 149 Separation equipment 153 (SD3) can be destilling tower.From tower 153, obtain high-purity DCPD bottom steams 155 and comprising CPD and The top stream 157 of other C5 hydrocarbon.Stream 155 can be by least 90wt%, such as 92wt%, 94wt%, 95wt% or even Higher concentration includes DCPD, the total weight of the C10 hydrocarbon based on the stream 155.Stream 155 can follow-up destilling tower (not Display) in purifying to obtain (1) high-purity DCPD, press at least 90wt%, such as 92wt%, 94wt%, 95wt% or even Higher concentration includes DCPD, the total weight based on the stream；(2) lightweight richness washing oil stream can be recycled to above-mentioned Container 163 and/or washing 123 (not shown) of container.

DCPD streams 147 and 155 can be used as product to sell or convey.These streams can be converted back to CPD by user Or other compounds, this depends on expected application.

Top stream 157 (it is the third richness C5 fractions in the method for the present invention) can be fed third dipolymer reactor (not shown), wherein wherein remaining CPD can be converted to the DCPD of additional amount, if desired, the can be used as Three richness DCPD fractions are detached and are recycled in the 4th separation equipment (not shown).If using third dipolymer reactor, first The preferred operation mode of dipolymer reactor and the second dipolymer reactor can be generated advantageously for best in quality level The purpose of DCPD products (respectively with optimised quantity) is adjusted.Typically, third richness DCPD fractions will have than in above-mentioned side The first and second low purity of richness DCPD fractions that method upstream generates.

As shown in Figure 1, C5 grades of part-streams 157 of third richness from third separation equipment 153 are divided into two 159 Hes of stream 161.The degree that C6+ can also be included other than C5 hydrocarbon to stream 157,159 and 161, then by stream in destilling tower 163 161 separation are to obtain the 5th richness C5 streams 165 and richness C6 streams 167 of depleted C6+.Then stream 165 can be regard as stream 109 are recycled to first reactor 113 (R1), as described above.Stream 167 can purge to or be used for other application, such as without The motor petrol component of processing, as described below.It has been found that in this particular embodiment, without destilling tower 163, if Stream 161 and the weight ratio of stream 159 are higher than 0.4:0.6, then the accumulation of C6+ substances may occur in such systems.Highly It is desirable that stream 161 is allowed to undergo the purifying in tower 163, first reactor is then recycled to eliminate to the recycle ratio Such limitation.

Stream 159 (and optionally, the part of first C5 grades of part-streams 137 of richness and second C5 grades of part-streams 145 of richness A part, do not shown in Fig. 1) can be used for many purposes, this is attributed to many useful components wherein contained：CPD、 Pentamethylene, cyclopentene, amylene, pentadiene, 2-methyl butadiene etc..

For example, can be by selective hydrogenation by stream 159 (and other C5 grades of part-streams of richness, and richness C6 streams 167) portion Divide or is completely converted into motor petrol component so that at least part of diene therein is converted to monoolefine and/or saturation Object.The high concentration of pentamethylene and cyclopentene after adding hydrogen in stream 159 makes it be particularly suitable for motor petrol blending, this returns Because in the starting material relative to acyclic C5 hydrocarbon such as pentane, the high-octane rating and lower Randt's steam of pentamethylene and cyclopentene Pressure value.Rich C6 streams 167 can equally be directly used as motor petrol component after selective hydrogenation.

It, can be by (and the other C5 grades of sub-materials of richness of stream 159 before or after selective hydrogenation for another example Stream) it detaches to obtain at least one pure material stream of following substance：Pentamethylene, cyclopentene, amylene, 1,3- pentadienes, 1,4- penta 2 Alkene and 2-methyl butadiene.

Fig. 2 schematically shows method and system for use in the present invention, be particularly useful for Fig. 1 illustrate it is exemplary Exemplary first isolated subsystem 201 of method.The first isolated subsystem 201 in Fig. 2 includes compression device group comprising more Stage compression, cooling and liquid/vapor separation.It, first will be washed comprising being obtained from tower 123 in the method for this attached drawing The most top stream 129 of the first reactor effluent feeds first stage compressor 203, is obtained from the compressor 203 Obtain the stream 205 in higher pressure.Then stream 205 is cooled down to obtain liquid/vapor by first stage heat exchanger 207 Mixture stream 209, by the liquid/vapor mixture stream 209 feed the first stage liquid/vapor separation equipment (such as Drum) 211 to obtain the first stage lower part liquid stream 215 comprising C5 hydrocarbon but depleted hydrogen and C1-C4 hydrocarbon and comprising C5 hydrocarbon and rich The first stage uppermost vapor stream 213 of hydrogen and C1-C4 hydrocarbon.Then by 217 compressed stream 213 of second stage compressor to obtain The stream 219 with even higher pressure is obtained, is then cooled down the stream 219 to obtain by second stage heat exchanger 221 Second stage lower temperature liquid/vapor mixture stream 223 is obtained, in second stage liquid/vapor separation equipment (such as bulging) 225 detach the liquid/vapor mixture stream 223 to obtain include C5 hydrocarbon but depleted hydrogen and C1-C4 hydrocarbon second Stage lower part liquid stream 229 and second stage vapor stream 227 comprising C5 hydrocarbon and hydrogen rich gas and C1-C4 hydrocarbon.Then pass through third rank Then section 231 compressed stream 227 of compressor passes through phase III heat exchanger to obtain the stream 233 with even higher pressure 235 cool down the stream 233 to obtain lower temperature phase III liquid/vapor mixture stream 237, in phase III liquid It includes that C5 hydrocarbon is still poor to detach liquid/vapor mixture stream 237 to obtain in body/vapor separation device (such as bulging) 239 Hydrogen and the phase III lower part liquid stream 241 and hydrogen rich gas and C1-C4 hydrocarbon of C1-C4 hydrocarbon and, optionally, by low concentration packet The phase III uppermost vapor stream 161 of the hydrocarbon containing C5.Then by 161 supply container 163 of stream, as shown in Figure 1 and as described above.

As shown in Fig. 2, can by stream 215 (to it can include can not ignore concentration washing oil, C7 and C8+ (such as At least one of) DCPD degree) together with stream 127 heavy wash oil removal column 135 is fed, wherein processing it to obtain The rich C5 streams 137 for obtaining depleted heavy wash oil, as above in conjunction with described in Fig. 1.It can be by downstream stream 229 and 241 (often to them Include the degree of the heavy wash oil of low concentration, C7 and C8+) it combines to form single stream 134, then by the single stream 134 are combined as being fed directly into the first richness C5 fractions of the first dipolymer reactor 139 (R2) with stream 137, as shown in Figure 1.

Although it is contemplated that do not show, can by stream 215,229 and 241 (may all contain to them can not ignore it is dense The degree of at least one of heavy wash oil, C7 and the C8+ (such as DCPD) of degree) all weight is transported to together with stream 127 Matter washing oil removal column 135, wherein obtaining richness C5 streams 137 and being transported to the first dipolymer reactor 139.

Although not showing, it is further contemplated that, it can (all may be by sufficiently low dense to them by stream 215,229 and 241 The degree degree of (if having really) containing heavy wash oil, C7 and C8+) it is combined with stream 137, then directly it is transported to the one or two Poly- reactor 139.

Industrial applicibility

In acyclic C₅What is obtained during method for transformation contains cyclic annular, branched and linear C₅Hydrocarbon and, optionally contain hydrogen, C₄With lighter by-product or C₆Any combination of first hydrocarbon reactor effluent of more heavy byproduct itself and it is naturally Value product.Preferably, CPD and/or DCPD can be detached with the reactor effluent and can be used for preparing to obtain The purified product stream of various high-value products.

For example, the purified product stream containing 50wt% or more or preferably 60wt% or more DCPD can be used for preparing hydrocarbon Resin, unsaturated polyester resin and epoxide resin material.Purifying containing 80wt% or more or preferably 90wt% or more CPD Product stream can be used for preparing the Diels-Alder reaction product formed according to following reaction process (I)：

Flow chart I

Wherein R is hetero atom or substituted hetero atom, substituted or unsubstituted C1-C50 alkyl (usual double bond containing hydrocarbon Base), aromatic group or any combination of them.Preferably, substituted group contains one or more 13-17, the preferably the 15th or The element of 16 races, more preferable nitrogen, oxygen or sulphur.In addition to the monoolefine Diels-Alder reaction product described in flow (I) it Outside, the purified product stream containing 80wt% or more or preferably 90wt% or more CPD can be used for being formed CPD with it is following One or more Diels-Alder reaction products in substance：Another CPD molecules, conjugated diene, acetylene, allene, The substitution pattern of disubstituted alkene, trisubstituted alkene, cyclic olefin and above-mentioned substance.Preferred diels-Alder is anti- It includes norbornene, ethylidene norbornene, substituted norbornene (including oxygen-containing norbornene), norbornadiene to answer product And tetracyclododecane, as shown in the following structure：

Aforementioned Diels-Alder reaction product can be used for producing cycloolefine polymer and cycloolefin and alkene (such as ethylene) The copolymer of copolymerization.Gained cyclic olefine copolymer and cyclic olefin polymer can be used for various applications, such as packaging film.

Such as ring-opening metathesis polymerization is may be used in containing the purified product logistics more than or equal to 99wt%DCPD (ROMP) catalyst produces DCPD polymer.DCPD polymer products can be used to form product, especially molded parts, such as wind-force Turbine blade and automotive component.

Also additional component can be detached from reactor effluent and is used to form high-value product.For example, the ring of separation Amylene can be used for producing polycyclic amylene, also referred to as poly- pentamer, as discribed in flow chart (II)：

Flow chart 11

The pentamethylene of separation can be used as foaming agent and solvent.Linear and branched C₅Product can be used for being converted to more advanced alkene And alcohol.Cyclic annular and non-annularity C₅Product can be used as octane enhancer and transport fuel blending group optionally after adding hydrogen Point.

The pentamethylene of separation can be used as foaming agent and be used as solvent.Linear and branched C₅Product can be used for being converted to more advanced Alkene and alcohol.Cyclic annular and non-annularity C₅Product optionally after hydrogenation can be used as octane enhancer and transport fuel is total Mixed object component.

Embodiment

Following non-limiting embodiment 1-7 illustrates the present invention.Embodiment 1-5 is obtained by using simulation test.At these In embodiment, by each the first reactor effluent by similar manner as discussed above supply forward quenching/washing section (123), Compression device group section (SD1,131) and debutanization section (163).Will by quenching/washing section (135), compression device group section (SD1, 131) and all recycling richness C5 fractions for generating of debutanization section (163) are transmitted to heavy wash oil removal column (135), and then to the One dipolymer reactor (R2,139), extreme high purity DCPD recovery towers (SD2,143), the second dipolymer reactor (R3,149), then High-purity DCPD recovery towers (SD3,153).

Embodiment 1

In this embodiment, the first reactor effluent by pure isopentane feeds, have 1:2 hydrogen/pentane mole The pure hydrogen of ratio is total to raw material generation, without co-feeding light hydrocarbon or any downstream richness C5 fractions to the cycle of the first reactor. Processing temperature, pressure, weight (hourly) space velocity (WHSV) and molecular weight at reactor inlet are 475 DEG C respectively, (401.9 kPas absolutely by 62psia To pressure), 15hr^-1And 49.01g/mol.It is 575 DEG C and 10psia (68.9 respectively in the temperature and pressure of reactor exit KPa absolute pressure).Reaction generates additional 1.87 molecular in the first reactor effluent for leaving outlet, is based on Each molecular in the combined feed material of inlet.This 1.87 times of moles of extensions have the molecular weight of stream mixture and Density is reduced to the 27.05g/mol in exit from the 49.01g/mol of inlet respectively and from the 3.08kg/m of inlet³It reduces To the 0.26kg/m in exit³Effect.The pressure drop from the inlet to the outlet of first reactor is calculated as being about 52psi (359 KPa).In exit, the composition of the first reactor effluent is given in Table I below.

Entire third richness C5 fractions are used as the motor petrol blend of manufacture motor petrol, the motor petrol blend Composition equally provides in lower Table I.

In this embodiment, in order to generate 100 tons of CPD in stream 117,403 tons of pentane of total weight is fed Feed system (represents total CPD yields of 24.8wt%, the total weight based on pentane charging), generates 13.1 tons of total weight Hydrogen, that generate 82 tons of total weight is more than the UHP DCPD (stream 147) of 99.0wt% with purity level, generates total weight 11 Ton is more than the DCPD (stream 155) of 90.0wt% with purity level, and generates the motor petrol blending of 238 tons of total weight Object.

Embodiment 2

Reactor inlet and outlet temperature and pressure keep identical with example 1 above.However, in this embodiment In, rich C5 streams (are obtained as the third reactor effluent separation by will be generated by above-mentioned second dipolymer reactor The 35% of third richness C5 fractions generates) it is recycled to first reactor, wherein it and pentane are blended, then feed the first reaction Device.By 1:2 H₂/ (whole C5 hydrocarbon in addition to (different C5 hydrocarbon and CPD)) the co-feeding hydrogen of molar ratio.Tentatively send out Existing, the response path from different C5 hydrocarbon to CPD is at reaction conditions by kinetic inhibition.The composition of the combined feed of first reactor exists It is provided in lower Table I.

The residue 65% of the third richness C5 fractions is used as the motor petrol blend of manufacture motor petrol.Motor petrol is total The composition of mixed object equally provides in lower Table I.

In this embodiment, in order to generate 100 tons of CPD in stream 117,308 tons of pentane of total weight is fed Infeed system (represents the CPD yields of 32.5wt%, the total weight based on pentane charging), generates the hydrogen of 11.7 tons of total weight Gas, that generate 85 tons of total weight is more than the UHP DCPD (stream 147) of 99.0wt% with purity level, generates 8 tons of total weight With purity level be more than 90.0wt% DCPD (stream 155), and generation 146 tons of total weight motor petrol blend.

In order to generate same amount of CPD, embodiment 2 (the third richness C5 fractions have 35% to be recycled to first reactor) with Embodiment 1 (being recycled to first reactor without any richness C5 fractions) is compared to the fresh pentane charging for requiring few 23.4%.

In order to generate same amount of CPD, embodiment 2 generates 10.8% hydrogen less compared with Example 1, this is attributed to pair It is fed than fully saturated charging using part is unsaturated.This body with reduction in reactor (one or more) and upstream device The benefit of product flow.For example, the first reactor in embodiment 2 is shown reduces 7.8% than volume flow in embodiment 1.This can It can be to the equipment of downstream flash cold column (one or more), gas compressor (one or more) and debutanizing tower (one or more) Size, which has, to be significantly affected.

Enthalpy change across the stream of first reactor also shows in embodiment 2 and to be substantially reduced compared in embodiment 1.This turn 10.9% is turned in embodiment 2 in terms of heating furnace firing to reduce, this may to the equipment size of reactor (one or more) with Fuel cost, which has, to be significantly affected.When using the C5 raw materials of Partial Conversion, maintained required by the endothermic reaction in first reactor Heat significantly reduce.

In order to generate 100 tons of CPD, embodiment 2 shows the reduction for the material 38.6wt% for being transferred to motor petrol production.Separately Outside, from table i it can be seen that motor petrol stream in embodiment 2 have than in embodiment 1 C5+ by-products it is slightly greater Octane number, because more the limited isomerization of dynamics and aromatization products will be concentrated in less by-product stream.

It is therefore evident that it may be to have that at least part of the stream containing C5, which is recycled to CPD reactors (one or more), Profit.If reducing the demand to the C5 hydrocarbon of Partial Conversion, for example, can be blended when to the RVP specifications limitation of motor petrol C5 hydrocarbon amount certain seasons during, this is particularly useful.This allows equipment to continue by required DCPD Product Rates (product rate) is operated, and co-product quantity reduces.

Table I

Embodiment 3

In the indication embodiment that this is obtained by simulation test, it can obtain as motor petrol blend and have The corresponding portion of composition in following table II adds the model third richness C5 fractions of hydrogen car gasoline component：

Table II

Embodiment 4

In this embodiment, the first reactor effluent by pure isopentane feeds, have 1:1 hydrogen/pentane mole The pure hydrogen of ratio is total to raw material generation, without co-feeding light hydrocarbon or any downstream richness C5 fractions to the cycle of the first reactor. Processing temperature, pressure, weight (hourly) space velocity (WHSV) and molecular weight at reactor inlet are 475 DEG C respectively, (401.9 kPas absolutely by 62psia To pressure), than 1 lower weight (hourly) space velocity (WHSV) of embodiment to reach closer to thermodynamical equilibrium and 49.01g/mol.Go out in reactor Temperature and pressure at mouthful is 575 DEG C and 10psia (68.9 kPas of absolute pressures) respectively.In this embodiment, reaction system Also the catalyst system different from embodiment 1 is used.Reaction generates additional in the first reactor effluent for leaving outlet 2.02 moleculars, based on each molecular in the combined feed material of inlet.This 2.02 times of moles of extensions have will The molecular weight and density of stream mixture respectively from the 36.72g/mol of inlet be reduced to exit 18.16g/mol and from The 2.44kg/m of inlet³It is reduced to the 0.18kg/m in exit³Effect.The pressure drop from the inlet to the outlet of first reactor It is calculated as being about 52psi (359 kPas).In exit, the composition of the first reactor effluent is given in Table III below.

Entire third richness C5 fractions are used as the motor petrol blend of manufacture motor petrol, the motor petrol blend Composition equally provides in lower Table III.

In this embodiment, in order to generate 100 tons of CPD in stream 117,222 tons of pentane of total weight is fed Feed system (represents total CPD yields of 45.0wt%, the total weight based on pentane charging), generates 18.3 tons of total weight Hydrogen, that generate 54 tons of total weight is more than the UHP DCPD (stream 147) of 99.0wt% with purity level, generates total weight 44 Ton is more than the DCPD (stream 155) of 90.0wt% with purity level, and generates the motor petrol blend of 77 tons of total weight.

Table III

Embodiment 5

In the indication embodiment that this is obtained by simulation test, it can obtain as motor petrol blend and have The corresponding portion of composition in following table IV adds the model third richness C5 fractions of hydrogen car gasoline component：

Table IV

Embodiment 6-ZSM-5 carbon monoxide-olefin polymerics synthesize

By 10,000g deionizations (DI) water, 600g 50%NaOH solution, 45% sodium aluminate solutions of 25g, 730g n-propylamines 100% solution, 80g ZSM-5 seed crystals and 3,190g Ultrasil PM prepare the synthesis with~20.3% solid and mix Object.Then 5- gallons of autoclaves are added in the mixed and modified silica in 5- gallons of barrels upon mixing.The synthetic mixture It is formed with following mole：

SiO₂/Al₂O₃~470

H₂O/SiO₂~12.1

OH/SiO₂~0.16

Na/SiO₂~0.16

N-PA/Si~0.25.

It mixes with 250rpm at 230oF (110 DEG C) and reacts synthetic mixture 72 hours.The product of filtering gained is used in combination Then DI water washings are dried overnight at~250oF (121 DEG C) in an oven.By with three kinds at room temperature of ammonium nitrate solution Ion exchange will convert (for characterizing) at Hydrogen, then at 250oF (121 DEG C) by a part for the crystal of original sample when synthesis Drying is simultaneously calcined 6 hours at 1000oF (540 DEG C).The ZSM-5 crystal of gained has~414 SiO₂/Al₂O₃Molar ratio, 490(440+51)m²The total surface area (SA) of/g/(micropore SA+ mesoporous SA), 117mg/g hexane absorption and 31 α values (to institute State proton type measurement).The second part of the material is infiltrated for Pt as former state as when synthesis.

It will be with 414 SiO₂/Al₂O₃The ZSM-5 of the sodium content of molar ratio and 0.38wt% is in nitrogen in 900oF It is calcined 6 hours under (482 DEG C).After the cooling period, sample is heated to 900oF (482 DEG C) in nitrogen and is kept for three hours.So Afterwards by four gradually increment atmosphere is gradually changed to 1.1,2.1,4.2 and 8.4% oxygen.Each step is kept for 30 minutes. Temperature is increased to 1000oF (540 DEG C), oxygen content is increased to 16.8%, and keep material 6 small at 1000oF (540 DEG C) When.After the cooling period, using the aqueous solution of tetramine platinum hydroxide addition 0.5wt%Pt is infiltrated via incipient wetness.In air It is dried at room temperature for carbon monoxide-olefin polymeric 2 hours, is then kept for 4 hours at 250oF (121 DEG C), finally existed in air It is calcined 3 hours under 660oF (349 DEG C).Catalyst composition powder is suppressed into (15 tons), pulverizes and sieves to obtain 20-40 mesh Granularity.

Embodiment 7- carbon monoxide-olefin polymeric performance evaluations

Evaluate the performance of the above-mentioned material of embodiment 6.By carbon monoxide-olefin polymeric (0.5g) and quartzy (1.5g, 60-80 mesh) Physical mixed is simultaneously packed into reactor.The dry catalyst composition 1 at He (100mL/min, 30psig (207kPa), 250 DEG C) Hour, then in H₂It is restored 1 hour under (200mL/min, 30psig (207kPa), 500 DEG C).Then pentane, H are used₂And remaining The charging of part He, typically in 550 DEG C -600 DEG C, 5.0psia (35kPa-a) C₅H₁₂, 1.0 moles of H₂:C₅H₁₂、14.7h^{- 1}WHSV and 30psig (207kPa) amounts to the performance of lower test carbon monoxide-olefin polymeric.Lead at 550 DEG C -600 DEG C after initial stage test It crosses and uses H₂(200mL/min, 30psig (207kPa), 650 DEG C) handles 5 hours test carbon monoxide-olefin polymeric stability and renewable Property, then the re-test performance at 600 DEG C.

Cyclopentadiene and three equivalent hydrogen are generated by the dehydrogenation and cyclisation (equation 1) of pentane.This is by allowing positive penta Flowing reaches alkane at elevated temperatures on solid-state carbon monoxide-olefin polymeric containing Pt.Based on pentane conversion, ring-type C₅It generates (cC₅), the ZSM-5 (414 of cracking yield and estimation of stability embodiment 6:1) performance of/0.5%Pt.These results are summarised in In Table V, Table VI, Table VII and Table VIII.

Table V

Table VI

Table VII

Table VIII

Table V and Table VI are shown under transformation temperature (average value at each temperature in 8 hours) for 0.5g ZSM- 5(Si:Al₂Molar ratio 414:1) carbon monoxide-olefin polymeric of/0.5wt%Pt is in 5.0psia (35kPa-a) C₅H₁₂、1:1 mole of H₂: C₅, 14.7WHSV, 45psia (310kPa-a) amount under conditions of pentane conversion ratio and ring-type C₅, CPD, different C₅、C₁With C_2-4The selectivity and yield of crackate.In Table V, selectivity and yield are based on each ring-type C5, CPD, different for being formed by hydrocarbon The molar percentage of C5, C1 and C2-4 indicate；That is, molar selectivity is to be formed by each ring-type C₅、CPD、C₁And C_2-4Mole The total mole number of number divided by the pentane converted.In Table VI, selectivity and yield based on be formed by hydrocarbon each ring-type C5, The carbon percentage expression of CPD, different C5, C1 and C2-4；That is, carbon selectivity be formed by each ring-type C5, CPD, different C5, C1 and The total mole number of carbon in mole carbon number of C2-4 divided by the pentane converted.As can be seen, Table V and Table VI are shown in Under high WHSV be more than 80% conversion of pentane rate, and at 595 DEG C 40% the selectivity to cyclic annular C5 substances.Although without spy Determine final product, but can be by pentamethylene and cyclopentene cycle to generate CPD.

Table VI and VIII further provide for each iC5 components, they are shown as amounting in Table V and VII.IC5o is isoamyl Alkane；Including 2- methybutanes and 3- methybutanes.IC5=is iso-amylene, including 2- methyl butenes and 3- methyl butenes.IC5= It is isoprene；Including 2-methyl butadiene and 3- dimethyl butadienes.These results show that low-level isoprene is implemented Example catalyst is possible.

All documents described herein, including any priority documents and/or test procedure all with the present invention not contradiction Permission under be incorporated by reference.Although from above-mentioned general introduction and particular embodiment it is readily apparent that having illustrated and described The form of the present invention, but without departing from the spirit and scope of the present invention can be with various modification can be adapted.And it is therefore not desirable to The present invention is so limited.Similarly, term " including (comprising) " thinks synonymous with term " including (including) ". Equally, when composition, element or element group are before transitional term "comprising", it should be understood that also consider with Crossing property term " substantially by ... form ", " by ... form ", " being selected from " or "Yes" enumerate composition, element or Same combination before each element or element group, vice versa.

Claims (27)

1. a kind of method preparing the cyclic annular C5 containing cyclopentadiene (CPD) and/or dicyclopentadiene (DCPD), this method include：

It (I) will be in the C5 feedstocks to first reactor containing at least one acyclic C5 hydrocarbon；

(II) at least one acyclic C5 hydrocarbon is made to be contacted at conversion conditions with catalyst, the hydrocarbon stream to obtain first reactor goes out Object comprising：C5 components containing CPD and acyclic dienes hydrocarbon；The light components of hydrogen and C1-C4 hydrocarbon；Monocyclic aromatics； And polynuclear aromatic compound；

(III) hydrocarbon effluent for detaching first reactor, with first of the fraction and (ii) of the rich light components of production (i) containing CPD The fraction of rich C5；

(IV) fraction of the first richness C5 of at least part is supplied in the second reactor operated under the conditions of first group of dimerization；

(V) the first reactor effluent containing CPD and DCPD is obtained in the second reactor；With

(VI) at least part the first reactor effluent is detached, to obtain the first richness DCPD's containing dicyclopentadiene (DCPD) Fraction.

2. the method for claim 1 wherein：

The hydrocarbon effluent of first reactor includes the CPD of a concentration of C (CPD) 1wt% and total concentration is the acyclic of C (ADO) 1wt% Alkadienes, the two are based on the total weight of C5 components in the hydrocarbon effluent of first reactor；With

C(CPD)1/C(ADO)1≥1.5。

3. aforementioned any one the method for claim, wherein C5 raw materials include at least 50wt% pentanes.

4. aforementioned any one the method for claim, wherein catalyst are included in micropore metal silicate or silicate modified The 10th race's metal of at least one loaded on silica, the wherein catalyst include optionally one or more 1st races alkali gold Category, the 2nd race's alkaline-earth metal and/or the 11st race's metal.

5. aforementioned any one the method for claim, wherein conversion condition include ranging from 400 to 800 DEG C of temperature, range The absolute pressure for being 10 to 1,000kPa, and ranging from 1 to 100hr^-1WHSV.

6. aforementioned any one the method for claim, wherein：

The hydrocarbon effluent of first reactor includes the CPD that concentration range is 15wt% to 80wt%, the hydrocarbon based on first reactor The total weight of C5 components in effluent.

7. aforementioned any one the method for claim, wherein hydrogen be total to raw material to the molar ratio range of C5 raw materials be 0.1 to Under 3.0, hydrogen is total in feedstock to first reactor.

8. the method for claim 7, wherein before in C5 feedstocks to first reactor, at least part hydrogen is former altogether Material is mixed with C5 raw materials.

9. aforementioned any one the method for claim, wherein step (III) include it is following in an at least step：

(IIIa) hydrocarbon effluent of cooling first reactor；

(IIIb) increase the gross pressure of the first reaction effluent；

(IIIc) hydrocarbon effluent of at least part first reactor is washed with washing oil；

(IIId) light components are removed from the hydrocarbon effluent of first reactor；With

(IIIe) C8+ components are removed from the hydrocarbon effluent of first reactor.

10. aforementioned any one the method for claim, wherein step (III) include being washed with including following at least one washing oil Wash the hydrocarbon effluent of first reactor：Hexamethylene；Monoalkyl, dialkyl group and trialkyl hexamethylene；Benzene；Monoalkyl, dialkyl group and Trialkyl benzene；Monoalkyl, dialkyl group, trialkyl and tetraalkyl naphthalene；Other alkylation polynuclear aromatic compounds；And its mixture and Conjugate.

11. the method for claim 10, wherein：

Washing oil includes at least 50wt% toluene, the total weight based on the washing oil used in step (III).

12. the method for claim 10, wherein：

Washing oil includes the one or more alkylated naphthalenes of at least 50wt%, the gross weight based on the washing oil used in step (III) Amount.

13. aforementioned any one the method for claim, wherein step (III) include using with intersegmental cooling and steaming gas/liquid The compression device group of body separation, removes C4 and lighter component from the hydrocarbon effluent of first reactor.

14. aforementioned any one the method for claim, wherein the fraction of the first richness DCPD includes a concentration of at least 80wt% DCPD, the total weight of the fraction based on the first richness DCPD.

15. the method for claim 1-14 any one obtains the fraction of the second richness C5 containing CPD wherein in step (VI), Further comprise with this method：

(VII) fraction of the second richness C5 of at least part is fed to the third reactor operated under the conditions of second group of dimerization In；

(VIII) third reactor effluent is obtained from the third reactor containing CPD and DCPD；With

(IX) at least part third reactor effluent is detached, to obtain the fraction of the second richness DCPD.

16. the method for claim 15, wherein：

The fraction of second richness DCPD includes a concentration of at least DCPD of 60wt%, the total weight of the fraction based on the second richness DCPD.

17. the method for claim 16, wherein obtain the fraction of the third richness C5 containing CPD in step (IX), this method is into one Step includes：

(X) fraction of at least part third richness C5 is fed in the 4th reactor operated under the conditions of third group dimerization；

(XI) the 4th reactor effluent containing CPD and DCPD is obtained；With

(XII) the 4th reactor effluent of separation at least part, to obtain the grade of the fraction and the 4th richness C5 of third richness DCPD Point.

18. the method for claim 17, wherein：

The fraction of third richness DCPD includes a concentration of at least DCPD of 40wt%, the total weight of the fraction based on third richness DCPD.

19. the method for claim 15-18 any one, further comprises：

(XIII) at least part of at least one of following substance is directly or indirectly recycled to first reactor：First The fraction of rich C5, the fraction of the second richness C5, the fraction of the fraction of third richness C5 and the 4th richness C5.

20. aforementioned any one the method for claim, further comprises：

(XIV) fraction of the first richness of selective hydrogenation C5, the fraction of the second richness C5, the fraction of third richness C5 and if the generated At least part of at least one of the fraction of four richness C5, to obtain the charging of motor petrol component；With

(XV) it is fed by motor petrol component and forms engine gas blend.

21. the method for claim 20, wherein motor petrol component raw material is substantially free of alkadienes.

22. the method for claim 19-21 any one, including：

(XVI) in the fraction for detaching the fraction of the first richness C5, the fraction of the second richness C5, the fraction of third richness C5 and the 4th richness C5 At least one at least part, to obtain the fraction of the fraction and depleted C6 of richness C6；

(XVII) fraction of the depleted C6 of at least part is recycled in first reactor；With

(XVIII) the optionally fraction of selective hydrogenation at least part richness C6, is fed with obtaining motor petrol component.

23. the method for claim 15-22 any one, including：

(XIX) at least from the fraction of the fraction of the first richness C5, the fraction of the second richness C5, the fraction of third richness C5 and the 4th richness C5 It is obtained in one kind at least one of following：(i) fraction of rich pentamethylene；(ii) fraction of rich cyclopentene；(iii) richness 1,3- penta The fraction of diene；(iv) 2- methyl-1s, 3- butadiene fractions.

24. a kind of system preparing cyclopentadiene (CPD) and/or dicyclopentadiene (DCPD), the system include：

(A) it is that C5 raw material, non-essential hydrogen of the reception containing at least one acyclic C5 hydrocarbon are total to raw material and non-essential C1-C4 hydrocarbon is total Raw material and the first reactor constructed；

(B) the acyclic C5 hydrocarbon that can be catalyzed at conversion conditions inside first reactor is loaded in convert to produce first reactor hydrocarbon Catalyst, the first reactor hydrocarbon includes the C5 components containing CPD and acyclic dienes hydrocarbon；The lightweight of hydrogen and C1-C4 hydrocarbon Component；Monocyclic aromatics；And polynuclear aromatic compound；With

(C) be receive at least part first reactor hydrocarbon effluent and production (i) containing CPD and depleted hydrogen and C1-C4 hydrocarbon The fraction of the first richness C5 and the fraction of the rich light components of (ii) hydrogen and C1-C4 hydrocarbon and construct with first reactor stream First isolated subsystem of body connection.

25. the product derived from product prepared by the method by claim 1-23 any one.

26. the product of claim 25, the wherein product are derived from the diels-A Er by the product and double bond containing matrix The material that moral reaction obtains.

27. the product of claim 25, wherein product are：The wherein described product is selected from cyclopentadiene, dicyclopentadiene, ring penta Alkene, pentamethylene, amylene, pentadiene, norbornene, tetracyclododecane, substituted norbornene, the diels-of cyclopentadiene Alder reaction derivative, cyclic olefin copolymer, cyclic olefin polymer, polycyclic amylene, unsaturated polyester resin, hydrocarbon resin Tackifier, the epoxy resin of preparation, polydicyclopentadiene, norbornene or substituted norbornene or dicyclopentadiene or its The metathesis polymer of what combination, wind turbine blade, the composite material containing glass or carbon fiber, the adhesive of preparation, ethylidene Base norbornene, EPDM rubber, alcohol, plasticizer, foaming agent, solvent, octane enhancer, gasoline and its mixture.