CN108349833A - The preparation method and system of cyclopentadiene and/or dicyclopentadiene - Google Patents

The preparation method and system of cyclopentadiene and/or dicyclopentadiene Download PDF

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CN108349833A
CN108349833A CN201680064166.7A CN201680064166A CN108349833A CN 108349833 A CN108349833 A CN 108349833A CN 201680064166 A CN201680064166 A CN 201680064166A CN 108349833 A CN108349833 A CN 108349833A
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richness
hydrocarbon
reactor
oil
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L·L·亚西诺
K·C·P·梁
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ExxonMobil Chemical Patents Inc
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/373—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen with simultaneous isomerisation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
    • B01J29/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
    • C07C2/50—Diels-Alder conversion
    • C07C2/52—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
    • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
    • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
    • C07C5/333—Catalytic processes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C7/00—Purification; Separation; Use of additives
    • C07C7/10—Purification; Separation; Use of additives by extraction, i.e. purification or separation of liquid hydrocarbons with the aid of liquids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2529/00—Catalysts comprising molecular sieves
    • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
    • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
    • C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
    • C07C2529/44—Noble metals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/06—Systems containing only non-condensed rings with a five-membered ring
    • C07C2601/10—Systems containing only non-condensed rings with a five-membered ring the ring being unsaturated
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2603/00—Systems containing at least three condensed rings
    • C07C2603/56—Ring systems containing bridged rings
    • C07C2603/58—Ring systems containing bridged rings containing three rings
    • C07C2603/60—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members
    • C07C2603/66—Ring systems containing bridged rings containing three rings containing at least one ring with less than six members containing five-membered rings
    • C07C2603/68—Dicyclopentadienes; Hydrogenated dicyclopentadienes

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  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Water Supply & Treatment (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Abstract

The preparation method and system of cyclopentadiene and/or dicyclopentadiene include that acyclic C5 hydrocarbon (one or more) is converted to CPD to obtain product mixtures in the first reactor, the product mixtures are washed with washing oil, by the washed product mixtures separation to obtain the rich C5 fractions containing CPD in isolated subsystem such as compression device group, richness C5 fractions dimerization in dipolymer reactor is set then to detach the product effluent to obtain product effluent and obtain rich DCPD fractions.Washing oil can be recycled and be recycled.Multiple stages of dimerization and separating step can be used for obtaining the multiple richness DCPD fractions with various purity and amount.The rich C5 fractions in each stage of the method can be recycled to first reactor, or be converted to motor petrol component after selective hydrogenation.It can be optionally by rich C5 fractions and the separation of motor petrol component to generate value added chemicals.

Description

The preparation method and system of cyclopentadiene and/or dicyclopentadiene
Inventor：Larry L.Iaccino and Kevin C.P.Leung
Cross reference to related applications
It is submitted the present invention claims the USSN 62/250,692 submitted on November 4th, 2015 and on 2 2nd, 2016 The priority and interests of EP applications 16153728.7.
Technical field
The present invention relates to cyclic annular C5, include the preparation method and system of cyclopentadiene and/or dicyclopentadiene.Particularly, The present invention relates to the method and systems that cyclopentadiene and dicyclopentadiene are prepared by acyclic C5 hydrocarbon.
Background technology
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 lighter raw material (for example, ethane and propane feed), generate Less CPD, but 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.U.S.5,633,421 is generally disclosed C2-C5 paraffin dehydrogenations to obtain the side of corresponding alkene Method.Similarly, U.S.2,982,798 generally disclose the aliphatic hydrocarbon containing 3-6 (including the two endpoints) a carbon atom is de- The method of hydrogen.However, U.S.5,633,421 and U.S.2,982,798 all do not disclose by acyclic C5 hydrocarbon preparation CPD, the nothing Ring C5 hydrocarbon is desirable as raw material, because they are abundant and low cost.In addition, the CPD productions in design specially There are many challenges in method.For example, the reaction that C5 hydrocarbon is converted to CPD be extremely absorb heat and by low-pressure and high temperature Promote, but the notable cracking of pentane and other C5 hydrocarbon may occur under lower temperature (for example, 450 DEG C -500 DEG C).Its It, which is challenged, includes loss of catalyst activity caused by coking during preparation method and needs further processing with from urging Agent removes coke, and cannot use oxygen-containing gas directly to provide heat input without destroying catalyst to reactor.
From the viewpoint of storage and shipment, DCPD is easier to handle as the raw material ratio CPD for subsequent chemistry synthesis.DCPD It is interchangeable in numerous applications with CPD.In some applications, DCPD is preferably directly used instead of CPD.For wherein needing Want the other application of CPD, DCPD when in use can be via inverse diels-Alder (retro-diels-alder) reaction heat Depolymerization (aka crackings) is at CPD.
The conventional method for preparing CPD is typically generated by appropriate 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 distilling At a temperature of be reactive, so via conventional distil-lation from product mixtures recycling CPD be industrially infeasible.Routinely returning In debit's case, CPD is recycled from other C5 hydrocarbon using process for dimerization (one or more), the process for dimerization makes CPD undergo Di Er This-Alder reaction and generate the DCPD that can be easily detached with C5 hydrocarbon by conventional distil-lation.Lamentedly, CPD also can With other two alkene reactions present in stream and generate codimerization object, the codimerization object pollutes DCPD.In addition, causing more advanced The reaction of oligomer also issues life in neutral temperature to high temperature.These side reactions generate undesirable codimerization object and more advanced low Polymers, they make more down stream processing steps, for example, repeat, multistep cracking and dimerization become it is required, with generate have for many Using the DCPD of required enough purity.These methods are expensive, low yields, and may be susceptible to fouling.
Therefore, it is still necessary to solve the method and system for preparing CPD and/or DCPD of above-mentioned challenge.
Invention content
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 preparation method of CPD and/or DCPD, including：(I) will include at least one acyclic The C5 raw materials of C5 hydrocarbon feed first reactor；(II) the acyclic C5 hydrocarbon of at least one is made to be contacted at conversion conditions with catalyst To obtain first reactor hydrocarbon effluent, the first reactor hydrocarbon effluent includes：C5 groups including CPD and acyclic dienes Point；Light components including hydrogen and C1-C4 hydrocarbon；Monocyclic aromatics；And polynuclear aromatic compound；(III) make described One reactor hydrocarbon effluent is contacted with washing oil in washing container, to obtain：Include at least part and the institute of the washing oil State at least part of heavy stream of polynuclear aromatic compound；With at least part comprising the light components, the C5 At least part of component and optionally, the washed first reactor hydrocarbon effluent of a part for the washing oil；(IV) exist By the washed first reactor hydrocarbon effluent separation to obtain in first isolated subsystem：Including CPD and depleted described light First richness C5 fractions of matter component；First rich light components fraction of hydrogen and C1-C4 hydrocarbon；It is washed with non-essential first recycling Oil plant stream；(V) by the heavy stream and optionally, at least part of the non-essential first recovered wash oil stream supplies Subsystem is recycled to washing oil；(VI) it is obtained from washing oil recycling subsystem：Include the heavy oil grade of the polynuclear aromatic compound Point；Second recovered wash oil stream；With the non-essential recycling richness C5 streams comprising CPD；(VII) is by second recovered wash oil At least part of stream, and optionally, at least part of the non-essential first recovered wash oil stream and/or comprising The non-essential recycling richness C5 streams of CPD are either directly or indirectly recycled to the washing container.
Second aspect of the present invention is related to the preparation system of CPD and/or DCPD, including：(A) it is configured to receive comprising at least A kind of C5 raw materials of acyclic C5 hydrocarbon, non-essential hydrogen is total to raw material and non-essential C1-C4 hydrocarbon is total to the first reactor of raw material； (B) conversion of C5 hydrocarbon can be catalyzed to generate first reactor hydrocarbon at conversion conditions by being loaded in inside the first reactor The catalyst of effluent, the first reactor hydrocarbon effluent include：C5 hydrocarbon including CPD and acyclic dienes；Monocyclic aromatic Close object；Polynuclear aromatic compound；With the light components including hydrogen and C1-C4 hydrocarbon；(C) it is configured to receive (i) described first At least part of reactor hydrocarbon effluent and (ii) washing oil, and be configured to generate washed first reactor hydrocarbon effluent and Include the washing of at least part of the washing oil and at least part of heavy stream of the polynuclear aromatic compound Container；(D) it is configured to receive at least part of the heavy stream and generate comprising the polynuclear aromatic compound extremely The washing oil of at least part of heavy oil fraction and the second recovered wash oil stream recycles subsystem；(E) it is configured to described second time At least part for receiving washing oil stream is either directly or indirectly recycled to the washing oil fluid communication raceway groove of the washing container；(F) It is configured to supplying at least part of washed first reactor hydrocarbon effluent into the fluid communication ditch of the first isolated subsystem Road；(G) is configured to receive at least part of the washed first reactor hydrocarbon effluent and generation (i) to include CPD And the first richness C5 fractions of depleted hydrogen and C1-C4 hydrocarbon, the first rich light components fraction of (ii) hydrogen and C1-C4 hydrocarbon and (iii) the first isolated subsystem of non-essential first recovered wash oil stream being in fluid communication with the washing container.
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.
Specific implementation mode
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 in terms of the identical or different batch of material.For example, in a continuous process, although in method One step, which is right against, just to be fed the raw material of method starting point and carries out, but second step can simultaneously for by processing the The intermediate product for feeding the raw material of the method in early stage in one step and generating carries out.Preferably, the step is by described Sequence carries 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 is inherently containing certain horizontal error.
All numbers to the periodic table of elements and with reference to being 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 are 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 in condition and range (including environment temperature and pressure) via the condensation of diels-Alder spontaneously dimerization and form bicyclic penta Diene.
Term " acyclic " includes, but are not limited to linear and branched saturate and unsaturation object.
Term " alkyl " includes saturated hydrocarbyl, can be linear, branched, cricoid or cyclic annular, linear and/or branched line The combination of property.
Term " aromatics " refers to the flat annular alkyl for having conjugated double bond, such as benzene.Term aromatic used herein above Cover the compound containing one or more aromatic rings, including but not limited to, benzene, toluene and dimethylbenzene and multi-nucleus aromatic compound (PNA), include, but are not limited to naphthalene, anthracene,With their alkylation pattern.Term " C6+ aromatic compounds " includes being based on containing The compound of the aromatic ring of six or more annular atoms, including but not limited to, benzene, toluene and dimethylbenzene and multi-nucleus aromatic compound (PNA), include, but are not limited to naphthalene, anthracene,With their alkylation pattern.
Term " BTX " includes, but are not limited to the mixture of benzene, toluene and dimethylbenzene (adjacent and/or and/or to).
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 just container such as fractionating column or reactor it is positive top or side, It is above with and without additional stream.It is preferred that top stream is extracted out in the position of the near top of tower.It is preferred that tower top material Stream is extracted out at the position above at least one raw material." bottom steam " used herein is in the position less than the top stream Place is set, it can be just in the positive bottom or side of container, and if in side, with and without additional material below it Stream.Preferably, bottom steam is extracted out at the position near the bottom of tower.It is preferred that bottom steam is below at least one raw material Position at extract out." intermediate stream " used herein is the stream between top stream and bottom steam.
Term " partition wall destilling tower (divided-wall distillation column) " refers to by one or more Feed stream generates the destilling tower of top stream, bottom steam and intermediate stream, and inner space is being separated into two sections of shell There is partition wall in vivo, wherein one section includes the entrance for receiving feed stream, another section includes the outlet for spraying intermediate stream.Institute State the region that the substance in partition wall limitation shell is only delivered to above and below it.
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 (mogas) " refers to the organic compound for the fuel for being suitable as using in gasoline internal combustion engine The mixture of object.
Term " coke " includes, but are not limited to be adsorbed on the low hydrogen content hydrocarbon 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 comprising per molecule, saturated or unsaturated, such as pentane, 2- methyl Butane, 2,2- dimethyl pentanes, 1- amylenes, 2- amylenes, 2- methyl-2-butenes, 3- methyl-2-butenes, 1,3- pentadienes, 1,4- Pentadiene, 2- methyl-1s, 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 are 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 are not limited to Be, Mg, The mixture of Ca, Sr, Ba and two or more in them.
Term " the 11st race's metal " refers to the element in the 11st race of the periodic table of elements and includes, but are not limited to Cu, Ag, Au With 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 the space arrangement is tiled with three dimensions, it is described Crystal structure).The crystal structure the 5th edition, is carried out at " Atlas of Zeolite Framework Types " in 2001 It discusses, the entire content of the document 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 Diffractometers of the α bimodal (doublet) as incident ray and equipped with scintillation counter and associated computer 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 the ring-type C5 for foring 30 moles for every 100 moles of 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 raceway groove system Hole 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, in one or more embodiments, 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 packet It is saturated acyclic C5 hydrocarbon (one or more) containing about 50wt%- about 100wt%, it is desirable that pentane.Preferably, 2- methyl Butane is pressed to be existed 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 optionally, the hydrogen of light hydrocarbon such as C1-C4 hydrocarbon is total to raw material and also feeds first reactor.Preferably, hydrogen is total to At least part of at least part of raw material and C5 raw materials, preferably all blending, then feed first reactor.Hydrogen exists (wherein raw material is contacted with catalyst first) prevents or reduces coke in catalyst particles in raw mixture at the entry position Formation on grain.Carbon monoxide-olefin polymeric (will be described in more detail below) can include microporous crystalline metal silicate, excellent The restricted index having less than 12 is selected, the 10th race's metal is together with the 1st race's alkali metal and/or the 2nd race's alkaline-earth metal；Optionally 11st race's metal.Catalyst can be prepared by using the method being described more fully below.
First reactor can be plug 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 different reactors 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, those of ordinary skill in the art will easily approve that such statement includes two reactors 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 so that superficial gas velocity (U) is less than the rate required by the dilution phase pneumatic conveying of solid particle to maintain Solid Bed with the voidage less than 95%.In moving-burden bed reactor, solid (for example, catalyst material) can be slowly It can take out across reactor and from the bottom of the reactor and be added to the reactor top.Moving-burden bed reactor can To work under some flowing situations, including sedimentation or moving packed bed situation (U<Umf), be bubbled situation (Umf<U<Umb), slug Situation (Umb<U<Uc), transition and turbulent fluidised situation (Uc<U<Utr) and fast fluidization situation (U>Utr), wherein UmfIt is minimum stream Change rate, UmbIt is minimum bubbling rate, UcRate when being pressure oscillation peak value, UtrIt is delivery rate.These difference fluidisation shapes Gesture has been described in for example, Kunii, D., Levenspiel, O., Chapter 3of Fluidization Engineering, 2ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M., Chapter 6of Chemical Process Equipment,Revised 2ndIn Edition, Butterworth-Heinemann, Boston, 2010, they It is incorporated by reference herein.
Term as used herein " sedimentation bed " reactor refers to the wherein region of particle and air flow contacts or container so that 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 (Umf), U<Umf, and/or work under the rate higher than the minimum fluidization rate, It is maintained simultaneously along reactor beds gas axially upwards and/or solid performance (for example, temperature by using inside reactor structure Degree, 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,2nd Edition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M., Chapter 6of Chemical Process Equipment,Revised 2ndIt is provided in Edition, Butterworth-Heinemann, Boston, 2010.It is anti-to settle bed It can be " cycle sedimentation bed reactor " to answer device, refer to that there is solid (for example, catalyst material) to pass through the reactor Mobile and the solid (for example, catalyst material) the sedimentation bed at least partly recycled.For example, can be moved from the reactor Go out solid (for example, catalyst material), regenerate, reheats and/or detached with product stream, be 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 so that superficial gas velocity (U) is enough to make solid particle fluidisation (that is, being more than minimum fluidization rate Umf) 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 fluid bed (cascaded fluid-beds) " refers to that the arranged in series of each fluid bed allows to There are the gradients of gas and/or solid performance (for example, temperature, gas or solid composition, pressure etc.), when the solid or gas When being cascaded to another fluid bed from a fluid bed.The position of minimum fluidization rate for example, Kunii, D., Levenspiel,O.,Chapter 3of Fluidization Engineering,2nd Edition,Butterworth- Heinemann, Boston, 1991 and Walas, S.M., Chapter 6of Chemical Process Equipment, Revised 2ndIt is provided in Edition, Butterworth-Heinemann, Boston, 2010.Fluidized-bed reactor can be Mobile fluidized-bed reactor, such as " circulating fluid bed reactor " refer to passing through institute with solid (for example, catalyst material) State the fluid bed of the movement and the solid (for example, catalyst material) of reactor at least partly recycled.For example, can from institute It states reactor and removes solid (for example, catalyst material), regeneration is reheated and/or detached with product stream, is then returned to anti- Answer device.
Term as used herein " riser " reactor (also known as transport reactor) refers in fast fluidization or pneumatic defeated It send in fluidisation situation for the region of solid (for example, catalyst granules) being delivered up only or container (for example, right circular cylinder shape Pipe).Fast fluidization and pneumatic conveying flow situation are characterized in that superficial gas rate (U) is more than delivery rate (Utr).Soon Speed fluidisation and pneumatic conveying flow situation are also described in Kunii, D., Levenspiel, O., Chapter 3of Fluidization Engineering,2ndEdition, Butterworth-Heinemann, Boston, 1991 and Walas, S.M.,Chapter 6of Chemical Process Equipment,Revised 2nd 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 method for transformation
Acyclic C5 hydrocarbon is converted to the method for the product comprising ring-type C5 compounds including 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+H2Or
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), penta 2 Alkene (such as 1,3- pentadienes, 1,4- pentadienes), pentamethylene, cyclopentene, 2- methybutanes, 2-methyl-1-butene alkene, 3- methyl- 1- butylene, 2- methyl-1s, 3- butadiene, 2,2- dimethylpropanes etc.；C4 by-products such as butane, 1- butylene, 2- butylene, 1,3- Butadiene, 2- methylpropanes, 2- methyl-1-propylenes etc.；C3 by-products are such as propane, propylene；C2 by-products such as ethane and Ethylene, 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%, be reacted based on described first The total weight of C5 hydrocarbon in device hydrocarbon effluent；Can be independently 20,18,16 with b1≤C (ADO) 1≤b2, wherein b1 and b2, 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.Preferably, acyclic two Alkene includes 1,3-pentadiene by the concentration of C (PTD) 1wt%, based on the total of the C5 components in the first reactor hydrocarbon effluent Weight；Can be independently 20,18,16,15,14,12,10,8,6,5,4,3 with c1≤C (PTD) 1≤c2, wherein c1 and c2, 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 iron Silicate or other silicates containing metallic crystal (such as wherein metal or metal-containing compound is dispersed in crystalline silicate structure With can be or can not be those of described crystalline framework part).It can be used as the micropore knot of carbon monoxide-olefin polymeric here Brilliant metal silicate 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 micropore metal silicate used herein above include framework types MWW, MFI, LTL, MOR, BEA, Those of TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO and FAU, one or more of which is from the periodic table of elements the 8, the metal (preferably one or more in Fe, Cu, Ag, Au, B, Al, Ga and/or In) of 11 and 13 races is after synthesis or dipping It is incorporated in crystal structure during crystallization.According to approval, metal silicate can have existing one or more metals and example Such as, 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 useful Alumino-silicate have be less than 12, such as 1-12 or 3-12 restricted index, and include, but are 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 families 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 US4,016,218.It is each in the patent The entire content of a piece 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 EP0293032), 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 US6,756,030) 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 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 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 silico aluminate, which has, is more than about 3, or is more than about 25, or More than about 50, or it is more than about 100, or is more than 400, or about 100- about 400, or about 100- about 500, or about 25- about 2,000, or about 50- about 1,500, or about 100-1,200, SiO2/Al2O3 moles of about 100-1000 Than.
In another embodiment of the present invention, by microporous crystalline metal silicate (such as alumino-silicate) and the 10th race Metal or metallic compound and optionally, a kind of, two kinds, three or more 1st, 2 or 11 race's metals or metallic compound In conjunction with.
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；2nd race's alkaline-earth metal as oxide exist and the metal be selected from Be, magnesium, calcium, The mixture of Sr, Ba and two or more in them.
In one or more embodiments, the 11st race's metal includes, or is selected from silver, gold, copper, preferably silver or copper.It is described 11st race's tenor of carbon monoxide-olefin polymeric 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 have contains 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 Them are resistant 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 wood when prepared by the forms such as particle, the spray-dried granules that composite material is formed in bead, extrudate, pill, oil droplet The about 2- about 80wt% of material.
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), passes 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 is at least 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), DAVISON 952, DAVISON948 or DAVISON 955 (Davison Chemical Division of W.R.Grace and Company) pins Those of sell.
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 reactive diene substance in order to prevent, especially The too early Diels-Alder reaction of CPD cools down it once the first reactor hydrocarbon effluent leaves first reactor It is highly desirable to.For this purpose, the first reactor hydrocarbon effluent can be allowed to pass through at least one going out by 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 the 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 between CPD and acyclic dienes not Desired Diels-Alder reaction and the product formed.It is highly desirable to these heavy components, especially C8+ hydrocarbon extremely It is partially removed from the first reactor hydrocarbon effluent so that them is avoided to pollute richness C5 fractions and subsequent contamination richness DCPD fractions.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 The solid of fouling.Therefore, naphthalene and more heavy PNA are hopefully before first reactor hydrocarbon effluent further processing from it Middle removing.
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 into 10-300 DEG C, preferably 20-100 DEG C of temperature.Therefore, the washed of the first reactor hydrocarbon effluent and cooling are obtained from washing container Vapor stream.Alternatively, it is also possible to obtain washing oil liquid stream (also referred to as " the heavy material for including above-mentioned polynuclear aromatic compound Stream ").
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.
Washing oil recycles and/or cycle
The washing oil used in the present invention is recycled and is advantageously recycled.For this purpose, the heavy that will be left in washing lower vessel portion Stream supplies washing oil and recycles subsystem, and the heavy oil fraction that (i) includes given to polycyclic components is obtained from washing oil recycling subsystem, typical Ground is as bottom steam, the second recovered wash oil stream of (ii) depleted given to polycyclic components；(iii) includes non-essential time of CPD Receive richness C5 streams (being described more fully below).In addition, flux oil (aflux oil) can preferentially supply washing oil recycling subsystem And/or it is blended with the heavy stream in washing oil recycling subsystem upstream (for example, close to bottom of tower of washing container).This dilution Oil is chosen should be compatible with the heavy stream and heavy oil fraction；That is, the washing oil that is deposited in of insoluble substance is not allowed to return It receives under any of subsystem process conditions or occurs under the transport of any downstream or storage condition.The flux oil is hopefully With enough dissolving powers and suitable solvent volatility.Preferably, the flux oil is added by such amount, i.e., so that described The gained viscosity of flux oil and the mixture of heavy oil fraction at 50 DEG C is less than 600 centistokes(cst) (cSt, mm2/ the second), preferably smaller than 550cSt, or it is less than 530cSt, such as 150-550cSt's or 180-530cSt or 180-450cSt or 200-400cSt In range.The candidate sources of flux oil are straightrun virgin stream and/or cracked distillate stream, including cat cracker or steaming Those of generated in vapour cracker.
As described below, by the first isolated subsystem for detaching washed first reactor hydrocarbon effluent and/or other Upstream device and method can generate the heavy group of one or more heavy streams and/or depleted light components comprising washing oil Point.Such heavy stream (if any) can wash together with the heavy stream infeed rich in washing oil from washing container Oil recycling subsystem is with recovered wash oil and wherein other useful components.
In from first reactor to washing container (be included among them if there is heat exchanger) and washing container In the runner in portion, the dimerization between CPD molecules may occur and form DCPD, and CPD can react to be formed with acyclic dienes Other C10+ hydrocarbon.Major part (if formation) distribution of these heavy components is in the washing oil liquid stream for leaving washing container In (heavy stream).If washing oil liquid stream is directly sent to fuel configuration or other low values configure, the first reaction A part of the CPD generated in device will be downgraded to low value.It, can be inverse in promotion in order to reduce such undesirable loss of yield The washing oil recycling subsystem is operated under conditions of Diels-Alder reaction (be also suitable for be known as reverse dimerization) with by DCPD And other C10+ components are converted to CPD and other C5 substances, to obtain recovered overhead richness C5 streams and the C8+ containing residual and wash The bottom of tower richness washing oil stream of oil.The tower top richness C5 streams can either directly or indirectly be supplied second reactor as described in A part for first richness C5 fractions.The bottom of tower richness washing oil stream can further be distilled to recycle at least the one of the washing oil At least part of the washing oil can be either directly or indirectly recycled to washing container by part.Promote reverse dimerization (inverse Di Er Si-Alder reaction) these conditions include, for example, 150-350 DEG C, preferably 170-260 DEG C of temperature, 21-345 kPas Absolute pressure, the pressure within the scope of preferably 21-138 kPas of absolute pressure and 0.01-10 hours, stop in preferably 0.1-4 hours Time.
In an example, washing oil recycling subsystem includes two destilling towers being connected in series with.It will be from washing container Heavy stream, non-essential heavy stream (one or more) from the first isolated subsystem and other upstream devices and it is non-must Strategic point, flux oil feed the first destilling tower, are obtained from first destilling tower including washing oil and rich in polynuclear aromatic compound Bottom steam simultaneously feeds after-fractionating tower.First destilling tower advantageously operates under conditions of promoting above-mentioned reverse dimerization.From One destilling tower obtains recovered overhead richness C5 streams, and the recovered overhead richness C5 streams can be fed directly to second reaction Device (first dipolymer reactor, be described more fully below).Can washing oil optionally be recycled first in subsystem to steam Evaporate tower and washing container combination.From the after-fractionating tower that destilling tower receives bottom steam, tower top, the second recovered wash oil are obtained Stream and heavy oil grade part-streams including polynuclear aromatic compound and flux oil (if present).Heavy oil grade part-streams may be used as Fuel is abandoned.Can a part for the second recovered wash oil stream be either directly or indirectly recycled to washing container. Additionally or in the alternative, the second recovered wash oil stream can be used for washing the downstream vapor stream rich in light components at another The low concentration C5 hydrocarbon that recycling wherein contains in container (sometimes referred to as " debutanizing tower ", being described more fully below), is then recycled to Wash container.In general, boiling point recycles son close to the aggregation of the molecule of the heavy wash oil boiling point from the washing oil in order to prevent After-fractionating tower discharge side stream in system or purging.
In another example, washing oil recycling subsystem includes partition wall destilling tower.By the heavy material from washing container It flows (one or more)；Non-essential heavy stream from the first isolated subsystem and other upstream devices is (a kind of or more Kind)；Optionally, flux oil feeds the receiving side of the partition wall destilling tower as feed stream.From this single distillation Tower can from single column simultaneously generate rich in heavy fraction (including polynuclear aromatic compound and if there is flux oil) bottom of tower Effluent, recovered overhead richness C5 streams, and make on that side opposite with the feed stream (one or more) of partition wall For the intermediate effluent rich in washing oil of the second recovered wash oil stream.The heavy fraction bottom steam may be used as fuel or It abandons.A part for the second recovered wash oil stream can be either directly or indirectly recycled to associated with two tower examples Above-mentioned washing container.Because the major part of feed stream (one or more) can be washing oil, partition wall destilling tower makes With may be especially advantageous in terms of cost and energy efficiency.
The separation of first reactor hydrocarbon effluent
Then the first reactor hydrocarbon effluent is processed in the first isolated subsystem (preferably in above-mentioned first reactor Exit cooling, and washed in above-mentioned washing container) to obtain depleted C1-C4 hydrocarbon and hydrogen, and hopefully, depleted heavy The rich C5 fractions of component such as C8+ hydrocarbon.Due to the property of the reaction occurred in the first reactor, the substantial volume of hydrogen exists In the first reactor hydrocarbon effluent.Hydrogen and C1-C4 light hydrocarbons need to consider with efficiently separating for C5 hydrocarbon (including CPD) Some to C5 hydrocarbon may be kept as the steam in hydrogen/lightweight hydrocarbon flow.Therefore, it is intended that ground, it can be advantageous to use tool There is the compression device group that is detached with liquid/vapor of intermediate stage cooling as the first isolated subsystem so that C5 hydrocarbon is to the hydrogen With the minimization of loss in lightweight hydrocarbon flow.
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 from 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) Generate the non-essential stream containing heavy constituent, at a stage especially in early stage, the stream include 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 using higher boiling washing oil such as methyl naphthalene (one or more), such heavy stream may be by the amount that can not ignore.Such as Such heavy stream of fruit is generated by compression device group, then can be advantageously by it and the washing oil liquid by the generation of above-mentioned washing container Stream combines, and 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.If leaving the rich light components fraction of the first isolated subsystem by can not ignore Amount contain C5 components, then it can be washed in washing container (absorber), wherein it with solvent (for example, above-mentioned washing is held The washing oil used in device), such as fresh solvent stream and/or the second recovered wash oil stream that subsystem is recycled from above-mentioned washing oil At least part contact so that C5 components are substantially extracted by the solvent (such as washing oil).Then it can will come from described The bottom stream of absorber is transported to washing container to wash above-mentioned first reactor hydrocarbon effluent.Richness through so washing is light Matter component fraction then significantly depleted C5 hydrocarbon.
The cycle of the separation and hydrogen and/or light hydrocarbon of rich light components fraction
The master of rich light components fraction from the first isolated subsystem for detaching the first reactor hydrocarbon effluent It is hydrogen to want 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 Gas stream is desirable, can use or sell as the industrial gas for having height to be worth.For this purpose, various methods and setting It is standby to can be used to recycle and concentrating hydrogen, such as 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 it Any combinations, three kinds of gas streams can be obtained from rich light components fraction：Include hydrogen by at least purity of 95mol% Hydrogen rich stream, the total moles based on the hydrogen rich stream；Include the intermediate stream of hydrogen and C1-C4 hydrocarbon, the C1-C4 hydrocarbon is excellent Select C2+ hydrocarbon few；With can also be containing the rich C1-C4 hydrocarbon flows of C5+ hydrocarbon, the C5+ hydrocarbon can then pass through washing or low temperature point Evaporate (for example, absorber) recycling.A part for hydrogen rich stream and/or a part for intermediate stream are (if C1-C4 hydrocarbon supplied jointly Enter first reactor) it may loop to first reactor.Additionally or in the alternative, intermediate stream and/or C1-C4 hydrocarbon flows be at least A part may be used as fuel gas with certain steps (such as the conversion side in first reactor being produced as in the method for the present invention Method) required thermal energy.Alternatively, richness C1-C4 hydrocarbon flows may be used as other methods such as light olefin production raw material and/or Further processing 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 plug flow reactor, return Mixed reactor, continuous stirred tank reactor, boiling point reactors and/or baffle reactor；It is passed in addition, the reactor can contain Hot equipment such as coil.First dipolymer reactor can be by single container or in one or more of multiple containers Reaction zone forms 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 gross pressure of kPa absolute pressure and 20-200 minutes, such as 100-200 minutes residence times；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 CPD must be maintained horizontal less than certain with acyclic dienes and the amount of the codimerization object of monoolefine, enabling purity needed for obtaining DCPD。
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, bottom stream as bottom stream for example from the tower) of middle acquisition and the second C5 grades of richness Divide (for example, as overhead 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.Can obtain has at least 98wt%, and the ultra-high purity DCPD of the concentration of 99wt% or even 99.5wt% is (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 CPD concentration in the first 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 75-140 DEG C, such as 100-140 DEG C of temperature, the gross pressure of 689-3447 kPas of absolute pressure and 100-300 points Clock, such as 150-300 minutes residence times；Preferably, if using concatenated three dipolymer reactors in the system, 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 minutes Residence time.
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, limitation conversion ratio degree make maintain CPD with it is acyclic The amount of the codimerization object of diene and monoolefine is horizontal less than certain, enabling the DCPD of purity needed for obtaining.
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, bottom stream as bottom stream for example from the tower) and third Rich C5 fractions (for example, as overhead 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 has 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 at least part of the second richness DCPD fractions optionally be supplied at least another separation equipment, such as Destilling tower, wherein the purity of the second richness DCPD fractions can be further increased.Equally, in the third richness C5 fractions CPD concentration is often below the CPD concentration in the second 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 bottom stream 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 in the third richness C5 fractions CPD concentration.
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 produced in the methods of the invention It is raw) above-mentioned first reactor 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 generation) 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 from 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 that the Randt (Reid) of final mogas production steams Air pressure (RVP).The vapour pressure of motor petrol is its volatile measurement and high vapour pressure results in the high of hydrocarbon of smog and steams Send a manuscript to the compositor and puts.
For performance standpoint, the important attribute of motor petrol is its octane number grade.Linear alkanes are (that is, straight chain is full And molecule) often there is the octane number grade lower than other hydrocarbon such as aromatic compounds, alkene and branched paraffin.For this purpose, stone The many method of refining used in olein refinery are designed to generate the hydrocarbon with these molecular configurations below.For example, catalysis weight Whole is to be used for for the feed naphtha typically with low octane rating grade to be converted to high-octane rating product liquid with manufacturing The broad practice of commercial run of the advanced blending stock of motor petrol.The method is by alkane and cycloalkanes at higher octane It is worth 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 number, but RVP also has Unfavorable increase.The substance that pentane is converted to cyclopenta and internal olefinic (is sent out in this first reactor in the present invention It is raw) advantageously increase octane number 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 (if all generating in the methods of the invention) can be optionally with the additional stream containing diene (for example, steam at least partially Pressure naphtha, light cat naphtha, heavy catalytic naphtha) group merge can selectively plus hydrogen and generate motor petrol Component.Because the first, second, third, fourth and fifth richness C5 fractions contain the unsaturated C5 hydrocarbon of high concentration, including CPD And cyclopentene, once so partial hydrogenation, they just often have than supply first reactor without ring filling C5 raw material highers Octane number and lower Reid Vapour Pressure (RVP)." selective hydrogenation " method used herein is comprising diene and monoene The mixture of both hydrocarbon 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.It is highly desirable to, the choosing Selecting property adds the motor petrol component of hydrogen to include diene by the total concentration not higher than 1.0wt%, based on the motor petrol component Total weight.Therefore, then motor petrol component can be blended with additional motor petrol component and is formed with required with obtaining With the motor petrol of 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：Catalyst based on palladium or based on nickel.Illustratively add hydrogen item Part 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 (but institute such as control valve, pump, heat exchanger, reboiler, circulation loop Have in attached drawing without all showing) it is freely used during entire method to manipulate stream and equipment thermodynamic condition.
In system 101 shown in Fig. 1, by by for example, at least 50wt% include pentane C5 feed streams 103 with Hydrogen is total to feed stream 105 and combines to form combination stream 107, then expects the combination stream 107 and cycle third richness C5 Stream 109 is combined to form combination raw materials stream 111, and the combination raw materials stream 111 supply first reactor 113 (is also marked For R1).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 stream 111.Altogether The coke formation of feed hydrogen being mainly used for preventing on catalyst, the hydrogen especially generated in situ wherein are in relatively low At the position of concentration.Reactor 113 can be the fixed bed reactors for the bed for being wherein loaded with catalyst 115.Catalyst 115 selects From above-mentioned composition.Reaction of C5 hydrocarbon in the presence of catalyst granules is highly endothermic.It therefore, will reaction by outside heating Device 113 is heated 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.It will be in raw material 111 The most of of C5 hydrocarbon be converted to CPD and by-product such as acyclic dienes, acyclic list by the pentane total conversion of 50%-99% Alkene, pentamethylene, cyclopentene；Light components including hydrogen and C1-C4 hydrocarbon；Monocyclic aromatics；With polycyclic aromatic chemical combination Object.In the exit of first reactor 113, extraction in 500-800 DEG C of temperature and 20-700 kPas of absolute pressure it is total absolutely To the first reactor hydrocarbon effluent 117 of pressure.
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 A heat exchanger 119 cools down the first reactor hydrocarbon effluent stream 117 to obtain stream 121 to avoid undesirable immediately Side reaction such as thermal cracking, the too early Diels-Alder reaction of the condensation and reactivity two olefinic substances, especially CPD of PNA. A certain amount of washing oil (not shown) can be added before exchanger 191 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) and Include the light components stream 161 of 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, allow stream 161 further with fresh solvent (such as washing oil sometimes) stream 165 And/or recovered wash oil stream 168 contacts in container 163 (also referred to as " debutanizing tower " or " debutanization tower section ") to be included H2With C1-C4 hydrocarbon and the stream 167 of depleted C5 components.Then the debutanizing tower bottom steam of debutanizing tower container 163 will be left 125 are recycled to above-mentioned washing container 123.Can by using various device and method (not shown), such as PSA, RCPSA, TSA, cryogenic method and UF membrane further detach stream 167, one or more in following substance to obtain：(i) high-purity H2Stream；(ii)H2/ C1-C4 hydrocarbon mixture streams；(iii) richness C1-C4 hydrocarbon flows.
It (can be (one or more) comprising in C6, toluene, C8+ and washing oil by the concentration that can not ignore to it by stream 133 One or more degree) together with infeed heavy wash oil (for example, alkylnaphthalene) removal column 135 of above-mentioned stream 127, wherein obtaining Obtain the top stream 137 rich in C5 and depleted C10+, and the bottom steam 138 comprising C7 and C8+.Then stream 138 is fed Destilling tower 301 obtains tower top richness washing oil stream 305 and the bottom steam 307 rich in heavy oil from the destilling tower 301.By stream 305 (also be labeled as stream 168) are recycled to above-mentioned debutanizing tower container 163 (display) and (and/or are recycled to wash partially or completely Container 123 is washed, is not shown) remain C5 hydrocarbon to be extracted from rich light components stream 161.Then debutanizing tower 163 will be left The washing oil stream 125 slightly used be recycled to washing container 123.It should make great efforts to reduce heat exchanger 191, container 123,135 and The reaction between CPD and acyclic dienes in first isolated subsystem, 131 front end.Nevertheless, because these side reactions may Occur by various degree, so highly desirable operated under conditions of meeting compared to dimerization promotion reverse dimerization reaction Tower 135 so that by heavy component such as DCPD, the reaction product between DCPD and acyclic dienes is converted to CPD and other C5 groups Point, and therefore recycle at least partly otherwise the CPD that can be lost in side reaction and other C5 components.For this purpose, in tower 135 Condition advantageously comprises 150-350 DEG C, and (21-345 kPas absolutely by preferably 170-260 DEG C of column bottom temperature and 3psia-50psia Pressure), total absolute pressure of preferably 20psia-40psia (138-276 kPas of 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： 30-250 DEG C, preferably 70-140 DEG C, such as 90-130 DEG C of temperature and 50psia-1000psia (345-6895 kPas of absolute pressure Power), total absolute pressure of preferably 100psia-500psia (689-3447 kPas of absolute pressure) and 1-220 minutes, preferably 20- 200 minutes, such as 100-200 minutes residence times.By these condition optimizings to promote the dimerization reaction between CPD molecules simultaneously The reaction between CPD and other diene is 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 are to be further reduced the net introducing of fresh washing oil.
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 time.By these condition optimizings so that residue The recycling of CPD maximizes, while reaching conjunction specification (on-spec) 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 are to be further reduced the net introducing of fresh washing oil.
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 lower 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 can be used for the method for the present invention and system, it is particularly useful for the exemplary side that Fig. 1 illustrates Exemplary first isolated subsystem 201 of method.The first isolated subsystem 201 in Fig. 2 includes compression device group comprising multistage Section compression, the separation of cooling and liquid/vapor.In the method for this attached drawing, washed obtained from tower 123 will be included first The most top stream 129 of one reactor effluent feeds first stage compressor 203, is obtained from the compressor 203 Stream 205 in higher pressure.Then stream 205 is cooled down by first stage heat exchanger 207 and is mixed with obtaining liquid/vapor Material stream 209 is closed, the liquid/vapor mixture stream 209 is fed into first stage liquid/vapor separation equipment (such as bulging) 211 to obtain the first stage bottom liquid stream 215 comprising C5 hydrocarbon but depleted hydrogen and C1-C4 hydrocarbon and include C5 hydrocarbon and rich The first stage overhead vapor stream 213 of hydrogen and C1-C4 hydrocarbon.Then pass through 217 compressed stream 213 of second stage compressor To obtain the stream 219 with even higher pressure, then the stream 219 is cooled down by second stage heat exchanger 221 To obtain second stage lower temperature liquid/vapor mixture stream 223, second stage liquid/vapor separation equipment (such as Drum) 225 to detach the liquid/vapor mixture stream 223 to obtain include the of C5 hydrocarbon but depleted hydrogen and C1-C4 hydrocarbon Two-stage bottom liquid stream 229 and comprising C5 hydrocarbon and rich in hydrogen and C1-C4 hydrocarbon second stage vapor stream 227.Then By 231 compressed stream 227 of phase III compressor to obtain the stream 233 with even higher pressure, then pass through third Stage heat exchanger 235 by the stream 233 cool down to obtain lower temperature phase III liquid/vapor mixture stream 237, Liquid/vapor mixture stream 237 is detached to be included in phase III liquid/vapor separation equipment (such as bulging) 239 The phase III bottom liquid stream 241 of C5 hydrocarbon but depleted hydrogen and C1-C4 hydrocarbon and rich in hydrogen and C1-C4 hydrocarbon and inessential Ground is included the phase III overhead vapor stream 161 of C5 hydrocarbon by low concentration.Then by 161 supply container 163 of stream, such as Fig. 1 It is shown 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
Obtained during acyclic C5 method for transformation containing cyclic annular, branched and linear C5 hydrocarbon and optionally, containing hydrogen, Any combination of first hydrocarbon reactor effluent itself of C4 and lighter by-product or C6 and more heavy byproduct and it is naturally Value product.Preferably, CPD and/or DCPD can be detached from the reactor effluent and can be used for making to obtain The purified product stream of standby various high-value products.
For example, containing 50wt% or more, or the purified product stream of preferably 60wt% or more DCPD can be used for preparing hydrocarbon Resin, unsaturated polyester resin and epoxide resin material.Containing 80wt% or more, or preferably 90wt% or more CPD purifying Product stream can be used for preparing the Diels-Alder reaction product formed according to following reaction process (I)：
Flow 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, contain 80wt% or more, or preferably 90wt% or more CPD purified product stream 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：
Above-mentioned Diels-Alder reaction product can be used for preparing poly- with the cyclic olefin of alkene such as ethylene copolymerization Close object and copolymer.The cyclic olefin copolymer and cyclic olefin polymer product of gained can be used for various applications, such as pack Film.
The purified product stream of the DCPD containing 99wt% or more may be used in, for example, ring-opening metathesis polymerization (ROMP) is urged Agent prepares DCPD polymer.The DCPD polymer products can be used to form product, especially molded item, such as wind turbine Machine blade and automobile component.
Additional component can also be detached from the reactor effluent and be used to form high-value product.For example, The cyclopentene of separation can be used for preparing polycyclic amylene, also known as polycyclic amylene (polypentenamer), as described in flow (II) Like that.
Flow II
The pentamethylene of separation can be used as foaming agent and solvent.Linear and branched C5 products can be used for being converted to more advanced alkene And alcohol.Cyclic annular and non-annularity C5 products can be used as octane enhancer and transport fuel blends group optionally after adding hydrogen Point.
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 interests of product flow velocity.For example, the first reactor in embodiment 2 is shown reduces 7.8% than volume flow in embodiment 1.This can Tower (one or more), the equipment of gas compressor (one or more) and debutanizing tower (one or more) can be quenched to downstream 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 38.6wt% for the material for being transferred to motor petrol production.Separately Outside, from table i it can be seen that motor petrol stream in embodiment 2 compared in embodiment 1 with C5+ by-products slightly more High octane number, because more the limited isomerization of dynamics and aromatization products will be concentrated in smaller by-product stream.
It is therefore evident that it can 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, when to Reid vapour pressure (RVP) specification limit of motor petrol During the certain seasons for making the amount for the C5 hydrocarbon that can be blended, this is particularly useful.This allows equipment to continue to produce by required DCPD Object rate operates, 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.
In this embodiment, toluene is used as washing oil.The net introducing of toluene is estimated as being at most 7 tons, this is attributed to implantation The effective washing oil of this method recycles.It does not recycle, the net introducing of toluene will be added to 251 tons, be based on once-through operation.This is to whole The economic feasibility of a method, which can have, to be significantly affected.
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 synthesis mixing Object has following mole of composition：
SiO2/Al2O3~470
H2O/SiO2~12.1
OH/SiO2~0.16
Na/SiO2~0.16
N-PA/Si~0.25.
It mixes with 250rpm under 230 °F (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 under~250 °F (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 under 250 °F (121 DEG C) by a part for the crystal of original sample when synthesis Drying is simultaneously calcined 6 hours under 1000 °F (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 impregnated 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 at 900 °F It is calcined 6 hours under (482 DEG C).After the cooling period, sample is heated to 900 °F (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 1000 °F (540 DEG C), oxygen content is increased to 16.8%, and keep material 6 small under 1000 °F (540 DEG C) When.After the cooling period, using the aqueous solution of tetramine platinum hydroxide addition 0.5wt%Pt is impregnated via incipient wetness.In air It is dried at room temperature for carbon monoxide-olefin polymeric 2 hours, is then kept for 4 hours under 250 °F (121 DEG C), finally existed in air It is calcined 3 hours under 660 °F (349 DEG C).It suppresses (15 tons), pulverizes and screening catalyst composition powder is to obtain 20-40 mesh grains Degree.
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 at 550 DEG C -600 DEG C, 5.0psia (35kPa-a) C5H12, 1.0 moles of H2:C5H12、14.7h- 1WHSV and 30psig (207kPa) amounts to the performance of lower test catalyst composition.Lead at 550 DEG C -600 DEG C after initial trial It crosses and uses H2(200mL/min, 30psig (207kPa), 650 DEG C) handles 5 hours test catalyst composition stability and renewable Property, the then experimental performance again 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 high temperature on solid-state carbon monoxide-olefin polymeric containing Pt.(cC is generated based on pentane conversion, ring-type C55), split Change the ZSM-5 (414 of yield and estimation of stability embodiment 6:1) performance of/0.5%Pt.These results be summarised in Table V, Table VI, In Table VII and Table VIII.
Table V
Table VI
Table VII
Table VIII
Table V and Table VII 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 rubs You are H2:C5, 14.7WHSV, 45psia (310kPa-a) amount under conditions of pentane conversion ratio and ring-type C5, CPD, different C5、C1 And C2-4The selectivity and yield of crackate.In Table V, selectivity and yield based on be formed by hydrocarbon each ring-type C5, CPD, The molar percentage of different C5, C1 and C2-4 indicate；That is, molar selectivity is formed by each ring-type C5, CPD, C1 and C2-4 The total mole number of molal quantity divided by the pentane converted.In Table VII, selectivity and yield are based on each ring-type for being formed by hydrocarbon The carbon percentage expression of C5, CPD, different C5, C1 and C2-4；That is, carbon selectivity is to be formed by each ring-type C5, CPD, different C5, C1 With the total moles carbon number in mole carbon number of C2-4 divided by the pentane converted.As can be seen, Table V and Table VII are aobvious Show at high WHSV be more than 80% conversion of pentane rate, and at 595 DEG C 40% the selectivity to cyclic annular C5 substances.Although There is no specific 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 real It is possible to apply a catalyst.
All documents described herein, including any priority documents and/or test procedure all with the present invention not contradiction All permissions under be incorporated by reference.Although from above-mentioned general introduction and particular embodiment it is readily apparent that having been described above and retouching The form of the present invention has been stated, but without departing from the spirit and scope of the present invention can be with various modification can be adapted.Therefore, no Wish that the present invention is so limited.Similarly, term " including (comprising) " thinks same with term " including (including) " Justice.Equally, when composition, element or element group are before transitional term " including ", it should be understood that also consider tool By transitional term " substantially by ... form ", " by ... form ", " being selected from " or " being " enumerate composition, member Same combination before element or each element or element group, vice versa.

Claims (28)

1. the preparation method of cyclopentadiene (CPD) and/or dicyclopentadiene (DCPD), the method includes：
(I) first reactor will be fed comprising the C5 raw materials of at least one acyclic C5 hydrocarbon；
(II) the acyclic C5 hydrocarbon of at least one is made to contact to go out to obtain first reactor hydrocarbon stream at conversion conditions with catalyst Object, the first reactor hydrocarbon effluent include：C5 components including CPD and acyclic dienes；It is light including hydrogen and C1-C4 hydrocarbon Matter component；Monocyclic aromatics；And polynuclear aromatic compound；
(III) the first reactor hydrocarbon effluent is made to be contacted in washing container with washing oil, to obtain：
Include at least part of heavy stream of at least part of the washing oil and the polynuclear aromatic compound；With
Including at least part of the light components, at least part of the C5 components and the non-essential washing oil one Partial washed first reactor hydrocarbon effluent, depleted polynuclear aromatic compound；
(IV) the washed the first reactor effluent is detached to obtain in the first isolated subsystem：
Including the first richness C5 fractions of CPD and the depleted light components；
Include the first rich light components fraction of hydrogen and C1-C4 hydrocarbon；With
Non-essential first recovered wash oil stream；
(V) by the heavy stream and optionally, at least part of the non-essential first recovered wash oil stream supplies Washing oil recycles subsystem；
(VI) it is obtained from washing oil recycling subsystem：
Include the heavy oil fraction of the polynuclear aromatic compound；
Second recovered wash oil stream；With
Include the non-essential recycling richness C5 streams of CPD；With
(VII) by least part of the second recovered wash oil stream, and optionally, non-essential first recycling is washed At least part of oil plant stream is either directly or indirectly recycled to the washing container.
2. the method for claim 1 wherein the washing oil recycling subsystem include it is at least one at least partly washing oil recycle Under the conditions of the destilling tower that works make DCPD, inverse Di is then undergone in subsystem at least partly if there is being recycled in the washing oil Er Si-Alder reaction is to generate CPD.
3. the method for claim 1 or claim 2, wherein：
The washing oil recycling subsystem includes the first wash oil tower and the second wash oil tower；
In step (V), at least part of the heavy stream and the non-essential first recovered wash oil stream are supplied The first wash oil tower；
Include with step (VI)：
(VIa) top stream comprising recycling C5 hydrocarbon is obtained as the recycling richness C5 streams from the first wash oil tower, With the bottom steam comprising the washing oil and the polynuclear aromatic compound；
(VIb) at least part of the bottom steam is fed into the second wash oil tower；With
(VIc) it is obtained from the second wash oil tower：
Include at least part of heavy oil fraction of the polynuclear aromatic compound；With
The second recovered wash oil stream.
4. the method for claim 3, wherein flux oil is added to the first wash oil tower, the second wash oil tower And/or in the heavy oil fraction.
5. the method for claim 1 or claim 2, wherein：
The washing oil recycling subsystem includes the first washing oil partition wall destilling tower；
In step (V), at least part of the heavy stream and the non-essential first recovered wash oil stream are supplied The first washing oil partition wall destilling tower；
Include with step (VI)：
(VIa) it is obtained from the first washing oil partition wall destilling tower：
Including the top stream of recycling C5 hydrocarbon is as the recycling richness C5 streams,
Including the intermediate stream of the recovered wash oil is as the second recovered wash oil stream, and
Include the bottom steam of the heavy oil fraction, the heavy oil fraction includes at least one of the polynuclear aromatic compound Point.
6. the method for claim 5, wherein adding flux oil in the first washing oil partition wall destilling tower and/or the heavy oil In fraction.
7. claim 3 is to the method for any one of claim 6, wherein washing oil recycling subsystem is being washed at least partly It works under the conditions of oil recycling so that dicyclopentadiene (DCPD) recycles in subsystem then at least portion if there is in the washing oil Divide experience inverse Diels-Alder reaction in ground to generate CPD.
8. claim 2 is to the method for any one of claim 7, wherein：
The heavy stream and/or the non-essential first recovered wash oil stream include DCPD；
The second recovered wash oil stream includes CPD；With
The heavy oil fraction is substantially free of DCPD；Such as less than 10wt%DCPD.
9. claim 1 further includes to the method for any one of claim 8：
(VIII) at least part of the second recovered wash oil stream and the first rich light components fraction are fed into third Light components separation equipment；
(IX) it is obtained from the third separation equipment：
Include the second rich light components fraction of hydrogen and C1-C4 hydrocarbon, depleted C5+ hydrocarbon, and
Third washing oil stream；With
(X) the washing container being recycled at least part of the third washing oil stream in step (III).
10. claim 1 to the method for any one of claim 9, further includes feeding the fresh stream of washing oil to wash described in (i) Wash at least one of container and (ii) described third separation equipment.
11. claim 1 further includes to the method for any one of claim 10：
(XI) by least part of the first richness C5 fractions and optionally, the non-essential recycling richness C5 streams are fed The second reactor to work under the conditions of first group of dimerization；
(XII) the first reactor effluent is obtained from the second reactor comprising CPD and DCPD；With
(XIII) at least part of the first reactor effluent is detached to obtain：
Include the first richness DCPD fractions of DCPD；With
Second richness C5 fractions.
12. the method for claim 11, further includes：
(XIV) at least part of the second richness C5 fractions is fed to the third to work under the conditions of second group of dimerization to react Device；
(XV) third reactor effluent is obtained from the third reactor comprising CPD and DCPD；With
(XVI) at least part of the third reactor effluent is detached to obtain：
Second richness DCPD fractions；With
Third richness C5 streams.
13. the method for claim 11 or claim 12, further includes：
(XVII) at least part of the third richness C5 fractions is fed to the 4th reaction to work under the conditions of third group dimerization Device；
(XVIII) the 4th reactor effluent is obtained from the 4th reactor comprising CPD and DCPD；With
(XIX) at least part of the 4th reactor effluent is detached to obtain in the 4th separation equipment：
Third richness DCPD fractions；With
4th richness C5 streams.
14. claim 11 further includes to the method for any one of claim 13：
(XX) at least part of at least one of following substance is fed into the 5th separation equipment：(i) the first richness C5 material Stream；(ii) the non-essential recycling richness C5 streams；(iii) the second richness C5 streams；(iv) if there is the third it is rich C5 streams；(v) if there is the 4th richness C5 streams；With
(XXI) it is obtained from the 4th separation equipment：
5th richness C5 streams；With
The stream of rich one or more monocyclic aromatics.
15. the method for claim 14, further includes：
(XXII) at least part of the stream of the one or more monocyclic aromatics of richness is either directly or indirectly followed In the third separation equipment in the washing container and/or step (VIII) in ring to step (III).
16. the method for claim 14 or claim 15, wherein by the material of the one or more monocyclic aromatics of richness At least part of stream is distilled to get benzene-enriched stream and depleted benzene stream, and the depleted benzene stream is fed directly to (i) At least one of the third separation equipment in the washing container and/or (ii) step (VIII) in step (III).
17. claim 1 is to the method for any one of claim 16, wherein first isolated subsystem includes having centre Stage cools down and the compression device group of vapor/liquid separation.
18. claim 1 is to the method for any one of claim 17, wherein the washing oil includes at least one in following substance Kind：Hexamethylene；Monoalkyl, dialkyl group and trialkyl hexamethylene；Benzene；Monoalkyl, dialkyl group and trialkyl benzene；Monoalkyl, dioxane Base, trialkyl and tetraalkyl naphthalene；Other alkylation polynuclear aromatic compounds；Mixture with them and combination.
19. the method for claim 18, wherein：
The washing oil includes at least toluene of 50wt%, the total weight based on the washing oil used in step (III).
20. the method for claim 18, wherein：
The washing oil includes at least alkylnaphthalene of 50wt%, the total weight based on the washing oil used in step (III)；With
The non-essential first recovered wash oil stream obtains in step (IV).
21. claim 1 is to the method for any one of claim 20, wherein：
The first reactor hydrocarbon effluent includes CPD by the concentration of C (CPD) 1wt% and presses the total concentration packet of C (ADO) 1wt% Containing acyclic dienes, it is all based on the total weight of the C5 hydrocarbon in the first reactor hydrocarbon effluent；With
C(CPD)1/C(ADO)1≥1.5。
22. claim 1 is to the method for any one of claim 21, wherein：
Step (IV) includes：
(IVc) it is obtained from the described first rich light components fraction to obtain at least one of following substance：
(i) it includes H to press at least purity of 95mol%2Hydrogen rich stream；
(ii) include H2With hydrogen/C1-C4 hydrocarbon flows of the mixture of C1-C4 hydrocarbon；With
(iii) the C1-C4 hydrocarbon flows of depleted hydrogen.
23. claim 11 further includes to the method for any one of claim 22：
(XXIII) at least part of at least one of following substance is either directly or indirectly recycled to first reaction Device：The first richness C5 fractions, the non-essential recycling richness C5 streams, the second richness C5 fractions, C5 grades of the third richness Point, the 4th richness C5 fractions and/or if generation the 5th richness C5 fractions.
24. claim 11 further includes to the method for any one of claim 23：
(XXIV) from the first richness C5 fractions, the non-essential recycling richness C5 streams, the second richness C5 fractions, described If three richness C5 fractions and the 4th richness C5 fractions and the 5th richness C5 fractions generated obtain in following substance at least It is a kind of：(i) rich pentamethylene fraction；(ii) rich cyclopentene fraction；(iii) richness 1,3- pentadiene fractions；(iv) 2- methyl-1s, 3- Butadiene fraction.
25. the preparation system of cyclopentadiene (CPD) and/or dicyclopentadiene (DCPD), including：
(A) it is configured to receive C5 raw materials, non-essential hydrogen comprising at least one acyclic C5 hydrocarbon and is total to raw material and non-essential C1-C4 hydrocarbon is total to the first reactor of raw material；
(B) conversion of C5 hydrocarbon can be catalyzed to generate the first reaction at conversion conditions by being loaded in inside the first reactor The catalyst of device hydrocarbon effluent, the first reactor hydrocarbon effluent include：C5 hydrocarbon including CPD and acyclic dienes；Monocycle virtue Compounds of group；Polynuclear aromatic compound；With the light components including hydrogen and C1-C4 hydrocarbon；
(C) it is configured to receive at least part and (ii) washing oil of (i) described first reactor hydrocarbon effluent, and is configured to Generate washed first reactor hydrocarbon effluent and at least part comprising the washing oil and the polynuclear aromatic compound The washing container of at least part of heavy stream；
(D) it is configured to receive at least part of the heavy stream and generate comprising the polynuclear aromatic compound at least The heavy oil fraction of a part and the washing oil of the second recovered wash oil stream recycle subsystem；
(E) it is configured at least part of the second recovered wash oil stream being either directly or indirectly recycled to the washing Raceway groove is in fluid communication in the washing oil of container；
(F) it is configured at least part for being clean the first reactor effluent supplying first isolated subsystem Raceway groove is in fluid communication；With
(G) be configured to receive at least part of the washed first reactor hydrocarbon effluent and generation (i) include CPD and First richness C5 fractions of depleted hydrogen and C1-C4 hydrocarbon and (ii) include the first rich light components fraction of hydrogen and C1-C4 hydrocarbon The first isolated subsystem being in fluid communication with the washing container.
26. the product derived from product prepared by the method by any one of claim 1-24.
27. the product of claim 26, wherein the product is derived from materials described below：The material is by the product and contains double bond Matrix Diels-Alder reaction obtain.
28. the product of claim 26, wherein the product is：The wherein described product is selected from cyclopentadiene, dicyclopentadiene, ring Amylene, pentamethylene, amylene, pentadiene, norbornene, tetracyclododecane, substituted norbornene, the Di Er of cyclopentadiene This-Alder reaction derivative, cyclic olefin copolymer, cyclic olefin polymer, polycyclic amylene, unsaturated polyester resin, hydrocarbon Tackifier resin, the epoxy resin of preparation, poly- bicyclopentadiene, norbornene or substituted norbornene or dicyclopentadiene or The metathesis polymer of any combination of them, wind turbine blade, the composite material containing glass or carbon fiber, the bonding of preparation Agent, ethylidene norbornene, EPDM rubber, alcohol, plasticizer, foaming agent, solvent, octane enhancer, gasoline are mixed with theirs Close object.
CN201680064166.7A 2015-11-04 2016-10-07 The preparation method and system of cyclopentadiene and/or dicyclopentadiene Pending CN108349833A (en)

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