TWI628003B - Fired tube conversion system and process - Google Patents

Abstract

Discloses a method for non-cyclic C ₅ feedstocks into C ₅ cyclic non-aromatic hydrocarbon methods and systems. A furnace and a reactor tube containing a catalyst compound are disclosed. Also discloses a non-cyclic C ₅ feed and contacting the catalyst composition obtained and cyclic hydrocarbons comprising C _5.

Description

Fuel tube conversion system and method [Cross-reference to related applications]

The present invention claims the priority and benefit of USSN 62/250,693, filed on Nov. 4, 2015, and EP Application No. 16153717.0, filed on Feb. 2, 2016.

The present invention is based on the burning of the reactor and its method of use of the non-cyclic C ₅ feedstocks into products comprising cyclic C ₅ compounds in the.

Cyclopentadiene (CPD) and its dimer dicyclopentadiene (DCPD) are highly demanding materials that are used throughout the chemical industry for a wide range of products (such as polymeric materials, polyester resins, synthetics). In rubber, solvents, fuels, fuel additives, etc.). Cyclopentadiene (CPD) is now a secondary by-product of vapor-cracking of liquid feeds, such as naphtha and heavier feeds. As existing and new steam cracking facilities move to lighter feeds, less CPD is produced and demand for CPD is rising. The high cost due to supply constraints affects the potential use of CPD in polymers. More CPD-based polymer products can be made if additional CPD can be produced at unconstrained rates and preferably at lower cost than steam cracking recovery. The combination of other cyclic C ₅ classes is also suitable. Cyclopentane and cyclopentene can be of high value as solvents, while cyclopentene can be used as a comonomer to make polymers and as a starting material for other high value chemicals.

Would be advantageous to be able to use the catalyst system for producing a raw material rich in C ₅ C ₅ cyclic compounds (including as a main product of CPD), to produce CPD, while the light (C _4-) for producing a byproduct of the least Chemical. Although lower hydrogen contents (e.g., cyclics, alkenes, and dienes) may be preferred because the endothermic heat of the reaction is reduced and the thermodynamic limitations on conversion are improved, the unsaturated analog is more expensive than the saturated feedstock. Since the chemical reactions and straight-chain C ₅ a relatively low C ₅ branched value (due to differences in octane) both straight-chain C ₅ backbone structure better than C ₅ branched backbone structure. The abundant C ₅ can be obtained from unconventional gas and shale oil and is reduced in motor fuel due to strict emission regulations. The C ₅ feedstock can also be produced from a biological feed.

Today use different techniques to the catalytic dehydrogenation of C ₃ and C ₄ alkanes manufactured mono- and diolefins, but not cyclic monoolefins or cyclic diolefins. A typical method uses Pt/Sn supported on alumina as the active catalyst. Another useful method is to use chromium oxide on alumina. See BVVora's Catalysis in 2012, Vol. 55, pp. 1297-1308, "Development of Dehydrogenation Catalysts and Processes," Topics in Catalysis, vol. 55, pp. 1297-1308 And "JCBricker's Catalysis in 2012, Vol. 55, pp. 1309-1314, "Advanced Catalytic Dehydrogenation Technologies for Production of Olefins," Topics in Catalysis, vol. 55, pp. 1309-1314).

Still another common method uses Pt/Sn supported on Zn and/or Ca aluminate to dehydrogenate propane. Although these methods successfully dehydrogenate the alkane, they do not carry out the cyclization necessary for the manufacture of CPD. Pt-Sn / alumina and Pt-Sn / aluminosilicate catalyst exhibits moderate conversion of n-pentane, but such a catalyst having a selectivity, poor yields and C ₅ cyclic product.

Pt supported on a chlorinated alumina catalyst is used to reconstitute a low octane petroleum brain into aromatics such as benzene and toluene. See US 3,953,368 (Sinfelt), "Polymetallic Cluster Compositions Useful as Hydrocarbon Conversion Catalysts". Although these catalysts are effective in dehydrogenating and cyclizing C ₆ and higher alkanes to form a C ₆ aromatic ring, they are less effective in converting acyclic C ₅ to cyclic C ₅ . The Pt supported on alumina in the catalyst by the chlorination of a cyclic C ₅ exhibits a low yield and presentation within two hours of time on stream before the passivation. Cyclization C ₆ alkanes and C ₇ of the assisted formation of an aromatic ring, which does not occur in the form of the C ₅ ring. This effect may be partly due to the fact that the formation heat of CPD (a cyclic C ₅ ) is much higher than that of benzene (a cyclic C ₆ ) and toluene (a cyclic C ₇ ). This is also exhibited by Pt/Ir and Pt/Sn supported on chlorinated alumina. While these alumina dehydrogenation catalyst C ₆₊ substances and cyclized to form an aromatic C ₆ ring, will require different catalysts to the conversion of non-cyclic C ₅ to C ₅ cyclic.

A Ga-containing ZSM-5 catalyst is used in a method of producing aromatics from light alkanes. A study by Kanazirev et al. shows that n-pentane is readily converted by Ga ₂ O ₃ /H-ZSM-5. See Kanazirev et al., 1991, Catalysis, Vol. 9, pp. 35-42, "Conversion of C ₈ Aromatic and n-Pentane Using Ga ₂ O ₃ /H-ZSM-5 Mechanically Mixed Catalyst" (Conversion of C ₈ aromatics and n-pentane over Ga ₂ O ₃ /H-ZSM-5 mechanically mixed catalysts," Catalysis Letters, vol. 9, pp. 35-42, 1991. No production of cyclic C _{5 was} reported, but 6 wt% or more of aromatics are produced at 440 ° C and 1.8 hr ^-1 WHSV. Mo/ZSM-5 has also been shown to dehydrogenate and/or cyclize alkanes (especially methane). See Y.Xu, S. Liu , X.Guo, L.Wang, and M.Xie, "Methane activation using Mo/HZSM-5 zeolite catalyst without the use of oxides", pp. 135-149, Catalysis, Vol. 30, 1994 (" Methane activation without using oxidants over Mo/HZSM-5 zeolite catalysts, "Catalysis Letters, vol. 30, pp. 135-149." High n-pentane conversion using Mo/ZSM-5 was confirmed without a ring The production of C ₅ has a high yield of the cleavage product. This shows that the ZSM-5-based catalyst converts the alkane to the C ₆ ring, but does not require the production of a C ₅ ring.

US 5,254,787 (Dessau) describes the NU-87 catalyst used in the dehydrogenation of alkanes. This catalyst displays a C ₂ -C ₆₊ dehydrogenated to each other for producing an unsaturated analog of. In this patent, a clear distinction is made between the dehydrogenation of C _2-5 and C ₆₊ alkenes: C _2-5 alkanes to produce linear or branched monoolefins or diolefins, but the removal of C ₆₊ alkanes Hydrogen produces aromatics. US 5,192,728 (Dessau) pertains to similar chemistry but utilizes tin-containing crystalline microporous materials. Since the use of NU-87 catalyst, C ₅ show only the dehydrogenation manufacturing a linear or branched monoolefins or diolefins rather than CPD.

US 5,284,986 (Dessau) describes a two-stage process for the manufacture of cyclopentane and cyclopentene from n-pentane. An example is carried out in which the first stage comprises dehydrogenating and dehydrocycling n-pentane to a mixture of alkanes, monoolefins and diolefins and naphthenes using a Pt/Sn-ZSM-5 catalyst. This mixture is then led to a second stage reactor consisting of a Pd/Sn-ZSM-5 catalyst wherein the dienes (especially CPD) are converted to olefins and saturated species. Cyclopentene is the desired product in this process, but CPD is a useless by-product. Comparative examples were carried out at different temperatures using Pt/Sn-ZSM-5 catalyst and are discussed below.

US 2,438,398; US 2,438,399; US 2,438,400; US 2,438,401; US 2,438,402; US 2,438,403; and US 2,438,404 (Kennedy) discloses: CPD is made from 1,3-pentadiene using various catalysts. Low operating pressures, low single pass conversion rates, and low selectivity make this method undesirable. In addition, 1,3-pentadiene is not an easily available raw material, unlike n-pentane. See also "Formation of Cyclopentadiene from 1,3-Pentadiene" by Kennedy et al., Industrial and Engineering Chemistry, Vol. 42, pp. 547-552, 1950. , "Industial and Engineering Chemistry, vol. 42, pp. 547-552).

Fel'dblyum et al. 2009 Dockray chemically section 424 "nm using a platinum catalyst and in the cyclization and dehydrocyclization of hydrogen sulfide in the presence of C ₅ hydrocarbons" on pages 27-30 ( "Cyclization And dehydrocyclization of C ₅ hydrocarbons over platinum nanocatalysts and in the presence of hydrogen sulfide, " Doklady Chemistry , vol. 424, pp. 27-30, 2009) reports: from 1,3-pentadiene, n-pentene, and CPD is produced from n-pentane. The yields of converting 1,3-pentadiene, n-pentene, and n-pentane to CPD using 2% Pt/SiO ₂ at 600 ° C are generally as high as 53%, 35%, and 21%, respectively. At the beginning of the observation of the manufacture of CPD, vigorous catalyst passivation was observed within a few minutes before the reaction. Experiments on Pt-containing vermiculite have shown that Pt-Sn/SiO ₂ has moderate conversion of n-pentane, but has poor selectivity and yield of cyclic C ₅ product. The use of H ₂ S as a cyclization promoter for 1,3-pentadiene is described below by Fel'dblyum and in Marcinkowski "Isomerization and Dehydrogenation of 1,3-Pentadiene"("Isomerization and Dehydrogenation of 1" , 3-pentadiene, ") MS, University of Central Florida, 1977 was proposed. Marcinkowski showed a conversion of 80% 1,3-pentadiene with H ₂ S at 700 ° C and a CPD selectivity of 80%. High temperatures, limited raw materials, and possibly sulfur-containing products that may require subsequent washing make this method undesirable.

López et al., 2008, Catalysis, Vol. 122, pp. 267-273, "Non-Pentane Hydroisomerization on Pt Containing" using Pt-containing HZSM-5, HBEA and SAPO-11. HZSM-5, HBEA and SAPO-11, " Catalysis Letters , vol. 122, pp. 267-273, 2008", studied the reaction using n-butane containing Pt zeolite including H-ZSM-5. (250-400 ° C), they report the use of the Pt-zeolite n-pentane for efficient hydroisomerization, but no discussion of the formation of cyclopentene. Want to avoid this harmful chemistry, because of the branched type C ₅ is not as straight-chain C ₅ as efficiently producing a cyclic C _5, as discussed above.

Li et al. also studied the use of Pt-containing zeolites in the "Catalytic dehydroisomerization of n-alkanes to isoalkenes," Journal of Catalysis , vol. 255, pp. 134-137, 2008, pp. 255-137 of the Catalysis Journal , Vol. The n-pentane is dehydrogenated, wherein Al has been heteromorphously substituted with Fe. These Pt/[Fe]ZSM-5 catalysts are dehydrogenating and isomerizing n-pentane efficiently, but under the reaction conditions used, no cyclic C _{5 is} produced and undesired backbone isomerization occurs. .

No. 5,633,421 discloses a process for the dehydrogenation of C ₂ -C ₅ alkanes to obtain the corresponding olefins. Similarly, US 2,982,798 discloses a process for the dehydrogenation of aliphatic hydrocarbons containing from 3 to 6 carbon atoms. However, US 5,633,421 and US 2,982,798 are not disclosed CPD manufactured from a non-cyclic C ₅ hydrocarbons, the non-cyclic C ₅ hydrocarbons suitable as a raw material, because he is the lowest and the amount.

No. 5,243,122 describes a steam active catalytic process utilizing a fixed catalyst bed for the dehydrogenation of alkanes to alkenes, wherein the reduction in catalytic activity is maintained by maintaining a substantially fixed reaction effluent temperature while allowing for manufacturing time The average temperature of the fixed catalyst bed rises and slows down. Similarly, US 2012/0197054 discloses a process for the dehydrogenation of alkanes in a number of reactors of adiabatic, temperature change, isothermal, and combinations thereof.

In addition, there are many challenges in designing an on-purpose CPD manufacturing method. For example, the C ₅ hydrocarbons to CPD reaction is very endothermic and having the benefit of low temperature and low pressure, but the n-pentane and other hydrocarbons C ₅ significant cracking may occur at relatively low temperatures (e.g. 450 ℃ -500 ℃) . Additional challenges include loss of catalyst activity due to coking during the process and additional processing required to remove coke from the catalyst, and the inability to use oxygenated gas to provide directly without destroying the catalyst Heat is input to the reactor.

Thus, there remains a need for a preferred non-cyclic C ₅ feed conversion as a method of non-aromatic cyclic C ₅ hydrocarbons (especially cyclopentadienyl) at commercial rates and conditions. Further, there is a need for a catalytic process for producing cyclopentadiene is intended, its manufacture without excessive cleavage product of C _4- catalyst and has acceptable aging properties, the cyclopentadiene is generated from the C ₅ rich material of high yield Alkene. Further, there is a need of a non-cyclic C ₅ hydrocarbons intentional CPD process and reactor system for manufacturing, which deal with the above-described challenges.

The present invention relates to a non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbons (including, but not limited to, cyclopentadiene ( "CPD")) method, the method comprising: a) providing a reactor comprising a parallel tube the furnace tube reactor containing such catalyst composition; b) providing a raw material of a non-cyclic C ₅ hydrocarbons; c) the contacting feedstock with a catalyst composition, and d) obtaining the C ₅ hydrocarbon comprises a cyclic the reactor effluent, wherein the cyclic hydrocarbon comprises a C ₅ cyclopentadiene.

In one aspect of the invention, i) the reactor tube is positioned vertically such that the feedstock is provided from the top and the reactor effluent is withdrawn from the bottom, and ii) the furnace comprises at least one burner positioned at the burner Near the top of the reactor tube, there is a flame burning in the downward direction to provide a heat flux at the top that is greater than the heat flux near the bottom of the reactor tube. In a related aspect, a barrier blocks at least a portion of the radiation from the burner flame of the bottom portion of the reactor tube. In another related aspect, the barrier is a flue gas channel.

Another aspect of the invention pertains to a reactor tube having an inverse temperature profile.

Another aspect of the invention pertains to a reactor tube having an isothermal or substantially isothermal temperature regime.

Yet another aspect of the invention relates to the transfer of heat from a flue gas to a rejuvenation gas, a regeneration gas, a vapor, and/or a feedstock by convection in a convection zone of the furnace.

Still another aspect of the invention relates to i) providing two or more furnaces, each furnace comprising parallel reactor tubes, the reactor tubes containing a catalyst composition and ii) providing a reactivation gas or a regeneration gas to one or more furnaces And at the same time, the raw materials containing acyclic C ₅ hydrocarbons are supplied to different one or more furnaces.

Further another aspect of the present invention based on the steps comprising: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons; b) providing a gas comprising H ₂ of the resurrection; c) with the catalyst composition of the gas resurrection contacting the catalyst to remove coke material composition of at least a portion; and d) stops supplying gas and resurrection resumes providing material comprising a non-cyclic C ₅ hydrocarbons.

Aspect of the present invention is also based on the further step comprising: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons; b) from the reaction tube chased any combustible gas (comprising reactor products and raw materials) And c) contacting a regeneration gas comprising an oxidizing material with the catalyst composition to oxidize at least a portion of the coke material removed on the catalyst composition; d) driving the regeneration gas from the reactor tube; and The regeneration of the regeneration gas is stopped and the supply of the raw material containing the acyclic C ₅ hydrocarbon is restarted.

The present invention also relates to a non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbon conversion system, wherein the conversion system comprises: a) a raw material of a non-cyclic C ₅ hydrocarbon stream; b) parallel to the reactor tube comprising the furnace, the reactor tube containing the catalyst composition; and c) generated by the feedstock is contacted with the catalyst composition to include cyclic C ₅ hydrocarbon stream of reactor effluent, wherein the C ₅ hydrocarbon cyclic Contains cyclopentadiene.

One aspect of the invention relates to i) vertical positioning of the reactor tube, the feedstock being provided by the top, and the reactor effluent being from the counter The bottom of the reactor tube is discharged and ii) the furnace additionally comprises at least one burner positioned adjacent the top of the reactor tube and having a flame burning downwardly to provide a heat flux near the top that is greater than the reaction Heat flux near the bottom of the tube. A related aspect of the invention is a barrier that blocks at least a portion of the radiation from the burner flame of the bottom portion of the reactor tube. Another related aspect of the invention is wherein the barrier is a flue gas passage.

Another aspect of the invention relates to fins or contours inside or outside the reactor tube that promote heat transfer from the tube wall to the catalyst composition.

Still another aspect of the invention relates to a mixing internal device positioned within a reactor tube to provide mixing in a radial direction, wherein the mixing internal device is positioned i) in a bed of the catalyst composition or ii) Two or more zones of the catalyst composition are separated in portions of the reactor tube.

Yet another aspect of the invention relates to the furnace, further comprising a convection zone for providing heat from the flue gas by convection to the reactivation gas, regeneration gas, vapor, and/or the feedstock.

Another aspect of the invention relates to another furnace or furnaces, each furnace comprising parallel reactor tubes, the reactor tubes containing a catalyst composition such that a reactivation gas or a regeneration gas can be supplied to one or more furnaces, and simultaneously providing the material comprising a non-cyclic C ₅ hydrocarbons to one or more of the different furnaces.

10‧‧‧Materials

11‧‧‧ catheter

12‧‧‧Switch

13‧‧‧ catheter

14‧‧‧Inlet manifold

15‧‧‧ catheter

20‧‧‧ furnace

21‧‧‧radiation zone

22‧‧‧ Convection area

23‧‧‧Parallel reactor tubes

24‧‧‧ burner

25‧‧‧ barrier

26‧‧‧ chimney

30‧‧‧ catheter

31‧‧‧Export manifold

32‧‧‧Reactor effluent

40‧‧‧Resurrection system

41‧‧‧ catheter

42‧‧‧Switch

43,44‧‧‧ catheter

45‧‧‧Revitalizing gas

50‧‧‧Raykin System

51,52‧‧‧ catheter

53‧‧‧Renewable gas

54‧‧‧ Driving gas

60‧‧‧Vapor

61‧‧‧Switch

62‧‧‧ catheter

200‧‧‧Renewable gas supply manifold

201‧‧‧ Raw material header

202‧‧‧Resurrection gas supply header

203‧‧‧Resurrection effluent header

204‧‧‧Common product header

205‧‧‧Regeneration effluent header

206, 207, 208, 209‧ ‧ catheter

210,211,212,213‧‧‧ furnace

214, 215, 216, 217‧ ‧ catheter

Figure 1 illustrates the configuration of a multiple furnace.

Figure 2 is a diagram of a furnace.

Figure 3 illustrates the overall carbon yield in Example 3 C ₅ cyclic hydrocarbons relative time (TOS) on the stream, while maintaining the temperature of the inverse situation (6 inches up to 500 deg.] C after 600 ℃) isothermal temperature or a situation (the 6吋 is 600°C from head to tail).

Figure 4 illustrates the total carbon yield of C ₁ -C ₄ hydrocarbons relative to TOS in Example 3 while maintaining a reverse temperature regime (500 ° C over 6 Torr to 600 ° C) or an isothermal temperature regime (the 6 吋 from start to finish) 600 ° C).

Figure 5 illustrates in Example 5, in an oil continuous reactor operating under intermittent H ₂ strategy and resurrection reactor operation strategy, address cyclic hydrocarbon of C ₅ - time - yield (STY) (i.e. cC5 The number of moles / Pt of the mole / second) relative TOS.

definition

For the purposes of this specification and the accompanying claims, many terms and phrases are defined below.

As used in the disclosure and the claims, the singular "s" and "the"

The words "and/or" as used in the phrase (such as "A and/or B" herein) are intended to include "A and B", "A or B", "A" and "B".

As used herein, the term "about" refers to a range that adds or subtracts a value of 10% from a particular value. For example, the phrase "about 200" includes 200 plus or minus 10% or from 180 to 220.

The term "saturated" includes, but is not limited to, alkanes and naphthenes.

The term "unsaturated" includes, but is not limited to, alkenes, dienes, alkynes, cycloolefins, and cyclodienes.

The term "cyclic C _5" or "cC _5" include, but are not limited to cyclopentane, cyclopentene, cyclopentadiene, and mixtures of two or more. The term "cyclic C _5" or "cC _5" also includes analogs of any of the foregoing alkyl persons e.g. methylcyclopentane, methyl cyclopentene, cyclopentadiene and methyl. For the purposes of the present invention, it is recognized that cyclopentadiene spontaneously dimerizes over time to form dicyclopentadiene via Dimes-Adel condensation under a range of conditions including ambient temperature and pressure. .

The term "acyclic" includes, but is not limited to, linear and branched saturated and unsaturated.

The term "aromatic" means a planar cyclic hydrocarbon group having a conjugated double bond such as benzene. As used herein, the term "aromatic" encompasses compounds containing one or more aromatic rings including, but not limited to, benzene, toluene, and xylene, and polynuclear aromatics (PNA) (which include naphthalene, anthracene, Benzophenanthrene, and its alkylation variants). The term "C ₆₊ aromatic" includes compounds having an aromatic ring having 6 or more ring atoms as a substrate (including but not limited to benzene, toluene, and xylene), and polynuclear aromatic (PNA) (including Naphthalene, anthracene, benzophenanthrene, and their alkylation variants).

The term "BTX" includes, but is not limited to, a mixture of benzene, toluene and xylene (ortho and/or meta and/or para).

The term "coke" includes, but is not limited to, hydrocarbons of low hydrogen content which are adsorbed onto the catalyst composition.

The term " _Cn " means a hydrocarbon (class) of n carbon atoms per molecule, where n is a positive integer.

The term " _Cn+ " means a hydrocarbon (class) having at least n carbon atoms per molecule.

The term " _Cn- " means a hydrocarbon (class) having no more than n carbon atoms per molecule.

The term "C ₅ raw material" includes raw materials containing n-pentane, such as mainly n-pentane and isopentane (also known as methylbutane) with a lower ratio of cyclopentane and neopentane (also known as Raw material for 2,2-dimethylpropane).

The term "hydrocarbon" means a compound containing hydrogen bonded to carbon and encompasses a mixture of (i) a saturated hydrocarbon compound, (ii) an unsaturated hydrocarbon compound, and (iii) a hydrocarbon compound (saturated and/or unsaturated). A mixture comprising hydrocarbon compounds having different values of n.

As used herein, the term "oxygen" means oxygen and oxygen containing compounds (including but not limited to O ₂ , CO ₂ , CO, H ₂ O), and oxygenated hydrocarbons (such as alcohols, esters, Ethers, etc.).

All numbers and references to the periodic table of elements are based on new markers listed in Chemical and Engineering News, 63(5), 27 (1985), unless otherwise stated.

The term "Group 10 metal" means an element in Group 10 of the periodic table and includes Ni, Pd, and Pt.

The term "Group 11 metal" means an element in Group 11 of the Periodic Table and includes, but is not limited to, Cu, Ag, Au, and a mixture of two or more thereof.

The term "group 1 alkali metal" means the first group in the periodic table. Elements in the group include, but are not limited to, Li, Na, K, Rb, Cs, and mixtures of two or more thereof, and excluding hydrogen.

The term "Group 2 alkaline earth metal" means an element in Group 2 of the Periodic Table and includes, but is not limited to, Be, Mg, Ca, Sr, Ba, and a mixture of two or more thereof.

The term "constraint index" is defined in US 3,972,832 and US 4,016,218, both of which are incorporated herein by reference.

As used herein, the phrase "MCM-22 molecular sieve" (or "MCM-22-based material" or "MCM-22-based material" or "MCM-22-based zeolite" includes one or more of the following: molecular sieves It is made of a common first crystal building block unit lattice, and the unit cell has a MWW framework phase. (The unit cell is a spatial arrangement of atoms, which is described in the three-dimensional space. These crystal structures are in the "Atlas of Zeolite Framework Types", 5th edition, 2001. In the discussion, the overall content is incorporated as a reference); molecular sieves, which are made of ordinary second-degree building blocks, are two-dimensionally laid out of the phase unit lattice of these MWW structures, forming a unit lattice thickness. a single layer (preferably a c-unit lattice thickness); a molecular sieve, which is made of a common second-degree building block, is a multilayer having one or more than one unit lattice thickness, wherein the one has more than one The layer of unit lattice thickness is made by stacking, stacking, or combining at least two single layers having a unit lattice thickness. The stack of such second building blocks can be Regular, irregular, random, or any combination thereof; and molecular sieves made by any regular or random 2- or 3-dimensional combination of unit cells having a phase of the MWW architecture.

The MCM-22 series includes those molecular sieves having X-ray diffraction patterns including maximum d-spacings of 12.4 ± 0.25, 6.9 ± 0.15, 3.57 ± 0.07, and 3.42 ± 0.07 angstroms. The X-ray diffraction pattern used to characterize the material is obtained by using a K-alpha dipole of copper as the incident radiation and a standard technique of a diffractometer equipped with a scintillation counter and associated computer as the collection system.

As used herein, the term "molecular sieve" is used synonymously with the terms "microporous crystalline material" or "zeolite".

As used herein, the term "carbon selectivity" is meant the ring formed by dividing the individual C _5, CPD, C _1, and the mole number of C _2-4 carbons in the conversion of the pentane The total number of moles of carbon. The phrase "at least 30% selectivity to ₅ carbon cyclic C" means: in the transformed pentane per 100 mole of carbon-carbon-based mole 30 is formed in the cyclic C _5.

As used herein, the term "conversion" means the molar number of carbon is converted to a non-cyclic C ₅ feed of the product. The phrase "the non-cyclic C ₅ to the feed product is at least 70% conversion" is meant that the non-cyclic C ₅ molar number of the raw material is at least 70% conversion to product.

As used herein, the term "reactor system" refers to a system that includes one or more reactors and all necessary and optional equipment used in the manufacture of cyclopentadiene.

As used herein, the term "reactor" refers to any tank in which a chemical reaction takes place. The reactor comprises two different reactors, as well as a reaction zone in a single reactor unit and, if applicable, a reaction zone through a plurality of reactors. In other words, and as is common, a single reactor can have multiple reaction zones. In the case where the description refers to the first and second reactors, one of ordinary skill in the art will readily appreciate that such references include two reactors, as well as a single reactor having first and second reaction zones. Likewise, the first reactor effluent and the second reaction effluent will be understood to include effluent from the first reaction zone and the second reaction zone, respectively, from a single reactor.

For the purposes of the present invention, 1 psi is equal to 6.895 kPa. In particular, 1 psia is equal to 1 absolute kPa (kPa-a). Similarly, 1 psig is equal to 6.895 kPa (kPa-g).

The present invention relates to a non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbons, wherein the method comprises: providing a furnace comprising the parallel reactor tube, the reactor tube such catalyst composition comprising; providing a non- cyclic hydrocarbons of the C ₅ material; feedstock with the catalyst composition and contacting the reactor effluent is obtained comprising a cyclic hydrocarbon of C _5, C ₅ wherein the cyclic hydrocarbon comprises cyclopentadiene. Aspects of the conversion system and method can maintain a reverse temperature regime in the reactor tube while advantageously minimizing the formation of carbonaceous materials. Aspects of the system and method of conversion or may be enabled to maintain isothermal or substantially isothermal temperature trend in the reactor tube, the catalyst may advantageously increase efficiency, and by reducing the low value of cracked (i.e. C _{4 -} The amount of by-products to improve product yield.

Other aspects of the present invention allows an operator to exit the reactor at less than atmospheric pressure to form a cyclic C ₅ to strengthen the product.

raw material

Useful non-cyclic C ₅ feed may be crude oil or natural gas condensate obtained herein, and may include chemical methods and by refining (such as a fluid catalytic cracking (the FCC), recombinant, hydrocracking, hydrotreating, coking, and Vapor cracking) produced cracked C ₅ (different unsaturation: alkenes, dienes, alkynes).

In one or more specific embodiments, the present invention is useful in the methods of non-cyclic C ₅ feed comprising pentane, pentene, pentadiene, and mixtures of two or more. Preferably, in one or more embodiments, the acyclic C ₅ feedstock comprises at least about 50 wt%, or 60 wt%, or 75 wt%, or 90 wt% n-pentane, or from about 50 wt% to about 100 wt% N-pentane in the range.

The acyclic C ₅ starting material optionally contains no C ₆ aromatic compound such as benzene, preferably the C ₆ aromatic compound is present in an amount of less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight. , preferably 0 wt%.

The acyclic C ₅ feedstock optionally contains no benzene, toluene, or xylene (ortho, meta, or para), preferably the benzene, toluene, or xylene (ortho, meta, or para) The compound is present in an amount of less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight, preferably 0% by weight.

The acyclic C ₅ starting material optionally contains no C ₆₊ aromatic compound, preferably the C ₆₊ aromatic compound is present in an amount of less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight. , preferably 0 wt%.

The acyclic C ₅ starting material optionally contains no C ₆₊ compound, preferably the C ₆₊ compound is present in an amount of less than 5% by weight, preferably less than 1% by weight, preferably less than 0.01% by weight, preferably less than 0.01% by weight, preferably 0wt%.

Preferably, the C ₅ feedstock is substantially free of oxygenates. As used herein, "substantially free of" means that the feedstock comprises less than about 1.0 wt%, such as less than about 0.1 wt%, less than about 0.01 wt%, less than about 0.001 wtg, based on the weight of the feed. %, less than about 0.0001% by weight, less than about 0.00001% by weight of oxygenates.

Preferably, the free hydrogen containing hydrogen and light hydrocarbons (such as C ₁ -C ₄ hydrocarbons) also co-feed is fed into the first reaction. Preferably, the co-feed hydrogen in at least a portion of the feed material blended with the C ₅ prior to the first reactor. At the inlet location where the feed is first contacted with the catalyst, the presence of hydrogen in the feed mixture prevents or reduces the formation of coke on the catalyst particles. C ₁ -C ₄ hydrocarbons may also be co-fed with the C ₅ .

Acyclic C ₅ transformation method

The first aspect of the present invention is a non-cyclic C ₅ feedstock into product C comprising a cyclic compound of ₅ the. The method comprises a non-cyclic C ₅ at conversion conditions in one or more catalyst compositions (described herein including but not limited to the composition of the catalyst) in the presence of free contact with the feedstock and hydrogen to form the product A step of.

A second aspect of the present invention is also a non-cyclic C ₅ feedstock into a product comprising a compound of the cyclic C _5, which comprises a non-cyclic C ₅ at conversion conditions in one or more catalyst compositions ( The step of contacting the starting material and optionally hydrogen to form the product, including but not limited to the catalyst composition described herein.

In one or more particular embodiments, the method of converting the product non-cyclic C ₅ to include cyclic C ₅ feed compound. The cyclic C ₅ compound comprises one or more of cyclopentane, cyclopentene, cyclopentadiene, and a mixture thereof. In one or more embodiments, the cyclic C ₅ compound comprises at least about 20 wt%, or 30 wt%, or 40 wt%, or 50 wt% cyclopentadiene, or from about 10 wt% to about 80 wt%, alternatively It is in the range of 10 wt% to 80 wt%.

In one or more embodiments, the acyclic C ₅ conversion conditions include at least temperature, reactor outlet pressure, reactor pressure drop (reactor inlet pressure - reactor outlet pressure), and hourly weight space velocity (WHSV) . The temperature is in the range of from about 450 ° C to about 800 ° C, or from about 450 ° C to about 650 ° C, preferably from about 450 ° C to about 600 ° C. The reactor outlet pressure is in the range of from about 1 to about 50 psia, or in the range of from about 4 to about 25 psia, preferably from about 4 to about 10 psia. Advantageously, at a subatmospheric pressure of operating the reactor outlet to form a cyclic C ₅ to strengthen the product. The reactor pressure drop is in the range of from about 1 to about 100 psi, or in the range of from about 1 to about 75 psi, preferably from about 1 to about 45 psi, such as from about 5 to about 45 psi. The weight hourly space velocity is in the range of from about 1 to about 1000hr ^-1 of, or in the range of from about 1 to about 100hr ^-1 of the, preferably from about 2 to about 20hr ^-1. Such conditions include the free of hydrogen co-feed molar ratio of the non-cyclic C ₅ material in the range of about 0 to 3, or in the range from about 1 to about 2. Such conditions may also include a co-feed C ₁ -C ₄ hydrocarbons from the non-cyclic C ₅ feed. Preferably, the co-feed (if present) ₁ -C ₄ hydrocarbons, or whether both comprising hydrogen, C, does not substantially contain oxygen-containing compounds. As used herein, "substantially free of" means that the co-feed comprises less than about 1.0 wt%, such as less than about 0.1 wt%, less than about 0.01 wt%, less than about 0.001 by weight of the co-feed. Wt%, less than about 0.0001% by weight, less than about 0.00001% by weight oxygenate.

In one or more specific embodiments, the invention relates to a process for converting n-pentane to cyclopentadiene comprising the steps of: a reactor outlet temperature of from 550 ° C to 650 ° C, from 4 to about 20 psia. Reactor outlet pressure, reactor pressure drop of from about 1 to about 45 psi (such as from about 5 to 45 psi), and hourly weight space velocity of from 2 to about 20 hr ^{-1 to} give n-pentane and optionally hydrogen (if present, H) _{2 is} generally present in the ratio of 0.01 to 3.0 for the n-pentane system) in contact with one or more catalyst compositions including, but not limited to, the catalyst compositions described herein to form cyclopentadiene. Preferably, the reactor tube has a pressure drop from the reactor inlet to the reactor outlet of less than 20 psi (more preferably less than 5 psi) during contact of the feedstock with the catalyst composition.

Catalyst compositions useful herein include microporous crystalline metal silicates such as crystalline aluminosilicates, crystalline ferric silicates, or crystalline silicates containing other metals such as those metals or Metal containing The compound is dispersed within the crystalline tellurite structure and may or may not be part of the crystalline structure). There are microporous crystalline metal citrate construction types used as catalyst compositions in this paper including, but not limited to, MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR. , EUO, and FAU.

Particularly suitable for use in the microporous metal silicates herein including MWW, MFI, LTL, MOR, BEA, TON, MTW, MTT, FER, MRE, MFS, MEL, DDR, EUO, and FAU construction types ( Such as zeolite beta, mordenite, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, And MCM-22-based material), wherein one or more of the metals of Groups 8, 11 and 13 of the Periodic Table of the Elements (preferably one of Fe, Cu, Ag, Au, B, Al, Ga, and/or In) Or more) incorporated into the crystal structure during synthesis or impregnated after crystallization. It is recognized that metal citrate may have one or more metals present and, for example, one material may be referred to as a ferrite, but it is most likely still containing a small amount of aluminum.

The microporous crystalline metal silicate preferably has a limiting index of less than 12, or 1 to 12, or 3 to 12. Aluminosilicates useful herein have a limiting index of less than 12, such as from 1 to 12, or from 3 to 12, and include, but are not limited to, zeolite beta, mordenite, faujasite, zeolite L, ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, ZSM-57, ZSM-58, and MCM-22 based materials, and mixtures of two or more thereof. In a preferred embodiment, the crystalline aluminosilicate has a limiting index of from about 3 to 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 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. ZSM-57 is described in US 4,873,067. ZSM-58 is described in US 4,698,217. The restriction index and its assay are described in US 4,016,218. The entire contents of each of the above patents are incorporated herein by reference.

The MCM-22 series material is selected from the group consisting of 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 a mixture of two or more thereof.

Materials of the MCM-22 series include MCM-22 (described in US 4,954,325), PSH-3 (described in US 4,439,409), SSZ-25 (described in US 4,826,667), ERB-1 (in EP) It is described in 0 293 032), ITQ-1 (described in US 6,077,498), and ITQ-2 (described in WO 97/17290), MCM-36 (described in US 5,250,277), MCM-49 (described in US 5,236,575), MCM-56 (described in US 5,362,697), and mixtures of two or more thereof. The relevant zeolites to be included in the MCM-22 series are UZM-8 (described in US 6,756,030) and UZM-8HS (described in US 7,713,513), both of which are also suitable for use as the MCM-22 line. Molecular sieve.

In one or more embodiments, the Si/M molar ratio of the crystalline metal ruthenate (where M is a Group 8, 11 or 13 metal) is greater than about 3, or greater than about 25, or greater than about 50, Or greater than about 100, or greater than about 400, or in the range of from about 100 to about 2,000, or from about 100 to about 1,500, or from about 50 to about 2,000, or from about 50 to about 1,200.

In one or more embodiments, the crystalline metal silicate has a SiO ₂ /Al ₂ O ₃ molar ratio of greater than about 3, or greater than about 25, or greater than about 50, or greater than about 100, or greater than about 400, Or in the range of from about 100 to about 400, or from about 100 to about 500, or from about 25 to about 2,000, or from about 50 to about 1,500, or from about 100 to about 1,200, or from about 100 to about 1000.

In another embodiment of the present invention, the microporous crystalline metal citrate (such as an aluminosilicate) and a Group 10 metal or metal compound and optionally one, two, three, or more 2. A combination of a Group 11 metal or a metal compound.

In one or more embodiments, the Group 10 metal includes or is selected from the group consisting of Ni, Pd, and Pt, preferably Pt. The Group 10 metal content of the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the Group 10 content is in the range of from about 0.005 wt% to about 10 wt%, or from about 0.005 wt% to about 1.5 wt%, by weight of the catalyst composition.

In one or more specific examples, the Group 1 alkali metal comprises or is selected from the group consisting of Li, Na, K, Rb, Cs, and mixtures of two or more thereof, preferably Na; Hydrogen is excluded.

In one or more embodiments, the Group 2 alkaline earth metal includes or is selected from the group consisting of Be, Mg, Ca, Sr, Ba, and mixtures of two or more thereof.

In one or more specific examples, the Group 1 alkali metal is present in the form of an oxide and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and two or more thereof. mixture. In one or more embodiments, the Group 2 alkaline earth metal is present in the form of an oxide and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof. . In one or more specific examples, the Group 1 alkali metal is present in the form of an oxide and the metal is selected from the group consisting of Li, Na, K, Rb, Cs, and two or more thereof. a mixture; and the Group 2 alkaline earth metal is present in the form of an oxide and the metal is selected from the group consisting of Be, magnesium, calcium, Sr, Ba, and mixtures of two or more thereof.

In one or more embodiments, the Group 11 metal includes or is selected from the group consisting of silver, gold, copper, preferably silver or copper. The Group 11 metal content of the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition. In one or more embodiments, the Group 11 content is in the range of from about 0.005 wt% to 10 wt%, or from about 0.005 wt% to about 1.5 wt%, by weight of the catalyst composition.

In one or more embodiments, the catalyst composition has an alpha value of less than about 25 (preferably less than about 15) as measured prior to the addition of the Group 10 metal, preferably platinum.

In one or more specific examples of aluminosilicate, the first group The molar ratio of alkali metal to Al is 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 specific examples of the aluminosilicate, the molar ratio of the Group 2 alkaline earth metal to Al is 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 Group 11 metal to the Group 10 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 embodiments, the Group 11 alkaline earth metal is present as an oxide and the metal is selected from the group consisting of gold, silver, and copper, and mixtures of two or more thereof.

In one or more specific examples, at a temperature in the range of from about 550 ° C to about 600 ° C in a non-cyclic C ₅ conversion condition of a raw material containing n-pentane and isomol H ₂ at the inlet of the reactor The use of the catalyst composition of the present invention provides at least about 70%, or at least about 75, at an hourly weight space velocity of between 3 and 10 psia of n-pentane and 10 to 20 hr ^-1 of n-pentane. %, or at least about 80%, or the conversion of non-cyclic C ₅ material is in the range from about 60% to about 80% of the.

In one or more specific examples, at a temperature ranging from about 550 ° C to about 600 ° C, including a non-cyclic C ₅ conversion condition of n-pentane starting material and isomol H ₂ , at the inlet of the reactor The use of any of the catalyst compositions of the present invention provides at least about 30% at a sub-pentane partial pressure of 3 and 10 psia, and an hourly weight space velocity of n-pentane between 10 and 20 hr ^-1 . or at least about 40%, or at least about 50%, selectivity or carbon cyclic C ₅ compounds in the range of from about 30% to about 80% of the.

In one or more specific examples, at a temperature ranging from about 550 ° C to about 600 ° C, including a non-cyclic C ₅ conversion condition of n-pentane starting material and isomol H ₂ , at the inlet of the reactor The use of any of the catalyst compositions of the present invention provides at least about 30 at a partial pentane partial pressure between 3 and 10 psia and an hourly weight space velocity of n-pentane between 10 and 20 hr ^-1 The carbon selectivity of cyclopentadiene in %, or at least about 40%, or at least about 50%, or in the range of from about 30% to about 80%.

The catalyst composition of the present invention can be combined with a matrix or binder material to render it resistant to abrasion and more resistant to the harsh conditions that are exposed during use in hydrocarbon conversion applications. The combined composition may contain from 1 to 99% by weight of the material of the invention based on the combined weight of the substrate (adhesive) and the material of the invention. The relative proportions of microcrystalline material and matrix can vary widely, and the crystal content ranges from about 1 to 90 wt%, and more often the composite is prepared to have the composite in the range of from about 2 to about 80 wt%. The material is in the form of beads, extrudates, pellets, particles formed by oil droplets, spray dried particles, and the like.

The shape and design of the catalyst composition is preferably configured to minimize pressure drop, increase heat transfer, and minimize mass transport phenomena. The catalyst composition can be formed into particles that are randomly loaded into the reactor or can be formed into a structured catalyst shape within the reactor.

The shape and design of suitable catalyst particles are described in WO 2014/053553, which is incorporated herein by reference. The catalyst composition may be an extruded body having a diameter of 2 mm to 20 mm (for example, 2 mm to 10 mm, or 5 mm to 15 mm). Optionally, the catalyst consists of The cross-section of the object can be shaped to have one or more leaves and/or concave sections. Additionally, the leaves and/or concave sections of the catalyst composition are spiraled. The catalyst composition may be an extruded body having a diameter of 2 mm to 20 mm (for example, 2 mm to 10 mm, or 5 mm to 15 mm); and the catalyst composition may be shaped to have one or more leaves and/or concave sections in cross section; The leaves and/or concave sections of the catalyst composition can be spiraled. Particle shapes for fixed bed reactors (combustion tubes, convection tubes, and circulation), vane type, concave type, spiral type, etc. are particularly useful and are used in fluid bed reactors, and spherical particle shapes are particularly useful. Preferably, the particles for a fixed bed (eg, a circulating fixed bed reactor, a gas tube reactor, a convection heating tube reactor, etc.) are generally extruded bodies having a diameter of 2 mm to 20 mm; and the catalyst composition cross section It can be shaped to have one or more leaves and/or concave sections; and the leaves and/or concave sections of the catalyst composition can be spiraled. The shape may also include holes or perforations in the shape to increase voidage and improve mass transfer.

Examples of the shape of the structured catalyst include a catalyst coating on the inner wall of the reactor and/or on other formed inorganic support structures. Suitable shaped inorganic support structures can be metallic or ceramic. Preferred ceramics are those having high thermal conductivity such as tantalum carbide, aluminum nitride, boron carbide, and tantalum nitride. Suitable shaped inorganic support structures can be ordered structures such as extruded ceramic monoliths and extruded or crimped metal monoliths. In general, suitable shaped inorganic support structures can also include ceramic or metal foam and 3D printed structures. The active catalyst coating can be applied to the support structure by lotion coating or other measures known in the art. Preferably, the coating has a thickness of less than 1,000 microns; more preferably less than 500 microns; optimally Between 100 and 300 microns.

During the use of the catalyst composition in the process of the present invention, coke can be deposited on the catalyst composition whereby the catalyst composition loses a portion of its catalytic activity and becomes passivated. The passivated catalyst composition can be regenerated by a technique comprising high pressure hydrogen treatment and coke burning on the catalyst composition with oxygen such as air or O ₂ gas.

Useful catalyst compositions comprise crystalline aluminosilicate or ferrite, optionally in combination with one, two, or a plurality of additional metals or metal compounds. Preferred combinations include: 1) crystalline aluminosilicates (such as ZSM-5 or zeolite L), which are associated with a Group 10 metal (such as Pt), a Group 1 alkali metal (such as sodium or potassium), and/or Group 2 alkaline earth metal combination; 2) crystalline aluminosilicate (such as ZSM-5 or zeolite L), which is combined with a Group 10 metal (such as Pt) and a Group 1 alkali metal (such as sodium or potassium); 3) Crystallization Aluminosilicate (such as ferric or iron-treated ZSM-5) combined with a Group 10 metal (such as Pt) and a Group 1 alkali metal (such as sodium or potassium); 4) Crystalline aluminosilicate a salt (zeolite L) which is combined with a Group 10 metal (such as Pt) and a Group 1 alkali metal (such as potassium); 5) a crystalline aluminosilicate (such as ZSM-5) which is associated with a Group 10 metal (such as Pt), a Group 1 alkali metal such as sodium, and a Group 11 metal such as silver or copper.

Another useful catalyst composition is a Group 10 metal (such as Ni, Pd, and Pt, preferably Pt) supported on a vermiculite (e.g., cerium oxide) which is a Group 1 base. Metal citrates (such as Li, Na, K, Rb, and/or Cs citrates) and/or Group 2 alkaline earth metal citrates (such as Mg, Ca, Sr, and/or Ba citrate) The modification is preferably modified with potassium citrate, sodium citrate, calcium citrate and/or magnesium citrate, preferably with potassium citrate and/or sodium citrate. The Group 10 metal content of the catalyst composition is at least 0.005 wt% based on the weight of the catalyst composition, preferably from about 0.005 wt% to about 10 wt%, or about from the weight of the catalyst composition. From 0.005 wt% to about 1.5 wt%. The vermiculite (SiO ₂ ) may be any vermiculite generally used as a catalyst carrier such as those marketed under the trademark DAVISIL 646 (Sigma Aldrich), Davison 952, Davison 948 or Davison 955 (Davison Chemical Division of WR Grace and Company).

In various aspects, the catalyst material (and optional matrix material) can have an average diameter of from about 5 [mu]m to about 50 mm (such as from about 25 [mu]m to about 3500 [mu]m). Preferably, the catalyst material (and optional matrix material) may have from about 25 μm to about 1200 μm (more preferably from about 50 μm to about 1000 μm, more preferably from about 10 μm to about 500 μm, more preferably from about 30 μm to about 400 μm, More preferably, the average diameter is from about 40 μm to about 300 μm.

For particles in the range of 1 to 3500μm, the "average diameter" Mastersizer measurement system 3000 using a Malvern Instruments Ltd., Worcestershire, England OBTAINED, ^TM. The particle size at point D50 was determined unless otherwise stated. D50 is the particle diameter value at the 50% point in the cumulative distribution. For example, if D50 = 5.8 μm, 50% of the particles in the sample are equal to or greater than 5.8 μm and 50% are less than 5.8 μm. (In contrast, if D90 = 5.8 μm, 10% of the particles in the sample are equal to or greater than 5.8 μm and 90% are less than 5.8 μm.) For particles in the range of 3 mm to 50 mm, the "average diameter" is used. A micrometer was used to determine a representative sample with 100 particles.

For information on useful catalyst compositions, please see the following applications: 1) USSN 62/250,675, dated November 4, 2015; 2) USSN 62/250,681; 3) 2015, November 4, 2015 USSN 62/250,688, filed on November 4, 4) USSN 62/250,695, filed on November 4, 2015; and 5) USSN 62/250,689, filed on November 4, 2015; In this article.

Conversion system

The feedstock is fed to a conversion system comprising a furnace and parallel reactor tubes positioned in the radiant zone of the furnace. Optionally, the feedstock is fed to the adiabatic pilot reaction zone before being fed to the furnace. For more information on the use of adiabatic lead reaction zones, see USSN 62/250,697, issued Nov. 4, 2015, which is incorporated herein by reference. While any known radiant furnace reactor tube configuration can be used, preferably the furnace comprises a plurality of parallel reactor tubes. Suitable furnace reactor tube configurations include those in US 5,811,065; US 5,243,122; US 4,973,778; US 2012/0060824; And as described in US 2012/0197054, these are incorporated by reference in their entirety.

The tubes can be positioned in the furnace in any configuration. Preferably, the tubes are positioned vertically such that the feed enters from the top of the reactor and the product exits with the reactor effluent exiting the bottom of the reactor tube. Preferably, the reactor tube is straight rather than having a coiled or curved path through the radiant furnace (although coiled or curved tubes may be used). Additionally, the tubes can have cross-sections that are circular, elliptical, rectangular, and/or other known shapes. Advantageously, the tubes have a small cross-sectional dimension to minimize the temperature gradient of the cross-section. However, for a particular production rate, reducing the cross-sectional dimensions of the tubes increases the number of tubes. Therefore, the optimal tube size selection is preferably optimized in terms of minimizing cross-sectional temperature gradients and minimizing construction costs. A suitable cross-sectional dimension of e (i.e., the diameter of the cylindrical tube) may be from 1 cm to 20 cm, more preferably from 2 cm to 15 cm, and most preferably from 3 cm to 10 cm.

The tubes are heated by radiant heat provided by at least one burner located within the radiation zone of the furnace. Any burner known in the art, such as a burner mounted on a ceiling, a wall, and a floor, can be used. Preferably, the burner is positioned to provide a heat flux near the inlet of the reactor tube that is greater than the heat flux near the outlet of the reactor tube. If the reactor tubes are oriented vertically, the burners are preferably positioned adjacent the top inlet of the reactor tubes and have a flame that burns in a downward direction along the length of the tubes. Orienting the burner adjacent the top of the vertical reactor tube and combusting downward provides a heat flux near the inlet (top) of the reactor tube, the heat flux being greater than the heat flux near the outlet of the reactor tube the amount. Higher heating is required at the reactor tube inlet to, for example, provide heat of reaction and heat required to heat the feed to the desired reaction temperature. A sufficient spacing should be provided between the burner and the tube to prevent hot spots; this offset can range between 30 cm and 300 cm, but is preferably about 100 cm. Preferably, the burners are arranged on both sides of the tubes and each tube is separated by a distance of 0.25 to 2.0 tube diameters to provide uniform heating of the tubes.

The furnace may also optionally include one or more barriers positioned to block at least a portion of the burner flame radiation from the outlet portion of the reactor tube, wherein less heat flux is desired to avoid higher than desired The temperature, e.g., the temperature that promotes undesired coking and/or cracking, occurs at temperatures above the temperature of the conversion conditions desired for the particular catalyst, operating pressure, and residence time. If the reactor tube is oriented vertically with the burner that is combusted downward, at least one barrier can be positioned to block a portion of the flame radiation from the bottom portion of the reactor tube. Preferably, the barrier is a flue gas duct whose function is to direct the flue gas produced by the burner away from the radiant zone of the furnace.

The reactor tube contains a catalyst composition. The catalyst composition can be applied to the inner surface of the reactor tube or can be part of a fixed bed of catalyst within the tubes, which includes a random and structured bed. Preferably, the reactor tube contains a fixed bed of catalyst composition and inert material. Suitable stacking and/or design methods for fixed beds of reactor tubes include US 8,178,075, which is incorporated herein by reference. The reactor tube can include at least one internal structure (e.g., a concentric outer casing) to carry the catalyst composition and/or reduce the pressure drop within the reactor tube. The reactor tube can contain A mixing internal structure positioned within the reactor tube to provide mixing in the radial direction. The mixing internal structure can be positioned within the bed of the catalyst composition or in portions of the reactor tube to separate two or more regions of the catalyst composition. The reactor tube can include fins or contours inside or outside the reactor tube to facilitate heat transfer from the tube wall to the catalyst composition. The fins or profiles can be positioned to provide a heat flux near the inlet of the reactor tube that is greater than the heat flux near the outlet of the reactor tube. Examples of suitable internal structures include a plurality of baffles, sheds, trays, tubes, rods, fins, profiles, and/or distributors. These internal structures can be coated with a catalyst. Suitable internal structures can be metallic or ceramic. Preferred ceramics are those having high thermal conductivity such as tantalum carbide, aluminum nitride, boron carbide, and tantalum nitride.

The temperature profile of the reaction zone can be manipulated by controlling the heat input rate (based on hardware design, catalyst loading, combustion, etc.). Nonetheless, as long as the heat flux near the inlet of the reactor tube is greater than the heat flux near the outlet of the reactor tube, a substantially isothermal temperature regime can be provided, which is measured along the centerline of the tube. An advantage of the substantially isothermal temperature regime is that it maximizes the efficient use of the catalyst and minimizes the manufacture of unwanted C4 _- byproducts. As used herein, "isothermal temperature regime" means that the temperature at each point between the reactor inlet and the reactor outlet remains substantially fixed when measured along the tube centerline of the reactor, for example at At the same temperature or in the same narrow temperature range, wherein the difference between the upper limit temperature and the lower limit temperature is not more than about 40 ° C; more preferably not more than 20 ° C. Preferably, the isothermal temperature situation is such that the difference between the inlet temperature of the reactor and the outlet temperature of the reactor is within about 40 ° C, or within about 20 ° C, or within about 10 ° C, or within about 5 ° C. Or the reactor inlet temperature is the same as the reactor outlet temperature. Alternatively, the isothermal temperature regime is within about 20% of the reactor inlet temperature and the reactor outlet temperature, or within about 10%, or within about 5%, or within about 1%.

Preferably, the isothermal temperature profile is such that the temperature along the length of the reaction zone within the reactor varies by no more than about 40 ° C, or no more than about 20 ° C, or no More than about 10 ° C, or no more than about 5 ° C. Alternatively, the isothermal temperature regime is wherein the temperature along the length of the reaction zone within the reactor is wherein the counter inlet temperature change is within about 20% of the reactor inlet temperature, or within about 10%, Either within about 5%, or within about 1% of the inlet temperature of the reactor tube.

However, to minimize catalyst passivation rate, it may be desirable to optimize the radiation zone and reactor tube design to maintain a substantially inverse temperature regime within the reactor tube. As used herein, "inverse temperature regime" means that the reactor inlet temperature is below the reactor outlet temperature. Preferably, the tube centerline temperature at the tube inlet is lower than the tube centerline temperature at the tube outlet. "Inverse temperature regime" includes systems in which the temperature of the tube or system varies, as long as the temperature at the inlet of the reactor tube is lower than the temperature at the outlet of the reactor tube. The "inverse temperature regime" additionally encompasses a reactor tube having a centerline temperature T1; the centerline temperature drops to a temperature T2 along some length of the reactor tube; along one of the reactor tubes On the other length, the centerline temperature rises to temperature T3; finally, the centerline temperature at the outlet of the reactor tube drops to T4; where T3 > T4 > T1 > T2.

The temperature measured when the raw material first contacts the catalyst composition near the inlet of the reactor is about 0 ° C lower than the temperature measured when the effluent is not in contact with the catalyst composition near the outlet of the reactor. It is between about 200 ° C, preferably from about 25 ° C to about 150 ° C, more preferably from about 50 ° C to about 100 ° C. Preferably, the tube is measured when the material first contacts the catalyst composition near the inlet of the tube and the tube is measured when the effluent is not in contact with the catalyst composition adjacent the tube outlet. The centerline temperature is between about 0 ° C and about 200 ° C lower, preferably from about 25 ° C to about 150 ° C, more preferably from about 50 ° C to about 100 ° C.

Maintaining a reverse temperature regime in the reactor tube may advantageously minimize the formation of carbonaceous material at the inlet which can contribute to coking of the catalyst composition. The reverse situation may also be provided a temperature sufficient length of time to react in the reactor tube to be manufactured at lower operating temperature than the outlet temperature of a sufficient amount of H _2, but can be formed in the carbonaceous material of the effluent outlet minimize.

The conversion system furnace includes a radiant zone, a convection zone, and a flue gas chimney. The hot flue gas is produced by at least one burner in the radiant zone of the furnace and is conducted to and from the atmosphere via the convection zone. Heat from the flue gas may be transferred from the flue gas by convection to heat a plurality of streams (e.g., feedstock, vapor), preheat the fuel, and/or preheat the combustion air, through an exchanger, or across the convection zone. The tube bundle is transmitted. The furnace convection zone may contain at least one exchanger or bundle of tubes wherein the heat of the flue gas is convected to the feedstock and/or vapor.

The conversion system can additionally comprise a plurality of furnaces. Conversion system Two or more furnaces may be included, each furnace containing a radiant zone comprising parallel reactor tubes containing a catalyst composition. Optionally, the conversion system comprises a single convection zone and a flue gas stack that is in fluid communication with the two or more furnace radiant zones.

resurrection

During the conversion process, a carbonaceous material or coke material is formed on the catalyst composition to reduce the activity of the catalyst composition. The coke deposited on the catalyst during a conversion cycle is referred to as incrementally deposited coke. Substantially free of reactive oxygen-containing compounds and hydrogen (H ₂₎ gas is supplied to the revival of the reactor tube. As used herein, "substantially free" means that the reactivation gas comprises less than about 1.0 wt.%, such as less than about 0.1 wt.%, less than about 0.01 wt.%, based on the weight of the reactivation gas. About 0.001 wt.%, less than about 0.0001 wt.%, less than about 0.00001 wt.% of the oxygenate. A "reactive oxygenate" is a compound in which oxygen can be utilized to react with the catalyst, in contrast to an inert oxygenate such as CO which does not react with the catalyst.

The flow of the reactivation gas may be in the same or opposite direction to the flow of the stopped feedstock. The reactivation gas comprises ≧50 wt% H ₂ (such as ≧ 60 wt%, ≧ 70 wt%, preferably ≧ 90 wt% H ₂ ). The reactivation gas may additionally contain inert materials (eg, N ₂ , CO), and/or methane.

The reactivation gas is contacted with the catalyst composition inside the reactor tube to form a light hydrocarbon and remove at least 10 wt% (≧ 10 wt%) of the incrementally deposited coke material. The incrementally deposited coke material removed is between about 10 wt% and about 100 wt%, preferably between about 90 wt% and about 100 wt%. After removal of coke materials, the flow of gas is suspended and the resurrection non-cyclic C ₅ feed flow is restarted.

The revival in the illustrated conversion system advantageously has a length of time of ≦90 min, such as ≦60 min, ≦30 min, ≦10 min, such as ≦1 min, or ≦10 sec. Contact of the catalyst composition with the reactivation gas occurs at a temperature of from about 500 ° C to about 900 ° C, preferably from about 575 ° C to about 750 ° C. The reactor tube outlet pressure is between about 5 psia to about 250 psia, preferably between about 25 psia and about 250 psia, during the reactivation cycle. After the start of the illustrated transformation process, the revival can be advantageously carried out for 10 minutes, for example 30 minutes, 2 hours, 5 hours, 24 hours, 2 days, 5 days, 20 days.

The rejuvenating effluent leaving the reactor tube and containing light hydrocarbons, unreacted hydrogen, and coke particles can be sent to a compression unit and subsequently sent to a separation unit where a gas that concentrates light hydrocarbons and a gas that depletes light hydrocarbons are produced . The light hydrocarbon gas can be carried away, for example as a fuel gas. The depleted light hydrocarbon stream can be combined with supplemental hydrogen and constitute at least a portion of the reactivation gas provided to the reactor tube. The separation apparatus can be a membrane system, an adsorption system (e.g., a pressure swing type or a temperature change type), or other system known to separate hydrogen from light hydrocarbons. A particle separation device (e.g., a cyclonic separation drum) may be provided in which coke particles are separated by the effluent reactivation gas.

regeneration

During this conversion process, some of the carbonaceous material or coke material is formed on the catalyst composition, the catalyst composition to not resurrected by the removed oxygen-containing gas using the resurrection of H _2. Oxidative regeneration is used to remove at least a portion of this coke material from the catalyst composition. The regeneration cycle begins in the following manner based by: stopping the flow of feed to the reactor tube, and chased using gas (e.g. N _2), from the reaction tube chased combustible hydrocarbon gas, comprising a reactor feed or product (Acyclic and cyclic C ₅ hydrocarbons). After the hydrocarbon flooding (e.g., to a concentration below the flammable concentration limit), a regeneration gas (e.g., air) containing an oxidizing material such as oxygen is supplied to the reactor tube. A regeneration gas system is contacted with the catalyst composition inside the reactor tube to oxidatively remove at least 10 wt% (≧ 10 wt%) of the coke material present at the beginning of regeneration. The coke material is removed between about 10 wt% and about 100 wt%, preferably between about 90 wt% and about 100 wt%. After the coke material is removed, the flow of the reactivation gas is suspended and the purge gas is redirected to drive the oxygen-containing regeneration gas from the reactor tube, for example, to a concentration below the flammable concentration limit. After the oxygen is purged, the flow of the raw material can then be restarted.

Regeneration (including flooding before or after coke oxidation) takes less than 10 days, preferably less than about 3 days to complete. Regeneration is carried out between once every 6 days and once every 180 days, preferably between once every 10 days and once every 40 days.

Multi-furnace cycle configuration

The conversion system can include providing two or more furnaces, each furnace containing parallel reactor tubes. The reactor tubes contain the catalyst composition described. The conversion process of the conversion system described may comprise providing a gas or revival to one or more regeneration gas furnace, while providing a feedstock comprising a non-cyclic C ₅ to hydrocarbons of one or more different furnaces.

Figure 1 illustrates a configuration 220 for a multi-furnace for parallel interconnection. Feedstock containing C ₅ hydrocarbons (e.g. non-cyclic C ₅ hydrocarbons) of a material can be distributed by the manifold 201 to all such furnaces (not all of each conduit to the manifold of each reactor is shown in FIG. 1)). Products can be collected from all furnaces via product header 204. For information on possible equipment for the products collected, please see the following applications: 1) USSN 62/250,678, dated November 4, 2015; 2) USSN 62/250,692, 3 November 2015; 3) 2015 USSN 62/250,702; and 4) USSN 62/250,708, filed on Nov. 4, 2015; hereby incorporated by reference.

Likewise, there may be a reactivation gas supply header 202 for the reactivation gas and/or a regeneration gas supply header 200 for regeneration gas that is distributed to all of the furnaces. The regeneration effluent header 205 can collect regeneration effluent from all of these furnaces. Likewise, the resurrection effluent header 203 can collect resurrection effluent from all of these furnaces. Although the configuration of four (4) furnaces is shown in Figure 1, the invention is not limited by this number. A multi-furnace configuration having 2, 3, 4, 5, 6, 7, 8, 9, 10, or more furnaces is suitable for the present invention.

Comprises a non-cyclic C ₅ feed of the raw material collector tube 201 may be provided to at least a furnace (e.g., via a conduit 206 to the furnace 210 and / or 212 via a conduit 208 to the furnace) as the converted "on an oil (on-oil)" Part of the loop. Leaving the "on oil" furnace (e.g., via conduit 214 and / or 216) and comprising the reaction product of a cyclic C ₅ effluent product is bound and via a common manifold 204 is turned off. Simultaneously with this "on-oil" conversion, the reactivation gas can be supplied to one or more furnaces, such as via conduit 207 to furnace 211. Likewise, the regeneration gas and purge gas may be simultaneously supplied to one or more furnaces through the regeneration gas supply header 200 (e.g., via conduit 209 to furnace 213). The regeneration effluent may be collected by the one or more furnaces that are supplied with regeneration gas and purge gas. For example, regeneration effluent may be collected by furnace 213 via conduit 217 to regeneration effluent header 205. The resurrection effluent may be collected by the one or more furnaces that are provided with a reactivation gas. For example, the resurrection effluent may be collected by furnace 211 via conduit 215 to resurrection effluent header 203. Each furnace is designed to have a valve conditioning system (not shown) to allow it to be connected and separated from all of the different headers depending on whether the reactor is being used for feed conversion, reactivation, and/or regeneration cycles on the oil. . The figure indicates the flow at a particular point in time. It should be recognized that the flow at other points in time may deviate from the one shown in the figure because the reactor may be periodically exposed to oil feedstock conversion, reactivation, and/or regeneration cycles. Any valve conditioning system and control system (e.g., double blocking and extraction) known in the art can be used to prevent contact between the combustible gas and the oxidant gas.

Advantageously, the conversion process can comprise a cyclic configuration for simultaneous "on-oil" feedstock conversion, revival, and/or regeneration in a multi-furnace conversion system. The "on-oil" conversion time is generally more than 10 minutes, often from about 10 minutes to about 20 days. The reactivation time is generally from about 10 seconds to about 2 hours. The configuration 220 specified in Figure 1 allows for multiple furnaces, such as furnaces 210, 211, and 212. The "on-oil" conversion and reactivation of the spin cycle can be repeated while at least one other furnace (e.g., furnace 213) completes the regeneration. When regeneration of the furnace (e.g., furnace 213) is completed, it can be returned to the "on-oil" conversion/reactivation cycle while another furnace (e.g., furnace 210) can be recycled for regeneration as needed. Advantageously, this configuration provides a more consistent product composition while reducing the amount of equipment required.

Another specific example

Further on the present invention: 1. A specific example of the method of non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbons (including cyclopentadiene), wherein the method comprises: a) providing a furnace comprising parallel reactors of the tube, such reactor tube containing the catalyst composition; b) providing a raw material of a non-cyclic C ₅ hydrocarbons; c) the contacting feedstock with a catalyst composition, and d) obtaining the reactor comprises a cyclic C ₅ hydrocarbons outflow And wherein the cyclic C ₅ hydrocarbon comprises cyclopentadiene.

Specific Example 2. The method of Specific Example 1, wherein i) the reactor tube is positioned vertically such that the feedstock is provided from the top and the reactor effluent is withdrawn from the bottom and ii) the furnace comprises at least one burner, the burner Positioned near the top of the reactor tube, there is a flame burning in a downward direction to provide a heat flux near the top that is greater than the heat flux near the bottom of the reactor tube.

Specific Example 3. The method of Specific Example 1 or 2, wherein a barrier is blocked At least a portion of the radiation from the burner flame from the bottom portion of the reactor tube.

Specific Example 4. The method of Specific Example 3, wherein the barrier is a flue gas channel.

The method of any of embodiments 1-4, wherein the reactor tube has an inverse temperature profile.

The method of any one of the examples 1-5, wherein the contacting of the raw material with the catalyst composition is carried out in the presence of a gas comprising H ₂ and/or C ₁ to C ₄ hydrocarbons.

The method of any of embodiments 1-6, further comprising facilitating heat transfer from the tube wall to the catalyst by providing fins or contours inside or outside the reactor tube Composition.

The method of any one of the embodiments 1-7, further comprising: mixing the raw material and the converted cyclic C ₅ hydrocarbon in the radial direction by providing the internal device for mixing in the reactor tube Where the mixing internal device is positioned i) in the bed of the catalyst composition or ii) in each portion of the reactor tube to separate two or more zones of the catalyst composition.

The method of any of embodiments 1-8, wherein the contacting step c) occurs at a temperature of from about 450 °C to about 800 °C.

The method of any of embodiments 1-9, wherein the feedstock provided to the reactor tube inlet has a temperature of from about 450 °C to about 550 °C.

The method of any of embodiments 1-10, wherein the reactor tube has an outlet pressure of from about 4 psia to about 50 psia during the contacting step c).

The method of any of embodiments 1-11, wherein the reactor tube has a pressure drop of about 1 psi measured from the reactor inlet to the reactor outlet during contact of the feedstock with the catalyst composition. Up to about 100 psi.

Specific examples of the method of Example 13. DETAILED one of 1-12, wherein the non-cyclic C ₅ hydrocarbons is at least about 30% by weight is converted into cyclopentadiene.

The method of any one of the items 1-13, wherein the catalyst composition comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on citrate modification. on a stone.

The method of embodiment 14, wherein the catalyst composition additionally comprises an inert material.

The method of any one of the examples 1-15, wherein the catalyst composition is an extruded body having a diameter of from 2 mm to 20 mm.

The method of any of embodiments 1-16, wherein the catalyst composition is cross-sectionally shaped to have one or more leaves and/or concave sections.

The method of embodiment 17, wherein the leaf and/or concave section of the catalyst composition is spiraled.

The method of any one of embodiments 1 to 18, wherein the hourly weight space velocity in terms of the active catalyst content in the reactor tube is from 1 to 1000 hr ^-1 .

The method of any of embodiments 1-19, wherein the inner diameter of the reactor tube is from about 20 mm to about 200 mm.

The method of any one of embodiments 1 to 20, wherein i) the raw material, the regeneration gas, or the reactivation gas is guided through the inlet and outlet manifolds Go back and forth to the reactor tube.

The method of any one of the embodiments 1 to 21, further comprising: transferring heat from the flue gas by convection to a reactivation gas, a regeneration gas, a vapor, and/or the convection zone in the furnace raw material.

The method of any one of the embodiments 1 to 2, further comprising i) providing two or more furnaces, each furnace comprising parallel reactor tubes, the reactor tubes containing catalyst composition and ii) The reactivation gas or regeneration gas is supplied to one or more furnaces, and at the same time, the raw materials containing the acyclic C ₅ hydrocarbons are supplied to different one or more furnaces.

The method of any one of embodiments 1 to 23, further comprising: a) discontinuing the supply of the raw material comprising the acyclic C ₅ hydrocarbon; b) providing the reactivation gas comprising H ₂ ; c) resurrection gas is contacted with the catalyst composition to remove the catalyst composition at least part of the char material; and d) stops supplying gas and resurrection resumes providing material comprising a non-cyclic C ₅ hydrocarbons.

Specific Example 25. The method of Specific Example 24, wherein the length of the step a via d is 1.5 hours or less.

The method of embodiment 24 or 25, wherein contacting the reactivation gas occurs at a temperature of from about 500 ° C to about 900 ° C.

The method of any of embodiments 24-26, wherein the reactor tube has an outlet pressure of from about 5 psia to about 250 psia during contact with the reactivation gas.

The method of any one of embodiments 24-27, wherein contacting the reactivation gas occurs at a temperature of from about 575 ° C to about 750 ° C.

The method of any one of embodiments 24-28, wherein the reactor tube has an outlet pressure of from about 25 psia to about 250 psia during contact with the reactivation gas.

The method of any one of embodiments 24-29, wherein at least a portion of the coke material is incrementally deposited and at least 10 wt% of the incrementally deposited coke material is removed by the catalyst composition.

Specific examples of the method of Example 31. DETAILED to any one of 1-30, further comprising: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons; b) from the reaction tube chased any combustible gas (which comprises a raw material and a reactor product); c) contacting a regeneration gas comprising an oxidizing material with the catalyst composition to oxidize at least a portion of the coke material removed on the catalyst composition; d) being driven by the reactor The net regeneration gas; and e) stopping the regeneration of the regeneration gas and restarting the supply of the raw material containing the acyclic C ₅ hydrocarbon.

32. A specific example of a non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbon conversion system, wherein the conversion system comprises: a) feed stream comprising hydrocarbons of the non-cyclic C _5; b) parallel to the reactor tube comprising the furnace, the reactor tube containing the catalyst composition; and c) to include cyclic C ₅ hydrocarbons of the reactor effluent stream by contacting the feedstock with the catalyst composition is produced, wherein the C ₅ hydrocarbon comprises a cyclic Cyclopentadiene.

Specific Example 33. The system of embodiment 32, wherein i) the reactor tube is vertically positioned, the feedstock is provided from the top, and the reactor effluent is withdrawn from the bottom of the reactor tube and ii) the furnace additionally comprises at least one combustion The burner is positioned near the top of the reactor tube and has a flame that burns in a downward direction to provide a heat flux near the top that is greater than the heat flux near the bottom of the reactor tube.

The method of embodiment 32 or 33, further comprising a barrier that blocks at least a portion of the radiation from the burner flame from the bottom portion of the reactor tube.

The system of embodiment 34, wherein the barrier is a flue gas channel.

The system of any of embodiments 32-35, further comprising a gas stream comprising H ₂ and/or C ₁ to C ₄ hydrocarbons.

The system of any of embodiments 32-36, further comprising providing a fin or profile inside or outside the reactor tube to facilitate heat transfer from the tube wall to the catalyst composition.

The system of any of embodiments 32-37, further comprising a mixing internal device positioned within the reactor tube to provide mixing in the radial direction, wherein the mixing internal device is positioned i In the bed of the catalyst composition or ii) in the various portions of the reactor tube to separate two or more zones of the catalyst composition.

The system of any of embodiments 32-38, wherein the catalyst composition comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on vermiculite.

The system of embodiment 39, wherein the catalyst composition additionally comprises an inert material.

The system of any of embodiments 32-40, wherein the catalyst composition is an extruded body having a diameter of from 2 mm to 20 mm.

The system of any of embodiments 32-41, wherein the catalyst composition is cross-sectionally shaped to have one or more leaves and/or concave sections.

The method of embodiment 42 wherein the leaf and/or concave section of the catalyst composition is helical.

The system of any of embodiments 32-43, wherein the reactor tube has a diameter of from about 20 mm to about 200 mm.

The system of any of embodiments 32-44, further comprising an inlet and outlet manifold in fluid communication with the reactor tube, wherein the feedstock, regeneration gas, or reactivation gas is passed through the inlet and outlet manifolds It is guided to and from the reactor tube.

The system of any one of embodiments 32-45, wherein the furnace further comprises a convection zone for providing indirect heat transfer from the flue gas to the reactivation gas, regeneration gas, vapor, and/or by convection raw material.

The system of any one of embodiments 32-46, further comprising one or more additional furnaces, each furnace comprising parallel reactor tubes, the reactor tubes containing a catalyst composition to enable resurrection gas or regeneration gas is supplied to the furnace, and one or more, and at the same feedstock comprising acyclic hydrocarbons of the C ₅ to provide one or more different furnace.

The system of any one particular embodiment 48. In particular embodiments 32-47, further comprising: a) a _gas stream of H resurrection; and b) for the gas is in contact with the resurrection catalyst composition to remove the A device for at least a portion of the coke material on the catalyst composition.

The system of any of embodiments 32-48, further comprising: a) a purge stream comprising an inert gas and a regeneration gas stream comprising an oxidation material; and b) a device for: i) Any combustible gas (including feedstock and reactor products) is purged from the reactor tube and ii) the regeneration gas is contacted with the catalyst composition to oxidatively remove at least a portion of the coke material on the catalyst composition.

Industrial utilization

In this non-cyclic C ₅ obtained during the conversion process comprising cyclic, branched and straight-chain C ₅ hydrocarbons and optionally containing hydrogen, and any combination thereof C ₄ by-product of the lighter, or a C ₆ and heavier The first hydrocarbon reactor effluent of the by-product is itself a valuable product. Preferably, the CPD and/or DCPD can be separated from the reactor effluent to obtain a purified product stream useful for the manufacture of a variety of high value products.

For example, a purified product stream containing 50 wt% or higher (or preferably 60 wt% or higher) DCPD is useful in the manufacture of hydrocarbon resins, unsaturated polyester resins, and epoxy materials. A purified product stream containing 80 wt% or more (or preferably 90 wt% or more) of CPD is used to produce a Diels-Alder reaction formed according to the following reaction scheme (I). product: Wherein R is a hetero atom, a substituted hetero atom, a substituted or unsubstituted C ₁ -C ₅₀ hydrocarbyl group (often a hydrocarbyl group containing a double bond), an aromatic group, or any combination thereof. Preferably, the substituted group or group contains one or more elements of Groups 13-17 (preferably Groups 15 or 16), more preferably nitrogen, oxygen, or sulfur. In addition to the Dier-Adel reaction product of the monoolefins set forth in Scheme (I), a purified product stream containing 80 wt% or more (or more preferably 90 wt% or more) of CPD can also be used. To form a DPD-Adel reaction product of CPD with one or more of the following: another CPD molecule, a conjugated diene, an acetylene, a heavy olefin, a disubstituted olefin, a trisubstituted olefin Classes, cyclic olefins, and substituted forms of the foregoing. The preferred Dier-Adel reaction product includes a drop Alkene, ethylene drop Alkene Alkene Alkene), methacrylic, and tetracyclododecene, as illustrated in the following structures:

The aforementioned Diles-Alder reaction product is a copolymer for producing a cyclic olefin polymer and a cyclic olefin copolymerized with an olefin such as ethylene. The resulting cyclic olefin copolymer and cyclic olefin polymer product are useful in a variety of applications such as packaging films.

Purified product streams containing 99 wt% or higher DCPD are useful in the manufacture of DCPD polymers using, for example, ring opening metathesis polymerization (ROMP) catalysts. The DCPD polymer product is used to form articles, particularly molded parts, such as wind turbine blades and automotive parts.

Additional ingredients can also be separated from the reactor effluent and used to form high value products. For example, isolated cyclopentenes are useful in the manufacture of polycyclopentenes (also known as polypentenamers) as described in Scheme (II).

The isolated cyclopentane is used as a foaming agent and as a solvent. Straight-chain and branched C ₅ based product for conversion of olefins and alcohols into higher. Cyclic and non-cyclic C ₅ product, optionally after hydrogenation, a system for delivering fuel octane enhancer and the blend components.

[example]

The following examples illustrate the invention. Many modifications and variations are possible and are understood to be within the scope of the appended claims. It can be implemented in ways other than those specifically described herein.

Example 1

Referring to FIG 2, comprising a non-cyclic C ₅ hydrocarbon feedstock 10 is supplied to the parallel reactors 20 in the radiant section of the furnace 21 of pipe 23. This feedstock is contacted within the reactor tube 23 with a catalyst composition (not shown). Contains cyclic C ₅ hydrocarbons (e.g., cyclopentadiene) of the reactor effluent 32 is turned off as a product or for further processing. The reactor tube 23 is positioned vertically (vertically) such that the feedstock 10 enters the reactor tube from the top and the reactor effluent 32 exits the reactor tube from the bottom. A burner 24 is positioned adjacent the top of the reactor tube such that the flame of the burner burns in a downward direction to provide a heat flux near the top of the reactor tube 23 that is greater than the reactor tube 23 Heat flux near the bottom. The barrier 25 blocks at least a portion of the flame radiation from the burner 24 from the bottom portion of the reactor tube 23. The barrier 25 additionally functions as a flue gas passage through which the flue gas (not shown) produced by the burner 24 is directed away from the radiant zone 21 to the convection zone 22 of the furnace 20. The convective heat from the flue gas is passed in the convection zone 22 to heat i) the feedstock 10 in the exchanger 12, ii) the reactivation or regeneration gas 41 in the exchanger 42, and iii) in the exchanger 61. Vapor in the 60. The heated vapor produced in exchanger 61 is directed away via conduit 62 for other uses and also serves as a facility stream. Flue gas (not shown) exits furnace 20 via chimney 26.

Feedstock 10 is directed via conduit 11 to exchanger 12, preheated to about 450 ° C to about 550 ° C, and directed to reactor tube 23 by exchanger 12 via conduit 13, inlet manifold 14 and conduit 15. The feedstock 10 is in reactor tube 23 and is contacted with a catalyst composition (not shown) at a temperature of from about 450 °C to about 800 °C. The reactor tube 23 is heated by a burner 24 such that the reactor tube has an internal temperature of the tube centerline which increases from the inlet to the outlet along the length of the tube. The outlet pressure of the reactor tube 23 is maintained between about 4 psia to about 50 psia during the contact. The feedstock 10 and transformed cyclic C ₅ hydrocarbons (e.g., cyclopentadiene) based by mixing 23 inside of the reactor tube internal device (not shown) to mix in the radial direction. In the raw material 10 at least 30wt% of the non-cyclic C ₅ hydrocarbons are converted into cyclopentadiene. The pressure drop across the reactor tube 23 during contact is from about 1 psi to about 100 psi.

The stream of material 10 can be stopped for resurrection. The reactivation gas 45 containing H ₂ is supplied via the reactivation system 40 and the conduit 41. The reactivation gas 45 is optionally heated in convection heat in the heat exchanger 42 and directed to the reactor tube 23 via conduit 43, inlet manifold 14, and conduit 15. The reactivation gas 45 is internal to the reactor tube 23 and is contacted with the catalyst composition (not shown) at a temperature of from about 400 ° C to about 800 ° C to remove at least a portion of the coke material (not shown) from the catalyst composition. . The outlet pressure of reactor tube 23 is from about 5 psia to about 250 psia during contact with reactivation gas 45. At least 10% by weight of the incrementally deposited coke material is removed from the catalyst composition.

The resurrection effluent exits the reactor tube 23 and is directed to the reactivation system 40 via conduit 30, outlet manifold 31, and conduit 44. Resurrection system Within 40, the rejuvenating effluent comprising light hydrocarbons, unreacted hydrogen, and coke particles is sent to a compression unit (not shown) and subsequently sent to a separation unit (also not shown) wherein the light hydrocarbons are concentrated gases and light hydrocarbons The depleted gas is produced. The light hydrocarbon gas (not shown) is carried away for use, in particular, as a fuel gas. The light hydrocarbon depleted stream (also not shown) is combined with fresh reactivation gas 45 in reactivation system 40 and supplied to the reactor tube. After the coke is sufficiently removed, the flow of the reactivation gas 45 is stopped and the supply of the raw material 10 is restarted.

The flow of the raw material 10 can be stopped for regeneration. The purge gas 54 is provided via a regen system 50, a conduit 51, an inlet manifold 14, and a conduit 15. The flow of purge gas 54 is provided to drive off any combustible gases (including feedstock and reactor products) from the reactor tubes 23 and associated conduits and manifolds. After the purge, the regeneration gas 53 containing the oxidizing material (e.g., air) is supplied via the Raychem system 50 and the conduit 51. The regeneration gas 53 is led to the reactor tube 23 via a conduit 51, an inlet manifold 14, and a conduit 15. Regenerating gas 53 is contacted within the reactor tube 23 with the catalyst composition (not shown) to remove at least a portion of the coke material (not shown) from the catalyst composition by oxidation with regeneration gas 53. The regeneration effluent exits the reactor tube 23 and is conducted to the Thundering system 50 via conduit 30, outlet manifold 31, and conduit 52. Regeneration after sufficient coke (eg, at least 10 wt% coke) has been removed or when no further oxidation is detected by a low concentration of oxidation products (such as CO or CO ₂ ) leaving the reactor tube 23 The flow of the gas 53 is stopped. The flow of the purge gas 54 is restarted to drive the regeneration gas from the reactor tube 23. After the purge, the flow of the raw material 10 is restarted.

Example 2

Mixture with ~22% solids by mixing 8,800 g of DI water, 600 g of 50% NaOH solution, 26 g of 43% sodium aluminate solution, 730 g of 100% n-propylamine solution, 20 g in a 5 gallon drum type container Prepared by ZSM-5 crystals and 3,190 g of Sipernat-340 vermiculite. This mixture was subsequently filled in a 5 gallon autoclave. The mixture has the following molar composition: SiO ₂ /Al ₂ O ₃ ~470 H ₂ O/SiO ₂ ~10.7 OH/SiO ₂ ~0.16 Na/SiO ₂ ~0.16 n-PA/Si~0.25.

In the autoclave, the mixture was stirred at 350 rpm and reacted at 210 °F (99 °C) for 72 hours. The resulting reaction slurry was discharged and stored in a 5 gallon drum type container. The XRD pattern of the composite material (not shown) shows the typical pure phase of ZSM-5 phase theory. The SEM of the composite material (not shown) shows that the material consists of a crystal mixture having a thickness of 0.5 to 1 micron. The synthesized crystals had a SiO ₂ /Al ₂ O ₃ molar ratio of ~467 and ~0.25 wt% Na.

This material was calcined in nitrogen at 900 °F (482 °C) for 6 hours. After cooling, the sample was reheated to 900 °F (482 °C) in nitrogen for 3 hours. In the four-step increment, the atmosphere gradually changed to 1.1. 2.1, 4.2, and 8.4% oxygen. After each step, the original state is maintained for 30 minutes. The temperature was raised to 1000 °F, the oxygen content was increased to 16.8%, and the material was held at 1000 °F for 6 hours. After cooling, 0.29 wt% Ag was added via initial wet impregnation using an aqueous solution of silver nitrate. The sample was dried at 250 °F (120 °C) for 4 hours. Subsequently, 0.44 wt% Pt was added via initial wet impregnation using an aqueous solution of platinum tetraamine. The catalyst was dried in air at room temperature, then at 250 °F (120 °C), and calcined in air at 610 °F (320 °C) for 1 hour.

Example 3

The catalyst of Example 2 was tested at two reactor temperature regimes: a substantially isothermal temperature regime and a reverse temperature regime. The catalyst (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and filled into a 3/8" OD, 18" long stainless steel reactor. The catalyst bed is held in place with quartz wool and the reactor void space is filled with coarse quartz particles. The catalyst in He (100mL / min, 30psig, 250 ℃) was dried for 1 hour, then reduced under _{H 2 (200mL / min, 30psig} , 500 ℃) 1 hour. The catalyst was followed by a feed test performance containing n-pentane, H ₂ , and make-up He.

The test conditions for maintaining the isothermal temperature regime are: 0.5 g ZSM-5 (400:1) / 0.4% Pt / 0.2% Ag, C ₅ H ₁₂ at a reactor inlet of 5 psia, H _{2 at} 1:1 : C ₅ feed, and the total pressure of 60 psia under the complement of He, WHSV is 16.1 h ^-1 , 600 ° C bed temperature. The test conditions used to maintain the reverse temperature regime are: 0.5 g ZSM-5 (400:1) / 0.4% Pt / 0.2% Ag, C ₅ H ₁₂ at 5 psia at the reactor inlet, H _{2 at} 1:1: C ₅ feed and a total pressure of He in the make up of 60psia, WHSV of 4.0h ^-1 for the test and applying a linear gradient a temperature gradient of 500 deg.] C to 600 deg.] C. The performance results for Example 3 are shown in Figures 4 and 5.

As shown in Figure 3, operation of the reactor in an inverse or gradient temperature regime (i.e., at a lower temperature of the inlet and a higher temperature at the outlet) results in the catalyst being isothermally operated at the same outlet temperature. The reactor has a higher stability. In particular, Figure 3 shows: While the temperature of the total momentum of the two kinds of cyclic hydrocarbons C ₅ initially yield similar, the temperature of the temperature trend and the like having a reactor, after 53 hours, the yield decreased to its original initial value 43%. In contrast, the yield in the reverse temperature situational operation plan was only reduced to 73% of its original value, and this yield decline occurred over a longer period of 57 hours. Shown in Figure 4, when it is desired that the minimum byproduct C ₁ -C ₄ hydrocarbon cracking product yield, isothermal operation of the reactor or the ratio of the temperature gradient by the inverse situation the operator may be beneficial.

Example 4

The mixture having ~22% solids was prepared by mixing 950 g of DI water, 53.5 g of 50% NaOH solution, 76.8 g of 100% n-propylamine solution, 10 g of ZSM-5 crystals, and 336 g in a 2 liter vessel. of Ultrasil PM ^TM Modified silica, and 4.4g of silver nitrate was prepared. This mixture was subsequently filled in a 2 booster. The mixture has the following molar composition: SiO ₂ /Al ₂ O ₃ >1000 H ₂ O/SiO ₂ ~10.98 OH/SiO ₂ ~0.17 Na/SiO ₂ ~0.17 n-PA/Si~0.25.

In the autoclave, the mixture was mixed at 250 rpm and reacted at 230 °F (110 °C) for 72 hours. The resulting product was filtered and washed with deionized water and subsequently dried overnight at 250 °F. The XRD pattern of the composite material (not shown) shows the typical pure phase of ZSM-5 phase theory. The SEM of the composite material (not shown) shows that the material consists of a large crystal mixture having a size < 1 micron. The resulting ZSM-5 crystal had a SiO ₂ /Al ₂ O ₃ molar ratio of >800 and ~0.28 wt% Na and 0.9 wt% Ag.

This material was calcined in nitrogen at 900 °F for 6 hours. After cooling, the sample was reheated to 900 °F in nitrogen for 3 hours. The atmosphere gradually changed to 1.1, 2.1, 4.2, and 8.4% oxygen in a four-step increment. After each step, the original state is maintained for 30 minutes. The temperature was raised to 1000 °F, the oxygen content was increased to 16.8%, and the material was held at 1000 °F for 6 hours. After cooling, 0.45 wt% Pt was added via initial wet impregnation using an aqueous solution of platinum tetraamine. The catalyst was dried in air at room temperature, then at 250 °F, and calcined at 660 °F for 3 hours in air. The catalyst powder was pressurized (15 tons), crushed, and sieved to obtain a particle size of 40-60 mesh.

Example 5

The catalyst of Example 4 was tested under two reactor operating strategies: a continuous oil on strategy and a batch H ₂ revival strategy. The catalyst (0.5 g) was physically mixed with quartz (1.5 g, 60-80 mesh) and filled into a 3/8" OD, 18" long stainless steel reactor. The catalyst bed is held in place with quartz wool and the reactor void space is filled with coarse quartz particles. The catalyst in He (100mL / min, 30psig, 250 ℃) was dried for 1 hour, then reduced under _{H 2 (200mL / min, 30psig} , 500 ℃) 1 hour. The catalyst was followed by a feed test performance containing n-pentane, H ₂ , and make-up He. The test conditions for the continuous oil operation strategy are: 0.5 g of [0.96% Ag]-ZSM-5/0.5% Pt, 5.0 psia of C ₅ H ₁₂ , 1:1 molar H ₂ : C ₅ , 14.7 WHSV, 45 psia total pressure over the oil. The test conditions for the intermittent H ₂ revival strategy are the following: the reactor is on 1 hour oil and 1 hour on H ₂ revival (at 600 ° C at 200 cm ³ min ^-1 H ₂ and 45 psia total H ₂ , That is, there is no other He cycle. The efficacy results for the two operating strategies are shown in Figure 5 as the address-time-yield of the cyclic C5 (i.e., cC5 moles/Pt moles per second). Figure 5 illustrates the resurrection H ₂ can improve the ability of the catalyst after the time of the catalytic C ₅ hydrocarbon ring.

To the extent that they are not inconsistent with this text, all documents described herein are hereby incorporated by reference in their entirety in their entirety in the entire entireties in The invention has been shown and described with reference to the preferred embodiments of the invention and the invention Therefore, no intention is intended to limit the invention. Similarly, the term "comprising" is synonymous with the term "including". Similarly, whenever a group of components, elements, or elements has been When the phrase "contains" is used, it is understood that we also ponder the composition or group of elements, which has a transitional phrase "consisting essentially of", "consisting of", and consisting of the following groups Select "or" in the "Before the description of the constituent elements or elements, etc."

Claims (23)

A non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbons method comprising: a) providing a parallel reactor furnace tubes, the tubes of such reactors containing catalyst composition; b) providing a non-cyclic a raw material of a C ₅ hydrocarbon; c) contacting the raw material with a catalyst composition, and d) obtaining a reactor effluent comprising a cyclic C ₅ hydrocarbon, wherein the cyclic C ₅ hydrocarbon comprises cyclopentadiene; wherein i) The reactor tube is positioned vertically such that the feedstock is provided from the top and the reactor effluent is withdrawn from the bottom and ii) the furnace comprises at least one burner positioned adjacent the top of the reactor tube with a downward direction The burning flame provides a heat flux near the top that is greater than the heat flux near the bottom of the reactor tube. A method of claim 1, wherein a barrier blocks at least a portion of the radiation from the burner flame from the bottom portion of the reactor tube. The method of claim 2, wherein the barrier is a flue gas passage. The method of claim 1, wherein the reactor tube has an inverse temperature profile or an isothermal temperature profile. The method of claim 1, wherein the contacting of the raw material with the catalyst composition is carried out in the presence of a gas comprising H ₂ and/or C ₁ to C ₄ hydrocarbons. The method of claim 1, further comprising facilitating heat transfer from the tube wall to the catalyst composition by providing fins or contours inside or outside the reactor tube. The method of claim 1, further comprising mixing the raw material and the converted cyclic C ₅ hydrocarbon in the radial direction by providing mixing internals in the reactor tube, wherein The mixing internal device is positioned i) in the bed of the catalyst composition or ii) in the portion of the reactor tube to separate two or more zones of the catalyst composition. The method of claim 1, wherein the contacting step c) occurs at a temperature of from about 450 ° C to about 800 ° C. The method of claim 1, wherein the feed to the reactor tube inlet has a temperature of from about 450 °C to about 550 °C. The method of claim 1, wherein the reactor tube has an outlet pressure of from about 4 psia to about 50 psia during the contacting step c). The method of claim 1, wherein the reactor tube has a pressure drop from about 1 psi to about 100 psi measured from the reactor inlet to the reactor outlet during contact of the feedstock with the catalyst composition. The method according to Claim 1 patentable scope, wherein the non-cyclic C ₅ hydrocarbons is at least about 30% by weight is converted into cyclopentadiene. The method of claim 1, wherein the catalyst composition comprises platinum on ZSM-5, platinum on zeolite L, and/or platinum on the silicate-modified vermiculite. The method of claim 1, wherein the catalyst composition is an extruded body having a diameter of from 2 mm to 20 mm. The method of claim 1, wherein the catalyst composition is cross-sectionally shaped to have one or more leaves and/or concave sections, and wherein the leaves and/or concave sections of the catalyst composition are spiral or It is straight. The method of claim 1, wherein the inner diameter of the reactor tube is from about 20 mm to about 200 mm. The method of claim 1, further comprising transferring heat from the flue gas by convection to a rejuvenation gas, a regeneration gas, a vapor, and/or the feedstock in a convection zone of the furnace. The method of claim 1, further comprising i) providing two or more furnaces, each furnace comprising parallel reactor tubes, the reactor tubes containing a catalyst composition and ii) providing a reactivation gas or a regeneration gas To one or more furnaces, and at the same time, the raw materials containing acyclic C ₅ hydrocarbons are supplied to different one or more furnaces. The method of claim 1, further comprising: a) discontinuing the supply of the raw material comprising the acyclic C ₅ hydrocarbon; b) providing the reactivation gas comprising H ₂ ; c) composing the reactivation gas with the catalyst contacting the catalyst to remove coke material composition of at least a portion; and d) stops supplying gas and resurrection resumes providing material comprising a non-cyclic C ₅ hydrocarbons. The method according to Claim 1 patentable scope, further comprising: a) providing a feedstock comprising a non-stop cyclic C ₅ hydrocarbons; b) from the reaction tube chased combustible gas (including feedstock and reactor product) to The concentration is below the flammable concentration limit; c) contacting the regeneration gas comprising the oxidizing material with the catalyst composition to oxidize at least a portion of the coke material removed on the catalyst composition; d) being driven by the reactor the net regeneration gas concentration to a concentration below the flammable limit; and e) the regeneration gas is stopped and re-started to provide chased feedstock comprising a non-cyclic C ₅ hydrocarbons. A non-cyclic C ₅ hydrocarbons to C ₅ cyclic hydrocarbon conversion system, wherein the conversion system comprises: a) feed stream comprising hydrocarbons of the non-cyclic C _5; b) comprising parallel furnace tubes of the reactor, the reactor tube containing the catalyst composition; and c) by contacting the feedstock with the catalyst composition of the resulting cyclic C ₅ hydrocarbon comprising the reactor effluent stream, wherein the cyclic hydrocarbon comprises a cyclopentadiene C ₅ Wherein i) the reactor tube is positioned vertically such that the feedstock is provided from the top and the reactor effluent is withdrawn from the bottom and ii) the furnace comprises at least one burner positioned adjacent the top of the reactor tube A flame that burns in a downward direction to provide a heat flux near the top that is greater than the heat flux near the bottom of the reactor tube. The method of claim 1, wherein the catalyst composition is formed into a structured catalyst shape. The method of claim 1, further comprising providing the feedstock to the at least one adiabatic reaction zone prior to the contacting of c).